Cumene (Isopropylbenzene)

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HO

Rx-ID: 2011775 View in Reaxys 1/481 Yield 98 %

Conditions & References 5 :Example 5: Transfer hydrogenolysis of 2-Phenyl-2-propan-2-ol.Pd/C (5 molpercent, 42 mg, 0.021 mmol) is weighed into a reaction flask. A solvent mixture consisting of ethanol (2.4 mL) and water (0.6 mL) and ammonium formate (6 mg, 0.095 mmol, 30 molpercent) is added, the reaction flask is capped with a rubber septa and the mixture is heated (80 °C) for 2 minutes. Formic acid (50 μ^, 1.05 mmol, 3 equivalents) and then 2-Phenyl-2-propan-2-ol (58 μΙ^, 0.42 mmol) are added by syringe. The reaction is run for 10-40 minutes and the reaction is quenched with brine. The product is extracted by DCM and the organic phase is dried by Na2S04. The product isopropylbenzene was analyzed

by NMR and produced in 98percent yield.

With formic acid, ammonium formate, 5 palladium on charcoal in ethanol, water, T= 80 °C Patent; SAMEC, Joseph; LUNDSTEDT, Anna; SAWADJOON, Supaporn; KAT2BIZ AB C/O INTERPARES KONSULT AB; WO2012/121659; (2012); (A1) English View in Reaxys

92 %

With diphosphorous tetraiodide in benzene, Time= 6h, Heating Suzuki, Hitomi; Tani, Hiroyuki; Kubota, Hirohisa; Sato, Naofumi; Tsuji, Junko; Osuka, Atsuhiro; Chemistry Letters; (1983); p. 247 - 248 View in Reaxys

49 %

With indium(III) chloride, dimethylmono-chlorosilane, benzil in dichloromethane, Time= 3h, T= 20 °C Yasuda, Makoto; Yamasaki, Satoshi; Onishi, Yoshiyuki; Baba, Akio; Journal of the American Chemical Society; vol. 126; nb. 23; (2004); p. 7186 - 7187 View in Reaxys

55 % Spectr.

With dimethyl-dichlorosilane, sodium iodide in dichloromethane, acetone, Time= 22h, Ambient temperature Wiggins, J. Mark; Synthetic Communications; vol. 18; nb. 7; (1988); p. 741 - 750 View in Reaxys

79 % Chromat.

With triphenyl phosphite, tetraethylammonium bromide in acetonitrile, constant current electrolysis, 50 mA Maeda, Hatsuo; Maki, Toshihide; Eguchi, Kaoru; Koide, Takashi; Ohmori, Hidenobu; Tetrahedron Letters; vol.

35; nb. 24; (1994); p. 4129 - 4132 View in Reaxys With hydrogen, palladium on activated charcoal in ethanol, T= 50 °C , var. solv.: isooctane with promotors aryl halides, Product distribution Marques, Carlos Alberto; Selva, Maurizio; Tundo, Pietro; Gazzetta Chimica Italiana; vol. 126; nb. 6; (1996); p.

317 - 328 View in Reaxys 1 : Example 1 A cumene solution containing 25percent by weight of cumyl alcohol was passed together with hydrogen through a reactor in which a copper-chromium catalyst was packed to react them. In this case, the total concentration of formic acid and acetic acid in the cumene solution was 10 ppm by weight. A molar ratio of hydrogen to cumyl alcohol of 8, LHSV of cumene of 1.5 hour-1, and reaction pressure of 1 MPa-G(gauge pressure) were adopted. Only cumene was produced in the reaction of cumyl alcohol. The result is shown in Table 1.

With hydrogen, copper-chromium powder, p= 7500.75Torr Patent; Sumitomo Chemical Company, Limited; EP1471061; (2004); (A1) English View in Reaxys 1 : Comparative Example 1 Comparative Example 1 It was carried out in the same manner as in Example 1 except that the total concentration of formic acid and acetic acid in the cumene solution was 300 ppm by weight. The result is shown in Table 1.

With hydrogen, copper-chromium powder, p= 7500.75Torr

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Patent; Sumitomo Chemical Company, Limited; EP1471061; (2004); (A1) English View in Reaxys 2 : Example 2 Example 2 It was carried out in the same manner as in Example 1 except that the total concentration of formic acid and acetic acid in the cumene solution was 40 ppm by weight. The result is shown in Table 1 With hydrogen, copper-chromium powder, p= 7500.75Torr Patent; Sumitomo Chemical Company, Limited; EP1471061; (2004); (A1) English View in Reaxys 3 : Example 3 Example 3 It was carried out in the same manner as in Example 1 except that the total concentration of formic acid and acetic acid in the cumene solution was 100 ppm by weight. The result is shown in Table 1.

With hydrogen, copper-chromium powder, p= 7500.75Torr Patent; Sumitomo Chemical Company, Limited; EP1471061; (2004); (A1) English View in Reaxys 1 : Example 1 While passing cumene through a fixed-bed flow reactor in which 40 g of an unreduced copper-chromium catalyst precursor was packed, the pressure and temperature in the reactor were elevated to 1 MPaG and 150°C, respectively. At this time, the flow amount was set to a LHSV of 1.5 h-1 and cumene flown from the reactor was used by feeding again to the reactor after separated from water produced by reduction. Hydrogen was flown so that the hydrogen concentration in cumene became 0.01percent by weight, and the reactor temperature was elevated to 160°C. The flowing was continued for 16 hours at the same temperature to terminate the reduction. During the reduction, the maximum temperature in the reactor was 161 to 162°C. The XRD of a catalyst obtained was measured, and as the result, the particle diameter of copper was 23 nm in (111) face. After the reduction, the reactor was heated to 220°C and a cumene solution containing 20percent by weight of cumyl alcohol was fed at 0.9 g/minute thereto and hydrogen was fed at 500 Ncc/minute. The reaction liquid after 25 hours from the beginning of the feed, was analyzed, and as the result, the conversion of cumyl alcohol was higher than 99percent and the selectivity of cumene was 100percent.

Stage 1: With hydrogen, unreduced copper-chromium catalyst precursor, Time= 10 - 16h, T= 110 - 200 °C , p= 7500.75Torr Stage 2: With hydrogen, Time= 25 - 50h, T= 220 °C Patent; Sumitomo Chemical Company, Limited; EP1433770; (2004); (A1) English View in Reaxys I.IB :The 6-20 mesh particles of reduced T-366 catalyst, prepared by the procedure of Illustrative Embodiment I, were loaded into the reflux zone of a thick walled 31 cm long Vigreux column with an internal diameter of 1. 5 cm while inside a nitrogen filled glove box. A small piece of glass wool was used to support the catalyst particles. The column was attached to a thick walled 250 ml round bottomed flask which served as the bottom segment of the reactor for catalytic distillation. Hydrogen gas was added via a regulator to the apparatus to maintain a pressure between 1 and 10 bar. The flow rate was adjusted to maintain twice the amount of hydrogen required for the reaction stoichiometry. 50 grams of 2-phenyl-2-propanol (cumyl alcohol) from Avacado Chemical was added to the 250 mL flask, containing a magnetic stir bar. The flask containing the CUMYL alcohol was lowered into a heater and the temperature was raised until the liquid refluxed in the Vigreux column containing the catalyst. Lower boiling cumene and water were distilled out from the top of the column. Additional cumyl alcohol was continually added with a slight molar excess of hydrogen to replace the amount of CUMYL alcohol that was converted to cumene and distilled off. The cumene product easily separated from the denser water phase. It was optionally dried further with 3A molecular sieves. The results are provided in Table 2 below. As shown, the top product stream produced, (after removal of the water), had a purity of cumene OF >99. 5 wt. percent. No measurable cumyl alcohol (<0.01 wt. percent) was found in the cumene product. When desired, the bottoms can be removed, optionally diluted with cumene and sent to a fixed bed hydrogenation reactor to make additional cumene.

With hydrogen, reduced copper on silica (T-366) catalyst, p= 750.075 - 7500.75Torr , Heating / reflux Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys

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I.ID :The reduced Pd-Mordenite catalyst, prepared by the procedure of Illustrative Embodiment IC above, was loaded into the reflux zone of a thick walled 31 cm long Vigreux column with an internal diameter of 1.5 cm while inside a nitrogen filled glove box. The same procedure as described in IB above was followed for the set-up and operation of a catalytic distillation operation. The results are provided in Table 3 below. As shown, the top product stream produced, after removal of water, had a purity of cumene of >99.5 wt. percent. No measurable cumyl alcohol (<0. 01 wt. percent) was found in the cumene product. When desired, the bottoms can be removed, optionally diluted with cumene and sent to a fixed bed hydrogenation reactor to make additional cumene.

With hydrogen, reduced Pd-Mordenite catalyst, p= 750.075 - 7500.75Torr , Heating / reflux Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys With samarium diiodide, water in tetrahydrofuran, decane, T= 20 °C Ankner, Tobias; Hilmersson, Goeran; Tetrahedron; vol. 65; nb. 52; (2009); p. 10856 - 10862 View in Reaxys 3 :Example 3According to the method described in the specification as schematically shown in FIG. 3, using cumene as the alkylbenzene, an oxidation reaction liquid (101) containing 25percent to 30percent by weight of cumene hydroperoxide was obtained by oxidizing cumene with air in the oxidation step. An epoxidation reaction liquid (102) containing mainly propylene oxide, cumyl alcohol, unreacted propylene, and cumene was obtained by passing the oxidation reaction liquid and propylene through a reactor filled with a titanium-containing silicon oxide catalyst in the epoxidation step. Cumyl alcohol is an alcohol comes from the cumene hydroperoxide. The unreacted propylene (103) was separated and removed from the resulted reaction liquid (102) to obtain a reaction liquid (104) after recovering propylene. The reaction liquid (104) after recovering propylene was separated into a liquid fraction (105) containing mainly cumyl alcohol and cumene and a fraction containing mainly propylene oxide in the propylene oxide purification step, and then the fraction containing mainly propylene oxide was distilled with a plurality of distillation columns including extraction distillation so as to obtain a propylene oxide product which satisfies the product qualities. The liquid fraction (105) containing mainly cumyl alcohol and cumene as a continuous phase and a hydrogen gas as a dispersed phase was fed through the reactor in up-flow mode which was provided with i) a catalyst bed comprising an activated alumina catalyst and a palladium containing catalyst and ii) the gas-liquid dispersion device according to the present invention at the middle of the reactor, so that cumyl alcohol was reduced to cumene. The conversion of cumyl alcohol to cumene was more than 98percent. The obtained cumene was recycled to the oxidation step. FIG. 3 illustrates the schematic flow-chart of Example 3 described in the specification.

With hydrogen, activated alumina catalyst, palladium containing catalyst, the gas-liquid dispersion device, Industry scale, Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; US2011/4009; (2011); (A1) English View in Reaxys 91.2 2 :Example 2In a 1 L autoclave (reactor), 100 g of a toluene solution containing 0.05percent by mass of ammonia, %Chromat. and 10percent by mass of 2-phenyl-2-propanol, and 3.0 g of palladium/alumina catalyst were charged. The atmosphere of the reactor was replaced with nitrogen gas, and then pressurized with hydrogen gas by 0.9 MPa (absolute pressure), warmed to 200° C. under stirring, and thereafter reacted for 6 hrs. The reaction solution was withdrawn and analyzed by gas-chromatography, which revealed that conversion rate of 2-phenyl-2-propanol was 99.9percent, selectivity to cumene was 9L3percent and cumene yield was 91.2percent.

With ammonia, hydrogen, palladium/alumina in toluene, Time= 6h, T= 200 °C , p= 6750.68Torr , Autoclave, Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2012/253073; (2012); (A1) English View in Reaxys 87 %Spectr.

With formic acid, 5 palladium on charcoal, ammonium formate in methanol, water, T= 80 °C Sawadjoon, Supaporn; Lundstedt, Anna; Samec, Joseph S.M.; ACS Catalysis; vol. 3; nb. 4; (2013); p. 635 - 642 View in Reaxys With carbon dioxide, 5 palladium on charcoal, hydrogen in methanol, Time= 1h, T= 49.84 °C , p= 7500.75Torr , Autoclave, Green chemistry, Pressure, Solvent Lin, Hsin-Wei; Yen, Clive H.; Hsu, Han; Tan, Chung-Sung; RSC Advances; vol. 3; nb. 38; (2013); p. 17222 17227

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View in Reaxys

Br

Rx-ID: 632490 View in Reaxys 2/481 Yield

Conditions & References

59 %

General procedure for Si-AlClx catalyzed Friedel-Crafts alkylation:#10; General procedure: Anhydrous benzene (1.00 mL, 11.2 mmol) was added to a heterogenous mixture of Si-AlClx (0.611 g, 1.02 mmol [loading: 1.67 mmol/g]) in anhydrous CH2Cl2 (10 mL) in a 50 mL PTFE lined glass reactor, followed by slow addition of 2-bromobutane (1.11 mL, 10.2 mmol). The glass reactor was capped with a plastic releasing valve top and irradiated in a Milestone START Microwave at 750 W with a ramp to 140 °C over 2 min, and then maintained for an additional 3 min. The flask was cooled, underwent vacuum filtration, washed with a solution of 2percent CH3OH in EtOAc, and the combined filtrate was concentrated under reduced pressure. Column chromatography (hexanes) afforded a sec-butylbenzene (1.26 g, 92percent) as clear colorless liquid. #10; With silica-supported aluminum chloride in dichloromethane, Time= 0.0833333h, T= 140 °C , Microwave irradiation, Friedel-Crafts Alkylation Zupp, Laurine R.; Campanella, Veronica L.; Rudzinski, Diandra M.; Beland, Franois; Priefer, Ronny; Tetrahedron Letters; vol. 53; nb. 39; (2012); p. 5343 - 5346 View in Reaxys With silica-alumina, T= 300 - 320 °C Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys With aluminum tri-bromide Gustavson; Chemische Berichte; vol. 11; (1878); p. 1251; Bulletin de la Societe Chimique de France; vol. <2> 30; (1878); p. 23 View in Reaxys Silva; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 317,588 View in Reaxys

(v4)

S – O

(v3) (v4)

N N (v4) (v4) Li++ O(v3) – Li (v4) S N (v4) N

S S

Rx-ID: 40062458 View in Reaxys 3/481 Yield 66 %, 23 %

Conditions & References B : Decomposition of [Li2{CH2S(O)Ph}2(TMEDA)2] (1) (B) In a closed Schlenk tube equipped with a condenser, a solution of freshly prepared crystals of 1 (150 mg) in toluene (25 mL) was heated to reflux for 4 h, during which time the initial pale yellow solution became brown in color.

Subsequently the gaseous phase was analyzed by means of GC-MS showing exclusively the formation of ethylene.

Then, an aqueous solution of NH4Cl (25 mL; 30percent) was added.

After phase separation and extraction of the aqueous phase with diethyl ether (3 * 10 mL), the combined organic phases were analyzed by GC-MS showing the formation of diphenyl disulfide (66percent), ethylbenzene (4percent), m/o/p-xylene (3percent), isopropylbenzene (23percent) and n-propylbenzene (4percent) (newly formed products were summed up to 100percent).

Stage 1: in toluene, Time= 4h, T= 110 °C , Inert atmosphere, Schlenk technique Stage 2: With ammonium chloride in water, toluene, Inert atmosphere, Schlenk technique Ludwig, Gerd; Ströhl, Dieter; Schmidt, Harry; Steinborn, Dirk; Inorganica Chimica Acta; vol. 429; (2015); p. 30 33 View in Reaxys

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Rx-ID: 850147 View in Reaxys 4/481 Yield 100 %

Conditions & References With hydrogen, lt;Ir(COD)P(i-Pr)3pygt;PF6 in dichloromethane, Time= 1h, T= 0 °C , reaction rate; various catalysts, Product distribution Collman; Kosydar; Bressan; Lamanna; Garrett; Journal of the American Chemical Society; vol. 106; nb. 9; (1984); p. 2569 - 2579 View in Reaxys

100 %

With hydrogen, sodium tetrahydroborate, Ni(2-ethylhexanoate)n + NaBH4, Time= 24h, p= 1520Torr , Ambient temperature Collman; Kosydar; Bressan; Lamanna; Garrett; Journal of the American Chemical Society; vol. 106; nb. 9; (1984); p. 2569 - 2579 View in Reaxys

Ca. 100 %

With 2,6-dimethoxy-9,10-dihydroanthracene in diphenyl ether, T= 320 °C , Inert atmosphere, Kinetics, Thermodynamic data, Reagent/catalyst, Temperature, Solvent, Concentration Keller, Friedrich; Ruechardt, Christoph; Journal fuer Praktische Chemie/Chemiker-Zeitung; vol. 340; nb. 7; (1998); p. 642 - 648 View in Reaxys

100 %

With C28H18Co(1-)*K(1+)*2C4H10O2, hydrogen in toluene, Time= 24h, T= 60 °C , p= 1500.15Torr , chemoselective reaction Gaertner, Dominik; Welther, Alice; Rad, Babak Rezaei; Wolf, Robert; Von Wangelin, Axel Jacobi; Angewandte Chemie - International Edition; vol. 53; nb. 14; (2014); p. 3722 - 3726; Angew. Chem.; vol. 126; nb. 14; (2014); p.

3796 - 3800,5 View in Reaxys

100 %

With anhydrous iron chloride, lithium aluminium tetrahydride, hydrogen in tetrahydrofuran, Time= 3h, T= 18 °C , p= 750.075Torr , Inert atmosphere, Sealed tube, Reagent/catalyst Gieshoff, Tim N.; Villa, Matteo; Welther, Alice; Plois, Markus; Chakraborty, Uttam; Wolf, Robert; Jacobi Von Wangelin, Axel; Green Chemistry; vol. 17; nb. 3; (2015); p. 1408 - 1413 View in Reaxys

100 %

With hydrogen, Super-Hydride® in tetrahydrofuran, Time= 18h, T= 23 °C , p= 30402Torr , Inert atmosphere, Schlenk technique, Catalytic behavior Manna, Kuntal; Zhang, Teng; Carboni, Michal; Abney, Carter W.; Lin, Wenbin; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13182 - 13185 View in Reaxys

100 %

With hydrogen in methanol, Time= 0.75h, T= 40 °C , p= 7757.43Torr Sharma, Priti; Singh; RSC Advances; vol. 4; nb. 102; (2014); p. 58467 - 58475 View in Reaxys

99 %

With water, zinc, bis[chlorido(η2,η2-cycloocta-1,5-diene)rhodium-(I)] in 1,4-dioxane, Time= 20h, T= 90 °C Sato, Takashi; Watanabe, Shoji; Kiuchi, Hiroyoshi; Oi, Shuichi; Inoue, Yoshio; Tetrahedron Letters; vol. 47; nb.

44; (2006); p. 7703 - 7705 View in Reaxys

99 %

With FeCl3·6H2O, hydrazine hydrate in ethanol, Time= 24h, T= 50 °C Lamani, Manjunath; Ravikumara, Guralamata S.; Prabhu, Kandikere Ramaiah; Advanced Synthesis and Catalysis; vol. 354; nb. 8; (2012); p. 1437 - 1442 View in Reaxys

99 %

With oxygen, GNO3, hydrazine hydrate in ethanol, Time= 24h, T= 20 °C , p= 760.051Torr , chemoselective reaction

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Lamani, Manjunath; Guralamata, Ravikumara Siddappa; Prabhu, Kandikere Ramaiah; Chemical Communications; vol. 48; nb. 52; (2012); p. 6583 - 6585 View in Reaxys > 99 %

With bis-triphenylphosphine-palladium(II) chloride, Triethoxysilane, (Z)-N,N-diisopropyl-2-styrylbenzamide in tetrahydrofuran, Time= 24h, T= 65 °C , Inert atmosphere, chemoselective reaction Bai, Xing-Feng; Xu, Li-Wen; Zheng, Long-Sheng; Jiang, Jian-Xiong; Lai, Guo-Qiao; Shang, Jun-Yan; Chemistry - A European Journal; vol. 18; nb. 26; (2012); p. 8174 - 8179 View in Reaxys

> 99 %

With hydrogen in isopropyl alcohol, Time= 20h, T= 40 °C , p= 750.075Torr , Schlenk technique, Inert atmosphere Dehe, Daniel; Wang, Lei; Müller, Melanie K.; Dörr, Gunder; Zhou, Zhou; Klupp-Taylor, Robin N.; Sun, Yu; Ernst, Stefan; Hartmann, Martin; Bauer, Matthias; Thiel, Werner R.; ChemCatChem; vol. 7; nb. 1; (2015); p. 127 - 136 View in Reaxys

98%

With hydrogen in ethanol, Time= 1.5h, T= 20 °C , p= 760.051Torr Kim, Eunsuk; Jeong, Han Saem; Kim, B. Moon; Catalysis Communications; vol. 45; (2014); p. 25 - 29 View in Reaxys

98 %

With hydrogen in water, ethyl acetate, Time= 1.5h, T= 40 °C , p= 15001.5Torr Huang, Jianping; Yang, Hengquan; Chemical Communications; vol. 51; nb. 34; (2015); p. 7333 - 7336 View in Reaxys

95 %

With hydrogen, Super-Hydride® in tetrahydrofuran, Time= 20h, T= 23 °C , p= 30003Torr , Autoclave, Reagent/catalyst Zhang, Teng; Manna, Kuntal; Lin, Wenbin; Journal of the American Chemical Society; vol. 138; nb. 9; (2016); p.

3241 - 3249 View in Reaxys

94 %

With hydrogen, Time= 1h, T= 80 °C , p= 7500.75Torr , Autoclave Upadhyay, Praveenkumar; Srivastava, Vivek; RSC Advances; vol. 5; nb. 1; (2015); p. 740 - 745 View in Reaxys

93 %

With hydrogen in ethanol, T= 40 °C , p= 3724.25Torr , Flow reactor, chemoselective reaction Osako, Takao; Torii, Kaoru; Tazawa, Aya; Uozumi, Yasuhiro; RSC Advances; vol. 5; nb. 57; (2015); p. 45760 45766 View in Reaxys

92 %

With sodium hydrogen telluride in ethanol, Time= 2.5h, Heating Barton, Derek H. R.; Bohe, Luis; Lusinchi, Xavier; Tetrahedron; vol. 46; nb. 15; (1990); p. 5273 - 5284 View in Reaxys

92 %

With 2C2H3O2 (1-)*Pd(2+)*3Na(1+)*C18H12O9PS3 (3-), hydrogen, glycerol, Time= 2h, T= 100 °C , p= 2250.23Torr , Schlenk technique Chahdoura, Faouzi; Pradel, Christian; Gomez, Montserrat; Advanced Synthesis and Catalysis; vol. 355; nb. 18; (2013); p. 3648 - 3660 View in Reaxys

89 %

With sodium tetrahydroborate, 1 mol Pd/C, acetic acid in isopropyl alcohol, Time= 0.25h, T= 20 °C Tran, Anthony T.; Huynh, Vincent A.; Friz, Emily M.; Whitney, Sara K.; Cordes, David B.; Tetrahedron Letters; vol. 50; nb. 16; (2009); p. 1817 - 1819 View in Reaxys

89 %

With [Re(NO)(.eta.(2)-H2)Br2(PiPr3)2], dimethylamine borane, hydrogen, Time= 6.5h, T= 90 °C , p= 7500.75Torr , Autoclave

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Jiang, Yanfeng; Hess, Jeannine; Fox, Thomas; Berke, Heinz; Journal of the American Chemical Society; vol.

132; nb. 51; (2010); p. 18233 - 18247 View in Reaxys 74 %

With hydrazine hydrate, Ni(0) nanoparticles/K-10 Montmorillonite clay in ethanol, Time= 8h, T= 70 °C Dhakshinamoorthy, Amarajothi; Pitchumani, Kasi; Tetrahedron Letters; vol. 49; nb. 11; (2008); p. 1818 - 1823 View in Reaxys

70 %

With FeH(CO)2(P(C6H5)3) in diethyl ether, Time= 2h, Ambient temperature Roustan, Jean-Louis A.; Forgues, Alain; Merour, Jean-Yves; Venayak, Narinder D.; Morrow, B. A.; Canadian Journal of Chemistry; vol. 61; (1983); p. 1339 - 1346 View in Reaxys With hydrogen, anhydrous magnesium hydroxide, rhodium in ethanol, T= 30 °C , further catalysts, Rate constant Nakao, Yukimichi; Kaeriyama, Kyoji; Chemistry Letters; (1983); p. 949 - 950 View in Reaxys With hydrogen, monoaluminum phosphate, silica gel, platinum in methanol, T= 27 °C , p= 3750.3Torr , initial reduction rate was determined Aramendia, M. A.; Borau, V.; Jimenez, C.; Marinas, J. M.; Acta Chimica Academiae Scientiarum Hungaricae; vol.

110; nb. 1; (1982); p. 97 - 101 View in Reaxys With hydrogen, nickel-palladium, T= 52.9 - 118.9 °C , p= 750.06Torr , Ea; other temperatures, pressures, catalysts, Thermodynamic data Lebedeva, V. I.; Gryaznov, V. M.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 37; nb. 5; (1988); p. 1018 - 1020; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 5; (1988); p. 1158 - 1160 View in Reaxys With HW(CO)3(C5H5), T= 100 °C , var. catalysts, Rate constant Sweany, Ray L.; Comberrel, David S.; Dombourian, Maureen F.; Peters, Natasha A.; Journal of Organometallic Chemistry; vol. 216; nb. 1; (1981); p. 57 - 63 View in Reaxys With HCo(CO)4, carbon monoxide in dichloromethane, T= 0 °C , Rate constant Roth, Jerome A.; Wiseman, Paul; Ruszala, Lois; Journal of Organometallic Chemistry; vol. 240; nb. 3; (1982); p.

271 - 276 View in Reaxys With n-butyllithium, hydrogen, bis(cyclopentadienyl)titanium dichloride, Time= 3h, with various titanium complexes, at various times, Rate constant Booth, B. L.; Ofunne, G. C.; Stacey, C.; Tait, P. J. T.; Journal of Organometallic Chemistry; vol. 315; (1986); p. 143 - 156 View in Reaxys With hydrogen, palladium on activated charcoal in methanol, T= 25 °C , p= 759.8Torr , various catalysts, Rate constant Kacer, Petr; Laate, Leiv; Cerveny, Libor; Collection of Czechoslovak Chemical Communications; vol. 63; nb. 11; (1998); p. 1915 - 1926 View in Reaxys With ethanol, sodium Klages; Chemische Berichte; vol. 35; (1902); p. 3507 View in Reaxys Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 134; (1902); p. 846; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 166

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View in Reaxys 100 % Spectr.

With sodium hydrogen telluride in ethanol, Time= 2.5h, Heating Barton, Derek H. R.; Bohe, Luis; Lusinchi, Xavier; Tetrahedron Letters; vol. 28; nb. 52; (1987); p. 6609 - 6612 View in Reaxys With Ni(mesal)2, sulfuric acid, tri-isobutyl aluminium, 1.) at room temp., 1 h, Yield given. Multistep reaction Giacomelli, Giampaolo; Bertero, Luigi; Lardicci, Luciano; Tetrahedron Letters; vol. 22; (1981); p. 883 - 886 View in Reaxys

90 % Spectr.

With hydrogen, lt;CpFe(CO)2(CH3)gt; in tetrahydrofuran, T= 110 °C , p= 37503Torr Brunner, Henri; Fisch, Konrad; Angewandte Chemie; vol. 102; nb. 10; (1990); p. 1189 - 1191 View in Reaxys With BH3*THF, acetic acid, 1.) THF, RT, 1 h; 2.) THF, 30 deg C, 7 h, Yield given. Multistep reaction Brown, Herbert C.; Murray, Kenneth J.; Tetrahedron; vol. 42; nb. 20; (1986); p. 5497 - 5504 View in Reaxys

91 % Chromat.

With ammonia, lithium, tert-butanol in tetrahydrofuran, Heating Paddon-Row, Michael N.; Hartcher, Robert; Australian Journal of Chemistry; vol. 33; nb. 4; (1980); p. 785 - 794 View in Reaxys

78 % Spectr.

With methanol, ytterbium in tetrahydrofuran, Time= 18h, Ambient temperature Hou, Zhaomin; Taniguchi, Hiroshi; Fujiwara, Yuzo; Chemistry Letters; (1987); p. 305 - 308 View in Reaxys With 9,10-dihydroanthracene, Heating Gerst, Matthias; Morgenthaler, Jens; Ruechardt, Christoph; Chemische Berichte; vol. 127; nb. 4; (1994); p. 691 - 696 View in Reaxys With acridine in pyridine, T= 280 °C , Yield given Friebolin, Heike; Ruechardt, Christoph; Liebigs Annalen; nb. 7; (1995); p. 1339 - 1342 View in Reaxys

99 % Chromat.

With LiH-NICRA in tetrahydrofuran, Time= 20h Fort, Yves; Tetrahedron Letters; vol. 36; nb. 34; (1995); p. 6051 - 6054 View in Reaxys

95 % Chromat.

With aluminum oxide, sodium tetrahydroborate, nickel dichloride in hexane, T= 30 °C , Catalytic hydrogenation Yakabe; Hirano; Morimoto; Tetrahedron Letters; vol. 41; nb. 35; (2000); p. 6795 - 6798 View in Reaxys

98 % Chromat.

With hydrogen, (iPrPDI)Fe(N2)2 in toluene, Time= 3.5h, T= 22 °C , p= 760Torr Bart, Suzanne C.; Lobkovsky, Emil; Chirik, Paul J.; Journal of the American Chemical Society; vol. 126; nb. 42; (2004); p. 13794 - 13807 View in Reaxys With hydrogen, triethylamine, {[bis(2-diPhphosphinoxynaphthalen-1-yl)methane]-Rh(COD)}BF4 in tetrahydrofuran, Time= 2h, T= 70 °C , p= 5171.48Torr Punji, Benudhar; Mague, Joel T.; Balakrishna, Maravanji S.; Dalton Transactions; vol. 6; nb. 10; (2006); p. 1322 1330 View in Reaxys With [Ir2(μ-H)(μ-Pz)2H2(OSO2CF3)(NCMe)(PiPr3)2] in 1,2-DICHLOROETHANE, Time= 4h, T= 59.85 °C , p= 750.06Torr

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Martin, Marta; Sola, Eduardo; Tejero, Santiago; Lopez, Jose A.; Oro, Luis A.; Chemistry - A European Journal; vol. 12; nb. 15; (2006); p. 4057 - 4068 View in Reaxys With hydrogen, [RuCl(C10H14)-2,6-C5H3N{CH2OP(-OC10H6)S(C10H6O-)}2-P,P][Cl] in tetrahydrofuran, T= 80 °C , p= 3040Torr , Product distribution, Further Variations: reaction time Punji, Benudhar; Balakrishna, Maravanji S.; Journal of Organometallic Chemistry; vol. 692; nb. 8; (2007); p. 1683 - 1689 View in Reaxys With hydrogen, palladium/alumina in various solvent(s), mesh microreactor, Activation energy, Further Variations: Catalysts Abdallah, Radwan; Meille, Valerie; Shaw, John; Wenn, David; De Bellefon, Claude; Chemical Communications; nb. 4; (2004); p. 372 - 373 View in Reaxys With 1,3-bis-(diphenylphosphino)propane, caesium carbonate, isopropyl alcohol, di-μ-chloro-bis(η4-1,5-cyclooctadiene)diiridium in toluene, Time= 15h, T= 80 °C Sakaguchi; Yamaga; Ishii; Journal of Organic Chemistry; vol. 66; nb. 13; (2001); p. 4710 - 4712 View in Reaxys 100 % Chromat.

With hydrogen, triethylamine, cis-[Rh(COD){κ2-P,O-Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}][OTf] in tetrahydrofuran, Time= 0.666667h, T= 20 °C , p= 3040.2Torr Venkateswaran, Ramalingam; Balakrishna, Maravanji S.; Mobin, Shaikh M.; European Journal of Inorganic Chemistry; nb. 13; (2007); p. 1930 - 1938 View in Reaxys 1 :A cumene solution containing 25percent by weight of cumyl alcohol and hydrogen were passed upwardly through a single reactor, in which activated alumina as a dehydration catalyst and 60 wtpercent copper/silica as a hydrogenation catalyst were packed in this order, from the dehydration catalyst side. At this time, the pressure was 1 MpaG, the temperature was 205 DEG C at the inlet of the reactor, hydrogen of 1.5 times by mole of cumyl alcohol was used and the gas linear velocity was 14 cm/sec (converted under the normal temperature and pressure). The conversion of cumyl alcohol at the outlet of activated alumina was 99percent, the conversion of α-methyl styrene at the outlet of the copper/silica was 99percent and the overall selectivity of cumene was 99percent.

With hydrogen, 60 copper/silica, T= 205 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1598330; (2005); (A1) English View in Reaxys 11 With Sodium bromate, acetic acid, hydrazine, Triethylene glycol dimethyl ether in water, toluene, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 8 With Sodium bromate, acetic acid, hydrazine, tetrabutylammomium bromide in water, ethyl acetate, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 9 With Sodium bromate, acetic acid, hydrazine, tetrabutylammomium bromide in water, toluene, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese

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View in Reaxys 6 With Sodium bromate, acetic acid, hydrazine, tetrabutylammomium bromide in water, acetonitrile, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 7 With Sodium bromate, acetic acid, hydrazine, tetrabutylammomium bromide in methanol, water, Time= 6h, T= 50 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 10 With Sodium bromate, acetic acid, hydrazine, PEG-600 in water, toluene, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 12 With Sodium bromate, acetic acid, hydrazine in water, Time= 5h, T= 60 °C , Product distribution / selectivity Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; JP2005/350427; (2005); (A) Japanese View in Reaxys 2 :It was carried out in the same manner as in Example 1 except that the pressure was changed to 1.4 MPaG and hydrogen was used 2.0 times by mole of cumyl alcohol. The conversion of cumyl alcohol at the outlet of activated alumina was 99percent, the conversion of α-methyl styrene at the outlet of the copper/silica was 99percent and the overall selectivity of cumene was 99percent.

With hydrogen, 60 copper/silica, T= 205 °C , p= 10501.1Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1598330; (2005); (A1) English View in Reaxys 3 :A cumene solution containing 25percent by weight of cumyl alcohol and hydrogen were passed upwardly through a single reactor in which activated alumina as a dehydration catalyst and 0.05 wtpercent palladium/alumina as a hydrogenation catalyst were packed in this order, from the dehydration side. At this time, the pressure was 1.4 MPaG, the temperature was 205 DEG C at the inlet of the reactor, hydrogen of 1.5 times by mole of cumyl alcohol was used and the gas linear velocity was 14 cm/sec (converted under the normal temperature and pressure). The conversion of cumyl alcohol at the outlet of activated alumina was 99percent, the conversion of α-methyl styrene at the outlet of the palladium/alumina was 99percent and the overall selectivity of cumene was 99percent.

Stage 1: With hydrogen, 0.05 palladium/alumina, T= 205 °C , p= 10501.1Torr Stage 2:, T= 205 °C , p= 10501.1Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1598330; (2005); (A1) English View in Reaxys 1; 2 :EXAMPLE 1; The following example was conducted in a pilot plant having a reactor with an internal diameter of 21 mm. The pilot plant had a single catalyst bed which consisted of silicon carbide and a nickel catalyst, wherein the catalyst had a volume of 35 mL. The reactor was designed to operate at a pressure between 0.1 and 1 MPa (15 and 150 psia), and a temperature between 50° and 70° C. (122° and 158° F.). The reactor, having a trickle bed with a nickel catalyst having a 16 percent by weight metal content, a trilobe shape and a surface area of 112 m2/g, was operated at 0.7 MPa (100 psia) and 70° C. (158° F.), with an LHSV of 16 hr-1. The feed stream consisted of approximately 96 weight percent cumene and approximately 4 weight percent AMS, and was supplied to the reactor where it combined with hydrogen present in an excess of 10-30percent. Hydrogenation of the AMS to cumene was approximately 85 percent, with side product isopropylcyclohexane present in a concentration of 34 ppm.; EXAMPLE 2; A

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hydrogenation reaction according to a reactor described in example 1 is given. The reactor employed a trickle bed with a nickel hydrogenation catalyst with a 16 percent by weight metal content, a trilobe shape, and a surface area of 112 m2/g, was operated at 0.5 MPa (72 psia) and 50° C. (122° F.), with an LHSV of 12 hr-1. The feed stream, consisting of approximately 96 weight percent cumene and approximately 4 weight percent AMS, was supplied to the reactor where it combined with a 10-30percent excess of hydrogen. Hydrogenation of the AMS to cumene was 99.7 percent, with side product isopropyl cyclohexane present in a concentration of approximately 43 ppm.

With hydrogen, single bed consist of silicon carbide and nickel catalyst (16 percent metal content), T= 50 - 70 °C , p= 3750.38 - 5250.53Torr , Product distribution / selectivity Patent; KELLOGG BROWN AND ROOT, INC.; US2006/135830; (2006); (A1) English View in Reaxys 3; 4 :EXAMPLE 3; Hydrogenation of a cumene/AMS feed in a reactor having a two catalyst system is given. A cumene/AMS feed comprising 50 weight percent AMS was supplied at a rate of 1000 kg/hr. Hydrogen was added to the cumene/AMS feed at a rate of 100 Nm3/hr. A cumene diluent stream, recycled from the product stream, was added to the feed stream at a rate of 10,000 kg/hr, resulting in a feed to the reactor that contained approximately 5 weight percent AMS. The first reactor included a nickel catalyst having a volume of 1.06 m3. The feed was supplied to the reactor at an LHSV of 12 hr-1, and at a temperature that varied from 45° C. (113° F.) at the start of the reaction to 100° C. (212° F.) at the end of the reaction. The reactor was operated at 0.4 MPa (60 psia) at the start of the reaction and 0.8 MPa (120 psia) at the end of the reaction. The product was produced at a rate of 1008 kg/hr and consisted of 0.5 weight percent AMS, corresponding to the hydrogenation of 88.2 percent of the initial AMS feed in the first catalyst bed. The temperature varied from 65° C. (149° F.) at the start of the reaction to 119° C. (246° F.) at the end of the reaction. The product stream from the first catalyst bed, having an AMS content of approximately 0.5 weight percent, was supplied to the second reactor at a rate of 1008 kg/hr. Hydrogen was added at a rate of 10 Nm3/hr. The second reactor included a trickle bed having 0.13 m3 of a palladium hydrogenation catalyst. The feed was supplied to the reactor at an LHSV of 9 hr-1, and a temperature that varied from 60° C. (140° F.) at the beginning of the reaction and 100° C. (212° F.) at the end of the reaction. The reactor was operated at a pressure of between 0.4 MPa (60 psia) at the start of the reaction, and 0.8 MPa (120 psia) at the end of the reaction. Cumene product was produced at a rate of 1008 kg/hr, and had an AMS content of approximately 0.02 weight percent, corresponding to the hydrogenation of 95.4 percent of the AMS supplied to the second reactor, and an overall hydrogenation of 99.9 percent of the initial AMS feed. Side product isopropylcyclohexane (IPCH) concentration in the product stream was no greater than 50 ppmw. Material balances for the first and second catalyst sections are given in Tables 1 and 2 respectively.; EXAMPLE 4; In this example, the hydrogenation reactor consists of a vessel having a diameter of approximately 0.85 m and a height of approximately 8 m. The reactor includes two catalyst beds arranged in series in the same reactor shell. The reactor consists of a distributor section which supplies a cumene/AMS feed and hydrogen to a first catalyst bed consisting of a trickle bed having a length of approximately 2.5 m, an L/D of 3, and containing a nickel based catalyst. The cumene/AMS is supplied to the first catalyst bed at an LHSV of 12-16 hr-1.

The product effluent is supplied to a second distributor which mixes the first catalyst bed effluent with hydrogen gas, and supplies the mixture to a second catalyst bed. The second catalyst bed is a trickle bed having a length of approximately 0.88 m, with an L/D of between 1 and 3, and containing a palladium based hydrogenation catalyst. The product stream from the first catalyst bed is supplied at an LHSV of 8-12 hr-1. The reactor also includes an empty volume located below the second catalyst bed to allow for retrofitting of the reactor if desired.

Stage 1: With hydrogen, nickel, T= 45 - 100 °C , p= 3000.3 - 6000.6Torr Stage 2: With hydrogen, palladium catalyst, T= 60 - 100 °C , p= 3000.3 - 6000.6Torr , Product distribution / selectivity Patent; KELLOGG BROWN AND ROOT, INC.; US2006/135830; (2006); (A1) English View in Reaxys 1 :A cumene solution (containing 0 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol and hydrogen were passed through a fixed bed flow reactor in which activated alumina was packed, at a rate of 1.6g/minute and 105 Ncc/minute, respectively. In addition, LHSV(Liquid Hourly Space Velocity) was 9 h-1, the pressure was 1.0 MPaG, and the temperature was 200°C. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 97percent.

With hydrogen, aluminum oxide in cumol, T= 200 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1674439; (2006); (A1) English View in Reaxys

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2; 3; 1 :It was carried out in the same manner as in Example 1 except that a cumene solution (containing 110 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 97percent.; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 1200 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 96percent.; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 12500 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 68percent.

With hydrogen, propyleneoxide, aluminum oxide in cumol, T= 200 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1674439; (2006); (A1) English View in Reaxys 1 :Example 1; According to the method described in the specification, an oxidization reaction solution (1) containing 31percent by weight of cumene hydroperoxide was obtained by oxidizing cumene with an oxygen-containing gas (air) in an oxidation step. An epoxidation reaction solution (2) containing mainly propylene oxide, cumyl alcohol, unreacted propylene, and cumene was obtained by passing the oxidization reaction solution and propylene through a reactor filled with a titanium-containing silicon oxide catalyst in an epoxidation step. The unreacted propylene (3) was separated and removed from the resulting reaction solution (2) to obtain a reaction solution (4) after recovering propylene. The reaction solution (4) after recovering propylene was used in the following Example 3 and Comparative Example 1.First, the reaction solution (4) after recovering propylene was separated into a fraction of a solution (5) containing mainly cumyl alcohol and cumene and a fraction containing mainly propylene oxide in a propylene oxide purification step, and then the fraction containing mainly <n="27"/>propylene oxide was distilled with a plurality of distillation columns including extraction and distillation so as to satisfy product quality to obtain a propylene oxide product. Regarding the fraction of the solution (5) containing mainly cumyl alcohol and cumene, cumyl alcohol was subjected to a dehydration reaction and a hydrogenation reaction in a hydrogenation step to obtain cumene, which was recycled to the oxidization step.Fig. 1 is a schematic flow chart described in the specification.

With hydrogen, Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; WO2008/123384; (2008); (A1) English View in Reaxys With (2-Me2N-α-Me3Si-benzyl)2Sr*(THF)2, hydrogen in benzene, Time= 25h, T= 60 °C , p= 7500.75Torr , Inert atmosphere, Autoclave Spielmann, Jan; Buch, Frank; Harder, Sjoerd; Angewandte Chemie - International Edition; vol. 47; nb. 49; (2008); p. 9434 - 9438 View in Reaxys > 99 With 4,4'-di-tert-butylbiphenyl, lithium, isopropyl alcohol, nickel dichloride in tetrahydrofuran, T= 20 - 76 °C , Inert %Chromat. atmosphere, chemoselective reaction Alonso, Francisco; Riente, Paola; Yus, Miguel; Tetrahedron; vol. 65; nb. 51; (2009); p. 10637 - 10643 View in Reaxys Stage 1: With Cp(η5-(1-neomenthyl-4,5,6,7-tetrahydroindenyl))ZrCl2, diisobutylaluminium hydride in toluene, Time= 40h, T= 40 °C , Inert atmosphere Stage 2: With hydrochlorid acid, water in toluene, T= 0 °C Parfenova, Lyudmila V.; Berestova, Tatyana V.; Tyumkina, Tatyana V.; Kovyazin, Pavel V.; Khalilov, Leonard M.; Whitby, Richard J.; Dzhemilev, Usein M.; Tetrahedron Asymmetry; vol. 21; nb. 3; (2010); p. 299 - 310 View in Reaxys 100 With C30H44ClN2O4P2Rh, hydrogen, triethylamine in tetrahydrofuran, Time= 2h, T= 80 °C , p= 3040.2Torr , Auto%Chromat. clave Mohanty, Sasmita; Balakrishna, Maravanji S.; Journal of Chemical Sciences; vol. 122; nb. 2; (2010); p. 137 - 142 View in Reaxys 100 With RhCl[2,6-bis{1-(4-trifluoromethylphenyl)iminoethyl}pyridine], potassium tert-butylate, hydrogen in isopropyl al%Chromat. cohol, Time= 0.0833333h, T= 60 °C , p= 760.051Torr

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Buil, Maria L.; Esteruelas, Miguel A.; Niembro, Sandra; Olivan, Montserrat; Orzechowski, Lars; Pelayo, Cristina; Vallribera, Adelina; Organometallics; vol. 29; nb. 19; (2010); p. 4375 - 4383 View in Reaxys 1 :Example 1 Using the apparatus as shown in FIG. 1, Example 1 was carried out. A liquid (2) (a cumene solution containing about 25percent by weight of cumyl alcohol) and a gas (3) (hydrogen) were fed through the bottom of the column (1), and the resulting mixed fluid of the gas and the liquid was flowed upward through the column. Within the column, there was provided the gas-liquid dispersing device according to the present invention comprising the plate (4) which was arranged perpendicular to the flow direction of the fluid and blocked the flow of the fluid. The plate had holes (5) for gas-liquid mixed fluid, the holes were connected to the conduits (6) extending downward from the plate, and three passages (7) for the gas per one conduit were provided through the side surface of the conduit. As was described above, in order that the positional relationship in the levels of the passages for the gas through the conduit flexibly accommodates the change in the height of the space of the gas in accordance with the change of the operation conditions and the throughput, the first passage for the gas was provided at the level of 75 mm downward from the plate, the second one was at the level of additionally 40 mm downward from the first passage and the third one was at the level of further additionally 40 mm downward from the second passage. The ratio of H/L was about 12.7, wherein height of the column (1) was H and length of conduits (6) was L.The structure of the end (8) of the lower part of the conduit had a structure which was closed by a cap. And, two small holes as the passages for the liquid per one conduit were provided through the conduit at the same level of 45 mm upward from the lower end of the conduit.The diameter of the hole of the plate was generally the same as that of the conduit.The ratio of N/S was 15/m2 wherein N is the number of the holes of the plate and S is an area [m2] of the lower surface of the plate.The linear velocity (v) of the gas-liquid mixed fluid flowing through the hole of the plate was about 2 m/s which is based on the volume of the fluid of the entrance (lower) side of the hole for the gas-liquid mixed fluid.The velocity (g) of the gas flowing through the passage for the gas provided through the side surface of the conduit was about 54 m/s which is based on the volume of the gas of the entrance side of the passage for the gas.The velocity (h) of the liquid flowing through the passage for the liquid provided through the conduit was about 6 m/s.Thus, it was confirmed that a space (with a thickness of 380 mm) containing the gas was formed by flowing the liquid and the gas at a predetermined ratio through the conduit from the down side to the upper side of the plate. The value of dPG-dPL was 8.7 kPa at this point.Above the gas-liquid dispersion device, there was provided a bed (10) of packing comprising spherical alumina catalysts (partially supporting a noble metal). Under the conditions of a catalyst bed temperature of about 200° C. to 230° C. and a column top pressure of about 1.5 MPaG to 2 MPaG, cumyl alcohol was intra-molecularly dehydrated to α-methylstylene, and α-methylstylene was successively converted to cumene by reacting with hydrogen. When the state of the gas-liquid dispersion is insufficient, there would be caused channeling in the reactor, and thereby an insufficient hydrogenation zone and an excessive hydrogenation zone would be partially formed. The formation of such zones is one of factors which worsen the loss of cumene in the hydrogenation step. Then, the state of the dispersion was evaluated by the following index. The index for the insufficient hydrogenation was a concentration of αmethylstylene at the outlet of the column (referred to as a leak-concentration of α-methylstylene). As a result, the obtained reaction product had the leak-concentration of α-methylstylene (the index for the insufficient hydrogenation) was 323 ppm by weight. In Table 1, the results of Example 1 are shown with "with dispersion plate".

With hydrogen, T= 200 - 230 °C , the gas-liquid dispersion device, Industry scale, Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; US2011/4009; (2011); (A1) English View in Reaxys With triethylsilane, [ReBr(η2-C2H4)(NO)(η3-Sixantphos)], hydrogen in toluene, T= 120 °C , p= 7500.75Torr , Autoclave, Kinetics, Reagent/catalyst Dudle, Balz; Rajesh, Kunjanpillai; Blacque, Olivier; Berke, Heinz; Journal of the American Chemical Society; vol. 133; nb. 21; (2011); p. 8168 - 8178 View in Reaxys 16.3 g

With palladium/alumina, hydrogen, Time= 1.5h, T= 20 °C , neat (no solvent) Oyamada, Hidekazu; Naito, Takeshi; Kobayashi, Shu; Beilstein Journal of Organic Chemistry; vol. 7; (2011); p.

735 - 739; Art.No: 83 View in Reaxys

96 %Spectr.

With tris (α-naphthyl)phosphine, hydrogen in dichloromethane-d2, Time= 240h, T= 50 °C , p= 3750.38Torr , Inert atmosphere, Glovebox, Sealed tube

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Greb, Lutz; Paradies, Jan; Ona-Burgos, Pascual; Schirmer, Birgitta; Grimme, Stefan; Stephan, Douglas W.; Angewandte Chemie, International Edition; vol. 51; nb. 40; (2012); p. 10164 - 10168,5; Angewandte Chemie; vol.

124; nb. 40; (2012); p. 10311 - 10315,5 View in Reaxys 99 %Chromat.

With [H(OEt2)2]+[[3,5-(CF3)2C6H3]4B]-, C32H63CoNP2Si, hydrogen in tetrahydrofuran, Time= 24h, T= 25 °C , p= 760.051Torr Zhang, Guoqi; Scott, Brian L.; Hanson, Susan K.; Angewandte Chemie - International Edition; vol. 51; nb. 48; (2012); p. 12102 - 12106; Angew. Chem.; (2012); p. 12077 View in Reaxys

48 %Chromat.

With [NiH(bis[2-(dicyclohexylphosphanyl)ethyl]amine)]B(C6H5)4, hydrogen in tetrahydrofuran-d8, Time= 48h, T= 80 °C , p= 3040.2Torr , Sealed tube Vasudevan, Kalyan V.; Scott, Brian L.; Hanson, Susan K.; European Journal of Inorganic Chemistry; nb. 30; (2012); p. 4898 - 4906 View in Reaxys With sodium formate in water, Time= 4h, T= 79.84 °C , p= 30003Torr , Concentration, Reagent/catalyst, Solvent, Time, chemoselective reaction Indra, Arindam; Maity, Prasenjit; Bhaduri, Sumit; Lahiri, Goutam Kumar; ChemCatChem; vol. 5; nb. 1; (2013); p. 322 - 330 View in Reaxys With iron(III) trifluoromethanesulfonate, Super-Hydride® in tetrahydrofuran, N-Methyl-2-pyrrolidone, Time= 16h, T= -20 - 20 °C , Inert atmosphere Carter, Tom S.; Guiet, Lea; Frank, Dominik J.; West, James; Thomas, Stephen P.; Advanced Synthesis and Catalysis; vol. 355; nb. 5; (2013); p. 880 - 884 View in Reaxys With ammonium hydroxide, hydrazine hydrate in ethanol, Time= 10h, T= 60 °C , Catalytic behavior Dhakshinamoorthy, Amarajothi; Navalon, Sergio; Sempere, David; Alvaro, Mercedes; Garcia, Hermenegildo; Chemical Communications; vol. 49; nb. 23; (2013); p. 2359 - 2361 View in Reaxys

77 %Chromat.

With hydrochlorid acid, hydrogen in water, ethyl acetate, Time= 2h, T= 20 °C , p= 760.051Torr , pH= 3 - 4 Yang, Hengquan; Zhou, Ting; Zhang, Wenjuan; Angewandte Chemie - International Edition; vol. 52; nb. 29; (2013); p. 7455 - 7459; Angew. Chem.; vol. 125; nb. 29; (2013); p. 7603 - 7607,5 View in Reaxys

99.9 The typical procedure for hydrogenation of unsaturated carbon-carbon bonds using the H2-MNB-basedstrat%Chromat. egy General procedure: The hydrogenation was carried out in a 100 mL vial equipped with an MNB-generator withoutadditional stirring. Alkene or alkyne 1 (20 mmol) was dissolved in MeOH (80 mL), and then warmed to 30 °C.Using the MNB-generator (MA3-FS), H2-MNBs were introduced into the reactor in the presence of palladium onalumina spheres (0.5percentPd, 2–4 mm, 0.1 mmol, 0.5 molpercent) at an H2-flow rate of 5 mL/min. The samples of thereaction mixture were taken out periodically to monitor the reaction progress using the GC analysis. After thecompletion of the hydrogenation reaction, MeOH was evaporated in vacuo to afford the desired alkane 1 withexcellent purity.

With hydrogen in methanol, Time= 3h, T= 30 °C Mase, Nobuyuki; Isomura, Shogo; Toda, Mitsuo; Watanabe, Naoharu; Synlett; vol. 24; nb. 17; (2013); p. 2225 2228 View in Reaxys With hydrogen in ethanol, Time= 2h, T= 40 °C , p= 1500.15Torr , Autoclave Rasero-Almansa, Antonia M.; Corma, Avelino; Iglesias, Marta; Sanchez, Felix; Green Chemistry; vol. 16; nb. 7; (2014); p. 3522 - 3527 View in Reaxys

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> 99 With formic acid in water, Time= 0.25h, T= 24.84 °C , Green chemistry %Chromat.

Gong, Ling-Hong; Cai, Yi-Yu; Li, Xin-Hao; Zhang, Ya-Nan; Su, Juan; Chen, Jie-Sheng; Green Chemistry; vol.

16; nb. 8; (2014); p. 3746 - 3751 View in Reaxys 99 %Chromat.

With N,N′-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine, hydrogen, isopropylmagnesium chloride, iron(II) chloride in tetrahydrofuran, Time= 5h, T= -20 - 20 °C , p= 37503.8Torr Frank, Dominik J.; Guiet, Lea; Kaeslin, Alexander; Murphy, Elliot; Thomas, Stephen P.; RSC Advances; vol. 3; nb. 48; (2013); p. 25698 - 25701 View in Reaxys

100 With hydrogen, caesium carbonate in toluene, Time= 0.25h, T= 100 °C , p= 760.051Torr , Inert atmosphere, Schlenk %Chromat. technique Sabater, Sara; Mata, Jose A.; Peris, Eduardo; ACS Catalysis; vol. 4; nb. 6; (2014); p. 2038 - 2047 View in Reaxys With hydrogen in water, Time= 1.5h, T= 40 °C , p= 2625.26Torr , Autoclave Fu, Luman; Li, Shuru; Han, Zhongyuan; Liu, Huifang; Yang, Hengquan; Chemical Communications; vol. 50; nb.

70; (2014); p. 10045 - 10048 View in Reaxys 99 %Chromat.

2.3. Catalytic activity test General procedure: Typically, 1.0 mmol nitrobenzene, styrene or benzaldehyde, 10 mg catalyst and 2 mL EtOH were added into a glass tube (50 mL), respectively. Then, it was exchanged with H2 and the reaction was carried out in the presence of H2 at atmospheric pressure (H2 balloon) at the given temperature. After reaction, 154 mg biphenyl and 10 mL EtOH were added for quantitative analysis by GC-FID (Agilent 7890A).

With hydrogen in ethanol, Time= 0.5h, T= 25 °C , p= 760.051Torr Wang, Yanan; Deng, Youquan; Shi, Feng; Journal of Molecular Catalysis A: Chemical; vol. 395; (2014); p. 195 201 View in Reaxys With hydrogen in toluene, Time= 1h, T= 27 °C , Catalytic behavior, Time Acham, Vaibhav R.; Biradar, Ankush V.; Dongare, Mohan K.; Kemnitz, Erhard; Umbarkar, Shubhangi B.; ChemCatChem; vol. 6; nb. 11; (2014); p. 3182 - 3191 View in Reaxys With hydrogen, T= 30 - 200 °C , Inert atmosphere Nishiwaki, Nagatoshi; Hamada, Sayaka; Watanabe, Tomoe; Hirao, Shotaro; Sawayama, Jun; Asahara, Haruyasu; Saigo, Kazuhiko; Kamata, Toru; Funabashi, Masahiko; RSC Advances; vol. 5; nb. 6; (2015); p. 4463 4467 View in Reaxys

40 %Chromat.

With hydrazine hydrate in chloroform, Time= 24h, T= 25 °C , p= 760.051Torr , Reagent/catalyst Imada, Yasushi; Osaki, Motonari; Noguchi, Mikiko; Maeda, Takatoshi; Fujiki, Misa; Kawamorita, Soichiro; Komiya, Naruyoshi; Naota, Takeshi; ChemCatChem; vol. 7; nb. 1; (2015); p. 99 - 106 View in Reaxys With (bis-1,2-diphenylphosphinoethane)Co(CH2SiMe3)2, hydrogen in toluene, Time= 2h, T= -196.15 - 25 °C , p= 3040.2Torr , Sealed tube, Reagent/catalyst Friedfeld, Max R.; Margulieux, Grant W.; Schaefer, Brian A.; Chirik, Paul J.; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13178 - 13181 View in Reaxys With C54H57F3N4O6RuS, hydrogen in dichloromethane, Time= 1h, T= 25 °C , p= 15001.5Torr , Inert atmosphere, Sealed tube, Reagent/catalyst

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Pranckevicius, Conor; Fan, Louie; Stephan, Douglas W.; Journal of the American Chemical Society; vol. 137; nb.

16; (2015); p. 5582 - 5589 View in Reaxys With bromobenzene-d5, C21H30Si, C18H15FP(1+)*C24H20B(1-), Time= 24h, T= 100 °C , p= 3040.2Torr , Schlenk technique, Inert atmosphere, Cooling with liquid nitrogen Vom Stein, Thorsten; Perz, Manuel; Dobrovetsky, Roman; Winkelhaus, Daniel; Caputo, Christopher B.; Stephan, Douglas W.; Angewandte Chemie - International Edition; vol. 54; nb. 35; (2015); p. 10178 - 10182; Angew.

Chem.; vol. 54; (2015); p. 10178 - 10182,5 View in Reaxys 33 %Spectr.

With 2,4,6-trimethylcyclohexa-1,4-diene, tris(pentafluorophenyl)borate, Time= 8h, T= 20 °C , Glovebox, Inert atmosphere Chatterjee, Indranil; Qu, Zheng-Wang; Grimme, Stefan; Oestreich, Martin; Angewandte Chemie - International Edition; vol. 54; nb. 41; (2015); p. 12158 - 12162; Angew. Chem.; vol. 54; nb. 41; (2015); p. 12158 - 12162,5 View in Reaxys

99 %Chromat.

A general procedure for the recycling of Fe3O4 catalyst in olefin reductions General procedure: To an oven-dried, two-necked 25 mL round-bottom flask equipped with a magnetic stir bar and a reflux condenser, Fe3O4 (92 mg, 0.40 mmol) and ethanol (6.0 mL) were added, and the mixture was sonicated in an ultrasonic bath for 1 minute under N2 atmosphere. Styrene (1.0 mmol) and hydrazine monohydrate (380 μL, 8 equiv) were added. Then the reaction mixture was stirred at 80 °C under argon atmosphere until the reaction was completed. After magnetic separation of the catalyst (see Fig. 2), the remaining solution was decanted, then directly analyzed with gas chromatography. The remaining catalyst was washed with ethanol (5 mL × 2), dried under vacuum, and reused for the next cycle of the reaction.

With Fe3O4, hydrazine hydrate in ethanol, Time= 28h, T= 80 °C , Inert atmosphere Kim, Eunsuk; Kim, Seyoung; Moon Kim; Bulletin of the Korean Chemical Society; vol. 32; (2011); p. 3183 - 3186 View in Reaxys 2.3.1. Hydrogenation reaction General procedure: Hydrogenation reaction for the catalytic activity of synthesizedcatalysts were performed in 100 ml Parr autoclave with suitablehydrogen pressure and temperatures. To check the catalytic activ-ities of catalysts like RhCl(PPh3)3and Cata.1a/1b/1c/1d,a knownamount of olefins (10 mmol), catalysts [neat RhCl(PPh3)3complex:5 mg or Cata.1a/1b/1c/1d: 15 mg] and 55 ml toluene were takenin an auto clave and stirred continuously with hydrogen pressure(150 Psi) at room temperature (28–32C). Moreover, the catalyticactivites of neat RuHCl(CO)(PPh3)3complex and Cata.2a/2b/2c/2dwere investigated by using a procedure as: a known amountof olefins (10 mmol), catalyst [neat RuHCl(CO)(PPh3)3complex:12 mg or Cata.2a/2b/2c/2d: 25 mg] and 55 ml toluene were takenin an auto clave and stirred continuously with hydrogen pressure(250 Psi) at 90C. The progress of the reaction in all synthesizedcatalysts were monitored by the withdrawing samples at differ-ent time intervals and analyzed by Gas Chromatography (HP 6890)equipped with a flame ionized detector and a capillary column(HP-5, 5 m cross-linked methyl silicone gum, 0.2 mm × 50 m).

With hydrogen in toluene, Time= 6h, T= 90 °C , p= 12929Torr , Autoclave, Reagent/catalyst Lazar, Anish; George, Shoy C.; Jithesh; Vinod; Singh; Applied Catalysis A: General; vol. 513; (2016); p. 138 146 View in Reaxys With hydrogen in methanol, Time= 0.25h, T= 30 °C , p= 3750.38Torr , Autoclave, Catalytic behavior, Temperature Lazar, Anish; Vinod, Chathakudath P.; Singh, Anand Pal; New Journal of Chemistry; vol. 40; nb. 3; (2016); p.

2423 - 2432 View in Reaxys

O

Rx-ID: 36727416 View in Reaxys 5/481

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Yield 50 %, 5 %

Conditions & References General procedure for the catalytic decarbonylation process General procedure: A mixture of freshly distilled aldehyde (1 mmol which amountsto ca. 0.8 wt.percent of the expected microemulsion), TDW (15–20 ml,90.1 wt.percent), cetyltrimethylammonium bromide (CTAB, 0.4–0.8 g, ca.2.5 wt.percent) and 1-propanol (1.2 ml, 6.6 wt. percent) was stirrer magneticallyat room temperature (25 C) until a clear transparent mixture thatscatters laser beams was formed. In some cases the addition of afew drops of 1-propanol was necessary.The sol–gel entrapped catalyst (10–200 mg) was roughly groundand placed together with 2,5-di-tertbutylhydroquinone (10 mg)and a freshly prepared microemulsion of an aldehyde in a miniautoclave equipped with a sampler through which small samplescould been removed periodically. The reaction mixture wasparched with nitrogen, stirred magnetically and heated with a controllablethermostat at the required temperature for the desiredlength of time. The reaction mixture was cooled to 20 C. With 2,5-dihydroxy-1,4-di-tert-butyl benzene, N-hexadecyl-N,N,N-trimethylammonium bromide in propan-1-ol, water, Time= 45h, T= 180 °C , Autoclave, Inert atmosphere, Green chemistry Dahoah, Shirel; Nairoukh, Zackaria; Fanun, Monzer; Schwarze, Michael; Schomaecker, Reinhard; Blum, Jochanan; Journal of Molecular Catalysis A: Chemical; vol. 380; (2013); p. 90 - 93 View in Reaxys

polyisopropylbenzene Rx-ID: 6416612 View in Reaxys 6/481 Yield

Conditions & References With hydrogen fluoride, T= 150 °C Patent; Phillips Petr. Co.; US2420073; (1942) View in Reaxys With aluminium trichloride, T= 20 °C Firla; Roczniki Chemii; vol. 14; (1934); p. 87 View in Reaxys T= 400 °C , Leiten ueber Aluminiumsilicat Kutz; Corson; Industrial and Engineering Chemistry; vol. 38; (1946); p. 761,764 View in Reaxys Mamedalijew; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1947); p. 197,200; ; (1948); p. 4959 View in Reaxys 1 :According to the procedures of FIG. 2, the first transalkylation reactor was loaded with 20 g of a catalyst of Beta zeolite, and the second transalkylation reactor was loaded with 50 g of a catalyst of MCM-22 zeolite. The reaction conditions of the first transalkylation reactor comprised: a reaction temperature of 150 degrees C., a reaction pressure of 1.2 MPa, a flow rate of the first benzene stream (stream 7) of 40 g/hr, a feeding rate of the polyisopropyl benzene (stream 13) of 20 g/hr, and a content of diisopropylbenzene in stream 13 of 98percent. The reaction conditions of the second transalkylation reactor comprised: a reaction temperature of 180 degrees C., a reaction pressure of 1.5 MPa, a flow rate of the second benzene stream (stream 8) of 80 g/hr, a flow rate of the polyisopropyl benzene (stream 12) of 80 g/hr, and a content of tri-isopropylbenzene in stream 12 of 10percent. The reaction was carried out continuously for 5 days. [0034] The operation conditions of the polyisopropyl benzene column comprised: a column top temperature of 132 degrees C., a column bottom temperature of 215 degrees C., and an operation pressure of −80 MPa. [0035] Reaction results: a conversion of the poly-isopropyl benzene of 65percent and a content of n-propyl benzene in the isopropyl benzene of 450 ppm for the first transalkylation reactor; and a conversion of the poly-isopropyl benzene of 55percent and a content of n-propyl benzene in the isopropyl benzene of 520 ppm for the second transalkylation reactor.

Stage 1: With Beta zeolite, T= 150 °C , p= 9000.9Torr Stage 2: With MCM-22 zeolite, T= 150 °C , p= 11251.1Torr , Temperature, Pressure, Concentration Patent; Shanghai Research Institute of Petrochemical Technology, SINOPEC; China Petroleum and Chemical Corporation; Gao, Huanxin; Zhou, Bin; Wei, Yilun; Gu, Ruifang; Fang, Hua; Ji, Shufang; Yao, Hui; US2013/237730; (2013); (A1) English

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View in Reaxys

HO

Rx-ID: 23426135 View in Reaxys 7/481 Yield

Conditions & References II.IIB :20.0 cc of the above Cu/Zn/Zr catalyst from IIA was crushed and sized into 6-20 mesh particles. The catalyst was mixed with 45 grams of 80 mesh silicon carbide and centered inside a 69 cm long stainless steel reactor tube between beds of 20 mesh SiC and glass wool. The reactor tube had an internal diameter of 1. 5cm. The catalyst was slowly reduced by heating the catalyst particles at a rate of 3°C per minute from 20°C to 180°C while flowing 0.05 wt. percent hydrogen in nitrogen at a rate of 10 L/Hr. The catalyst was allowed to reduce at 180°C for 2 hours and then the hydrogen content in the nitrogen was doubled every 2 hours until the gas was 3.2 wt. percent hydrogen in nitrogen. The catalyst was reduced for a final two-hour period after which the gas was switched to 99.999percent hydrogen and the reactor was pressurized with hydrogen to a gauge pressure of 290 psig (20 bar) while the catalyst bed was maintained at 180OC. The hydrogen flow rate was adjusted to 2 L/Hr. A mixture containing about 25.5 wt. percent of 2-phenyl-2-propanol (obtained from AVOCADO CHEMICAL) AND 74.5 WTpercent OF CUMENE (OBTAINED FROM ALDRICH CHEMICAL CO. ) WAS fed the reactor at a feed rate of 33.5 g/hr. while maintaining the hydrogen flow rate and a bed temperature of 180°C. After a week of operation, a sample of the reactor product was collected, dried of water and analyzed by gas chromatography. The product contained 8.1 wt. percent 2-phenyl-2propanol, 91.2 wt. percent OF CUMENE, 0.1 wt. percent alpha-methyl styrene, 0.1 wt. percent of i-propylcyclohexane and 0.5 wt. percent of cumene dimers.

Stage 1: With α6H-SiC, hydrogen, Cu/Zn/Zr catalyst, T= 20 - 180 °C Stage 2: With hydrogen, T= 180 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys II.IIE :A feedstock containing about 25 wt. percent cumyl alcohol* (>98percent purity, obtained from Avocado Chemical) in 75 wt. percent cumene (>99percent purity obtained from Aldrich Chemical) was made by blending. The hydrogenolysis reaction was conducted under the conditions provided in the Table 4 below. Two hydrogen flowrates were used during the testing, 2L/Hr or 4/Hr. The results of the testing are shown in Table 5 and Table 6. As demonstrated, this fixed bed process produces a cumene product stream of about 91 wt. percent purity having 7.9 wt. percent of unconverted cumyl alcohol, 0.6 wt. percent of cumene dimers and 0.1 wt. percent OF ISOPROPYLCYCLOHEXANE as side products.

With hydrogen, reduced copper chromite catalyst (G-22/2), Time= 600 - 800h, T= 180 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys II.IIC :The experiment of IIB was repeated using the copper on silica catalyst described in Example 1B (T-366) obtained from Sud Chemie. 20 cc of the catalyst was used. Due to the higher activity of the reduced T-366 catalyst, the testing was conducted at a temperature of 150°C. After 200 hours of operation, the dried product contained 9.7 wt. percent 2-phenyl-2- propanol, 88.4 WT. percent of cumene, 0.1 wt. percent alpha-methyl styrene, 0.1 wt. percent of iPROPYLCYCLOHEXANE and 1.7 wt. percent of cumene dimers. When operated at 180°C, the product contained less than 5 wt. percent 2-phenyl-2-propanol.

With hydrogen, reduced copper on silica (T-366) catalyst, T= 150 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys

(v2)

Zn

(v2)

Zn

Rx-ID: 28596372 View in Reaxys 8/481 Yield 96 %

Conditions & References With iron (III) acetylacetonate, ethylene dibromide in tetrahydrofuran, Time= 3h, T= 20 °C , Inert atmosphere Cahiez, Gerard; Foulgoc, Laura; Moyeux, Alban; Angewandte Chemie, International Edition; vol. 48; nb. 16; (2009); p. 2969 - 2972

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View in Reaxys

O O O

O

Rx-ID: 29042030 View in Reaxys 9/481 Yield

Conditions & References

80 %

With methanol, palladium 10 on activated carbon, hydrogen, Time= 24h, T= 20 °C , p= 760.051Torr , Inert atmosphere Wilsily, Ashraf; Nguyen, Yen; Fillion, Eric; Journal of the American Chemical Society; vol. 131; nb. 43; (2009); p.

15606 - 15607 View in Reaxys

Br

Rx-ID: 632491 View in Reaxys 10/481 Yield

Conditions & References

8 %, 24 %

With LuCl3, T= 65 °C Mine, Norioki; Fujiwara, Yuzo; Taniguchi, Hiroshi; Chemistry Letters; (1986); p. 357 - 360 View in Reaxys

24 %, 8 %

With LuCl3, T= 65 °C Mine, Norioki; Fujiwara, Yuzo; Taniguchi, Hiroshi; Chemistry Letters; (1986); p. 357 - 360 View in Reaxys With hydrogen fluoride, T= 80 °C , kupfernes Gefaess Simons; Archer; Journal of the American Chemical Society; vol. 60; (1938); p. 2953 View in Reaxys General procedure for AlCl3 catalyzed Friedel-Crafts alkylation: General procedure: Anhydrous benzene (1.00 mL, 11.2 mmol) was added to a heterogenous mixture of AlCl3 (0.136 g, 1.02 mmol) in anhydrous CH2Cl2 (10 mL) in a 50 mL PTFE lined glass reactor, followed by slow addition of 2bromobutane (1.11 mL, 10.2 mmol). The glass reactor was capped with a plastic releasing valve top and irradiated in a Milestone START Microwave at 750 W with a ramp to 140 °C over 2 min, and then maintained for an additional 3 min. The flask was cooled, H2O (25 mL) was added, extracted with EtOAc (3 × 20 mL), and the combined organic layer was washed with H2O (3 × 20 mL), dehydrated with MgSO4, filtered, and concentrated under reduced pressure. Column chromatography (hexanes) afforded sec-butylbenzene (0.356 g, 26percent) as clear colorless liquid.

With AlCl3, aluminium chloride in dichloromethane, Time= 0.0833333h, T= 140 °C , Microwave irradiation, FriedelCrafts Alkylation, Overall yield = 14 percent Zupp, Laurine R.; Campanella, Veronica L.; Rudzinski, Diandra M.; Beland, Franois; Priefer, Ronny; Tetrahedron Letters; vol. 53; nb. 39; (2012); p. 5343 - 5346 View in Reaxys

Br

Rx-ID: 772938 View in Reaxys 11/481 Yield 66 %

Conditions & References With titanium oxide on silica alumina support, T= 180 °C , Mechanism

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Kumar, V. G.; Shoba, T. S.; Rao, K. V. C.; Tetrahedron Letters; vol. 26; nb. 27; (1985); p. 3281 - 3284 View in Reaxys 66 %

With titanium oxide on silica-alumina support, T= 180 °C Kumar, V. G.; Shoba, T. S.; Rao, K. V. C.; Tetrahedron Letters; vol. 26; nb. 27; (1985); p. 3281 - 3284 View in Reaxys

48 %

General procedure for Si-AlClx catalyzed Friedel-Crafts alkylation:#10; General procedure: Anhydrous benzene (1.00 mL, 11.2 mmol) was added to a heterogenous mixture of Si-AlClx (0.611 g, 1.02 mmol [loading: 1.67 mmol/g]) in anhydrous CH2Cl2 (10 mL) in a 50 mL PTFE lined glass reactor, followed by slow addition of 2-bromobutane (1.11 mL, 10.2 mmol). The glass reactor was capped with a plastic releasing valve top and irradiated in a Milestone START Microwave at 750 W with a ramp to 140 °C over 2 min, and then maintained for an additional 3 min. The flask was cooled, underwent vacuum filtration, washed with a solution of 2percent CH3OH in EtOAc, and the combined filtrate was concentrated under reduced pressure. Column chromatography (hexanes) afforded a sec-butylbenzene (1.26 g, 92percent) as clear colorless liquid. #10; With silica-supported aluminum chloride in dichloromethane, Time= 0.0833333h, T= 140 °C , Microwave irradiation, Friedel-Crafts Alkylation, Reagent/catalyst Zupp, Laurine R.; Campanella, Veronica L.; Rudzinski, Diandra M.; Beland, Franois; Priefer, Ronny; Tetrahedron Letters; vol. 53; nb. 39; (2012); p. 5343 - 5346 View in Reaxys With silica-alumina, T= 300 - 320 °C Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys With aluminium trichloride Haworth; Barker; Journal of the Chemical Society; (1939); p. 1299,1301 View in Reaxys With aluminium trichloride Konowalow; Bulletin de la Societe Chimique de France; vol. <3> 16; (1896); p. 864 View in Reaxys Konowalow; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 27; (1895); p. 457; Bulletin de la Societe Chimique de France; vol. <3> 16; (1896); p. 864 View in Reaxys With aluminium trichloride Stratford; Annales de l'Office National des Combustibles Liquides (France); vol. 4; (1929); p. 321; Chem. Zentralbl.; vol. 100; nb. II; (1929); p. 1286 View in Reaxys Bert; Bulletin de la Societe Chimique de France; vol. <4> 37; (1925); p. 1264 View in Reaxys With aluminum tri-bromide Gustavson; Chemische Berichte; vol. 11; (1878); p. 1251; Bulletin de la Societe Chimique de France; vol. <2> 30; (1878); p. 23 View in Reaxys Silva; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 317,588 View in Reaxys

Rx-ID: 3923372 View in Reaxys 12/481 Yield 85 %, 7 %

Conditions & References With Ti(III)-citrate, Tris buffer, tetra(n-butyl)ammonium hydroxide, B12 in ethanol, pH= 8

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Shey, Justin; McGinley, Chris M.; McCauley, Kevin M.; Dearth, Anthony S.; Young, Brian T.; Van der Donk, Wilfred A.; Journal of Organic Chemistry; vol. 67; nb. 3; (2002); p. 837 - 846 View in Reaxys 79 %, 11 % With methanol, Time= 2h, UV-irradiation Shimakoshi, Hisashi; Hisaeda, Yoshio; ChemPlusChem; vol. 79; nb. 9; (2014); p. 1250 - 1253 View in Reaxys With hydrogen in acetone, Time= 0.5h, T= -78 °C , p= 2Torr Beeri,A.; Berman,E.; Vishkautsan,R.; Journal of the American Chemical Society; vol. 108; (1986); p. 6413 View in Reaxys

(v2)

Zn

(v2)

Zn

Rx-ID: 28596358 View in Reaxys 13/481 Yield

Conditions & References

79 %

With iron (III) acetylacetonate, ethylene dibromide in tetrahydrofuran, Time= 3h, T= 20 °C , Inert atmosphere Cahiez, Gerard; Foulgoc, Laura; Moyeux, Alban; Angewandte Chemie, International Edition; vol. 48; nb. 16; (2009); p. 2969 - 2972 View in Reaxys

(v2)

Zn

I

Rx-ID: 28596370 View in Reaxys 14/481 Yield

Conditions & References

75 %

Stage 1: With Et2CHMgCl in tetrahydrofuran, Time= 0.333333h, T= 0 °C , Inert atmosphere Stage 2: With methylzync chloride in tetrahydrofuran, Time= 0.25h, T= 20 °C , Inert atmosphere Stage 3: With iron (III) acetylacetonate, ethylene dibromide in tetrahydrofuran, Time= 3h, T= 20 °C , Inert atmosphere Cahiez, Gerard; Foulgoc, Laura; Moyeux, Alban; Angewandte Chemie, International Edition; vol. 48; nb. 16; (2009); p. 2969 - 2972 View in Reaxys

O

Rx-ID: 745201 View in Reaxys 15/481 Yield

Conditions & References With zinc chloride on alumina, T= 300 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2410553; (1944) View in Reaxys 8 :Example 8; Using a fixed bed reaction device equipped with a high-pressure feed pump, a high-pressure hydrogen mass flow, a high-pressure nitrogen mass flow, an electric furnace, a reactor having a catalyst charge part, and a backpressure valve, pressurized liquid phase flow reaction by a down flow was carried out. In a SUS 316 reactor having an inner diameter of 1 cm, 1.0 g of a powder (having been classified as that of 250 to 500 μ) of a copper-zinc catalyst (available from Sud-Chemie AG, product name: Shift Max 210, mass percent of element: Cu 32 to 35percent, Zn 35 to 40percent, Al 6 to 7percent, atomic ratio of Zn to Cu: 1.0 to 1.2) was first charged from the exit side of the reactor as a catalyst layer on the upstream side. After quartz wool was packed, 3.0 g of the aforesaid MCM-22 (obtained by compression molding a catalyst prepared in accordance with VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001, p. 225, at 20 MPa and then classifying it as that of 250 to 500 μ, Si/Al molar ratio: 20) was charged as a catalyst layer on the downstream side. The reactor was pressurized to 3 MPa with hydrogen, and then reduction treatment was carried out at 200°C for 3 hours in a stream of hydrogen at 12.5 ml/min

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given from the entrance side of the reactor. Still in a stream of hydrogen at 12.5 ml/min, the temperature was lowered to 175 °C, and a mixed liquid of benzene/acetone (3/1 by mol) was fed from the entrance side of the reactor and passed through the reactor at a rate of 2.50 g/hr. By the use of the high-pressure nitrogen mass flow, nitrogen was introduced at 200 ml/min into the middle part between the reactor exit and the backpressure valve. In the line after the backpressure valve, a switching valve was installed, then a reaction gas was introduced into an injection of gas chromatography through a sampling tube of 0.2 ml, and the product was determined by gas chromatography analysis. The reaction result is set forth in Table 1. By separating the copper-zinc catalyst and MCM-22 from each other, side production of propane was decreased though acetone remained, and cumene was obtained highly selectively.

With hydrogen, Shift Max 210, MCM-22, T= 175 - 200 °C , p= 22502.3Torr , Inert atmosphere, Product distribution / selectivity Patent; Mitsui Chemicals, Inc.; EP2123622; (2009); (A1) English View in Reaxys 3 :[Example 3]; Cu-Zn catalyst (cylindrical columns 3 mm in diameter x 3 mm in height, manufactured by SuedChemie Catalysts Japan, Inc., elemental mass percent: Cu 32 to 35percent, Zn 35 to 40percent, Al 6 to 7percent, Zn to Cu atomic ratio: 1.0 to 1.2) weighing 885 g was loaded in the reactor described in Example 1. β-zeolite catalyst (pellets 1.5 mm in diameter, manufactured by TOSOH CORPORATION) weighing 1806 g was loaded at a lower part of the reactor. A catalyst layer was thereby formed which had a layer 1 of the Cu-Zn catalyst and a layer 2 of the βzeolite catalyst. The catalyst was washed and pretreated in the same manner as in Example 1. While the reactor pressure was maintained at 3 MPaG and the preheating temperature at 173°C, benzene: 7.65 L/h, acetone: 0.59 L/h and hydrogen: 2090 NL/h were supplied from the top of the reactor to perform reaction. A mixture of the reaction liquid and gas that was discharged from the reactor bottom was separated in a gas-liquid separation tank, and the oil phase and the aqueous phase were separated in an oil-water separation tank. When the reaction had been continuously carried out for 12 hours, the reaction liquid and the waste gas were each analyzed by gas chromatography.

The acetone conversion was 98.5percent and the cumene selectivity was high at 98.9percent. The results are set forth in Table 1. In Example 3, the flow state was in a trickle-bed zone and the reaction gas flow rate at the layer 2 was 0.285.

With hydrogen, Cu 32 to 35 wtpercent, Zn 35 to 40 wtpercent, Al 6 to 7 wtpercent, Zn to Cu atomic ratio: 1.0 to 1.2, β-zeolite, Time= 12h, T= 173 °C , Product distribution / selectivity Patent; Mitsui Chemicals, Inc.; EP2292573; (2011); (A1) English View in Reaxys 1 :A fixed bed reaction apparatus was used which was equipped with a high-pressure feed pump, a high-pressure hydrogen mass flow controller, a high-pressure nitrogen mass flow controller, an electric furnace, a reactor having a catalyst-packing part, and a back pressure valve. A pressurized liquid-phase downflow reaction was carried out in the reaction apparatus.The reactor was a SUS 316 reactor having an inner diameter of 1 cm. The 10percent Ag/ silica gel catalyst was compacted at 20 MPa and was classified to 250 to 500 μm. The silver-containing catalyst in an amount of 6.0 g was mixed with 1.0 g of β-zeolite (manufactured by JGC Catalysts and Chemicals Ltd., compacted at 20 MPa and classified to 250 to 500 μm), and the mixture was packed in the reactor to form a catalyst layer.The pressure was increased to 4.5 MPa with hydrogen. Under a stream of hydrogen at 8.3 ml/min, a benzene/ acetone (5/1 molar ratio) mixture liquid was passed at 175° C. at a rate of 0.50 g/h (WHSV=0.07/h, hydrogen/ acetone molar ratio=20).The reaction products were sampled at the outlet of the reactor. The gas phase and the liquid phase were analyzed by gas chromatography.The reaction results are set forth in Table 1. The cumene selectivity is high compared to the result in Comparative Example 1 below.

With hydrogen, T= 175 °C , p= 33753.4Torr Patent; Mitsui Chemicals, Inc.; US2012/4471; (2012); (A1) English View in Reaxys With copper chromite, hydrogen, Time= 1h, T= 150 °C , p= 22502.3Torr Shutkina; Ponomareva; Ivanova; Petroleum Chemistry; vol. 53; nb. 1; (2013); p. 20 - 26 View in Reaxys

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O

N N

O

N

N

N

N

HO

N

HO

NH

O

N N

N N

NH N

O

O

O

OH

HN

O

N

O

N

N N O

N

N

N N

NH N

N

N N

O

Rx-ID: 28028326 View in Reaxys 16/481 Yield

Conditions & References

55 %

1 :Comparative Example 1.- Preparation of Valsartan by direct hydrogenation starting from compound of general formula (I) wherein R is cumyl.; ValsartanFollowing a similar process to that described in Example 2, compound of general formula (I) wherein R is cumyl was hydrogenated with hydrogen using Pd/C as catalyst and in the presence of dicyclohexylamine as organic base. Samples of the reaction mass were collected at different times: 1.5 h, 6.5 h, 11.5 h, 15.5, h and 18.5 h, and were analyzed by HPLC to determine the content of the different compounds. The results are shown in Table I in the description. Finally, Valsartan was isolated in 55percent yield.

With hydrogen, N,N-dicyclohexylamine, palladium 10 on activated carbon in isopropyl alcohol, toluene, Time= 1.5 18.5h, T= 65 °C , p= 2250.23Torr , Product distribution / selectivity Patent; QUIMICA SINTETICA, S.A.; WO2008/138871; (2008); (A1) English View in Reaxys

O B O

Rx-ID: 41316979 View in Reaxys 17/481 Yield 100 %

Conditions & References With oxygen, hydrazine hydrate in acetonitrile, Time= 3h, T= 32 °C , p= 760.051Torr , Schlenk technique Santra, Surojit; Guin, Joyram; European Journal of Organic Chemistry; vol. 2015; nb. 33; (2015); p. 7253 - 7257 View in Reaxys

O

Rx-ID: 34564560 View in Reaxys 18/481 Yield

Conditions & References General procedures for the reduction of citral with microwave irradiation General procedure: The reduction of citral was carried out in a quartz tube (10 mL) under microwave irradiation. The order of addition of the reagents plays an important role in the reactions [27]. We selected the following standard protocol. Hydrogen donor was first dissolved in a solvent in the reactor, catalyst was then added, and finally the substrate was added. Then, the reaction vessel was sealed and the reaction was carried out under microwave irradiation at 300 W with a stirring speed of 900 r/min. The reaction time was started to count when the reaction mixture reached the desired temperature. After the reaction, the mixture was extracted with n-hexane and the resulting solution was analyzed with gas chromatography (GC-Shimadzu-14C, FID, Capillary column Rtx-Wax 30 m-0.53 mm0.25 mm) and gas chromatography/mass spectrometry (GC/MS, Agilent 5890). The gas phases were analyzed by Shimadzu GC-14C with TCD and a TDX-01 packed column. The reactions in the autoclave (50 mL) were also carried out in a water-bath with the same procedures.

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With formic acid, palladium 10 on activated carbon, sodium formate in water, Time= 0.5h, T= 80 °C , Sealed tube, Microwave irradiation, Reagent/catalyst, Solvent Liu, Ruixia; Wang, Yu; Cheng, Haiyang; Yu, Yancun; Zhao, Fengyu; Arai, Masahiko; Journal of Molecular Catalysis A: Chemical; vol. 366; (2013); p. 315 - 320 View in Reaxys

O

N O

Rx-ID: 2037442 View in Reaxys 19/481 Yield 92 %

Conditions & References With 2,2-azobisbutyronitrile, tri-n-butyl-tin hydride in benzene, Time= 1.5h, Heating Ono, Noburu; Miyake, Hideyoshi; Tamura, Rui; Kaji, Aritsune; Tetrahedron Letters; vol. 22; nb. 18; (1981); p.

1705 - 1708 View in Reaxys

92 %

With tri-n-butyl-tin hydride, 2,2'-azo-bisisobutyronitrile in various solvent(s), Time= 1.5h, T= 80 °C , denitrohydrogenation of tertiary nitroalkanes with various methods, Product distribution Ono, Noboru; Miyake, Hideyoshi; Kamimura, Akio; Hamamoto, Isami; Tamura, Rui; Kaji, Aritsune; Tetrahedron; vol. 41; nb. 19; (1985); p. 4013 - 4024 View in Reaxys

75 %

With triethylsilane, tin(IV) chloride in dichloromethane, Time= 1h, T= 20 °C Ono, Noboru; Hashimoto, Toshihiro; Jun, Tuo Xiao; Kaji, Aritsune; Tetrahedron Letters; vol. 28; nb. 20; (1987); p. 2277 - 2280 View in Reaxys

75 %

With triethylsilane, tin(IV) chloride in dichloromethane, Time= 1h, T= 20 °C , denitrohydrogenation, Product distribution Ono, Noboru; Hashimoto, Toshihiro; Jun, Tuo Xiao; Kaji, Aritsune; Tetrahedron Letters; vol. 28; nb. 20; (1987); p. 2277 - 2280 View in Reaxys

79 % Chromat.

With meta-chloroperoxybenzoic acid, tri-n-butyl-tin hydride in benzene, Time= 18h, T= 90 °C , Product distribution Tanner, Dennis D.; Blackburn, Edward V.; Diaz, Gilberto E.; Journal of the American Chemical Society; vol. 103; nb. 6; (1981); p. 1557 - 1559 View in Reaxys With 2,2'-azo-bisisobutyronitrile, tri-n-butyl-tin hydride in benzene, T= 80 °C , Mechanism Kamimura, Akio; Ono, Noboru; Bulletin of the Chemical Society of Japan; vol. 61; (1988); p. 3629 - 3636 View in Reaxys

Rx-ID: 10662946 View in Reaxys 20/481 Yield

Conditions & References 1 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately

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placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 1; [0070] The catalyst sample of this Example 1 comprised 80wtpercent MCM-49 and20wtpercent alumina (Al2O3) and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at theSpecified NMR Pretreatment Temperature of 25O0C. The proton density was 1.71 mmol per gram of catalyst (first hydration state).[0071] A 0.5 gram portion of the catalyst sample of this Example 1 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex- situ Drying Temperature of 250°C and the Specified In-situ Drying Temperature of 170°C. The Catalyst Selectivity of this catalyst sample was 5.92, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (EPB/DIPB). TheCatalyst Activity of this catalyst sample was 363.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 1.71 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 8 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 8; [0088] The catalyst sample of this example comprised 65wtpercent MCM-22 and 35wtpercent alumina and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 2500C. The proton density was 1.46 mmol per gram of catalyst (first hydration state).[0089] A 1.0 gram

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portion of the catalyst sample of this Example 8 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 2500C and the Specified In-situ Drying Temperature of 1700C. The Catalyst Selectivity of the catalyst sample was 5.46, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (DPB/DIPB). The Catalyst Activity of this catalyst sample was 272.

With 65wtpercent MCM-22 and 35wtpercent alumina (Al2O3) having proton density 1.46 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 5 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 5; [0080] The catalyst sample of Example 1 was treated in nitrogen that was saturated with water vapor in accordance with Proton Content Adjustment Technique No.2 at a Contact Temperature of 220°C and a Contact Pressure of 50 psig. The resulting catalyst was then treated in accordance with Proton Content Adjustment Technique No.1, to produce the treated catalyst sample of this Example 5 having a third hydration state. The proton density of the treated catalyst was 1.76 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 25O0C. [0081] A 0.5 gram portion of the treated catalyst of this Example 5 was tested <n="25"/>in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situDrying Temperature of 25O0C and the Specified In-situ Drying Temperature of170°C. The Catalyst Selectivity of the catalyst sample was 6.80, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst sample was377.[0082] The PDI of the catalyst sample of this Example 5 was determined to be1.03, and represents a 3percent increase in proton content (determined as mmol of protons per gram of catalyst), as compared to the catalyst sample of Example 1.The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 5 displayed an increase of 15percent, and the Catalyst Activity displayed an increase of4percent, as compared to the catalyst sample of Example 1.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 1.76 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 2 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

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Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 2; [0072] Another portion of the catalyst sample of Example 1 was treated in accordance with Proton Content Adjustment Technique No.1 at a Contact Time of approximately 1 hour, to produce the treated catalyst sample of this Example 2 having a third hydration state. The proton density of the third hydration state of the treated catalyst sample was 1.85 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 25O0C.[0073] A 0.5 gram portion of the treated catalyst sample of this Example 2 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250°C and the Specified In-situ Drying Temperature of 170°C. The Catalyst Selectivity of this catalyst sample was 6.94, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst sample was 383.[0074] The PDI of the catalyst sample of this Example 2 was determined to be 1.08, and represents an 8percent increase in the proton content (determined as mmol of protons per gram of catalyst) as compared to the catalyst sample of Example 1. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 2 displayed an increase of 17percent, and the Catalyst Activity displayed an increase of 5.5percent, as compared to the catalyst sample of Example 1.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 1.85 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 10 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained con-

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nected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 10; [0094] The catalyst sample described in Example 6 was treated in accordance with Proton Content Adjustment Technique No.2 at a Contact Temperature of 220°C and a Contact Pressure of 50 psig in nitrogen that was saturated with water vapor. The resulting catalyst sample was then treated in accordance with to Proton Content Adjustment Technique No.1, to produce the treated catalyst of this Example 10 having a third hydration state. The proton density of this treated catalyst sample was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 15O0C. The proton density was 2.19 mmol per gram of catalyst (third hydration state). <n="28"/>[0095] A 0.5 gram portion of the treated catalyst sample of this Example 10 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 15O0C and the Specified In-situ Drying Temperature of 150°C. The Catalyst Selectivity of this catalyst sample was 7.09, determined as the weight ratio IPB/DIPB. The Catalyst Activity of this catalyst sample was 244.[0096] The PDI of the catalyst sample of this Example 10 was determined to be 1.03, and represents a 3percent increase in the proton content (determined as mmol of protons per gram of catalyst) as compared to the catalyst sample of Example 6. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of Example 10 displayed an increase of 20percent, and the catalyst activity decreased only slightly to 89percent of that of the catalyst of Example 6.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 2.19 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 6 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 6; [0083] The catalyst sample of this Example 6 comprised 80wtpercent MCM-49 and20wtpercent alumina and its proton density was determined in accordance with theNMR Procedure for Determining Proton Density, described above, at theSpecified NMR Pretreatment Temperature of 1500C. The proton density was found to be 2.59 mmol per gram of catalyst (first hydration state).

[0084] A 0.5 gram portion of the catalyst sample of this Example 6 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situDrying Temperature of 15O0C and the Specified In-situ Drying Tempera-

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ture of150°C. The Catalyst Selectivity of this catalyst sample was 5.92, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB). TheCatalyst Activity of this catalyst sample was 275.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 2.59 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 7 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 7; [0085] Another portion of the catalyst sample of Example 6 was treated in accordance with Proton Content Adjustment Technique No.1 at a Contact Time of approximately 1 hour, to produce the treated catalyst sample of this Example 7 having a third hydration state. The proton density of the treated catalyst was 3.16 mmol per gram of catalyst, determined in accordance with the NMR Procedure forDetermining Proton Density, described above, at the Specified NMR PretreatmentTemperature of 15O0C.[0086] A 0.5 gram portion of the treated catalyst of this Example 7 was tested <n="26"/>in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 1500C and the Specified In-situ Drying Temperature of 1500C. The Catalyst Selectivity of this catalyst sample was 7.81, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst was 251. [0087] The PDI of the catalyst sample of this Example 7 was determined to be 1.22, and represents a 22percent increase in proton content (determined as mol of protons per gram of catalyst), as compared to the catalyst sample of Example 6. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of Example 7 displayed an increase of 32percent, and the Catalyst Activity decreased only slightly to 91percent of that of the catalyst in Example 6.

With 80wtpercent MCM-49 molecular sieve and 20wtpercent alumina (Al2O3) having proton density 3.16 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 3 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene)

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before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 3; [0075] The catalyst sample of this Example 3 comprised 80wtpercent zeolite Beta and 20wtpercent alumina and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 25O0C. The proton density was 2.48 mmol per gram of catalyst (first hydration state).[0076] A 1.0 gram portion of the catalyst sample of this Example 3 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex- situ Drying Temperature of 250°C and the Specified In-situ Drying Temperature of 170°C. The Catalyst Selectivity of this catalyst sample was 5.62, determined as <n="24"/>the weight ratio of IPB/ DIPB. The Catalyst Activity of this catalyst sample was 23.

With 80wtpercent zeolite Β and 20wtpercent alumina (Al2O3) having proton density 2.48 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 4 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 4; [0077] Another portion of the catalyst sample of Example 3 was treated in accordance with Proton Content Adjustment Technique No.1 at a Contact Time

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of approximately 1 hour, to produce a treated catalyst of this Example 4 having a third hydration state. The proton density of the treated catalyst was 2.77 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 2500C.[0078] A 1.0 gram portion of the treated catalyst of this Example 4 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex- situ Drying Temperature of 250°C and the Specified In-situ Drying Temperature of 170°C. The Catalyst Selectivity of this catalyst sample was 9.35, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst sample was 4. [0079] The PDI of the catalyst sample of this Example 4 was determined to be 1.12, and represents a 12percent increase in proton content (determined as mmol of protons per gram of catalyst) as compared to the catalyst sample of Example 3. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 4 displayed an increase of 66percent, and the Catalyst Activity was still 17.4percent of that of Example 3.

With 80wtpercent zeolite Β and 20wtpercent alumina (Al2O3) having proton density 2.77 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 11 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 11 (Comparative); [0097] The catalyst sample of this Example 11 comprised porous noncrystalline tungsten-zirconia (WZrO2) and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 25O0C. The proton density was 0.37 mmol per gram of catalyst (first hydration state). [0098] A 0.5 gram portion of the catalyst sample of this Example 11 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250°C and the Specified In-situ Drying Temperature of 170°C. The Catalyst Selectivity was 13.70, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB). The Catalyst Activity of this catalyst sample was 1.

With porous noncrystalline tungsten-zirconia (WZrO2) having proton density 0.37 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 12 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

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Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained connected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 12 (Comparative); [0099] The catalyst sample of Example 11 was treated in accordance with the Proton Content Adjustment Technique No.1 at a Contact Time of approximately 1 hour, to produce a treated catalyst sample of this Example 12 having a third hydration state. The proton density of the treated catalyst sample was 0.41 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 25O0C. <n="29"/>[0100] A 0.5 gram portion of the treated catalyst of this Example 12 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 2500C and the Specified In-situ Drying Temperature of 1700C. The Catalyst Selectivity of this catalyst sample was 9.62, determined as the weight ratio IPB/DIPB. The Catalyst Activity of this catalyst sample was 1.[0101] The PDI of the catalyst sample of Example 12 was determined to be 1.11, and represents an 11percent increase in the proton content (determined as mmol of protons per gram of catalyst), as compared to the catalyst of Example 11. However, the Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 12 displayed a 29.8percent decrease, as compared to the catalyst sample of Example 11. The Catalyst Activity was 100percent of the catalyst sample of Example 11.

With porous noncrystalline tungsten-zirconia (WZrO2) having proton density 0.41 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 9 :Catalyst Reactivity Testing Procedure; [0059] To prepare a catalyst composition for reactivity testing, a specified amount of a catalyst sample was dried in the presence of air in an oven at a specified ex-situ drying temperature ("Specified Ex-situ Drying Temperature") for2 hours. The catalyst sample was removed from the oven and weighed.

Quartz chips were used to line the bottom of a basket followed by loading of the catalyst sample into the basket on top of the first layer of quartz. Quartz chips were then placed on top of the catalyst sample. The basket containing the catalyst sample and quartz chips were placed in an oven at the Specified Ex-situ DryingTemperature in the presence of air for about 16 hours.[0060] The reactor and all lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The basket containing the catalyst sample and quartz chips were removed from the oven, immediately placed in the reactor, and the reactor was immediately assembled. The reactor temperature was set to an in-situ drying temperature ("Specified In-situ DryingTemperature") and purged with 100 SCCM of nitrogen for 2 hours.[0061] The reactor temperature was then reduced to 13O0C, the nitrogen purge was discontinued and the reactor vent closed. A 156.1 gram quantity of benzene was loaded into a 300 cc transfer vessel, performed in a closed system.

The benzene vessel was pressurized to 100 psig with a nitrogen source and the benzene was transferred into the reactor. The agitator speed was set to 500 rpm and the reactor was allowed to equilibrate for 1 hour.[0062] A 75 cc Hoke transfer vessel was then filled with 28.1 grams of liquid propylene and connected to the reactor vessel, and then connected with 300 psig nitrogen source. After the one-hour benzene stir time had elapsed, the propylene <n="21"/>was transferred, from the Hoke vessel to the reactor. The 300 psig nitrogen source was maintained con-

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nected to the propylene vessel and open to the reactor during the duration of the test to maintain constant reaction pressure of 300 psig. Liquid product samples were taken at 30, 60, 120, 150, 180 and 240 minutes after addition of the propylene. These samples were then analyzed by Gas Chromatography with a Flame Ionization Detector and procedures known to those skilled in the art.[0063] In these examples, the selectivity of the catalyst sample ("Catalyst Selectivity") to the desired isopropylbenzene (cumene) product was calculated as the ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB) after propylene conversion reached 100percent. A higher IPB/DIPB ratio means a greater selectivity of the catalyst sample to isopropylbenzene (cumene). Also, in these examples the catalytic activity of the catalyst samples was determined by calculating the 2nd order kinetic rate constant using mathematical techniques well known to those skilled in the art ("Catalyst Activity").; Example 9; [0090] A portion of the catalyst sample of Example 8 that had become at least partially deactivated, such as if used commercially, was regenerated according to the following two-step procedure. First, the catalyst sample was heated to a temperature of 3850C in an atmosphere having less than 2.0 vol. percent hydrogen and hydrocarbons. The oxygen concentration was initially increased to 0.4 vol. percent, and then increased again to 0.7 vol. percent while the maximum catalyst temperature was maintained at 4670C. Second, the catalyst was heated to 45O0C in an <n="27"/>atmosphere having an oxygen concentration of 0.7 vol. percent, which was increased to 7.0 vol. percent while the maximum catalyst temperature was maintained at 510°C. [0091] This catalyst sample was then treated according to Proton Content Adjustment Technique No.1 at a Contact Time of approximately 1 hour, to produce the treated catalyst of this Example 9 having a third hydration state. The proton density of the treated catalyst was 1.97 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 2500C.[0092] A 1.0 gram portion of the treated catalyst sample of this Example 9 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250°C and the Specified rn-situ Drying Temperature of 170°C. The Catalyst Selectivity of this catalyst sample was 6.29, determined as the weight ratio IPB/DIPB. The Catalyst Activity of this catalyst sample was 174.

[0093] The PDI of the catalyst sample of Example 9 was determined to be 1.35, and represents a 35percent increase in the proton content (determined as mmol of protons per gram of catalyst), as compared to the catalyst sample of Example 8. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 9 displayed a 15percent increase, and the Catalyst Activity was still 64percent of that of the catalyst of Example 8.

With regenerated 65wtpercent MCM-22 and 35wtpercent alumina (Al2O3) having proton density 1.97 mmol per gram of catalyst in benzene, Time= 0.5 - 4h, T= 130 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2007/130055; (2007); (A1) English View in Reaxys 11 : Example 11 Example 11 Preparation of cumene from benzene and propylene using NU-85 molecular sieves.

Cumene was prepared from benzene and propylene by using NUZ-1 and NUZ-2 obtained in Example 10.

With silica gel in benzene Patent; China Petroleum and Chemical Corporation; Fushun Research Institute of Petroleum and Petrochemicals, Sinopec; EP2441733; (2012); (A1) English View in Reaxys

Rx-ID: 271005 View in Reaxys 21/481 Yield

Conditions & References T= 243 °C , Pyrolysis, Rate constant Ziegler; Deparade; Justus Liebigs Annalen der Chemie; vol. 567; (1950); p. 123,136 View in Reaxys T= 255 °C , Pyrolysis, Rate constant Ziegler; Deparade; Justus Liebigs Annalen der Chemie; vol. 567; (1950); p. 123,136 View in Reaxys T= 247 °C , Pyrolysis, Rate constant

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Ziegler; Deparade; Justus Liebigs Annalen der Chemie; vol. 567; (1950); p. 123,136 View in Reaxys 1 : Example; Example 1 A solution containing 1 percent by weight of 2,3-dimethyl-2,3-diphenylbutane was passed through a reactor filled with 16 cc of a copper-chromium catalyst (3 mmφ pellet) at a rate of 1 g/minute at a temperature of 220 to 260°C under a pressure of 1 MPaG together with 300 cc/minute of hydrogen. Results were shown in Table 1. [Table 1] Reaction temperature2,3-Dimethyl-2,3 -diphenylbutane conversion *1Cumene selectivity *2220°C84 percent100 percent240°C97 percent100 percent260°C100 percent100 percent*1: 2,3-Dimethyl-2,3-diphenylbutane conversion = converted 2,3-dimethyl-2,3-diphenylbutane (mol)/ / fed 2,3-dimethyl-2,3-diphenylbutane (mol) x 100*2: Cumene selectivity = 0. 5 X produced cumene (mol) / converted 2,3-dimethyl-2,3-diphenylbutane (mol) X 100 With hydrogen, copper-chromium catalyst, T= 220 - 260 °C , p= 7500.75Torr , Conversion of starting material Patent; Sumitomo Chemical Company, Limited; EP1375458; (2004); (A1) English View in Reaxys O

I I

C

O

Rx-ID: 1605191 View in Reaxys 22/481 Yield

Conditions & References

86 %

With copper, zinc, tetrakis(triphenylphosphine) palladium(0) in tetrahydrofuran, Time= 42h, p= 760Torr , Ambient temperature Tamaru, Yoshinao; Ochiai, Hirofumi; Yamada, Yoshimi; Yoshida, Zen-ichi; Tetrahedron Letters; vol. 24; nb. 36; (1983); p. 3869 - 3872 View in Reaxys

E

Rx-ID: 4927923 View in Reaxys 23/481 Yield 74 %, 13 %

Conditions & References With hydrogen, HRhlt;P(NC6H4)3gt;4, Time= 1.66667h, T= 79.9 °C , p= 3750.3Torr Trzeciak, Anna M.; Glowiak, Tadeusz; Ziolkowski, Jozef J.; Journal of Organometallic Chemistry; vol. 552; nb.

1-2; (1998); p. 159 - 164 View in Reaxys

O

O

O

Rx-ID: 34564561 View in Reaxys 24/481 Yield

Conditions & References General procedures for the reduction of citral with microwave irradiation General procedure: The reduction of citral was carried out in a quartz tube (10 mL) under microwave irradiation. The order of addition of the reagents plays an important role in the reactions [27]. We selected the following standard protocol. Hydrogen donor was first dissolved in a solvent in the reactor, catalyst was then added, and finally the substrate was added. Then, the reaction vessel was sealed and the reaction was carried out under microwave irradiation at 300 W with a stirring speed of 900 r/min. The reaction time was started to count when the reaction mixture reached the desired temperature. After the reaction, the mixture was extracted with n-hexane and the resulting solution was analyzed with gas chromatography (GC-Shimadzu-14C, FID, Capillary column Rtx-Wax 30 m-0.53 mm0.25 mm) and gas chromatography/mass spectrometry (GC/MS, Agilent 5890). The gas phases were analyzed by Shimadzu GC-14C with TCD and a TDX-01 packed column. The reactions in the autoclave (50 mL) were also carried out in a water-bath with the same procedures.

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With formic acid, palladium 10 on activated carbon, sodium formate in water, Time= 0.5h, T= 80 °C , Sealed tube, Microwave irradiation, Reagent/catalyst, Solvent Liu, Ruixia; Wang, Yu; Cheng, Haiyang; Yu, Yancun; Zhao, Fengyu; Arai, Masahiko; Journal of Molecular Catalysis A: Chemical; vol. 366; (2013); p. 315 - 320 View in Reaxys

O

Rx-ID: 40074641 View in Reaxys 25/481 Yield 90 %, 6 %

Conditions & References With hydrogen in water, Time= 3h, T= 270 °C , p= 16501.7Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017 View in Reaxys

Rx-ID: 846988 View in Reaxys 26/481 Yield 18 %

Conditions & References With Dichloromethylvinylsilane, Time= 3h, T= 169.9 °C Belov, N. N.; Russian Journal of Physical Chemistry; vol. 58; nb. 6; (1984); p. 968; Zhurnal Fizicheskoi Khimii; vol.

58; nb. 6; (1984); p. 1580 View in Reaxys

14.8 %

With Methyltrichlorosilane, further catalysts, Product distribution Kolesnikov; Journal of applied chemistry of the USSR; vol. 58; nb. 9 pt 1; (1985); p. 1829 - 1838 View in Reaxys

3 - 30 %

Experimental Tests An experimental reactor was built, as shown schematically in FIG. 4. Two types of catalysts were used: (1) protonated (H+ β) beta-zeolite in powder form (Si:Al2 25:1); and (2) pellets of 80percent Beta-zeolite(Si:Al2 24:1) and 20percent alumina binder, purchased from Zeolyst International. Benzene (Aldrich, 99+percent) was used without further purification. The alkylating agent, propylene 14.3percent in a balance of nitrogen, was purchased premixed from TriGas. Relative cumene yield was defined as the amount of cumene produced over the maximum amount of cumene calculated by stoichiometry. Cumene relative selectivity is the amount of cumene produced over the sum of all the products obtained. Initial studies were conducted to determine appropriate reaction temperatures and catalyst amounts. Though not fully optimized, 115° C. was chosen as a suitable temperature for these experiments; as it is the intermediate temperature between the boiling points of benzene and cumene (80 C and about 152 C). The choice of 115 C was made as a compromise between the components' relative volatility (which favors choosing a lower temperature, i.e., closer to 80 C, in order to maximize the ability to physically separate benzene vapor from liquid cumene in the column) and the reaction temperature (which favors using a higher temperature, i.e., closer to 152 C to increase the chemical reaction rate). Catalyst amounts of 200 mg for powder, or 400 mg for pellets, were chosen not only for the alkylation reaction to occur, but also for the separation of reactants and products. The reactive separation system in FIG. 4 consists of a reactant delivery section, a vertical flow-through catalytic column, and a collection part with a reboiler and condenser. The reactants are fed into the reactor by a mass flow controller that delivers 3.5 ccm of a gaseous mixture of 14.3percent of propylene in nitrogen, and a syringe pump that injects 2.7 cc/h of liquid benzene. The system is kept at atmospheric pressure. The reactants were fed through two separate inlets, which could be located at the same level, or at different points, in the vertical column (see configurations A, B, or C in FIGS. 5A, 5B, 5C). The vertical flow-through reactive column consisted of either a 3.5 in. or 6 in. stainless steel tube of OD, in which the catalyst was hand-packed and held in place by quartz glass wool and quartz beads.

Before beginning the reaction, the catalyst was pretreated by flowing 10 ccm of dry nitrogen through the column at around 115° C. for at least 30 minutes. Once the column was stable at the reaction temperature of 115° C., the reactants were fed in to start the reaction. A flexible heating tape connected to a heater was wrapped around the reactive column to keep the reactor at the desired temperature. A chilled-water circulated glass condenser was attached to the top of the column to cool and condense unreacted benzene vapor in a collection glass flask. A reboiler unit, composed of a collection glass bulb and a heating mantle connected to a heating controller, was attached to the bottom

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of the reactive column to provide heat, and to collect cumene and heavier products. This reboiler unit was kept around 80° C., the boiling point of benzene, in order to evaporate any unreacted liquid benzene and send it back up to the column. After 3 hours of reaction time, the flow of reactants was stopped and the products collected at the top and bottom of the column. The final volume of the collected products of the alkylation reaction was taken to 25 ml using hexane. Then, the products were identified by mass spectroscopy using a GC/MS Hewlett Packard 5890 Series II Plus, and quantitatively analyzed by a Hewlett Packard 5890A gas chromatograph equipped with a capillary column Bentone 34/DNDP SCOT (0.02 in..x.50 ft, or 0.5 mm.x.15.2 m) from Supelco and a flame ionization detector.

We discovered that the reactive separation column, packed with a solid acid catalyst, allowed separation of unreacted excess benzene from the products as they formed. The reactants propylene and benzene met inside the reactive column in the presence of a solid catalyst at 1 atm. and 115° C. As the benzene alkylation reaction proceeded, cumene was formed. At the same time, vapor benzene rose through the column and exited through the top of the tower, together with unreacted propylene, as the light stream; while produced liquid cumene, together with all the other by-products (mainly di-isopropylbenzenes, DIPB), dropped down the column and exited the bottom of the tower as the heavy stream. Ideally, all the unreacted benzene would escape to the top of the column, and all cumene formed would fall with the bottom products. Table 1 summarizes the results of these experiments. As can be seen, in all the reactor configurations relative cumene selectivity with respect to products was above 85percent for both powdered and pelletized catalysts; but the cumene reaction yield, and separation of unreacted benzene and produced cumene varied greatly from one design configuration to another. With configuration A (shown in FIG. 5A), a very low cumene reaction yield occurred, and most of the cumene formed was taken to the bottom, as desired, but most of the unreacted benzene also collected at the bottom. With configuration B (shown in FIG. 5B), the separation of unreacted benzene and produced cumene in the reactor was not very good; similar amounts of reactant and products were obtained in the amounts collected from both the top and bottom. Of the different reactors tested, configuration C shown in FIG. 5C gave the best results in terms of reactant-product separation for both pelletized and powdered catalysts.

When pellets were used, 76percent of the unreacted benzene rose to the top of the column, but 24percent of benzene dropped with the bottom products. With the cumene, 63percent dropped to the bottom, but 37percent of cumene rose to the top. For this reaction, relative cumene yield was about 30percent and cumene selectivity was 90percent. When powdered catalyst was used in reactor configuration C, 62percent of the unreacted benzene rose to the top of the column, and 86percent of the cumene formed in the reaction dropped with the bottom products. The cumene yield for this reaction was about 20percent and the relative selectivity was 85percent. As seen, although some of these nonoptimized system configurations do not have the high yield of the reactive distillation processes (above 98percent), they do not require the high operating pressures of the other processes; nor do they require the use of a reflux system for the top products. While complete 100percent separation of un-reacted benzene from the cumene formed did not generally appear to be possible in one pass, additional testing and design optimization should improve the separation results. The selectivity obtained with our catalytic separation reactions stayed in the 85 percentile at the relatively low reaction temperature of 115° C. and at only 1 atmosphere. To obtain the same selectivity in a conventional batch or fixed-bed reactor system would require a higher reaction temperature (likely above 150° C.). We have not tested the effect that a high benzene:propylene molar ratio, such as the one used in the reactive separation, (22:1) would have in a conventional batch or fixed bed system. The stability of the catalyst with reaction time remains to be studied, as a main drawback of the use of highly active zeolites in cumene production may be their quick deactivation. In these tests we studied the influence of catalyst morphology and reactant injection port locations. Testing of different reactor configurations for cumene production, using both powdered and pelletized Beta zeolite catalysts, helped in initial optimization of design and production yields. These initial studies showed that this design allowed for selectivity for catalytic separation reactions starting at 85percent and above at the relatively low reaction temperature of 115° C. Simultaneously, cumene reaction yield up to 30percent was achieved with up to 76percent of the unreacted benzene being separated from the products. The particular examples discussed above are cited to illustrate particular embodiments of the invention. Other applications and embodiments of the apparatus and method of the present invention will become evident to those skilled in the art. It is to be understood that the invention is not limited in its application to the details of construction, materials used, and the arrangements of components set forth in the following description or illustrated in the drawings. The scope of the invention is defined by the claims appended hereto. TABLE 1 Results of reactive separation of cumene, with reactor at 115° C. and 1 atm., feeding 3.5 ccm 14.5percent propylene/N2 and 2.7 ml liquid benzene, after 3 hr reaction. Rel. Rel. wt percent wt percent cumene cumene benzene cumene Reactor selectivity, yield, top top Run Catalyst configuration percent percent bottom bottom 1 200 mg A 87 3 31 11 powder 69 89 2 200 mg B 89 21 50 62 powder 50 38 3 400 mg B 88 6 51 54 pellets 49 46 4 200 mg C 85 20 62 14 powder 38 86 5 400 mg C 90 30 76 37 pellets 24 63 With zeolite, Time= 3h, T= 115 °C , p= 760.051Torr , Product distribution / selectivity Patent; Buelna, Genoveva; Nenoff, Tina M.; US2006/281958; (2006); (A1) English View in Reaxys With SiO2-Al2O3 fluorinated with CClF3, T= 350 °C , catalytic activities, depending on fluorination

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Kurosaki, Akito; Okazaki, Susumu; Bulletin of the Chemical Society of Japan; vol. 63; nb. 8; (1990); p. 2363 2367 View in Reaxys With aluminosilicate, Time= 2h, T= 25 °C , other catalysts, Product distribution Kolesnikov, I. M.; Mirgaleev, I. G.; J. Appl. Chem. USSR (Engl. Transl.); vol. 54; nb. 9; (1981); p. 2002 - 2009,1751 - 1757 View in Reaxys With trichlorovinylsilane, Time= 3h, T= 169.9 °C , p= 5320Torr , various time, Product distribution Belov, N. N.; Baidala, B. G.; Russian Journal of Physical Chemistry; vol. 57; nb. 2; (1983); p. 317; Zhurnal Fizicheskoi Khimii; vol. 57; nb. 2; (1983); p. 512 View in Reaxys With phosphoric acid, T= 150 - 250 °C , p= 12503.6Torr Patent; California Research Corp.; US2713600; (1953) View in Reaxys With phosphoric acid, T= 210 - 260 °C , p= 25007.3Torr Patent; Universal Oil Prod. Co.; US2860173; (1955) View in Reaxys With aluminium-dichloride hydrogen sulfate Toptschiew et al.; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 28; (1955); p. 976; engl.

Ausg. S. 929 View in Reaxys With silica-alumina, T= 320 °C Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys With hydrogen fluoride, T= 50 °C Patent; Phillips Petr. Co.; US2408173; (1943) View in Reaxys With HC600a, hydrogen fluoride Condon; Matuszak; Journal of the American Chemical Society; vol. 70; (1948); p. 2539,2540 View in Reaxys With hydrogen fluoride, boron trifluoride, T= 40 - 45 °C Patent; Standard Oil Co. of Ohio; US2408753; (1943) View in Reaxys Patent; Standard Oil Co. of Ohio; US2442342; (1942) View in Reaxys With BF3*H3PO4 Patent; Phillips Petr. Co.; US2412595; (1942) View in Reaxys Toptschijew; Pauschkin; Ssergatschewa; Doklady Akademii Nauk SSSR; vol. 64; (1949); p. 81; ; (1949); p. 4638 View in Reaxys Pauschkin; Toptschijew; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 21; (1948); p.

1065,1070; ; (1949); p. 1732 View in Reaxys With sulfuric acid, T= 0 - 25 °C Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1007

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View in Reaxys Patent; Stanley; Minkoff; Youell; US2143493; (1937) View in Reaxys Patent; Universal Oil Prod. Co.; US1994249; (1932) View in Reaxys Ipatieff; Corson; Pines; Journal of the American Chemical Society; vol. 58; (1936); p. 919,921; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1519,1523 View in Reaxys With sulfuric acid, T= 30 - 40 °C Newton; Journal of the American Chemical Society; vol. 65; (1943); p. 320 View in Reaxys With sulfuric acid, T= 60 °C Ipatieff; Corson; Pines; Journal of the American Chemical Society; vol. 58; (1936); p. 919,921; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1519,1523 View in Reaxys With sulfuric acid, boron trifluoride Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1007 View in Reaxys Slanina; Nieuwland; Journal of the American Chemical Society; vol. 57; (1935); p. 1547 View in Reaxys With sulfuric acid, phenol Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1007 View in Reaxys Slanina; Nieuwland; Journal of the American Chemical Society; vol. 57; (1935); p. 1547 View in Reaxys With kieselguhr, magnesium dihydrogen phosphate Patent; Universal Oil Prod. Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2387948; (1941) View in Reaxys With kieselguhr, Zn(H2PO4)2 Patent; Universal Oil Prod. Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2387948; (1941) View in Reaxys With copper(II) pyrophosphate, T= 280 - 350 °C Patent; Universal Oil Prod. Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2387948; (1941) View in Reaxys With aluminium trichloride, chloroethane, T= 200 °C Patent; Dow Chem. Co.; US2403785; (1943) View in Reaxys

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With aluminium silicate, T= 350 - 450 °C Patent; Universal Oil Prod. Co.; US2410111; (1939) View in Reaxys Patent; Universal Oil Prod. Co.; US2448160; (1946) View in Reaxys O'Kelly; Kellett; Plucker; Industrial and Engineering Chemistry; vol. 39; (1947); p. 154,157 View in Reaxys Mamedalijew; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1946); p. 458; ; (1948); p. 6331 View in Reaxys With hydrochlorid acid, aluminum oxide, silica gel, T= 250 - 260 °C Patent; Phillips Petr. Co.; US2408167; (1944) View in Reaxys With aluminum oxide, iron(II) chloride, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2329858; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2402847; (1941) View in Reaxys With hydrochlorid acid, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2357978; (1941) View in Reaxys With hydrochlorid acid, zinc oxide, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2357978; (1941) View in Reaxys With hydrochlorid acid, silica gel, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2357978; (1941) View in Reaxys With iron(III) chloride, T= 20 °C Potts; Carpenter; Journal of the American Chemical Society; vol. 61; (1939); p. 663 View in Reaxys With methanesulfonic acid, T= 65 - 75 °C , p= 2206.5Torr Proell; Adams; Industrial and Engineering Chemistry; vol. 41; (1949); p. 2217,2220 View in Reaxys With aluminium trichloride, T= 70 °C Berry; Reid; Journal of the American Chemical Society; vol. 49; (1927); p. 3145 View in Reaxys With boric acid, phosphorus pentoxide, T= 275 °C , p= 128714Torr Patent; Universal Oil Prod. Co.; US2652434; (1951) View in Reaxys With hydrogen fluoride, T= 0 - 20 °C Patent; du Pont de Nemours and Co.; US2423470; (1938) View in Reaxys Simons; Archer; Journal of the American Chemical Society; vol. 60; (1938); p. 2953 View in Reaxys Calcott; Tinker; Weinmayr; Journal of the American Chemical Society; vol. 61; (1939); p. 1010,1014 View in Reaxys

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With sulfuric acid, T= 35 - 40 °C , p= 8826.09Torr Horn; Bestian in K. Winnacker; L. Kuechler; View in Reaxys Asinger,F.; View in Reaxys McAllister; Anderson; Bullard; ; vol. 43; (1947); p. 189 T View in Reaxys With ACP, kieselguhr Patent; Universal Oil Prod. Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2387948; (1941) View in Reaxys With hydrochlorid acid, aluminum oxide, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2357978; (1941) View in Reaxys With boron trifluoride, isopropyl alcohol, T= 30 °C Patent; Phillips Petr. Co.; US2425839; (1942) View in Reaxys With phosphoric acid kieselguhr, T= 250 °C , p= 18387.7Torr Horn; Bestian in K. Winnacker; L. Kuechler; View in Reaxys Asinger,F.; View in Reaxys McAllister in B. T. Brooks et al.; View in Reaxys McAllister; Anderson; Bullard; ; vol. 43; (1947); p. 189 T View in Reaxys Patent; Universal Oil Prod. Co.; US2382318; (1942) View in Reaxys With aluminum oxide, magnesium chloride, T= 300 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2329858; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2402847; (1941) View in Reaxys With Ag4(pyrophosphate), T= 280 - 350 °C Patent; Universal Oil Prod. Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod. Co.; US2387948; (1941) View in Reaxys With aluminium silicate, T= 150 - 200 °C Patent; Phillips Petr. Co.; US2419599; (1942) View in Reaxys With aluminium trichloride, nitromethane, T= 0 - 40 °C Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys

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Patent; Universal Oil Prod. Co.; US2385303; (1941) View in Reaxys With copper(II) pyrophosphate, T= 216 °C Patent; Kellogg Co.; US2787648; (1954) View in Reaxys With boron trifluoride, monofluorophosphoric acid Toptschiew; Andronow; Doklady Akademii Nauk SSSR; vol. 112; (1957); p. 876; Doklady Chemistry; 112-117 <1957> 137 View in Reaxys With aluminum oxide, fluorinated with CClF3, silica gel, T= 350 °C Kurosaki, Akito; Okazaki, Susumu; Bulletin of the Chemical Society of Japan; vol. 63; nb. 8; (1990); p. 2363 2367 View in Reaxys With [Pd(MeCN)4][BF4] Sen, Ayusman; Lai, Ta-Wang; Journal of the American Chemical Society; vol. 103; nb. 15; (1981); p. 4627 - 4629 View in Reaxys With trichlorovinylsilane, Time= 3h, T= 169.9 °C , p= 5320Torr , Yield given Belov, N. N.; Baidala, B. G.; Russian Journal of Physical Chemistry; vol. 57; nb. 2; (1983); p. 317; Zhurnal Fizicheskoi Khimii; vol. 57; nb. 2; (1983); p. 512 View in Reaxys With chlorine Ayame, Akimi; Izumizawa, Takenori; Journal of the Chemical Society, Chemical Communications; nb. 10; (1989); p. 645 - 646 View in Reaxys bei hoeheren Temperaturen und Drucken und als Katalysatoren werden verschiedene Phosphate und Pyrophosphate vorgeschalgen Patent; Universal Oil Prod.Co.; US2412229; (1941) View in Reaxys Patent; Universal Oil Prod.Co.; US2290211; (1941) View in Reaxys Patent; Universal Oil Prod.Co.; US2387948; (1941) View in Reaxys 1 With trifluoromethanesulphonic acid/silica gel, T= 80 °C , Product distribution / selectivity Patent; Haldor Topsoe A/S; EP1184360; (2002); (A1) English View in Reaxys With zeolite catalyst, Industrial scale Patent; Sunoco, Inc. (RandM); US6355851; (2002); (B1) English View in Reaxys 4 :EXAMPLE 4 [0042] The catalytic distillation composite according to present invention was used in the preparation of isopropyl benzene from propylene and benzene through alkylation. The catalytic distillation composite was prepared according to the process described in Example 1-3, except that the porous metal corrugated sheets were formed into those having a peak height of 15 mm, pitch of 30 mm, corrugation angle of inclination of 30° and wall thickness of 0.5 mm and further into a φ500.x.200 mm structured porous metal packing tray. The obtained catalytic distillation composite was then installed in a reaction section of a φ500 mm catalytic distillation column comprising a reaction section and a stripping section wherein the reaction section was 9 m high, and the stripping section was 3 m high and was filled with the structured metal packing of type 250Y(φ500.x.200 mm). Operation conditions were:

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space velocity ( by weight) for propylene of 0.36 h-1, benzene/propylene molar ratio of 6:1, and system pressure of 0.8 MPa, and reaction temperature between 140 and 180° C. Under these conditions, the propylene conversion of 100percent and the average selectivity for isopropyl benzene of 98percent were achieved.

With catalytic distillation composite, T= 140 - 180 °C , p= 6000.6Torr , Product distribution / selectivity Patent; Yang, Yuanyi; Li, Dongfeng; Dai, Wei; Chen, Shuo; Wang, Guoqing; Liao, Lihua; Cheng, Jianmin; Guo, Yanlai; Peng, Hui; US2003/220187; (2003); (A1) English View in Reaxys 8 :EXAMPLE 8; A batch of MCM-22 type catalyst was loaded into a pilot plant alkylation reactor and tested for cumene synthesis. Between the catalyst on-stream hours of 5,603 and 5, 630, the benzene charge was about 65 grams per hour, and the propylene charge was about 29 grams per hour. The reactor temperature was 128°C, and the propylene conversion was stable at greater than 99.99percent. At 5,631 on-stream hours, the pure benzene feed was replaced with a prepared benzene feed spiked with 50 ppm NMP. At the same time, a guard bed in accordance with the present invention containing 22.5 grams of molecular sieve 13X was placed into service upstream of the pilot plant alkylation reactor to pretreat the benzene feed for removal of the NMP. The guard bed was maintained at an ambient temperature of about 25°C. No NMP was detected in the benzene feed at the outlet of the guard bed, and the catalyst in the alkylation reactor remained stable during this period. The propylene conversion remained above 99.99percent. This example demonstrated the effectiveness of a guard bed prepared and operated in accordance with this invention in removing NMP from the benzene feed thereby preventing catalyst deactivation. At 5,652 on-stream hours, the molecular sieve 13X guard bed was by-passed and the NMP-containing benzene feed was fed to the reactor without pretreatment in accordance with this invention. Changes were soon apparent in the reactor temperature profile suggesting catalyst poisoning was occurring. Later, the NMP-containing benzene feed was replaced with a pure benzene feed. At 5,676 hours on-stream, the propylene conversion was found to have dropped to below 99.98percent, thereby suggesting damage to or deterioration of the catalyst bed resulting from catalyst poisoning by the NMP. With MCM-22 type catalyst, T= 128 °C , Conversion of starting material Patent; WASHINGTON GROUP INTERNATIONAL, INC.; WO2003/74452; (2003); (A1) English View in Reaxys 8 :EXAMPLE 8; A batch of MCM-22 type catalyst was loaded into a pilot plant alkylation reactor and tested for cumene synthesis. Between the catalyst on-stream hours of 5,603 and 5, 630, the benzene charge was about 65 grams per hour, and the propylene charge was about 29 grams per hour. The reactor temperature was 128°C, and the propylene conversion was stable at greater than 99.99percent. At 5,631 on-stream hours, the pure benzene feed was replaced with a prepared benzene feed spiked with 50 ppm NMP. At the same time, a guard bed in accordance with the present invention containing 22.5 grams of molecular sieve 13X was placed into service upstream of the pilot plant alkylation reactor to pretreat the benzene feed for removal of the NMP. The guard bed was maintained at an ambient temperature of about 25°C. No NMP was detected in the benzene feed at the outlet of the guard bed, and the catalyst in the alkylation reactor remained stable during this period. The propylene conversion remained above 99.99percent. This example demonstrated the effectiveness of a guard bed prepared and operated in accordance with this invention in removing NMP from the benzene feed thereby preventing catalyst deactivation. At 5,652 on-stream hours, the molecular sieve 13X guard bed was by-passed and the NMP-containing benzene feed was fed to the reactor without pretreatment in accordance with this invention. Changes were soon apparent in the reactor temperature profile suggesting catalyst poisoning was occurring. Later, the NMP-containing benzene feed was replaced with a pure benzene feed. At 5,676 hours on-stream, the propylene conversion was found to have dropped to below 99.98percent, thereby suggesting damage to or deterioration of the catalyst bed resulting from catalyst poisoning by the NMP. With N-Methyl-2-pyrrolidone, MCM-22 type catalyst, T= 128 °C , Conversion of starting material Patent; WASHINGTON GROUP INTERNATIONAL, INC.; WO2003/74452; (2003); (A1) English View in Reaxys 5 :Example nr. 5; 0.4 g of beta zeolite prepared according to what is described in example l, previously dried to 120°C for 16 hours, are charged into an electrically heated autoclave with an internal volume equal to 0.5 litres, equipped with a mechanical stirrer and with all the necessary devices forthe feeding of the benzene and propylene reagents.The autoclave is closed, put under vacuum by suction with a pump connected externally, and 352 g of benzene are .bul. then charged by suction. The autoclave is pressurized with nitrogen until a pressure of about 6 bar is reached and the heating is initiated to the programmed temperature of 150°C. When the temperature inside the autoclave has stably reached the pre-selected value, 26 g of propylene are rap-idly fed, by means of a pressure tank, and the mixture i s left to react for a time of exactly l hour, calculated starting from the end of the propylene feed-

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ing.At the end of the reaction, the product is discharged and analyzed by gas chromatography. The following products are present in the mixture at the end of the reaction: benzene, cumene, C6 and C9 ol'igomers of propylene, diisopropyl benzenes, other diisopropyl benzene isomers (C6-phenyl = aromatic products generally indicated with the formula Ci2Hi8) / triisqpropyl benzenes, other triisopropyl benzene isomers (Cg-phenyl = aromatic products generally indicated with the formula CiSH24) , polyalkylated products with a mo-lecular weight higher than triisopropyl benzene (heavy polyalkylated products).The propylene conversion proves to be higher than97.0percent, the selectivity to mono-alkylated product (cumene)with respect to the converted propylene is equal to 91.3percentand the selectivity to (cumene + diisopropyl benzenes + triisopropyl benzenes) with respect to the converted pro-pylene is equal to 97.5percent.The weight ratio, called R, between the sum of (diisopropyl benzenes + triisopropyl benzenes + C6-phenyl + Cg-phenyl + heavy polyalkylated products) and the sum of (cumene + diisopropyl benzenes + triisopropyl benzenes + G6-phenyl + C9-phenyl + heavy polyalkylated products) proves to be equal to 0.052.This ratio R is a measurement of the total quantity ofthe polyalkylated by-products alone with respect to the to- tal products and alkylated by-products formed during thereaction.

With beta zeolite prepared from tetraethyl ammonium hydroxide, sodium aluminate, aluminum isopropylate and Ludox HS40, Time= 1h, T= 150 °C , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; ENITECNOLOGIE S.P.A.; WO2006/2805; (2006); (A1) English View in Reaxys 9; 11 :Example nr 9 (comparative); The beta zeolite of example 2 in ammo-nium/alkylammonium form is used for the preparation of a catalyst in pellet form adopting the procedure described in example 4 of EP 847,802. Alumina in the form of p-bohemite, is used. The catalyst thus formed is calcined for 5 hours at 550°C. The percentage of zeolite in the end-catalyst is equal to 55percent by weight, and the catalyst has the following porosi'ty characteristics:EPV (extra-zeolite porous volume) equal to 0.82 cc/g, frac-tion of pores having a radius > 100 Ae equal to 52percent.The catalyst thus obtained, called catalyst B, is not representative of the present invention.Catalyst B is used for carrying out a continuous cata-lytic test for the alkylation of benzene with propylene us-ing an experimental apparatus such aes that described in example 8 and with the same activation and operational procedure of the catalytic test itself.Samplings are taken of the reaction effluent after 47, 124, 165, 190 and 286 hours of reaction carried out in continuous under the same reaction conditions, which are sub-sequently subjected to gas-Chromatographie analysis.On the basis of the analysis effected on each sampleof reaction effluent, the propylene conversion proved to be always higher than 99.0percent. The following average perform-ances of catalyst B were also obtained:.bul. selectivity to cumene with respect to the converted pro- pylene equal to 87.5percent'with a Standard deviation equal to0.4percent;.bul. selectivity to (curaene + diisopropyl benzenes + triiso-propyl benzenes) with respect to the converted propyleneequal to 99.7percent with a Standard deviation equal to 0.03percent;.bul. concentration of n-propyl benzene with respect to the cu-mene equal t o 253 ppm with a Standard deviation equal t o8 ppm.bul. concentration of C6- to C9- oligomers of propylene withrespect to the curaene equal to 264 ppm.Also in this case, during the test, the position cor-responding to the maximum temperature was registered by means of the thermocouple sliding along the greater axis of the reactor, for measuring the advancing rate of the so-called hot point, which represents a direct measurement of the deactivation rate of the catalyst. By extrapolation of the measurement up to the end point of the catalytic bed, it was possible to estimate a cumene production referring to the total quantity of catalyst charged equal to 2,150 kg cumene/kg of catalyst B.Catalyst E, which is non-representative of the presentinvention, has a selectivity to cumene with respect to t he converted propylene, i.e, selectivity to mono-alkylated product, which is much lower than that obtained with cata-lyst A in accordance with the present invention, This is even tnore evident from the result relating to the selectivity to (cumene + diisopropyl benzene + triisopropyl ben-zenes) with respect to the converted propylene for catalyst B which, on the other hand, is substantially analogous to that already obtained for catalyst A. In other words, when using catalyst A according to the present invention, a dis-tribution of mono- and di-alkylated products is obtained which is more directed towards the mono-alkylated product than what is obtained with catalyst B, which is non-representative of the present invention, with the same selectivity towards the overall formation of mono- and di-alkylated products.Furthermore, catalyst B, most probably aes a result of the greater formation of CeC9 oligomeric products of propylene with respect to catalyst A, is characterized by a greater deactivation rate than that registered for catalyst A.; Example nr 11 (comparative)The same catalyst B already used in example 9 is subjected to a catalytic test under the same conditions de-scribed in example 10, with a reaction temperature which is set at 140°C.Samplings of the reaction effluent are taken after 28, 94, 100, 118 and 122 ,hours of reaction carried out in con-tinuous under the same reaction conditions, which are sub-sequently subjected to gas-Chromatographie analysis.On the basis of the gas-Chromatographie analysis, thepropylene conversion proved to be always higher than 99.0percent, The following average performances of catalyst B were also obtained:.bul. selectivity to cumene with respect to the converted pro- pylene equal to 87.,3percent with a Standard deviation equal to0,4percent;.bul. selectivity to (cumene + diisopropyl benzenes) with re- spect to the converted propylene equal to 99.2percent with aStandard deviation equal to 0.2percent;.bul. concentration of n-propyl benzene with respect to the cu- mene equal to 188 ppm with a Standard deviation equal to2 ppm.bul. concentration of C6- to Cg- oligomers of propylene withres-

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pect to the cumene equal to 443 ppm..Also in this case, during the test, the position cor-risponding to the maximum temperature was registered by means of the termocouple sliding along the greater axis the reactor, for measuring the advancing rate of the so-called hot point, which represents a direct measurement of the de-activation rate of the catalyst. By extrapolation of the measurement up to the end point of the catalytic bed, i t was possible to estimate a cumene production referring to the total quantity of catalyst charged equal to 1,020 kg cumene/kg of catalyst B.It is evident that also using catalyst B at a tempera-ture of 140°C, there is an effective reduction in the for-mation of npropyl benzene with respect to what is obtained with the same catalyst B when carrying out the reaction at a temperature of 150°C. This reduction, however, is associ-ated with a considerable increase in the formation of oli-gomers of propylene and a consequent significant reduction in the duration of the catalyst, which is much more dis-tinct than that obtained with catalyst A at the same temperature .Catalyst A, representative of the present invention, therefore allows the reaction to be carried out at more fa-vourable temperatures to obtain a reduction in the formation of npropyl benzene impurities which cannot be obtained, on the contrary, with catalyst B, non-representative of the present invention.

With beta zeolite prepared from tetraethyl ammonium hydroxide, sodium aluminate and Ludox HS40 (calcined for 5h at 550C), Time= 122 - 286h, T= 140 - 150 °C , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; ENITECNOLOGIE S.P.A.; WO2006/2805; (2006); (A1) English View in Reaxys 6 :Exatnple nr 6 (comparative); The catalytic test described in example 5 is repeated using the beta zeolite prepared according to example 2.On the basis of the gas-Chromatographie analysis of the reaction product-, a propylene conversion is calculated which is higher -than 97.0percent, together with a selectivity to mono-alkylated product (cumene) with respect to the converted propylene, equal to 90.9percent and a selectivity to (cumene + diisopropyl benzenes + triisopropyl benzenes) with respect to the converted propylene equal to 96.6percent. The ratio R, defined aes in example l, proves to be equal to 0.061.It is evident that by using the non-representative catalyst of the praesent invention, a higher fraction of polyalkylated by-products is obtained with respect to that obtained, on the contrary, using a catalyst according to the present invention.

With beta zeolite prepared from tetraethyl ammonium hydroxide, sodium aluminate and Ludox HS40 at 170C for 168h, Time= 1h, T= 150 °C , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; ENITECNOLOGIE S.P.A.; WO2006/2805; (2006); (A1) English View in Reaxys 7 :Example nr 7 (comparative); The catalytic test described in example 5 is repeated using the beta zeolite prepared according to what is described in example 3 .On the basis of the gas-Chromatographie analysis of the reaction product, a propylene conversion is calculated which is higher than 98.1percent, together with a selectivity to mono-alkylated product (cumene) with respect 'to the con-verted propylene, equal to 89.8percent and a selectivity to (cumene + diisopropyl benzenes + triisopropyl benzenes) with 'respect to the converted propylene equal to 95.0percent. The ratio R, defined aes in example l, proves to be equal to 0.064.It is evident that by using the non-representative catalyst of the present invention, a higher fraction of polyalkylated by-products is obtained with respect to that obtained, on the contrary, using a catalyst according to the present invention.

With beta zeolite prepared from tetraethyl ammonium hydroxide, sodium aluminate and Ludox HS40 at 170C for 24h, Time= 1h, T= 150 °C , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; ENITECNOLOGIE S.P.A.; WO2006/2805; (2006); (A1) English View in Reaxys 8; 10 :Example nr 8; The beta zeolite of example l in ammo-nium/alkylammonium form, i.e. in the form which has not un-dergone the final calcination step, is used for the prepa-ration of a catalyst in pellet form adopting the procedure described in example 4 of EP 847,802. Alumina in the form of p-bohemite, is used aes binder, The catalyst thus formed is calcined for 5 hours at 550°C. The percentage of zeolite in the end-catalyst is equal to 55percent by weight, and the catalyst has the following porosity characteristics: EPV (extra-zeolite porous volume) equal to 0.85 cc/g, frac>-tion of pores having a radius > 100 Ae equal to 51percent.The catalyst thus obtained, caelled catalyst A, is used for carrying out a continuous catalytic test for the alky-latlon of benzene with propylene using an experimental ap-paratus such aes that described below.The experimental apparatus consists of reagent tanks, independent feeding pumps, a static mixer of the reagents before being fed into the reaction, a steel reactor situ-ated inside an electric heating oven equipped with tempera-ture regulation inside the reactor, a regulation System of the pressure inside the reactor by means of a pneumatic valve, a cooler of the reaction effluent and a collection System of the liquid and gaseous products.The reactor, situated inside the heating oven, consists of a cylindrical steel tube, with a mechanical seal-ing System and an internal diameter equal to about 2 cm.A thermometric sheath having a diameter

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equal to l mm and containing a thermocouple which is free to slide along t he greater axis of t he reactor, is situated inside and along the greater axis of the reactor. Catalyst A, previ-ously ground and sieved in order to obtain a particle size ranging from l to 1.25 mm, is charged into the reactor, in a quantity equal to 5 g, for a total height of the catalytic bed equal to 6 cm.A quantity of inert quartz material is charged above and below the catalytic bed for a height equal to 3 cm above and 3 cm below the catalytic bed.. The electric heating of the reactor is activated, to-gether with a nitrogen flow in order to dry the catalyst, up to the temperature of 150°C programmed inside the reactor. Once the selected temperature has been reached, the nitrogen flow is maintained for 16 hours, after which it is interrupted and benzene is fed first for two hours followed by propylene so aes to obtain an overall WHSV equal to 20 hours"1 and a [benzene] / [propylene] molar ratio in the .bul.feeding equal to 7. The pressure at which the reaction is carried out is equal to 38 bar.Samplings are taken of the reaction effluent after 21, 93, 118, 260 and 284 hours of reaction carried out in con-tinuous under the same reaction conditions, which are sub-sequently subjected to gas-Chromatographie analysis.On the basis of the analysis effected on each sample of reaction effluent, the propylene conversion proved to be always higher than 99.0percent, The following average perform-ances of catalyst A were also obtained:.bul. selectivity to cumene with respect to the converted pro- pylene equal to 90.2percent with a Standard deviation equal to0.4percent;.bul. selectivity to (cumene + diisopropyl benzenes + triiso-propyl benzenes) with respect to the converted propyleneequal to 99.7percent with a Standard deviation equal to 0.06percent;.bul. . concentration of n-propyl benzene with respect to the cu-mene equal to 238 ppm with a Standard deviation equal to14 ppm.bul. concentration of C6- to C9- oligomers of propylene withrespect to the cumene equal to 204 ppm.During the test, the position corrisponding to the maximum temperature, determined by the exothermy of the reaction, was registered by means of the thermocouple sliding along the greater axis of the reactor. In this way, it is possible to measure the advancing rate of the so-called hot point which represents a direct measurement of the deacti-vation rate of the catalyst. By extrapolation of the measurement up to the end point of the catalytic bed, it was possible to estimate a cumene production upon reaching said end point of the catalytic bed, referring to the totalquantity of catalyst charged equal to 2,800 kg cumene/kg ofcatalyst A.; Example nr 10The same catalyst A already used in example 8 is sub-jected "to a catalytic test under the same conditions de-scribed in example 8 except for the temperature of the re-actor which is set at 140°C.Samplings of the reaction effluent are taken after 46, 119, 137, 142 and 160 hours of reaction carried out in con-tinuous under the same reaction conditions, which are sub-seguently subjected to gas-chromatographic analysis,On the basis of the gas-Chromatographie analysis, the propylene conversion proved to be always higher than 99.0percent. The following average performances of catalyst A were also obtained:.bul. selectivity to cumene with respect to the converted pro- pylene equal to 89.9percent with a Standard deviation equal to0.8percent;.bul. selectivity to (cumene + diisopropyl benzenes) with re- spect to the converted propylene equal to 99.5percent with aStandard deviation equal to 0.08percent;.bul. concentration of n-propyl benzene with respect to the cu- mene equal to 187 ppm with a Standard deviation equal to7 ppm.bul. concentration of C6- to C9- oligomers of propylene withrespect t o the cumene equal t o 279 ppm.Also in this case, during the test, the position cor-risponding to the maximurn temperature was registered by means of the thermocouple sliding along the greater axis of the reactor, for measuring the advancing rate of the so-called hot point, which represents a direct measurement ofthe deactivation rate of the catalyst. By extrapolation ofthe measurement up to the end point of the catalytic bed,it was possible to estimate a cumene production referringto the total quantity of catalyst charged equal to 1,730 kgcumene/kg of catalyst A,The formation of n-propyl benzene and propylene- oli-goraers impurities therefore follows the expected trend :the former decreases with a decrease in. the temperature,whereas the latter increases with a decrease in the tem- perature with respect to what was- already obtained withcatalyst , wherein the reaction is carried out at a highertemperature aes in the previous example 8.Lower reaction temperatures can consequently be &vse-lected

for the production of cumene having a particular andhigh degree

of purity.

With beta zeolite prepared from tetraethyl ammonium hydroxide, sodium aluminate, aluminum isopropylate and Ludox HS40 (calcined for 5h at 550C), Time= 160 - 284h, T= 140 - 150 °C , p= 28502.9Torr , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; ENITECNOLOGIE S.P.A.; WO2006/2805; (2006); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods

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known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 65 percentw MCM-22, 35 percentw alumina, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The cata-

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lyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 65 percentw MCM-22, 35 percentw alumina, 448 wppm H2O, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) fol-

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lowed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 65 percentw MCM-22, 35 percentw alumina, 922 wppm H2O, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted

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with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 80 percentw MCM-49, 20 percentw alumina, 474 wppm H2O, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor

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was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 80 percentw MCM-49, 20 percentw alumina, 885 wppm H2O, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply

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to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 80 percentw MCM-49, 20 percentw alumina, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst

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(65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 80 percentw zeolite β (Si:Al = 24), 20 percentw alumina, 872 wppm H2O, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys Feed Pretreatment; Benzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using. Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using. Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.; Catalyst Preparation and Loading; MCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference. Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Two grams of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of one gram of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours. Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying. A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively. The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kpa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kpa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene. Water was added to the reaction mixture by either of two methods. First, the water was added to the pretreated benzene supply to obtain the desired water level in the reaction mixture. Second, the pre-dried catalyst was humidified until the proper amount of water adsorbed corresponding to the desired amount of water in the reaction mixture was obtained.

The amount of water in the reaction product at end of test was measured by Karl Fischer Titrator (Mettler Toledo, Inc., Columbus, Ohio, USA) which is typically accurate to within 50 wppm.; EXAMPLES; One gram MCM-22 catalyst (65 wt. percent MCM-22 and 35 wt. percent alumina), one gram MCM-49 catalyst (80 wt. percent MCM-22 and 20 wt. percent alumina), and one gram zeolite beta catalyst (80 wt. percent Beta, Si/Al2 of 24, and 20 wt. percent alumina) were tested under the conditions and method described above. The activity of the zeolite beta catalyst increased

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by 88percent at 0 wppm H2O as comparing to the activity of the zeolite beta catalyst at same conditions except at a water content of 872 wppm. The activity of the zeolite MCM-22 catalyst increased by 544percent at 0 wppm H2O and 22percent at 448 wppm H2O as comparing to the activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The activity of the zeolite MCM-49 catalyst increased by 497percent at 0 wppm H2O and 39percent at 474 wppm H2O as compared to the activity of the zeolite MCM-49 catalyst at same conditions except water content of 885 wppm. The selectivity of the zeolite beta catalyst increased from 4.76 at 0 wppm H2O to 14.49 at 872 wppm H2O as compared to the selectivity of the zeolite beta catalyst at the same conditions except at a water content of 0 wppm. The selectivity of the zeolite MCM-22 catalyst increased by 44percent at 922 wppm H2O and 41percent at 211 wppm H2O as compared to the selectivity of the zeolite MCM-22 catalyst at same conditions except water content of 0 wppm. The selectivity of the zeolite MCM-49 catalyst increased by 78percent at 885 wppm H2O and 36percent at 474 wppm H2O as compared to the selectivity of the zeolite MCM-49 catalyst at same conditions except at a water content of 0 wppm.

With 80 percentw zeolite β (Si:Al = 24), 20 percentw alumina, Time= 0.5 - 4h, T= 130 °C , p= 16276.6Torr , Liquid phase, Product distribution / selectivity Patent; Clark, Michael C.; US2007/179329; (2007); (A1) English View in Reaxys 7 :Evaluation in Cumene Unit of Samples of Catalysts A, B, C and DEvaluation was carried out in a 300 ml autoclave reactor. 0.25 g of catalyst was transferred into the catalyst basket, and 6 gram of quartz chip was layer below and above the catalyst bed inside the basket. The catalyst and the basket were then dried in an oven at 260° C. (500° F.) for about 16 hours. This catalyst basket was then transferred into a 300 ml autoclave quickly with minimum exposure to ambient atmosphere. The catalyst was subsequently purged with dry nitrogen for 2 hours at 181° C. (358° F.) inside the reactor to remove air and moisture from the reactor. 156 g of benzene was transferred to the reactor under nitrogen and equilibrated with the catalyst for 1 hour at 130° C. (266° F.). 28 g of propylene was transferred into the reactor under 2.07 MPag (300 psig) of nitrogen pressure.The reaction started as soon as propylene was added and a constant pressure of 2.07 MPag (300 psig) nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene, diisopropylbenzene (DIPB), and triisopropylbenzene, using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter which is based on the propylene and benzene conversion. For a discussion of the determination of the kinetic rate parameter, reference is directed to "Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions" by L K Doraiswamy and M M Sharma, John Wiley Sons, New York (1994) and to "Chemical Reaction Engineering" by O Levenspiel, Wiley Eastern Limited, New Delhi (1972). Cumene selectivity was calculated from the weight ratio of DIPB/cumene which was expressed as percentage.The results of the evaluation of the catalysts of the invention A and D were compared with two different formulations of MCM-22 catalysts B, C as set out in the below table. The activity of the catalyst was normalized on the activity of Catalyst B. TABLE 1 Normalized Normalized Selectivity percent DIPB/ Catalyst Description Activity percent percent DIPB/IPB* IPB** A Example 1, in166 20.3 120 situ MCM-22 extrudate, 0.16 cm cylinder B Conventional 100 16.9 100 MCM-22 bound with alumina in 0.16 cm cylinder extrudate C Conventional 171 20.8 123 MCM-22 bound with alumina in 0.127 cm quadrulobe extrudate C (repeated run) 180 19.1 113 D Example 3, in- 274 21.1 125 situ Beta/MCM- 22 extrudate, 0.127 cm quadrulobe extrudate DIPB = diisopropylbenzene IPB = isopropylbenzene *Normalized to 1 gram cat load **Normalized to Catalyst B performanceIt is known that for propylene alkylation of benzene, the reaction is diffusion limited, and extrudate with a high surface to volume ratio should normally have a higher activity. From the results, catalyst A, despite having a lower surface to volume ratio in comparison to catalyst C, has similar activity and selectivity (percent DIPB/IPB). Also, in comparison to the conventionally produced MCM-22 catalyst B of the same extruded shape, catalyst A has much higher activity, and slightly higher percent DIPB/IPB. The catalyst comprising a molecular sieve as produced by the method of the present invention shows dramatically higher activity than an alumina bound conventionally produced MCM-22 extrudate.

With catalyst A (MCM-22) extrudate in cylinder, Time= 4h, p= 15526.6Torr , Product distribution / selectivity Patent; Lai, Wenyih Frank; Kay, Robert Ellis; Elia, Christine N.; Lo, Frederick Y.; Marler, David O.; US2007/191659; (2007); (A1) English View in Reaxys 7 :Evaluation in Cumene Unit of Samples of Catalysts A, B, C and DEvaluation was carried out in a 300 ml autoclave reactor. 0.25 g of catalyst was transferred into the catalyst basket, and 6 gram of quartz chip was layer below and above the catalyst bed inside the basket. The catalyst and the basket were then dried in an oven at 260° C. (500° F.) for about 16 hours. This catalyst basket was then transferred into a 300 ml autoclave quickly with minimum exposure to ambient atmosphere. The catalyst was subsequently purged with dry nitrogen for 2 hours at 181° C. (358° F.) in-

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side the reactor to remove air and moisture from the reactor. 156 g of benzene was transferred to the reactor under nitrogen and equilibrated with the catalyst for 1 hour at 130° C. (266° F.). 28 g of propylene was transferred into the reactor under 2.07 MPag (300 psig) of nitrogen pressure.The reaction started as soon as propylene was added and a constant pressure of 2.07 MPag (300 psig) nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene, diisopropylbenzene (DIPB), and triisopropylbenzene, using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter which is based on the propylene and benzene conversion. For a discussion of the determination of the kinetic rate parameter, reference is directed to "Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions" by L K Doraiswamy and M M Sharma, John Wiley Sons, New York (1994) and to "Chemical Reaction Engineering" by O Levenspiel, Wiley Eastern Limited, New Delhi (1972). Cumene selectivity was calculated from the weight ratio of DIPB/cumene which was expressed as percentage.The results of the evaluation of the catalysts of the invention A and D were compared with two different formulations of MCM-22 catalysts B, C as set out in the below table. The activity of the catalyst was normalized on the activity of Catalyst B. TABLE 1 Normalized Normalized Selectivity percent DIPB/ Catalyst Description Activity percent percent DIPB/IPB* IPB** A Example 1, in166 20.3 120 situ MCM-22 extrudate, 0.16 cm cylinder B Conventional 100 16.9 100 MCM-22 bound with alumina in 0.16 cm cylinder extrudate C Conventional 171 20.8 123 MCM-22 bound with alumina in 0.127 cm quadrulobe extrudate C (repeated run) 180 19.1 113 D Example 3, in- 274 21.1 125 situ Beta/MCM- 22 extrudate, 0.127 cm quadrulobe extrudate DIPB = diisopropylbenzene IPB = isopropylbenzene *Normalized to 1 gram cat load **Normalized to Catalyst B performanceIt is known that for propylene alkylation of benzene, the reaction is diffusion limited, and extrudate with a high surface to volume ratio should normally have a higher activity. From the results, catalyst A, despite having a lower surface to volume ratio in comparison to catalyst C, has similar activity and selectivity (percent DIPB/IPB). Also, in comparison to the conventionally produced MCM-22 catalyst B of the same extruded shape, catalyst A has much higher activity, and slightly higher percent DIPB/IPB. The catalyst comprising a molecular sieve as produced by the method of the present invention shows dramatically higher activity than an alumina bound conventionally produced MCM-22 extrudate.

With catalyst B (MCM-22 bound with alumina extrudate in cylinder), Time= 4h, p= 15526.6Torr , Product distribution / selectivity Patent; Lai, Wenyih Frank; Kay, Robert Ellis; Elia, Christine N.; Lo, Frederick Y.; Marler, David O.; US2007/191659; (2007); (A1) English View in Reaxys 7 :Evaluation in Cumene Unit of Samples of Catalysts A, B, C and DEvaluation was carried out in a 300 ml autoclave reactor. 0.25 g of catalyst was transferred into the catalyst basket, and 6 gram of quartz chip was layer below and above the catalyst bed inside the basket. The catalyst and the basket were then dried in an oven at 260° C. (500° F.) for about 16 hours. This catalyst basket was then transferred into a 300 ml autoclave quickly with minimum exposure to ambient atmosphere. The catalyst was subsequently purged with dry nitrogen for 2 hours at 181° C. (358° F.) inside the reactor to remove air and moisture from the reactor. 156 g of benzene was transferred to the reactor under nitrogen and equilibrated with the catalyst for 1 hour at 130° C. (266° F.). 28 g of propylene was transferred into the reactor under 2.07 MPag (300 psig) of nitrogen pressure.The reaction started as soon as propylene was added and a constant pressure of 2.07 MPag (300 psig) nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene, diisopropylbenzene (DIPB), and triisopropylbenzene, using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter which is based on the propylene and benzene conversion. For a discussion of the determination of the kinetic rate parameter, reference is directed to "Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions" by L K Doraiswamy and M M Sharma, John Wiley Sons, New York (1994) and to "Chemical Reaction Engineering" by O Levenspiel, Wiley Eastern Limited, New Delhi (1972). Cumene selectivity was calculated from the weight ratio of DIPB/cumene which was expressed as percentage.The results of the evaluation of the catalysts of the invention A and D were compared with two different formulations of MCM-22 catalysts B, C as set out in the below table. The activity of the catalyst was normalized on the activity of Catalyst B. TABLE 1 Normalized Normalized Selectivity percent DIPB/ Catalyst Description Activity percent percent DIPB/IPB* IPB** A Example 1, in166 20.3 120 situ MCM-22 extrudate, 0.16 cm cylinder B Conventional 100 16.9 100 MCM-22 bound with alumina in 0.16 cm cylinder extrudate C Conventional 171 20.8 123 MCM-22 bound with alumina in 0.127 cm quadrulobe extrudate C (repeated run) 180 19.1 113 D Example 3, in- 274 21.1 125 situ Beta/MCM- 22 extrudate, 0.127 cm quadrulobe extrudate DIPB = diisopropylbenzene IPB = isopropylbenzene *Normalized to 1 gram cat load **Normalized to Catalyst B performanceIt is known that for propylene alkylation of benzene, the reaction is diffusion limited, and extrudate with a high surface to volume ratio should normally have a higher activity. From the results, catalyst A, despite having a lower surface to volume ratio in comparison to catalyst C, has similar activity and selectivity (percent DIPB/IPB). Also, in comparison to the conventionally produced MCM-22 catalyst B of the same extruded shape, cat-

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alyst A has much higher activity, and slightly higher percent DIPB/IPB. The catalyst comprising a molecular sieve as produced by the method of the present invention shows dramatically higher activity than an alumina bound conventionally produced MCM-22 extrudate.

With catalyst C (Beta/MCM-22 quadrulobe extrudate), Time= 4h, p= 15526.6Torr , Product distribution / selectivity Patent; Lai, Wenyih Frank; Kay, Robert Ellis; Elia, Christine N.; Lo, Frederick Y.; Marler, David O.; US2007/191659; (2007); (A1) English View in Reaxys 7 :Evaluation in Cumene Unit of Samples of Catalysts A, B, C and DEvaluation was carried out in a 300 ml autoclave reactor. 0.25 g of catalyst was transferred into the catalyst basket, and 6 gram of quartz chip was layer below and above the catalyst bed inside the basket. The catalyst and the basket were then dried in an oven at 260° C. (500° F.) for about 16 hours. This catalyst basket was then transferred into a 300 ml autoclave quickly with minimum exposure to ambient atmosphere. The catalyst was subsequently purged with dry nitrogen for 2 hours at 181° C. (358° F.) inside the reactor to remove air and moisture from the reactor. 156 g of benzene was transferred to the reactor under nitrogen and equilibrated with the catalyst for 1 hour at 130° C. (266° F.). 28 g of propylene was transferred into the reactor under 2.07 MPag (300 psig) of nitrogen pressure.The reaction started as soon as propylene was added and a constant pressure of 2.07 MPag (300 psig) nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene, diisopropylbenzene (DIPB), and triisopropylbenzene, using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter which is based on the propylene and benzene conversion. For a discussion of the determination of the kinetic rate parameter, reference is directed to "Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions" by L K Doraiswamy and M M Sharma, John Wiley Sons, New York (1994) and to "Chemical Reaction Engineering" by O Levenspiel, Wiley Eastern Limited, New Delhi (1972). Cumene selectivity was calculated from the weight ratio of DIPB/cumene which was expressed as percentage.The results of the evaluation of the catalysts of the invention A and D were compared with two different formulations of MCM-22 catalysts B, C as set out in the below table. The activity of the catalyst was normalized on the activity of Catalyst B. TABLE 1 Normalized Normalized Selectivity percent DIPB/ Catalyst Description Activity percent percent DIPB/IPB* IPB** A Example 1, in166 20.3 120 situ MCM-22 extrudate, 0.16 cm cylinder B Conventional 100 16.9 100 MCM-22 bound with alumina in 0.16 cm cylinder extrudate C Conventional 171 20.8 123 MCM-22 bound with alumina in 0.127 cm quadrulobe extrudate C (repeated run) 180 19.1 113 D Example 3, in- 274 21.1 125 situ Beta/MCM- 22 extrudate, 0.127 cm quadrulobe extrudate DIPB = diisopropylbenzene IPB = isopropylbenzene *Normalized to 1 gram cat load **Normalized to Catalyst B performanceIt is known that for propylene alkylation of benzene, the reaction is diffusion limited, and extrudate with a high surface to volume ratio should normally have a higher activity. From the results, catalyst A, despite having a lower surface to volume ratio in comparison to catalyst C, has similar activity and selectivity (percent DIPB/IPB). Also, in comparison to the conventionally produced MCM-22 catalyst B of the same extruded shape, catalyst A has much higher activity, and slightly higher percent DIPB/IPB. The catalyst comprising a molecular sieve as produced by the method of the present invention shows dramatically higher activity than an alumina bound conventionally produced MCM-22 extrudate.

With catalyst C (MCM-22 bound with alumina in quadrulobe extrudate), Time= 4h, p= 15526.6Torr , Product distribution / selectivity Patent; Lai, Wenyih Frank; Kay, Robert Ellis; Elia, Christine N.; Lo, Frederick Y.; Marler, David O.; US2007/191659; (2007); (A1) English View in Reaxys 1 :Catalyst Activity and Selectivity; The activity and selectivity of a catalyst were measured based on benzene alkylation with propylene. Catalyst activity was calculated using the second order rate constant for the formation of cumene under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference.

Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene.Jet milling was performed on a Micron Master Jet Mill (Jet Pulverizer, in Moorestown, N.J., USA).The N2 pore size distribution was

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obtained on a Tristar 3000 Gas Adsorption Analyzer unit (Micromeritics.(R)., Norcross, Ga., USA) from the desorption leg of the N2 isotherm. The pore volumes for pore sizes in the 2-8 nm range were summed up to obtain cumulative pore volume.; EXAMPLE 1; MCM-49 was extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal and Versal-300 alumina (weight ratio 80:20) extruded with 0.05 wt percent PVA (based on the combined weight of MCM-49 crystal, Versal-300 alumina, and PVA) to 0.127 cm ( 1/20) extrudate.

This extrudate was then pre-calcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. The catalyst from Example 1 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With extrudate of MCM-49 and Versal-300 alumina, calcined, ammonium exchanged, Time= 0.5 - 4h, T= 130 °C , Product distribution / selectivity Patent; Kalyanoraman, Mohan; Elia, Christine N.; Lacy, Darryl D.; Beeckman, Jean W.; Clark, Michael C.; US2008/154080; (2008); (A1) English View in Reaxys 2 :Catalyst Activity and Selectivity; The activity and selectivity of a catalyst were measured based on benzene alkylation with propylene. Catalyst activity was calculated using the second order rate constant for the formation of cumene under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference.

Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene.Jet milling was performed on a Micron Master Jet Mill (Jet Pulverizer, in Moorestown, N.J., USA).The N2 pore size distribution was obtained on a Tristar 3000 Gas Adsorption Analyzer unit (Micromeritics.(R)., Norcross, Ga., USA) from the desorption leg of the N2 isotherm. The pore volumes for pore sizes in the 2-8 nm range were summed up to obtain cumulative pore volume.; EXAMPLE 2; MCM-49 was extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal and Condea alumina (weight ratio 80:20) extruded with 0.05 wt percent PVA (based on the combined weight of MCM-49 crystal, Versal-300 alumina, and PVA) to 0.127 cm ( 1/20) extrudate. This extrudate was then pre-calcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. The catalyst from Example 2 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With extrudate of MCM-49 and Condea alumina, calcined, ammonium exchanged, Time= 0.5 - 4h, T= 130 °C , Product distribution / selectivity Patent; Kalyanoraman, Mohan; Elia, Christine N.; Lacy, Darryl D.; Beeckman, Jean W.; Clark, Michael C.; US2008/154080; (2008); (A1) English View in Reaxys 4 :Catalyst Activity and Selectivity; The activity and selectivity of a catalyst were measured based on benzene alkylation with propylene. Catalyst activity was calculated using the second order rate constant for the formation of cumene under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference.

Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene.Jet milling was performed on a Micron Master Jet Mill (Jet Pulverizer, in Moorestown, N.J., USA).The N2 pore size distribution was obtained on a Tristar 3000 Gas Adsorption Analyzer unit (Micromeritics.(R)., Norcross, Ga., USA) from the desorption leg of the N2 isotherm. The pore volumes for pore sizes in the 2-8 nm range were summed up to obtain cumula-

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tive pore volume.; EXAMPLE 4; MCM-49 was extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal and Ultrasil silica (weight ratio 80:20) extruded with 2 wt percent PVA (based on the combined weight of MCM-49 crystal, silica, and PVA) to 0.127 cm ( 1/20) extrudate. This extrudate was then precalcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. The catalyst from Example 4 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With extrudate of MCM-49 and Ultrasil silica, calcined, ammonium exchanged, Time= 0.5 - 4h, T= 130 °C , Product distribution / selectivity Patent; Kalyanoraman, Mohan; Elia, Christine N.; Lacy, Darryl D.; Beeckman, Jean W.; Clark, Michael C.; US2008/154080; (2008); (A1) English View in Reaxys 3 :Catalyst Activity and Selectivity; The activity and selectivity of a catalyst were measured based on benzene alkylation with propylene. Catalyst activity was calculated using the second order rate constant for the formation of cumene under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference.

Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene.Jet milling was performed on a Micron Master Jet Mill (Jet Pulverizer, in Moorestown, N.J., USA).The N2 pore size distribution was obtained on a Tristar 3000 Gas Adsorption Analyzer unit (Micromeritics.(R)., Norcross, Ga., USA) from the desorption leg of the N2 isotherm. The pore volumes for pore sizes in the 2-8 nm range were summed up to obtain cumulative pore volume.; EXAMPLE 3; MCM-49 was jet pulverized (also called Jet milling) to reduce the average crystal aggregate size of the MCM-49 material from about 16 micron to about than 1.2 micron at high velocity mixing and extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal and Versal-300 alumina (weight ratio 80:20) extruded with 0.05 wt percent PVA (based on the combined weight of MCM-49 crystal, Versal-300 alumina, and PVA) to 0.127 cm ( 1/20) extrudate. This extrudate was then pre-calcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. The catalyst from Example 3 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With extrudate of jet pulverized MCM-49 and Versal-300 alumina, calcined, ammonium exchanged, Time= 0.5 - 4h, T= 130 °C , Product distribution / selectivity Patent; Kalyanoraman, Mohan; Elia, Christine N.; Lacy, Darryl D.; Beeckman, Jean W.; Clark, Michael C.; US2008/154080; (2008); (A1) English View in Reaxys 2; 3 :EXAMPLE 2; The experimental procedure used in testing the catalysts prepared for Example 1 was as follows.

A volume of the catalyst to be tested was loaded into a cylindrical reactor, however for the test of the stacked loading of Catalysts A and B, the bottom 30percent of the volume was loaded with Catalyst B and the upper 70percent of the volume was loaded with Catalyst A. The reactor was equipped with a thermocouple in a thermowell located to measure temperatures at distances along the length of the fixed catalyst bed. Dry benzene was passed downflow through the reactor at 260° C. (500° F.) and at a benzene LHSV of 6.7 hr-1 for 24 hours.Subsequently, the flow of fresh benzene was adjusted and the reactor inlet temperature was lowered to a temperature about 50° C. (90° F.) below the desired distance average bed temperature (DABT) for the initial testing conditions. As used herein, DABT means the temperature calculated by plotting the catalyst bed temperature versus distance along the catalyst bed, computing the area under the curve from the inlet to the outlet of the catalyst bed, and dividing the area by the length of the catalyst bed. Fresh propylene was introduced into the reactor. Then a portion of the reactor effluent was recycled so that a combined feed of the fresh benzene, the fresh propylene, and the recycled reactor effluent flowed to the reactor. The reactor inlet temperature was adjusted to maintain the desired DABT while the reactor effluent was sampled and analyzed. Then the reactor inlet temperature and/or the amount of recycled reactor effluent was adjusted, and the reactor effluent was sampled again. This process was repeated until measurements and samples were obtained at all of the desired DABTs and effluent recycle ratios (R/FF).The temperature within the catalyst bed rose as the

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incoming feed contacted the catalyst due to the exothermic nature of the reaction. At times during a period at test conditions, temperature profiles (bed temperature versus distance through the bed) were plotted. The rate of catalyst deactivation was taken to be the rate of progression of these temperature profiles through the bed. The position of each temperature profile was defined by the end of the active zone, which was a measure of the end of the temperature rise in the temperature profile. On a temperature profile, the end of the active zone was the distance in the bed at the intersection of the linear extrapolation of the linear part of the temperature rise and a horizontal line at the maximum bed temperature. Some catalyst deactivation occurred over the duration that the performance of each catalyst was measured, and it is believed that the deactivation rates of the catalysts were not significantly affected by differences in the operating conditions among the tests of each catalyst.The DABTs were between about 130° C. (236° F.) and about 160° C. (320° F.) for the tests for Catalyst A alone, about 160° C. (320° F.) and about 175° C. (347° F.) for the tests for Catalyst B alone, and about 150° C. (302° F.) and about 175° C. (347° F.) for the tests of the stacked loading of Catalysts A and B. The propylene WHSV was about 2.03 hr-1 for the tests of Catalyst A alone, about 1.88 hr-1 for the tests of Catalyst B alone, and about 1.03 hr-1 for the tests of the stacked loading of Catalysts A and B (or alternatively 1.77 hr-1 for Catalyst A and 2.48 hr-1 for Catalyst B. The molar ratio of fresh benzene to fresh propylene for these tests was about 2. The R/FF for these tests was about 6. Because the molar ratio of aryl groups per propyl group is essentially the same in the combined reactor feed stream and the total reactor effluent stream, the molar ratio of aryl groups per ethyl group is not significantly affected by recycling any portion of the reactor effluent stream.The results of the tests are shown in Table 3. Each test included almost 600 hours of operation, and the total selectivity to cumene and DIPB and TIPB, and the deactivation rates, reported in Table 3 are determined during the final 525 hours of operation. The average deactivation rate is computed from the location of the end of the active zone after about 50 hours of operation and the location of the end of the active zone after about 575 hours of operation.; These data show the unexpected result that the stacked loading of Catalysts A and B has a selectivity to cumene+DIPB+TIPB that is higher, and an average deactivation rate that is lower, than that of either Catalyst A alone or Catalyst B alone. Without being limited to any particular theory, it is believed that the combination of Catalyst A (UZM-8) and Catalyst B (beta) provides a synergistic effect. It is believed that the UZM-8 catalyst is instrumental in providing the high selectivity and that the beta catalyst is instrumental in providing the low average deactivation rate without adversely affecting the high selectivity.; EXAMPLE 3; To demonstrate the robustness of the stacked loading of Catalysts A and B to severe and adverse conditions, the test of the stacked loading was continued at various alkylation conditions for an additional approximately 700 hours after the end of the period reported in Example 2. Aside from a relatively insignificant incremental increase in catalyst deactivation, the performances of Catalysts A and B in the stacked loading were not significantly affected by this additional operation. During the final 77 hours (Period I) of this additional operation, the operating conditions of the stacked catalyst loading were lined out at a reactor inlet temperature of 109° C. (228° F.), a propylene WHSV of about 1.03 hr-1 , a molar ratio of fresh benzene to fresh propylene of about 2, and a R/FF of about 6. The concentration of water in the combined feed (i.e., fresh benzene, fresh propylene, and reactor effluent recycle) was less than 5 wt-ppm.To simulate the effect of high water contamination of the feed, water was introduced after Period I to obtain a water concentration in the combined feed of about 150 wt-ppm for about 62 hours (Period II). While maintaining this high water concentration in the combined feed, the inlet temperature was set at 113° C. (235° F.) for about 41 hours (Period III), then at 118° C. (244° F.) for about 23 hours (Period IV), and then at 128° C. (262° F.) for about 90 hours (Period V). Following period V, the plant was shutdown without unloading the catalyst. Prior to resuming propylene introduction to the reactor, benzene having a water concentration of about 150 wt-ppm was circulated through the stacked catalyst loading at an elevated temperature (i.e., between about 100° C. (212° F.) and 128° C. (262° F.) for more than 112 hrs. The plant was restarted on a combined feed having a water concentration of less than 5 wt-ppm, a propylene WHSV of about 1.03 hr-1, a molar ratio of fresh benzene to fresh propylene of about 2, and a R/FF of about 6. The reactor inlet temperature was set at 128° C. (262° F.) for about 14 hours (Period VI), then at 118° C. (244° F.) for about 42 hours (Period VII), and then at 108° C. (226° F.) for about 45 hours (Period VIII).The performance of the stacked loading is shown in Table 4. These data indicate that unexpectedly good performance can be achieved with a stacked loading of UZM-8 and beta catalysts, despite a high water contamination that caused a large drop in propylene conversion from 97percent to 75percent between Periods I and II. By increasing the reactor inlet temperature from of 109° C. (228° F.) in Period II to 128° C. (262° F.) in Period V, propylene conversion was increased during Period V prior to the shutdown to 93percent, or nearly the level achieved during Period I, without a significant decrease in the total selectivity to cumene and DIPB and TIPB or a significant increase in the selectivity to TIPB or to the byproduct nPB. Furthermore, the data after the restart during Periods VI-VIII indicate that the contaminating effect of water can be reversed and the reactor by returning to a relatively dry feed, despite the occurrence of an intervening shutdown. The inlet temperature was lowered from 128° C. (262° F.) in Period VI to 108° C. (226° F.) in Period VIII, while maintaining 97percent olefin conversion, 99.67 to 99.72 mol-percent selectivity to cumene+DIPB+TIPB and while decreasing the nPB/ cumene ratio to 132.; While only certain embodiments have been set forth, alternatives and modifications will be apparent from the above description to those skilled in the art. These and other alternatives are considered equivalents and within the spirit and scope of this disclosure and the appended claims.

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With 70wtpercent UZM-8 zeolite and 30wtpercent alumina, 70wtpercent β-zeolite and 30wtpercent alumina, Time= 600 - 1300h, T= 260 °C , Product distribution / selectivity Patent; Schmidt, Robert J.; US2008/171900; (2008); (A1) English View in Reaxys 2 :EXAMPLE 2; The experimental procedure used in testing the catalysts prepared for Example 1 was as follows. A volume of the catalyst to be tested was loaded into a cylindrical reactor, however for the test of the stacked loading of Catalysts A and B, the bottom 30percent of the volume was loaded with Catalyst B and the upper 70percent of the volume was loaded with Catalyst A. The reactor was equipped with a thermocouple in a thermowell located to measure temperatures at distances along the length of the fixed catalyst bed. Dry benzene was passed downflow through the reactor at 260° C. (500° F.) and at a benzene LHSV of 6.7 hr-1 for 24 hours.Subsequently, the flow of fresh benzene was adjusted and the reactor inlet temperature was lowered to a temperature about 50° C. (90° F.) below the desired distance average bed temperature (DABT) for the initial testing conditions. As used herein, DABT means the temperature calculated by plotting the catalyst bed temperature versus distance along the catalyst bed, computing the area under the curve from the inlet to the outlet of the catalyst bed, and dividing the area by the length of the catalyst bed. Fresh propylene was introduced into the reactor. Then a portion of the reactor effluent was recycled so that a combined feed of the fresh benzene, the fresh propylene, and the recycled reactor effluent flowed to the reactor. The reactor inlet temperature was adjusted to maintain the desired DABT while the reactor effluent was sampled and analyzed. Then the reactor inlet temperature and/or the amount of recycled reactor effluent was adjusted, and the reactor effluent was sampled again. This process was repeated until measurements and samples were obtained at all of the desired DABTs and effluent recycle ratios (R/FF).The temperature within the catalyst bed rose as the incoming feed contacted the catalyst due to the exothermic nature of the reaction. At times during a period at test conditions, temperature profiles (bed temperature versus distance through the bed) were plotted. The rate of catalyst deactivation was taken to be the rate of progression of these temperature profiles through the bed. The position of each temperature profile was defined by the end of the active zone, which was a measure of the end of the temperature rise in the temperature profile. On a temperature profile, the end of the active zone was the distance in the bed at the intersection of the linear extrapolation of the linear part of the temperature rise and a horizontal line at the maximum bed temperature. Some catalyst deactivation occurred over the duration that the performance of each catalyst was measured, and it is believed that the deactivation rates of the catalysts were not significantly affected by differences in the operating conditions among the tests of each catalyst.The DABTs were between about 130° C. (236° F.) and about 160° C. (320° F.) for the tests for Catalyst A alone, about 160° C. (320° F.) and about 175° C. (347° F.) for the tests for Catalyst B alone, and about 150° C. (302° F.) and about 175° C. (347° F.) for the tests of the stacked loading of Catalysts A and B. The propylene WHSV was about 2.03 hr-1 for the tests of Catalyst A alone, about 1.88 hr-1 for the tests of Catalyst B alone, and about 1.03 hr-1 for the tests of the stacked loading of Catalysts A and B (or alternatively 1.77 hr-1 for Catalyst A and 2.48 hr-1 for Catalyst B. The molar ratio of fresh benzene to fresh propylene for these tests was about 2. The R/FF for these tests was about 6. Because the molar ratio of aryl groups per propyl group is essentially the same in the combined reactor feed stream and the total reactor effluent stream, the molar ratio of aryl groups per ethyl group is not significantly affected by recycling any portion of the reactor effluent stream.The results of the tests are shown in Table 3. Each test included almost 600 hours of operation, and the total selectivity to cumene and DIPB and TIPB, and the deactivation rates, reported in Table 3 are determined during the final 525 hours of operation. The average deactivation rate is computed from the location of the end of the active zone after about 50 hours of operation and the location of the end of the active zone after about 575 hours of operation.; These data show the unexpected result that the stacked loading of Catalysts A and B has a selectivity to cumene+DIPB+TIPB that is higher, and an average deactivation rate that is lower, than that of either Catalyst A alone or Catalyst B alone. Without being limited to any particular theory, it is believed that the combination of Catalyst A (UZM-8) and Catalyst B (beta) provides a synergistic effect. It is believed that the UZM-8 catalyst is instrumental in providing the high selectivity and that the beta catalyst is instrumental in providing the low average deactivation rate without adversely affecting the high selectivity.

With 70wtpercent β-zeolite and 30wtpercent alumina, Time= 600 - 1300h, T= 260 °C , Product distribution / selectivity Patent; Schmidt, Robert J.; US2008/171900; (2008); (A1) English View in Reaxys 2 :EXAMPLE 2; The experimental procedure used in testing the catalysts prepared for Example 1 was as follows. A volume of the catalyst to be tested was loaded into a cylindrical reactor, however for the test of the stacked loading of Catalysts A and B, the bottom 30percent of the volume was loaded with Catalyst B and the upper 70percent of the volume was loaded with Catalyst A. The reactor was equipped with a thermocouple in a thermowell located to measure temperatures at distances along the length of the fixed catalyst bed. Dry benzene was passed downflow through the reactor at 260° C. (500° F.) and at a benzene LHSV of 6.7 hr-1 for 24 hours.Subsequently, the flow of fresh ben-

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zene was adjusted and the reactor inlet temperature was lowered to a temperature about 50° C. (90° F.) below the desired distance average bed temperature (DABT) for the initial testing conditions. As used herein, DABT means the temperature calculated by plotting the catalyst bed temperature versus distance along the catalyst bed, computing the area under the curve from the inlet to the outlet of the catalyst bed, and dividing the area by the length of the catalyst bed. Fresh propylene was introduced into the reactor. Then a portion of the reactor effluent was recycled so that a combined feed of the fresh benzene, the fresh propylene, and the recycled reactor effluent flowed to the reactor. The reactor inlet temperature was adjusted to maintain the desired DABT while the reactor effluent was sampled and analyzed. Then the reactor inlet temperature and/or the amount of recycled reactor effluent was adjusted, and the reactor effluent was sampled again. This process was repeated until measurements and samples were obtained at all of the desired DABTs and effluent recycle ratios (R/FF).The temperature within the catalyst bed rose as the incoming feed contacted the catalyst due to the exothermic nature of the reaction. At times during a period at test conditions, temperature profiles (bed temperature versus distance through the bed) were plotted. The rate of catalyst deactivation was taken to be the rate of progression of these temperature profiles through the bed. The position of each temperature profile was defined by the end of the active zone, which was a measure of the end of the temperature rise in the temperature profile. On a temperature profile, the end of the active zone was the distance in the bed at the intersection of the linear extrapolation of the linear part of the temperature rise and a horizontal line at the maximum bed temperature. Some catalyst deactivation occurred over the duration that the performance of each catalyst was measured, and it is believed that the deactivation rates of the catalysts were not significantly affected by differences in the operating conditions among the tests of each catalyst.The DABTs were between about 130° C. (236° F.) and about 160° C. (320° F.) for the tests for Catalyst A alone, about 160° C. (320° F.) and about 175° C. (347° F.) for the tests for Catalyst B alone, and about 150° C. (302° F.) and about 175° C. (347° F.) for the tests of the stacked loading of Catalysts A and B. The propylene WHSV was about 2.03 hr-1 for the tests of Catalyst A alone, about 1.88 hr-1 for the tests of Catalyst B alone, and about 1.03 hr-1 for the tests of the stacked loading of Catalysts A and B (or alternatively 1.77 hr-1 for Catalyst A and 2.48 hr-1 for Catalyst B. The molar ratio of fresh benzene to fresh propylene for these tests was about 2. The R/FF for these tests was about 6. Because the molar ratio of aryl groups per propyl group is essentially the same in the combined reactor feed stream and the total reactor effluent stream, the molar ratio of aryl groups per ethyl group is not significantly affected by recycling any portion of the reactor effluent stream.The results of the tests are shown in Table 3. Each test included almost 600 hours of operation, and the total selectivity to cumene and DIPB and TIPB, and the deactivation rates, reported in Table 3 are determined during the final 525 hours of operation. The average deactivation rate is computed from the location of the end of the active zone after about 50 hours of operation and the location of the end of the active zone after about 575 hours of operation.; These data show the unexpected result that the stacked loading of Catalysts A and B has a selectivity to cumene+DIPB+TIPB that is higher, and an average deactivation rate that is lower, than that of either Catalyst A alone or Catalyst B alone. Without being limited to any particular theory, it is believed that the combination of Catalyst A (UZM-8) and Catalyst B (beta) provides a synergistic effect. It is believed that the UZM-8 catalyst is instrumental in providing the high selectivity and that the beta catalyst is instrumental in providing the low average deactivation rate without adversely affecting the high selectivity.

With 70wtpercent UZM-8 zeolite and 30wtpercent alumina, Time= 600 - 1300h, T= 260 °C , Product distribution / selectivity Patent; Schmidt, Robert J.; US2008/171900; (2008); (A1) English View in Reaxys 1 :EXAMPLE 1; Tests were carried out with a hydrocarbon composition feed comprised of 66 weight percent benzene and 34 percent by weight of 2-methyl-hexane. Propylene was present in the hydrocarbon composition feed in amounts such that the propylene to benzene mole ratio of the feed ranged from 0.20 to 1.0. The test was conducted by passing the feed over a MCM-22 catalyst at a temperature of 130° C. and at a pressure sufficient to maintain the benzene in the liquid phase. FIG. 5 plots propylene oligomer impurities and shows significantly lower propylene oligomer impurities in the practice of the present disclosure.

With MCM-22, T= 130 °C , Liquid phase, Product distribution / selectivity Patent; Brown, Stephen Harold; US2008/194890; (2008); (A1) English View in Reaxys 1; 2; 5 :EXAMPLE 1; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalysts selected individually from Materials 1, 2 and 3. Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst for use in the present disclosure, i.e. Material 2, provided about 30percent reduction in the DIPB/IPB ratio. Also, Material 2 yielded about 288percent higher activity than Material 1, and about 600percent higher activity than Material 3.; EXAMPLE 2; In these experiments, cumene was manufactured by contacting 5.55 parts by weight

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benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the 0.127 cm MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 2). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that Material 2 again provided a 30percent reduction in the DIPB/IPB ratio.; EXAMPLE 5; In these experiments, cumene was manufactured by contacting 5.2 parts by weight benzene and 1 part by weight propylene in the fixed bed micro reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Fixed Bed Test over catalyst comprising the 0.127 cm MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 2). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that Example 8 provided a 54percent reduction in the DIPB/IPB ratio.

With MCM-49 quadrulobal catalyst (surface area to volume ratio of 78 1/cm), Time= 0.5 - 48h, T= 125 - 130 °C , p= 16269.1Torr , Product distribution / selectivity Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys 6 :EXAMPLE 6; In these experiments, cumene was manufactured by contacting 5.2 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the Beta quadrulobal catalyst (Material 5) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 6). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst Material 6 provided a 65percent reduction in the DIPB/IPB ratio before deactivation.

With β quadrulobal catalyst (surface area to volume ratio of 344 1/cm), Time= 0.5 - 4h, T= 130 °C , p= 16269.1Torr , Product distribution / selectivity Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys 6 :EXAMPLE 6; In these experiments, cumene was manufactured by contacting 5.2 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the Beta quadrulobal catalyst (Material 5) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 6). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst Material 6 provided a 65percent reduction in the DIPB/IPB ratio before deactivation.

With β quadrulobal catalyst (surface area to volume ratio of 78 1/cm), Time= 0.5 - 4h, T= 130 °C , p= 16269.1Torr , Product distribution / selectivity Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys 1; 3 :EXAMPLE 1; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalysts selected individually from Materials 1, 2 and 3. Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst for use in the present disclosure, i.e. Material 2, provided about 30percent reduction in the DIPB/IPB ratio. Also, Material 2 yielded about 288percent higher activity than Material 1, and about 600percent higher activity than Material 3.; EXAMPLE 3; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the MCM-22 cylindrical catalyst (Material 3) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 4). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst Material 4 provided a 13percent reduction in the DIPB/IPB ratio.

With MCM-22 cylindrical catalyst (surface area to volume ratio of 34.6 1/cm), Time= 0.5 - 4h, T= 130 °C , p= 16269.1Torr , Product distribution / selectivity

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Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys 3 :EXAMPLE 3; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the MCM-22 cylindrical catalyst (Material 3) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 4). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst Material 4 provided a 13percent reduction in the DIPB/IPB ratio.

With MCM-22 cylindrical catalyst (surface area to volume ratio of 344 1/cm), Time= 0.5 - 4h, T= 130 °C , p= 16269.1Torr , Product distribution / selectivity Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys 1; 2; 5 :EXAMPLE 1; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalysts selected individually from Materials 1, 2 and 3. Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that catalyst for use in the present disclosure, i.e. Material 2, provided about 30percent reduction in the DIPB/IPB ratio. Also, Material 2 yielded about 288percent higher activity than Material 1, and about 600percent higher activity than Material 3.; EXAMPLE 2; In these experiments, cumene was manufactured by contacting 5.55 parts by weight benzene and 1 part by weight propylene in the batch slurry reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Batch Test over catalyst comprising the 0.127 cm MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 2). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that Material 2 again provided a 30percent reduction in the DIPB/IPB ratio.; EXAMPLE 5; In these experiments, cumene was manufactured by contacting 5.2 parts by weight benzene and 1 part by weight propylene in the fixed bed micro reactor using the procedure detailed above for Test Sequence for Cumene Manufacture in a Fixed Bed Test over catalyst comprising the 0.127 cm MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 micron catalyst prepared from it by crushing and sieving (Material 2). Cumene (isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products were collected from each experiment and it was found that Example 8 provided a 54percent reduction in the DIPB/IPB ratio.

With MCM-49 quadrulobal catalyst (surface area to volume ratio of 344 1/cm), Time= 0.5 - 48h, T= 125 - 130 °C , p= 16269.1Torr , Product distribution / selectivity Patent; Clark, Michael C.; Elia, Christine N.; Lo, Frederick Y.; Vincent, Mathew J.; US2008/194897; (2008); (A1) English View in Reaxys With decane, (nitrosonium)(guanidinium)2(PW12O40), Time= 3h, T= 70 °C Khenkin, Alexander M.; Neumann, Ronny; Journal of the American Chemical Society; vol. 130; nb. 36; (2008); p.

11876 - 11877 View in Reaxys 4; 5; 6 :1.51 grams of catalyst made in example 1 was mixed with 3.21 grams of 80/120 mesh sand and tested for alkylation of benzene with propylene in a fixed-bed reactor. The catalyst and sand was loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm. The catalyst was dried at 130° C. and 2170 kPa-a in flowing benzene at 8.92 ml/hr. Liquid propylene feed was introduced from an ISCO pump at 2.48 ml/hr. Feed benzene/propylene molar ratio was 3:1. Liquid products were collected in a cold-trap (25° C. and 101.3 kPa-a) and analyzed off line. The results show that the EMM-10 catalyst has DiPB/Cumene around 10 wt. percent for benzene/propylene molar ratio 3:1, temperature 130° C. and pressure 2170 kPa-a and about 20 wt. percent for benzene/propylene molar ratio 1.5:1, temperature 130° C. and pressure 2170 kPa-a; Examples 5-6Testing ProceduresFeed PretreatmentBenzene (99.96 wt. percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2 L Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using.Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using.Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing

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absorbents which were dried at 260° C. for 12 hours before using.One gram of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of 0.1 gram or 0.5 grams of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours.Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying.A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively.Catalytic Activity and SelectivityThe activity and selectivity of a catalyst were measured based on benzene alkylation with propylene. Catalytic activity (CAP number) was calculated using the second order rate constant for the formation of cumene under the reaction conditions (temperature 130° C. and pressure 2170 kpa-a) times a constant of 909.09. Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes (DiPB) produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 15, 30, 60, 120, 180, and 240 min after addition of the propylene.0.1 gram (example 5) and 0.5 gram (example 6) of catalyst made in example 1 were loaded in a stirred autoclave and tested with a benzene/propylene molar feed of 3:1 for 4 hours at 130° C.CAP Activity and Selectivity results clearly showed that EMM-10 could alkylate benzene with propylene to produce cumene.

With EMM-10 molecular sieve, T= 130 °C , Conversion of starting material Patent; Roth, Wieslaw J.; Cheng, Jane C.; Kalyanaraman, Mohan; Kerby, Michael C.; Helton, Terry E.; US2009/163753; (2009); (A1) English View in Reaxys 2.2 :2. Alkylation Reaction; The catalyst obtained as described above was molded into 1 to 2 mm, and an alkylation reaction of benzene was performed by the method shown in Example 1.In the alkylation reaction, 0.50 g of the catalyst was used, the flow rate of benzene was 10.9 g/h, the flow rate of propylene was 12.5 Nml/min, the reaction pressure was 0.15 MPa, and the hot spot of a catalyst layer was 49.7° C.After 6 hours from initiation of the reaction, the reaction solution was sampled and analyzed by gas chromatography. The propylene conversion was 11.8percent, the cumene selectivity was 89.4percent, and the diisopropylbenzene selectivity was 3.79percent as a total of three isomers.

With 40 wt.percent Cs2.5H1.5SiW12O40/SiO2 mixed with α-alumina and calcinated at 250 C, Time= 6h, T= 49.7 °C , Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2009/209796; (2009); (A1) English View in Reaxys 2 :Example 2Another portion of the catalyst sample of Example 1 was treated in accordance with Proton Content Adjustment Technique No.1 at a Contact Time of approximately 1 hour, to produce the treated catalyst sample of this Example 2 having a third hydration state. The proton density of the third hydration state of the treated catalyst sample was 1.85 mmol per gram of catalyst (third hydration state), determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 250° C.A 0.5 gram portion of the treated catalyst sample of this Example 2 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250° C. and the Specified In-situ Drying Temperature of 170° C. The Catalyst Selectivity of this catalyst sample was 6.94, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst sample was 383.The PDI of the catalyst sample of this Example 2 was determined to be 1.08, and represents an 8percent increase in the proton content (determined as mmol of protons per gram of catalyst) as compared to the catalyst sample of Example 1. The Catalyst Selectivity (IPB/DIPB) of the catalyst sample of this Example 2 displayed an increase of 17percent, and the Catalyst Activity displayed an increase of 5.5percent, as compared to the catalyst sample of Example 1.

With 80 wt percent MCM-49/20 wt percent (Al2O3), T= 250 °C , p= 16274.9Torr , Product distribution / selectivity

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Patent; Clark, Michael C.; Xu, Teng; Vincent, Matthew J.; US2009/281361; (2009); (A1) English View in Reaxys 8 :Example 8The catalyst sample of this example comprised 65 wt percent MCM-22 and 35 wt percent alumina and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 250° C. The proton density was 1.46 mmol per gram of catalyst (first hydration state).A 1.0 gram portion of the catalyst sample of this Example 8 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250° C. and the Specified In-situ Drying Temperature of 170° C. The Catalyst Selectivity of the catalyst sample was 5.46, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB). The Catalyst Activity of this catalyst sample was 272.

With 65 wt percent MCM-22/35 wt percent (Al2O3), p= 16274.9Torr , Product distribution / selectivity Patent; Clark, Michael C.; Xu, Teng; Vincent, Matthew J.; US2009/281361; (2009); (A1) English View in Reaxys 3 :Example 3The catalyst sample of this Example 3 comprised 80 wt percent zeolite Beta and 20 wt percent alumina and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 250° C. The proton density was 2.48 mmol per gram of catalyst (first hydration state).A 1.0 gram portion of the catalyst sample of this Example 3 was tested in accordance with the Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250° C. and the Specified In-situ Drying Temperature of 170° C. The Catalyst Selectivity of this catalyst sample was 5.62, determined as the weight ratio of IPB/DIPB. The Catalyst Activity of this catalyst sample was 23.

With 80 wt percent zeolite Beta/20 wt percent (Al2O3), T= 250 °C , p= 16274.9Torr , Product distribution / selectivity Patent; Clark, Michael C.; Xu, Teng; Vincent, Matthew J.; US2009/281361; (2009); (A1) English View in Reaxys 11 :Example 11 (Comparative)The catalyst sample of this Example 11 comprised porous non-crystalline tungstenzirconia (WZrO2) and its proton density was determined in accordance with the NMR Procedure for Determining Proton Density, described above, at the Specified NMR Pretreatment Temperature of 250° C. The proton density was 0.37 mmol per gram of catalyst (first hydration state).A 0.5 gram portion of the catalyst sample of this Example 11 was tested in accordance with Catalyst Reactivity Testing Procedure at the Specified Ex-situ Drying Temperature of 250° C. and the Specified In-situ Drying Temperature of 170° C. The Catalyst Selectivity was 13.70, determined as the weight ratio of isopropylbenzene to diisopropylbenzene (IPB/DIPB). The Catalyst Activity of this catalyst sample was 1..

With WZrO2, p= 16274.9Torr , Product distribution / selectivity Patent; Clark, Michael C.; Xu, Teng; Vincent, Matthew J.; US2009/281361; (2009); (A1) English View in Reaxys II :Example II; We examined cumene yield as a function of propylene conversion in a batch operation. We used Catalyst A from Example I that had been crushed and screened to obtain catalyst particles of 20.x.40 mesh. Benzene and the catalyst were added to a batch reactor having a volume of 300 cm3 and heated to an initial reaction temperature while stirring. Propylene was added to the catalyst and benzene mixture while samples of the reaction mixture were analyzed at intervals by gas chromatography. The sampling continued after termination of propylene addition.

Residence time controlled propylene conversion.Experiments were run under three different sets of conditions shown in Table A. With β-zeolite/Al2O3 (70/30), T= 145 °C , Product distribution / selectivity Patent; UOP LLC; US7622622; (2009); (B1) English View in Reaxys EquipmentA 300 ml Parr batch reaction vessel equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively.Catalyst Pretreatment and LoadingTwo grams of catalyst were dried in oven (in air) at 260° C. for 2 hours. The catalyst was removed from the oven and immediately. A first layer of quartz chips was used to line the bottom of the basket followed by loading of one gram of the catalyst into the basket on top of the first layer of quartz chips. A second layer of quartz chips was then placed on top of the catalyst. The catalyst basket containing the catalyst and quartz chips was placed in an oven at 260° C. overnight in air (16 hrs).The reactor and all

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lines were cleaned with a suitable solvent (such as toluene) before each experiment. The reactor and all lines were dried in air after cleaning to remove all traces of cleaning solvent. The catalyst Basket containing the catalyst and quartz chips was removed from the oven and immediately placed in reactor and the reactor was immediately assembled.Test SequenceThe reactor temperature was set to 170° C. and purged with 100 standard cubic milliliter of ultra high purity N2 for 2 hours. After nitrogen had purged the reactor for two hours, reactor temperature was reduced to 130° C., the nitrogen purge was discontinued and the reactor vent closed. 156.1 g of benzene was loaded into a 300 ml transfer vessel, performed in a closed system. The benzene vessel was pressurized to 11622 kPa-a (100 psig) with ultra high purity nitrogen and the benzene was transferred into the reactor. The agitator speed was set to 500 rotation per minute (rpm) and the reactor was allowed to equilibrate for 1 hour. A 75 ml transfer vessel was then filled with 28.1 g liquid propylene and connected to the reactor vessel, and then connected with 31887 kPa-a (300 psig) ultra high purity nitrogen. After the one-hour benzene stir time had elapsed, the propylene was transferred from the vessel to the reactor. The 31887 kPa-a (300 psig) nitrogen source was maintained connected to propylene vessel and open to the reactor during the entire experiment to maintain constant reaction pressure during the test. Liquid samples were taken at 30, 60, 120, 150, 180 and 240 min after addition of the propylene.

With MCM-49 catalyst, T= 130 °C , p= 239176Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; US2009/306446; (2009); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene. , T= 120 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene. , T= 130 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene. , T= 120 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene. , T= 130 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene.

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, T= 120 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys CATALYTIC ACTIVITY OF RESINS The catalysts of this invention were tested for the reaction of benzene with propylene to produce cumene. A mixture of N2/benzene/propylene in a 6.0/3.5/0.5 ratio was passed over 1g of heated catalyst at 150psig using a gas hourly space velocity (GHSV) of 12000 l/kg/h. The results in Table 2 were unexpected. C3 below is propene. , T= 130 °C , p= 7757.43Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys 8 : Example 8 The following testing conditions were employed. A 1.00 g portion of the methanol-swollen and dried catalyst, mixed with approximately 8 ml of 3 mm Pyrex beads, was loaded into the gas-phase continuous downflow 316 stainless steel tubular reactor (0.75-inch outside diameter). The reactor contained an axial thermocouple well that was positioned so that it extended from the bottom of the catalyst bed in the reactor to the top of the reactor. This provided for a sliding thermocouple to monitor and control the temperature inside of the reactor. The catalyst bed was centered in the reactor using addition 3 mm Pyrex beads above and below the catalyst bed and separated from it by layers of approximately 1 cm Pyrex wool. A double wool plug was utilized below the catalyst bed. After loading the reactor, it was mounted in the self-contained testing system, purged with nitrogen, and then pressurized to 10.549 kg/cm (150 psig) with nitrogen at a flow rate of 130 ml/min to check for leaks. Maintaining the nitrogen gas flow at this flow rate, the reactor was slowly heated to 100°C over a period of 3 hr. Injection of benzene into the gas stream at the top of the reactor was then initiated by means of a calibrated Gilson Model 302 high pressure pump to yield a resultant gaseous benzene reactant flow rate of 70 ml/min. The liquid was vaporized in the heated inlet line to the reactor.

After equilibration of this mixture, the flow of nitrogen was replaced by an equilivalent flow of a 7.75percent propene/ nitrogen mixture. The flow rate was adjusted to yield a reactant gas mixture of N2/benzene/propene = 6.0/3.5/0.5.

These testing conditions corresponded to a N2 flow rate of 120 ml/min, a propene flow rate of 10 ml/min, and a benzene gas flow rate of 70 ml/min (liquid injection rate of approximately 0.30 ml/min). These feed rates correspond to about 2.90 mmol benzene/min and about 0.41 mmol propene/min. The corresponding total gas hourly space velocity (GHSV) was 12,000 P/kg catal/hr. Testing was carried out sequentially at 100, 110, 120, 130, 140, and 150 °C. Reactant and product analyses were carried out by gas chromatography (GC) using a dimethylpolysiloxane capillary column, a 15 ΦP sample loop, and a thermal conductivity detector (TCD). The reactor exit stream was typically sampled every 20-25 min using an in-line automated heated sampling valve. , T= 100 - 130 °C , p= 7759.55Torr , Conversion of starting material Patent; Rohm and Haas Company; EP1508556; (2005); (A1) English View in Reaxys 2 :250 mL of neat benzene is placed in a stirred pressure vessel with 10 g of FCC catalyst (Grace Davison, OCTACAT with 50percent zeolite). The reactor is heated to 300° F. and propylene is slowly added over 20 minutes until the pressure vessel reached a pressure of 145 psig. The benzene is alkylated with the propylene, resulting in a product containing 33 weight percent benzene, indicating approximately 70percent benzene conversion.

With Octacat with zeolithe, T= 148.879 °C , p= 8258.9Torr , Conversion of starting material Patent; CATALYTIC DISTILLATION TECHNOLOGIES; US2010/48970; (2010); (A1) English View in Reaxys 2 :MCM-49 was extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal, P25 titania, and Versal-300 alumina (weight ratio 80:10:10) extruded with 1 wt. percent PVA (based on the combined weight of MCM-49 crystal, P25 titania, Versal-300 alumina, and PVA) to 0.127 cm ( 1/20) extrudate. This extrudate was then pre-calcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. The catalyst of Example 2 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With titania, alumina, molecular sieve M-49; calcined, T= 230 °C , p= 16276.6Torr , Product distribution / selectivity Patent; Elia, Christine N.; Lo, Frederick Y.; Elks, Jeffrey T.; Lacy, Darryl D.; Kalyanaraman, Mohan; US2010/36184; (2010); (A1) English

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View in Reaxys 2 :Feed Pretreatment; Benzene (99.96 wt percent) was obtained from the ExxonMobil Baytown Chemical plant. The benzene was passed through a pretreatment vessel (2 Liter Hoke vessel) containing absorbent materials from inlet to outlet. All absorbent feed pretreatment materials were dried in a 260° C. oven for 12 hours before using.Polymer grade propylene was obtained from Scott Specialty Gases (Pasadena, Tex., USA). Propylene was passed through a 300 ml vessel containing absorbents which were dried in a 260° C. oven for 12 hours before using.Ultra high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through a 300 ml vessel containing absorbents which were dried at 260° C. for 12 hours before using.Alumina was obtained from UOP LLC (UOP LLC, 25 East Algonquin Road, Des Plaines, Ill. 60017-5017, U.S.A.) as Versal-300 alumina.Catalyst Preparation and LoadingMCM-22 catalyst was prepared according to U.S. Pat. No. 4,954,325, the whole content of which is incorporated herein as reference. MCM-49 catalyst was prepared according to U.S. Pat. No. 5,236,575, the whole content of which is incorporated herein as reference.Catalyst activity was calculated using the second order rate constant under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a). Reaction rate-constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", J. M. Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of cumene produced over di-isopropyl benzenes produced under the reaction conditions (temperature 130° C. and pressure 2170 kPa-a).One gram of catalyst was dried in air at 260° C. for 2 hours. The catalyst was removed immediately after drying. The bottom of a catalyst basket was packed with quartz chips followed by loading of 0.5 grams of catalyst into basket on top of the quartz chips. The catalyst was then covered by additional quartz chips. The catalyst basket containing the catalyst and quartz chips was dried at 260° C. in air for about 16 hours.Before each experiment the reactor and all lines were cleaned with a suitable solvent (such as toluene) followed by flowing of air after cleaning to remove all cleaning solvent. The catalyst basket containing the catalyst and quartz chips was placed in reactor immediately after drying.A 300 ml Parr.(R). batch reaction vessel (Series 4563 mini Bench top reactor with a static catalyst basket, Parr Instrument Company, Moline, Ill. USA) equipped with a stir rod and static catalyst basket was used for the activity and selectivity measurements. The reaction vessel was fitted with two removable vessels for the introduction of benzene and propylene respectively.The reactor was purged with 100 ml/min of the treated ultra high purity nitrogen, N2, for 2 hours at 170° C. Then, the reactor temperature was reduced to 130° C. under nitrogen flow. All inlets and outlets of the reactor were closed off afterward. Pretreated benzene (156.1 gram) was transferred into the reactor under 791 kPa-a ultra high purity nitrogen blanket. The reactor was stirred at 500 rpm for 1 hour. Pretreated liquid propylene (28.1 gram) under 2170 kPa-a ultra high purity nitrogen is then transferred to the reactor. The reactor was maintained at 2170 kPa-a by the 2170 kPa-a ultra high purity nitrogen. Liquid samples were taken at 15, 30, 60, 120, 180 and 240 min after addition of the propylene.Jet milling was performed on a Micron Master Jet Mill (Jet Pulverizer, in Moorestown, N.J., USA). Example 2MCM-49 was jet pulverized (also called Jet milling) at high velocity mixing. After jet milling, the average crystal agglomerate size of the MCM-49 material decreased from the 16.8 microns to 1.2 microns. The jet milled MCM-49 crystals were extruded in a 5.08 cm (2) extruder according to the following formulation: mixture of MCM-49 crystal and Versal-300 alumina (weight ratio 80:20) extruded with 0.05 wt percent PVA (based on the combined weight of MCM-49 crystal, Versal-300 alumina, and PVA) to 0.127 cm ( 1/20) extrudate. This extrudate was then pre-calcined in nitrogen at 510° C., ammonium exchanged with ammonium nitrate, and calcined in an air/N2 mixture at 538° C. FIG. 2 shows the SEM pictures of the jet pulverized MCM-49 molecular sieve crystal. The catalyst from Example 2 was tested in the batch autoclave liquid phase benzene alkylation test and results are listed in Table 1.

With 80wtpercent jet-milled MCM-49/20wtpercent Versal-300 alumina, ammonium-exchanged, calcined in air, Time= 4h, T= 130 °C , p= 16276.6Torr , Inert atmosphere, Autoclave, Product distribution / selectivity Patent; ExxonMobil Chemical Patents Inc.; US7737313; (2010); (B2) English View in Reaxys 1 :Example 1; Cumene Alkylation; Benzene and propylene of a molar ratio of 2.5 were introduced into a fixed bed reactor containing cylindrical extruded catalyst in 1/16'' diameter. A portion of the product effluent was recycled with an effluent to fresh feed ratio of 6.0 on a weight basis. A multiple point sampling device was installed so the product compositions including the unconverted propylene were monitored along the catalyst bed. The temperature profiles along the catalyst bed were also monitored to provide another mean to gauge the catalyst activity. The catalyst was loaded at a constant volume and the performance was plotted against zeolite contact time to differentiate performance of different zeolite on a constant zeolite weight basis.FIGS. 1-5 provide the results of Example 1. FIG. 1 is a chart showing the percent conversion of propylene versus contact time with respect to quantities up to the points where the product was sampled. FIG. 1 demonstrates that Catalyst C in particular achieved high olefin conversion at two different inlet temperatures, which achieved at least about 85percent conversion within about 0.1 hours of contact time in a laboratory sized reactor. This indicates that Catalyst C could be used in a commercial process yielding lower value end products at an olefin WHSV (with respect to zeolite) of up to about 10 hr-1 while still achieving complete olefin conversion. For higher value products, complete conversion (taking into account that it is difficult to ach-

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ieve 100percent conversion under laboratory conditions) occurred at about 0.33 hr. This indicates that Catalyst C could be used in a commercial operation at an olefin WHSV of between about 2.1 hr-1 to about 4.0 hr-1, more particularly between about 3.0 hr-1 to about 4.0 hr-1, while still achieving complete olefin conversion.FIG. 2 shows catalyst selectivity for Catalysts B, C, and G, and demonstrates. Catalyst C has a higher total alkylate selectivity than Catalyst G. FIG. 3 is a chart illustrating the activity of fresh and regenerated forms of Catalyst D, which was synthesized using the same procedure as UZM-8 formulated into Catalyst C. The activity of the regenerated UZM-8 Catalyst D was only slightly lower than the fresh Catalyst G made using MCM-22.FIGS. 4 and 5 illustrate catalyst activity stability as measured by either the movement of temperature profiles, e.g., the movement of end of active zone, or by changes of unconverted propylene at approximately 40percent into the catalyst bed as a function of WHSV. As shown in FIG. 6, Catalyst C made of UZM-8 zeolite showed little or no changes in the rates of movement of temperature profiles as WHSV doubled. As shown in FIG. 5, increasing WHSV with respect to Catalyst C also did not did not change the rate of propylene concentration increase with time at a sampling point approximately 40percent into the catalyst bed.The foregoing experimental results indicate that UZM-8 catalysts had better overall activity, selectivity and stability than MCM-22 catalysts in experiments simulating cumene production. These results indicated that UZM-8 catalysts, and in particular Catalyst C, could be used in a cumene alkylation process with a propylene WHSV of greater than 2.1 hr-1, more particularly, between about 3.0 hr-1 and about 4.0 hr-1.

With UZM-8 (70 wt percent zeolite and 30 wt percent Al2O3), Product distribution / selectivity Patent; Schmidt, Robert; Jan, Deng-Yang; James, Robert; US2010/160704; (2010); (A1) English View in Reaxys 2.9 :Comparative Example 2 High Performance BetaThe high performance beta ("HP" Beta) used in this example and Examples 8-19 was prepared in accordance with the method set forth in U.S. Pat. No. 6,809,055 in a form of 1.6 mm extrudates with 80 wt percent zeolite and 20 wt percent binder. The extrudates were resized to 12-20 mesh for reactor evaluation and for the acid treatment described in Examples 8-19. The testing results of this sample along with the acid-treated samples are summarized in Table 2.

With oxalic acid, Time= 1h, T= 70 °C , Autoclave, Product distribution / selectivity Patent; LUMMUS TECHNOLOGY INC.; US2010/179359; (2010); (A1) English View in Reaxys 1.b :Stage (b) - alkylation with propylene of the product coming from the previous stage (a)The catalyst used is the same catalyst as the previous stage (a) . The test is effected in the same reactor described in stage (a) to which the raw alkylated liquid deriving from the alkylation of benzene with ethylene is fed, after treatment on an alumina column. The propylene is fed in the liquid state by means of an isocratic pump and mixed with the alkylated liquid before entering the reactor.The conditions under which the test is carried out are the following: reaction temperature equal to 1400C, reaction pressure equal to 37 bar, space velocity expressed as LHSV equal to 3 hours"1, benzene/ propylene molar ratio equal to 2.7.The effluent from the reactor is collected in a tank and analyzed by means of gas chromatography according to the procedure described in stage (a) .Under the above reaction conditions, a quantitative conversion of propylene is obtained, with a selectivity to cumene of 65percent, a selectivity of propylene to useful aromatic compounds (intended as the sum of cumene and polyalkylbenzenes recoverable by transalkylation) of99.9percent and the formation of 2.96 kg of heavy products per ton of mono-alkylated product (ethylbenzene + cumene) , wherein the heavy products contain diphenyIethanes, alkyl diphenyIethanes, diphenylpropanes and alkyl diphenylpropanes .As can be observed, the additional alkylation with propylene of the alkylated liquid product coming from stage (a) does not lead to a significant deterioration in the formation of heavy products, wherein said heavy products represent the loss of material of the whole process .

With AlO(OH), T= 140 °C , p= 27752.8Torr , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A; BENCINI, Elena; DEL SEPPIA, Alessandro; WO2010/92466; (2010); (A1) English View in Reaxys 7 :Alkylation of benzene with propylene was carried out according to the process of the present invention. Alkylation of benzene with propylene to produce cumene was carried out in a 250 ml high-pressure reaction tank. 3.0 g supported phospho-tungstic acid (20 percent H3PW12O40/SiO2) prepared in Examples 1-3 was added into the reaction tank, and then 60.0 g benzene (analytic pure, a product of Beijing Chemical Plant), which contains 254 ppm HF, was added therein. With intense agitation, the temperature was increased to 75 °C, and the mixture was treated at this temperature for 2.5 hours. Then, benzene was discharged out of the reaction tank. Thereafter, 50.0 g benzene containing 110 ppm HF and 7.69 g propylene were added. Alkylation was carried out with intense agitation and stopped after the reaction lasted for 60 minutes. After the temperature dropped to ambient temperature, the amount of the

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unreacted propylene was measured with a precision flow meter, and the composition of the liquid phase reaction product was analyzed with a chromatograph. Reaction results are listed in Table 9.Comparative Example 7 The same catalyst and reaction steps as those used in Example 12 were employed, except that the catalyst was not treated with HF-containing benzene before alkylation. Reaction results are listed in Table 9.

Stage 1: With 20 H3PW12O40/SiO2, hydrogen fluoride, Time= 2.5h, T= 75 °C Stage 2:, Time= 1h, Product distribution / selectivity Patent; China Petroleum and Chemical Corporation; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC; EP1714952; (2006); (A1) English View in Reaxys 5 :The UZM-35 of Example 3 was pressed and meshed to 20-40 mesh prior to testing.

For alkylation of benzene with propylene to form cumene, 15 mL of meshed catalyst is mixed with 10 mL of gamma alumina of 20-40 mesh and loaded into the reactor.

With UZM-35, T= 148 °C , p= 26618.1Torr , Conversion of starting material Patent; NICHOLAS, CHRISTOPHER P.; Jan, Deng-Yang; Moscoso, Jaime G.; US2010/331594; (2010); (A1) English View in Reaxys 11 :Example 11Each of Catalysts A through G described above were evaluated according to the following procedure.

50 cc of a catalyst was loaded into a 22 mm internal diameter reactor equipped with thermal-well in a 3-zone furnace. The catalyst was dried in benzene at 250° C. at 3447 kPa(g) plant pressure. After the catalyst dry-down, the temperature was lowered to achieve a reactor inlet temperature of 120° C. Thereafter, a portion of the effluent benzene was recycled and propylene was introduced to achieve an olefin WHSV of around 1.1 hr-1, a benzene to propylene molar ratio of 2.0 and an effluent to fresh feed weight ratio of 6.0. The product effluent was sampled and analyzed using on-line GC. The desired product yield, e.g. cumene, is reported as the mole ratio of cumene produced divided by the sum of the cumene and DIPB produced and is reported as a percentage. The temperature profiles along the catalyst bed were monitored to determine the catalyst activity. The activity of the catalyst is defined as the end of active zone (EAZ), that is where olefin, e.g. propylene, consumption is complete, and is reported as a percentage of the length of the catalyst bed.The end of active zone, is derived by plotting the temperature profiles, i.e. the temperature relative to the position along the catalysts bed and is defined by the intersection of a line drawing through the linear portion of the temperature rise and a horizontal line defined by the maximum temperature and reported as a percentage of the catalyst bed. More active catalysts correspond to lower EAZ as a smaller fraction of catalyst bed is required to achieve complete olefin conversion. The test results are summarized below in table 1.

With zeolitic catalyst G of example 10, T= 120 °C , Product distribution / selectivity Patent; UOP LLC; US2011/77442; (2011); (A1) English View in Reaxys II :EXAMPLE II; We examined cumene yield as a function of propylene conversion in a batch operation. We used Catalyst A from Example I that had been crushed and screened to obtain catalyst particles of 20x40 mesh. Benzene and the catalyst were added to a batch reactor having a volume of 300 cm^ and heated to an initial reaction temperature while stirring. Propylene was added to the catalyst and benzene mixture while samples of the reaction mixture were analyzed at intervals by gas chromatography. The sampling continued after termination of propylene addition.

Residence time controlled propylene conversion.[0060] Experiments were run under three different sets of conditions shown in Table A. Table A: Experimental Conditions for Partial Propylene Conversion to CumeneThe results of the experiments are shown in FIG. 9. Temperature data for each experiment is shown in FIG. 10.[0061] The data shows that the cumene yield peaks between 92 and 99.5percent and drops upon approaching full propylene conversion.

Freeform lines indicate the trends. By controlling the propylene conversion at greater than 92 percent and less than 100 percent, an increase of 3 to 7 percent in cumene yield is possible under these experimental conditions depending on the benzene/propylene feed ratio. We believe that the advantages of increasedmonoalkylbenzene yield may be realized at as low as 92percent olefin conversion. Monoalkylate aromatic yield at 99.5percent olefin conversion was for one experiment far superior tomonoalkylate aromatic yield at olefin conversions approaching closer to 100percent.

With 70/30 β zeolite/alumina, particles of 20x40 mesh, T= 158 °C , Product distribution / selectivity Patent; UOP LLC; WOODLE, Guy B.; SCHMIDT, Robert J.; JAN, Deng-Yang; JOHNSON, James A.; MAURUKAS, Elena Z.; MILLER, Raelynn M.; WO2011/46547; (2011); (A1) English

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View in Reaxys 5 :The experiment was conducted in a fixed bed reactor equipped with on-line GC under the conditions of 3447 kPa gauge (500 psig) pressure, 115° C. inlet temperatures, benzene to olefin molar ratios between 1.9 and 4.0, and olefin WHSV of about 1.0 hr-1. Part of product effluent was recycled (effluent recycle to fresh feed ration is 7.4 wt./wt.) to mitigate the heat of reaction. The performance is summarized Table 6. It is clear that the UZM-37 containing catalyst gives very high total alkylated selectivity over a range of benzene to olefin ratios and the mono-alkylated selectivity is very close to equilibrium, while the olefin conversions are complete.

With aluminum oxide, T= 115 °C , p= 26618.1Torr , Product distribution / selectivity Patent; UOP LLC; US7985886; (2011); (B1) English View in Reaxys 5 :The UZM-35 of Example 3 was pressed and meshed to 20-40 mesh prior to testing. For alkylation of benzene with propylene to form cumene, 15 mL of meshed catalyst is mixed with 10 mL of gamma alumina of 20-40 mesh and loaded into the reactor. The reactor was pressurized to 500 psig with N2 and benzene flow was then started. Once the reactor attained the target temperature, the propylene was introduced. Results of the cumene synthesis tests are shown in Table 3. TABLE 3 n-Pr Temperature LHSV LHSV B/O Conversion Cumene benzene DIPB Heavy Catalyst (° C.) (olefin)(C6H6) ratio (mol percent) Selectivity Selectivity Selectivity Selectivity Example 5 148 0.7 5.4 7 ~100 84.8percent ;600 ppm 7.2percent 8percent UZM-35 Example 5 148 1.1 4.9 4 ~100 76.3percent 800 ppm 11.3percent 12.4percent UZM-35 Example 5 148 0.9 6.6 7 ~100 86.0percent 600 ppm 7.2percent 6.8percent UZM-35 Example 5 148 2.0 5.4 2.5 ~100 68.8percent 1550 ppm 14.0percent 17.2percent UZM-35 Not only does the UZM-35 catalyst exhibit good selectivity to cumene under these conditions, it is remarkably stable. In 16 hours of reaction at the first condition, no evidence of deactivation was observed. Indeed, over the 60 total hours of reaction time, no deactivation in conversion or change in selectivity due to deactivation was noted.

With aluminum oxide, T= 148 °C , Inert atmosphere, Gas phase, Product distribution / selectivity Patent; UOP LLC; US7982082; (2011); (B1) English View in Reaxys 16.88 With water, T= 175 °C , Gas phase %Chromat.

Vyawahare, Yogesh K.; Chumbhale, Vilas R.; Aswar, Anand S.; Revue Roumaine de Chimie; vol. 57; nb. 2; (2012); p. 107 - 113 View in Reaxys 1 :[0024] Alkylation of benzene with propylene was carried out in a fixed bed reactor, made from a 3/4 inch (19 mm) diameter Schedule 40 Stainless Steel 316 pipe with a total length of 34 inches (864 mm). A storage tank was used for benzene and another tank was used for propylene. A positive displacement pump was used for feeding the benzene feed into the reactor and another positive displacement pump was used for feeding propylene into the reactor.

The flow rates of the benzene feed and propylene were set by pump settings and monitored by electronic weight scales. The reactor operating conditions were controlled and monitored by an automatic control system. A portion of the reactor effluent was circulated back to the reactor inlet by a centrifugal pump to control the temperature rise across the catalyst bed. The feedstock and reactor effluent were analyzed by three Hewlett Packard 5890 Series II Gas Chromato graphs, the first one equipped with a Chrompack CP- Wax 52CB column having an inside diameter of 0.25 mm, film thickness of 0.5 μιη, and length of 60 meters, the second one equipped with an Agilent DB-1 column having an inside diameter of 0.32 mm, film thickness of 0.5 μιη, and length of 60 meters, and the third one equipped with an Agilent HP-PONA column having an inside diameter of 0.20 mm, film thickness of 0.5 μιη, and length of 50 meters. [0025] 43 grams of an MCM-22 family catalyst was loaded into the fixed bed reactor. The reactor was heated up in pure benzene and the catalyst dried out at 150°C. The reactor temperature was then lowered to 128°C before the propylene feed was introduced. The propylene feed weight hourly space velocity (WHSV) was 0.7 hr"1, the feed benzene to propylene ratio was 2: 1 molar, and the reactor inlet temperature was 128°C. The reactor circulation was adjusted to control the temperature rise across the catalyst bed below 30°C. The catalyst performance was stable.

[0026] The pure benzene feed was then switched to a feed containing 99percent benzene and 1percent tert-butylbenzene for four days during which period the catalyst performance remained stable. The analysis of the reactor effluent sample indicated that the tert-butylbenzene conversion was 27percent with the following selectivity: • 12percent to iso-butane; • 73percent to tert-butylcumenes; and • 15percent to compounds heavier than TIPB. [0027] The iso-butane produced can be easily purged out of the system as part of the benzene column overhead vent gas. The compounds heavier than TIPB can be effectively purged out of the system at the PIPB column bottoms as part of the residues due to their high boiling points. The tert-butylcumenes can be recovered as part of the recycle PIPB stream and recycled back to the transalkylator with benzene, where they can react with benzene to form cumene and tert-

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butylbenzene. The additional cumene made can be recovered by distillation in the cumene column as part of the desired cumene product and the tert-butylbenzene can be recovered at the PIPB column overhead and recycled back to alkylator until it goes to extinction.

With zeolite MCM-22, T= 128 °C Patent; BADGER LICENSING LLC; HWANG, Shyh-Yuan H.; JOHNSON, Dana E.; WO2014/3732; (2014); (A1) English View in Reaxys With sulfuric acid, T= 35 - 40 °C , p= 8826.09Torr McAllister in B. T. Brooks et al.; View in Reaxys With delaminated two-dimensional zeolite DS-ITQ-2, T= 124.84 °C , p= 26252.6Torr , Flow reactor, Catalytic behavior Margarit, Vicente J.; Martnez-Armero, Marta E.; Navarro, M. Teresa; Martnez, Cristina; Corma, Avelino; Angewandte Chemie - International Edition; vol. 54; nb. 46; (2015); p. 13724 - 13728; Angew. Chem.; vol. 127; nb. 46; (2015); p. 13928 - 13932,5 View in Reaxys With nanosized high-silica Beta zeolite with a silica/aluminum ratio of 15.3 in alkaline media, T= 124.84 °C , p= 26252.6Torr , High pressure, Autoclave, Reagent/catalyst Martnez-Franco, Raquel; Paris, Cecilia; Martnez-Armero, Marta E.; Martnez, Cristina; Moliner, Manuel; Corma, Avelino; Chemical Science; vol. 7; nb. 1; (2015); p. 102 - 108 View in Reaxys

Cl

Rx-ID: 847371 View in Reaxys 27/481 Yield 52 %

Conditions & References 10 :8.9 ml of benzene were reacted with 0.8 g iso-propylchloride in a batch process in the presence of 0.3 g of a heterogeneous catalyst according to the present invention, consisting of a high surface area AlF3 on alumina as support. The catalyst system AlF3/Al2O3 is used without any kind of activation. After stirring the mixture for 0.5 hours at room temperature the reaction was finished. Iso-propylbenzene as the reaction product is identified with an authentic sample by GC. Conversion of 74percent yield was found with a selectivity of 52percent. For comparison reasons: no conversion took place using a conventionally prepared AlF3 catalyst instead. GC conditions are as follow: wide pore quartz column, 15 m length, DB5 polysilixane modi-fied, internal standard dodecane.

With β-Al2O3/AlF3, Time= 0.5h, T= 20 °C Patent; Kemnitz, Erhard; Gross, Udo; Ruediger, Stephan; US2006/52649; (2006); (A1) English View in Reaxys With aluminium trichloride in nitromethane, T= 25 °C , E(a), ΔH(excit.), ΔS(excit.); mechanism var. temperature, Rate constant, Kinetics, Thermodynamic data DeHaan, Franklin P.; Delker, Gerald L.; Covey, William D.; Ahn, Jeffrey; Cowan, Robert L.; et al.; Journal of Organic Chemistry; vol. 51; nb. 9; (1986); p. 1587 - 1590 View in Reaxys With silica-alumina, T= 300 - 320 °C Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys With hydrogenchloride, T= 235 °C Simons; Hart; Journal of the American Chemical Society; vol. 66; (1944); p. 1309,1310; Journal of the American Chemical Society; vol. 69; (1947); p. 979

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View in Reaxys With aluminium amalgam Diuguid; Journal of the American Chemical Society; vol. 63; (1941); p. 3527 View in Reaxys With aluminium trichloride, nitromethane Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys With hydrogenchloride, aluminium turnings Radziewanowski; Chemische Berichte; vol. 28; (1895); p. 1139 View in Reaxys With aluminium trichloride, 2-Nitropropane Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys With silica gel, T= 150 - 350 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2402092; (1941) View in Reaxys

C

O

O

Rx-ID: 23484832 View in Reaxys 28/481 Yield

Conditions & References 48 :To a 70 mL autoclave were added the ligand (B-5 0.0398 g, 0.045 mmol), [Rh(cod)2(OAc)2 (0.0063g, 0.012 mmol), toluene (9.6 mL), and α-methylstyrene (0.525 g, 4.44 mmol) under nitrogen atmosphere and the autoclave was sealed. After replacing nitrogen to OXO gas (H2/CO = 1/1) in the autoclave, OXO gas was pressurized to 0.5 Mpa at room temperature. The reaction was conducted at 60 °C for 17 hrs. GC analysis of the reaction mixture showed that conversion was 14.9 percent. The products were 3-phenylbutanal and 2-phenylpropane. The enantiomeric purity of 3-phenylbutanal was 46.2percent ee analyzed by chiral GC. With hydrogen, 2C2H3O2 (1-)*4C8H12*2Rh(1+), C54H60O6P2 in toluene, Time= 17h, T= 20 - 60 °C , p= 3750.38Torr , Conversion of starting material Patent; MITSUBISHI CHEMICAL CORPORATION; THE RESEARCH FOUNDATION OF STATE UNIVERSITY OF NEW YORK; WO2004/76464; (2004); (A2) English View in Reaxys

I

Mg Cl

(v2)

Zn

Rx-ID: 28596369 View in Reaxys 29/481 Yield 51 %, 33 %

Conditions & References Stage 1: in tetrahydrofuran, Time= 0.333333h, T= 0 °C , Inert atmosphere Stage 2: With methylzync chloride in tetrahydrofuran, Time= 0.25h, T= 20 °C , Inert atmosphere Stage 3: With iron (III) acetylacetonate, ethylene dibromide in tetrahydrofuran, Time= 3h, T= 20 °C , Inert atmosphere Cahiez, Gerard; Foulgoc, Laura; Moyeux, Alban; Angewandte Chemie, International Edition; vol. 48; nb. 16; (2009); p. 2969 - 2972 View in Reaxys

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Mg Cl

Cl

Rx-ID: 33894535 View in Reaxys 30/481 Yield

Conditions & References Representative cross-coupling procedure General procedure: 1,3-Bis-(2,6-diisopropylphenyl)imidazolium chloride (0.1 mmol, 10 mol percent) was added to Vial 1 containing a stir bar which was then fitted with a septum. FeCl2*(H2O)4 (9.9 mg, 0.05 mmol, 5 mol percent) was added to Vial 2 containing a stir bar which was then fitted with a septum. Both Vial 1 and Vial 2 were evacuated and backfilled with argon. Chlorobenzene (102 μL, 1 mmol) was then added via syringe to Vial 2. Freshly distilled THF (10.5 mL) was added via syringe to Vial 1, and isobutylmagnesium chloride (1.5 mL of a 2 M solution in THF, 3 mmol) was added with stirring. Vial 1 was placed in an oil bath at 70 °C and stirred for 10 min. Then the contents of Vial 1 were transferred to Vial 2 via syringe, and Vial 2 was placed in the oil bath at 70 °C. After 3 h, the reaction was removed from the oil bath and allowed to cool to room temperature. The reaction mixture was poured into a separatory funnel followed by 15 mL of 1 M HCl and 15 mL of pentane. The pentane layer was washed with water (1 .x. 15 mL) and brine (1 .x. 15 mL). The pentane layer was dried over Na2SO4 and the solvent was removed in vacuo. The crude oil was purified by distillation resulting in a colorless oil (122 mg, 92percent). 1H NMR and GC-MS were consistent with known material.

With FeCl2*4H2O, 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride in tetrahydrofuran, Time= 3h, T= 70 °C , Inert atmosphere Perry, Marc C.; Gillett, Amber N.; Law, Tyler C.; Tetrahedron Letters; vol. 53; nb. 33; (2012); p. 4436 - 4439 View in Reaxys

OH

Rx-ID: 40074633 View in Reaxys 31/481 Yield 83 %, 8 %

Conditions & References With hydrogen in water, Time= 2h, T= 270 °C , p= 13501.4Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017 View in Reaxys OH

Rx-ID: 40074634 View in Reaxys 32/481 Yield 81 %, 10 %

Conditions & References With hydrogen in water, Time= 2h, T= 270 °C , p= 13501.4Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017 View in Reaxys

O

Rx-ID: 40074642 View in Reaxys 33/481 Yield 82 %, 5 %

Conditions & References With hydrogen in water, Time= 3h, T= 270 °C , p= 16501.7Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017 View in Reaxys

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OH

Rx-ID: 742299 View in Reaxys 34/481 Yield 70 %

Conditions & References With titanium oxide on silica alumina support, T= 180 °C , Mechanism Kumar, V. G.; Shoba, T. S.; Rao, K. V. C.; Tetrahedron Letters; vol. 26; nb. 27; (1985); p. 3281 - 3284 View in Reaxys

70 %

With titanium oxide on silica-alumina support, T= 180 °C Kumar, V. G.; Shoba, T. S.; Rao, K. V. C.; Tetrahedron Letters; vol. 26; nb. 27; (1985); p. 3281 - 3284 View in Reaxys With titanium tetrachloride Cullinane; Leyshon; Journal of the Chemical Society; (1954); p. 2942,2945 View in Reaxys With silica-alumina Turowa-Poljak et al.; Zhurnal Obshchei Khimii; vol. 29; (1959); p. 3243; engl. Ausg. S. 3207 View in Reaxys Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys Patent; Socony-Vacuum Oil Co.; US2542190; (1946) View in Reaxys With boron trifluoride, T= 60 °C McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 470 View in Reaxys With boron trifluoride, phosphorus pentoxide Toussaint; Hennion; Journal of the American Chemical Society; vol. 62; (1940); p. 1145 View in Reaxys Patent; du Pont de Nemours and Co.; US2390835; (1940) View in Reaxys With aluminium trichloride Huston; Hsieh; Journal of the American Chemical Society; vol. 58; (1936); p. 439 View in Reaxys Zukerwanik; Nasarowa; Zhurnal Obshchei Khimii; vol. 5; (1935); p. 767,769; Chem. Zentralbl.; vol. 108; nb. I; (1937); p. 579 View in Reaxys Zukerwanik; Zhurnal Obshchei Khimii; vol. 5; (1935); p. 117,120; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 2896 View in Reaxys With hydrogenchloride, aluminium trichloride Huston; Kaye; Journal of the American Chemical Society; vol. 64; (1942); p. 1576,1578 View in Reaxys With hydrogenchloride, zinc(II) chloride, T= 140 - 160 °C Zukerwanik; Zhurnal Obshchei Khimii; vol. 17; (1947); p. 1005,1006; ; (1948); p. 4541 View in Reaxys With copper(II) pyrophosphate, T= 300 - 425 °C Patent; Universal Oil Prod. Co.; US2412230; (1942) View in Reaxys

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With sulfuric acid, T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys With chlorosulfonic acid, T= 0 - 10 °C Rueggeberg; Cushing; Cook; Journal of the American Chemical Society; vol. 68; (1946); p. 192 View in Reaxys With BF3*H3PO4, T= 95 - 97 °C Toptschijew; Jegorowa; Wassilewa; Doklady Akademii Nauk SSSR; vol. 67; (1949); p. 475; ; (1949); p. 7915 View in Reaxys With hydrogen fluoride Simons; Archer; Journal of the American Chemical Society; vol. 62; (1940); p. 1623 View in Reaxys With iron(III) chloride Nasarowa; Zukerwanik; Zhurnal Obshchei Khimii; vol. 10; (1940); p. 1151,1152; Chem. Zentralbl.; vol. 112; nb. I; (1941); p. 3204 View in Reaxys With sulfuric acid, T= 70 - 100 °C Brun; Bulletin de la Societe Chimique de France; vol. <5> 12; (1945); p. 452 View in Reaxys Kirrmann; Graves; Bulletin de la Societe Chimique de France; vol. <5> 1; (1934); p. 1494,1496 View in Reaxys 6; 7; 8 :The benzene isopropylation reaction was carried out in a catalytic membrane reactor, with reactants (Betzene:IPA) mole ratio of 3:1, space velocity of 2.4 h-1, reaction temperature of 210 C. and a catalyst volume of 2.2 cc per 100 cc of reactor volume. The similar IPA conversion i.e. 99.53percent was observed with CMR as compared to conventional zeolite based fixed bed reactor process. The selectivity towards cumene was observed to be 100percent with CMR, as against 91.9percent with the conventional process. The total selectivity (cumene+DIPB) was observed to be 100percent with CMR, as against conventional process. The reactants (IPA:benzene) mole ratio used was 2.16 times lower than the conventional process. Catalyst volume/reactor volume ratio used was half i.e. 0.5 times lower as compared to conventional process. The results are presented in Table 1. [TABLE-US-00002] TABLE 1 Comparative Results on CMR with Conventional Reactor Vertical Vertical Vertical Con- CMR as in CMR as in CMR as in ventional Example Example Example Parameter reactor No. 6 No. 7 No. 8 Mole Ratio (IPA 1:6.5 1:3 1:3 1:2 Benzene) Catalyst volume 4.4 2.2 2.6 3.0 (cc) 100 cc Reactor Volume LHSV (h-1) 2.5 2.4 3.6 3.6 Reaction Temperature 210 210 210 220 ( C.) GC Product Distribution: Aliphatics 0.17 0.007 0.17 0.16 Benzene 78.40 80.2 70.99 72.57 Cumene 19.86 18.81 17.87 20.07 Toluene C8 Aromatics 0.30 0 0 0 n-Propylbenzene 0.07 0 0 0 C10 C11 Aromatics 0.09 0 0 0 DIPB 1.01 0 0 0 High boiling fractions 0.11 0 0 0 IPA Conversion (wt percent) 99.8 99.53 99.66 96.83 Cumene Selectivity (percent) 91.9 100 100 100 EXAMPLE 7 [0060] In an another example, the reaction was carried out in the catalytic membrane reactor at a space velocity of 3.6 h-1. The mole ratio (benzene:IPA) was 3:1, with a reaction temperature of 210 C. and the catalyst volume of 2.6 cc per 100 cc of reactor volume. The same conversion i.e. 99.6percent was observed with CMR as compared to conventional process. The cumene selectivity was observed to be 100percent as against 91.9percent with conventional process. The total (cumene+DIPB) selectivity was observed to be 100percent as compared to 96.9percent with conventional process. The reaction used almost half ratio of the catalyst volume/reactor volume ie. 2.6 as against 4.4 with conventional process, which helps to minimize byproduct formations, prolong the catalyst life and reduce reactant feed requirement. The results are tabulated in Table 1. EXAMPLE 8 [0061] The reaction was carried out at a mole ratio (benzene:IPA) of 2:1, using catalytic membrane reactor. The reaction temperature used at 220 C., with a space velocity of 3.6 h-1. The catalyst volume used is 3 cc per 100 cc of reactor volume. The comparable IPA conversion i.e. 98.83percent was observed as against 99.8percent with conventional process. The cumene and total (cumene+DIPB) selectivity was observed to be 100percent as against 91.9percent and 96.9percent respectively, with the conventional process. The reaction used 3.25 times lower reactant feed ratio as compared to conventional process. The catalyst/reactor volume ratio used was 1.46 times lower than the conventional process. The LHSV used was 1.44 times lower as against conventional process. The results are presented in Table 1.

With zeolite, T= 210 - 220 °C , Industry scale

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Patent; COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH; US2005/14982; (2005); (A1) English View in Reaxys 6; 7; 8 :Example 6 The benzene isopropylation reaction was carried out in a catalytic membrane reactor, with reactants (Benzene: IPA) mole ratio of 3: 1, space velocity of 2.4 H L, reaction temperature of 210°C and a catalyst volume of 2.2 cc per 100 cc of reactor volume. The similar IPA conversion i. e. 99.53 percent was observed with CMR as compared to conventional zeolite based fixed bed reactor process. The selectivity towards cumene was observed to be 100percent with CMR, as against 91.9percent with the conventional process. The total selectivity (cumene + DIPB) was observed to be 100percent with CMR, as against conventional process. The reactants (IPA : benzene) mole ratio used was 2.16 times lower than the conventional process. Catalyst volume/reactor volume ratio used was half i. e. 0.5 times lower as compared to conventional process. The results are presented in Table 1. Table 1. Comparative Results on CMR with Conventional Reactor Parameter Conventional Vertical Vertical Vertical reactor CMR as in CMR as in CMR as in Example Example Example No. 6 No. 7 No. 8 Mole Ratio (IPA: 1: 6.5 1: 3 1: 3 1: 2 Benzene) Catalyst volume 4.4 2.2 2.6 3.0 (cc) 100CC Reactor Volume LHSV (H-1) 2.5 2.4 3.6 3.6 Reaction Temperature 210 210 210 220 (°C) GC Product Distribution: Aliphatics 0.17 0.007 0.17 0.16 Benzene 78.40 80.2 70.99 72.57 Cumene 19. 86 18. 81 17. 87 20.07 Toluene CS AROMATICS 0.30 0 0 0 n-Propylbenzene 0.07 0 0 0 CIOCN AROMATICS 0.09 0 0 0 DIPB 1. 01 0 0 0 High boiling fractions 0.11 0 0 0 1PA Conversion. (wtpercent) 99.8 99.53 99.66 96.83 Cumene Selectivity (percent) 91.9 100 100 100 Example 7 In an another example, the reaction was carried out in the catalytic membrane reactor at a space velocity OF 3. 6H-1 The mole ratio (benzene: IPA) was 3: 1, with a reaction temperature of 210°C and the catalyst volume of 2.6 cc per 100 cc of reactor volume. The same conversion i. e. 99.6percent was observed with CMR as compared to conventional process. The cumene selectivity was observed to be 100percent as against 91.9percent with conventional process. The total (cumene +DIPB) selectivity was observed to be 100percent as compared to 96. 9percent with conventional process. The reaction used almost half ratio of the catalyst volume/reactor volume i. e. 2. 6 as against 4.4 with conventional process, which helps to minimize byproduct formations, prolong the catalyst life and reduce reactant feed requirement. The results are tabulated in Table 1. Example 8 The reaction was carried out at a mole ratio (benzene : IPA) of 2: 1, using catalytic membrane reactor. The reaction temperature used at 220°C, with a space velocity OF 3. 6 H- . The catalyst volume used is 3 cc per 100 cc of reactor volume. The comparable IPA conversion i. e 98.83percent was observed as against 99.8percent with conventional process. The cumene and total (cumene +DIPB) selectivity was observed to be 100percent as against 91.9percent and 96.9percent respectively, with the conventional process. The reaction used 3.25 times lower reactant feed ratio as compared to conventional process. The catalyst/reactor volume ratio used was 1.46 times lower than the conventional process. The LHSV used was 1.44 times lower as against conventional process. The results are presented in Table 1.

With catalytic membrane, T= 210 - 220 °C , Product distribution / selectivity Patent; COUNCIL OF SCIENTIFIC and INDUSTRIAL RESEARCH; WO2005/21469; (2005); (A1) English View in Reaxys 2 :Example 2; [0042] 30 grams of an MCM-49 catalyst was loaded into the fixed bed reactor described above. The reactor effluent was cooled to near ambient temperature and then the free water was removed in a decanter. A portion of the reactor effluent, after the free water was removed in the decanter, was circulated back to the 14reactor inlet by the centrifugal pump described in Example 1 to control the moisture content in the reactor.[0043] A feed comprised of 88.6 wtpercent benzene and 11.4 wtpercent isopropanol, equivalent to benzene to isopropanol molar ratio of 6: 1, was fed to the reactor at 134 grams per hour, giving an isopropanol WHSV of 0.5 hr"1. The reactor circulation was adjusted to give a moisture content of 10,300 ppm in the reactor. The inlet temperature was 2100C, the reactor pressure was maintained at 470 psig (3342 kPa), and the reaction took place in complete liquid phase. The isopropanol conversion was 100percent throughout the run. The Cumene/Isopropanol selectivity observed in this example was much higher than the Cumene/(Isopropanol+Propylene) selectivity observed in Example 1, due to reduced polyisopropylbenzenes production at higher benzene to (Isopropanol+Propylene) ratio in this example than in the previous example. As shown in Figure 2, the catalyst performance was stable throughout the run and no gradual or rapid aging as shown in the Examples of US Patent No. 6,512,153 was observed.

With MCM-49, T= 210 °C , p= 25066.7Torr , Product distribution / selectivity Patent; BADGER LICENSING, LLC; HWANG, Shyh-Yuan, Henry; JOHNSON, Dana, E.; PETERS, Joseph, C.; CHI, Chung-Ming; FALLON, Kevin, J.; DEMERS, Francis, A.; WO2010/42314; (2010); (A1) English View in Reaxys 1 :Example 1; [00059] A Raney Nickel catalyst 3110 provided by Grace Davison was tested as the hydrogenation catalyst. An acetone feed containing 35 wtpercent acetone and 65 wtpercent isopropanol was used. The hydrogenation reaction was carried out at (Acetone+Isopropanol) WHSV of 0.6 hr"1, hydrogen to (Acetone+Isopropanol) feed molar ratio of 6: 1 molar, a inlet temperature of 108cC, an effluent circulation to feed ratio of 1 1 : 1, and a reactor

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pressure of about 3,600 kPa. Two alkylation zones were used, each containing an MCM-22 catalyst provided by ExxonMobil. The alkylation reaction was carried out at (Acetone+Isopropanol) WHSV of 0.6 hr"1, benzene to (Acetone +Isopropanol) feed molar ratio of 3: 1, reactor circulation to feed ratio of 2: 1, reactor outlet pressure of 3,600 kPa, and inlet temperatures = 142°C and 195°C. Both the hydrogenation and alkylation zones mentioned above were operated in partial liquid phase and housed in the same reactor. Acetone and isopropanol conversions were both 100percent. Aromatics selectivity was 99percent.

With MCM-22, T= 142 - 195 °C , p= 27002.7Torr , Product distribution / selectivity Patent; BADGER LICENSING, LLC; HWANG, Shyh-yuan, Henry; JOHNSON, Dana, E.; PETERS, Joseph, C.; CHI, Chung-ming; FALLON, Kevin, J.; DEMERS, Francis, A.; WO2010/42315; (2010); (A2) English View in Reaxys 5 :EXAMPLE 5 A test is carried out in the same reactor and with the same catalyst as Example 1, at a temperature of 190°C and a pressure of 10 atm, feeding to the reactor 6.8 g/hour of a C6/C7 "heart cut" reformate mixture and 1.2 g/hour of isopropanol, with a benzene/alcohol molar ratio of 1.67 and a total WHSV of 1.6 hours"1. The C6/C7 mixture contains 37.6percent by weight of benzene and 5.2percent of toluene, the remaining percentage consisting of C6 and C7 paraffins. The organic effluent of the reaction collected between the 21st and 27th operating hour, after separation of the reaction water, is subjected to gaschromatograph analysis. The quantity of water separated from the effluent mixture of the reaction proves to be equal to 4.5 percent by weight with respect to the weight of the total effluent mixture . The data show a conversion of benzene of 43.7percent moles, a conversion of toluene of 31.8percent moles and isopropanol of 98.5percent moles. The selectivity to alkyl- aromatics with respect to the isopropanol is 83.6percent moles, with respect to the benzene and toluene >99.5percent moles, wherein alkyl-aromatics refer to the products isopropyl -benzene, di-isopropyl-benzene, poly- isopropyl-benzene, iso-propyl-toluene, di-isopropyl- toluene .

With catalyst prepared from β zeolite and bohemite, T= 190 °C , p= 7600.51Torr Patent; ENI S.P.A.; RIVETTI, Franco; MANTEGAZZA, Maria, Angela; BIANCHI, Daniele; WO2011/77242; (2011); (A1) English View in Reaxys 1 :EXAMPLE 1; An alkylation test of benzene is carried out with isopropyl alcohol, using the experimental device described below.The experimental device consists of tanks for the benzene and isopropyl alcohol reagents, feeding pumps of the reagents to the reactor, preheating units of the reagents, steel reactor situated inside an electric heating oven, regulation loop of the temperature inside the reactor, regulation loop of the pressure inside the reactor, cooling agent of the reactor effluent and collection system of the liquid and gaseous products.In particular, the reactor consists of a cylindrical steel tube with a mechanical sealing system and a diameter equal to about 2 cm.Along the greater axis of the reactor there is a thermometric cavity having a diameter equal to 1 mm containing in its interior a thermocouple free to slide along the greater axis of the reactor.A catalyst containing ZSM-12 zeolite prepared as described in Example 2 of U.S. 2003/0069459 is charged into the reactor.A quantity of inert material is charged above and below the catalytic bed to complete the bed.The benzene and isopropanol (IPA) reagents are fed to the reactor-preheated and premixed in an appropriate mixer-with up flow.The reaction products are analyzed via gas chromatography. The reaction conditions under which the test is carried out are the following:Reaction temperature: 190° C. Reaction pressure: 8 bar WHSV: 4 hours-1 [Benzene] [IPA] in the feeding: 3,25 moles/moles These conditions ensure that the reagents are in gaseous phase and the products partially in liquid phase.The attribution of the physical state of the reagent mixture is effected by both comparison with the phase diagrams existing for the components and the mixtures in question, and also by calculation, adopting the RKS state equation (Soave. G. Chem. Eng. Sci 27, 1197, (1972)). The interaction parameters for this equation are obtained from the regression of the experimental data of literature relating to the liquid-vapour equilibria and the reciprocal solubilities of the hydrocarbon-water mixtures (C. C. Li, J. J. McKetta Jul. Chem. Eng. Data 8 271-275 (1963) and C. Tsonopoulos, G. M. Wilson ALCHE Journel 29,990-999, (1983)).The reaction system to which the above equation is applied is assimilated, with respect to the compositions, to the system[benzene] [propylene]=3,25 and [benzene]/[water]=3,25 The concentration of total water present in the system with the complete conversion of the isopropyl alcohol reagent is equal to about 5percent.FIG. 1 indicates the trend of the molar selectivity [Ar]/[IPA] (Cumene+Diisopropylbenzenes+Triisopropylbenzenes with respect to the total of IPA converted) in relation to the productivity of the catalyst expressed in Kg cumene/Kg ZSM-12 zeolite and the trend of the molar selectivity [Cum]/[IPA] (Cumene with respect to the total of IPA converted) in relation to the productivity of the catalyst in Kg cumene/Kg ZSM-12 zeolite.For the whole duration of the test (about 620 hours) no signs of deactivation of the catalyst were observed, such as, for example, a drop in the conversion of the alcohol (not shown in FIG. 1 but quantitative for the whole duration of the test) or an increase in the polyalkylated fraction.The selectivities during the whole test, in fact, remained unaltered with values equal to about 82percent for the selectivity [Cum]/[IPA] and about 98,8percent for the selectivity [Ar]/[IPA].

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With ZSM-12 zeolite, T= 190 °C , p= 6000.6Torr , Product distribution / selectivity Patent; POLIMERI EUROPA S.P.A.; US2011/218366; (2011); (A1) English View in Reaxys 3 :Example 3; Benzene and isopropanol are fed to the tower operating at 200 psig. Approximately 0.25 lb (or 112 g) of Lummus Technology High Performance Beta CP759A catalyst is used, where the catalyst is loaded into ten 6 inch height by 1 inch diameter bales, each containing 11 g of catalyst. Approximately 24 inches of saddles is located above the catalyst, and approximately 78 inches of saddles located below the catalyst bed. Benzene feed is 99.9percent pure, and isopropanol feed is 97percent pure. Feed flow rates are 0.5 lb/hr for benzene and 0.7 lb/hr for isopropanol. Reflux is set at 4.5 lb/hr. The overhead flow rate is 0.5 lb/hr and the bottoms flow rate is 0.5 lb/hr, where the net mass balance includes some light gases being vented.Analysis of the composition of the overhead stream reveals 76percent benzene, 21percent isopropanol, about 1percent diisopropyl ether, with the remainder including other light hydrocarbons, each by weight. The bottom stream contains 17percent benzene, 64percent cumene (desired product) and 19percent diisopropylbenzene (poly-alkylated by-product), plus heavies, each by weight. Overall conversion of benzene to cumene is 44percent (mole).

With Lummus Technology High Performance Beta CP759A, p= 11103.3Torr , Reflux Patent; Catalytic Distillation Technologies; US8143466; (2012); (B2) English View in Reaxys 14.B :B. Isopropylation of BenzeneAfter the same material as used in Example 14A was placed in a fluidized reactor, it was activated at 550° C. After cooling the reacting temperature of the reactor to 210° C., the mixture of benzene and isopropyl alcohol (mol ratio of 6.5:1) was injected through a syringe pump at a fluid velocity of 0.005 mL/m.

Here, the velocity of the fluid of nitrogen gas was maintained at 20 mL/m, and the samples were analyzed periodically by using online gaschromatography. The distribution of the product is indicated in Table 2.

With MFI zeolite (ZSM-5), T= 210 °C , Product distribution / selectivity Patent; KOREA ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY; US2012/165558; (2012); (A1) English View in Reaxys 16.49 With zeolite H-mordenite, T= 210 °C , p= 760.051Torr , Gas phase %Chromat.

Vyawahare, Yogesh K.; Chumbhale, Vilas R.; Aswar, Anand S.; Revue Roumaine de Chimie; vol. 57; nb. 2; (2012); p. 107 - 113 View in Reaxys General procedure: Alkylation of benzene with these alcohols was carried out in ariser simulator under atmospheric pressure. This reactor is novelbench-scale equipment with an internal recycle unit invented byde Lasa [46]. Catalytic experiments were performed at a catalyst/reactant ratio of 3.75 (weight of catalyst = 0.60 g) for differentresidence times of 3, 5, 7, 10, 13, 15 and 20 s and at reaction temperaturesof 200, 250, 300, 350 and 400 C. Analytical grade (99percentpurity) benzene, isopropanol, ethanol and methanol were obtainedfrom Sigma–Aldrich. These chemicals were used as received. Thefeed molar ratio of benzene to alcohol is 1:1. A four-port valveenables the connection and isolation of the 45 cm3 reactor andthe vacuum box, and a six-port valve allows for the collection ofa sample of reaction products in a sampling loop. The productswere analyzed in an Agilent model 6890N gas chromatograph witha flame ionization detector and a capillary column INNOWAX, 60-mcross-linked methyl silicone with an internal diameter of 0.32 mm.During the course of the investigation, a number of runs wererepeated to check for reproducibility in the experiment results,which were found to be excellent. Typical errors were in the rangeof ±2percent.

With ZSM-5, T= 400 °C Odedairo; Al-Khattaf; Catalysis Today; vol. 204; (2013); p. 73 - 84 View in Reaxys 1 : Example 1 - Alkylation with Purchased Isopropanol [0054] Referring to Figure 1 , an alkylation test of benzene with purchased isopropanol was carried out in a fixed bed reactor 1 1 , made from a inch (19 mm) diameter Schedule 40 Stainless Steel 316 pipe with a total length of 34 inches (864 mm). A multi-point thermocouple probe (not shown) was placed along the center axis of the reactor 1 1 so that the temperature at various points in the reactor could be monitored. A positive displacement pump (not shown) was used to supply a mixture of benzene and isopropanol from a storage tank by way of line 12 to a heat exchanger 13 and then to the reactor 1 1. The flow rates of the benzene/isopropanol mixture were set by pump settings and monitored by electronic weight scales. The reactor operating conditions were controlled and monitored by

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an automatic control system. The effluent from the reactor 1 1 was fed by line 14 to a cooler 15, where the effluent was cooled to near ambient temperature before being fed to a decanter 16. Free water was removed from the effluent in the decanter 16 and a portion of the dewatered reactor effluent was circulated through line 17 back to the reactor 1 1 by a centrifugal pump to control the temperature rise and the moisture content in the reactor 1 1. The remainder of the dewatered reactor effluent was removed from the decanter 16 via line 18 for recovery of the cumene.

[0055] The feedstock and reactor effluent were analyzed by two Hewlett Packard 5890 Series II Gas Chromatographs, one equipped with a Chrompack CP-Wax 52CB column having an inside diameter of 0.25 mm, film thickness of 0.5 μηι, and length of 60 meters, and the other one equipped with an Agilent DB-1 column having an inside diameter of 0.25 mm, film thickness of 0.5 μηι, and length of 100 meters. [0056] In the test, 60 grams of an MCM-22 family catalyst was loaded into the fixed bed reactor and dried with benzene at 150°C for four days. A feed comprised of 79.6 wtpercent benzene and 20.4 wtpercent isopropanol purchased from Sigma-Aldrich, equivalent to a benzene to isopropanol molar ratio of 3: 1, was fed to the reactor at 150 grams per hour, giving an isopropanol WHSV of 0.5 hr"1. No nitrogen compounds were detected in this purchased isopropanol. The reactor circulation was adjusted to give a moisture content of about 1.0 wtpercent in the reactor effluent. The inlet temperature was 210°C, the reactor pressure was maintained at about 4,700 kPa, and the reaction took place in liquid phase. Because the isopropanol conversion remained 100percent throughout this example, the catalyst stability was also monitored by percent temperature rise at 22percent catalyst loading (PTR22) which is defined below: PTR22 = [ T22 - Tin,et ] / [ Toutlet " Tinlet ] X 00percent where Tjniet and Toutiet are the reactor temperature measured at the inlet and the outlet of the catalyst bed, respectively, and T22 is the temperature measured at 22percent of the length from the inlet of the catalyst bed. Because the isopropanol alkylation is an exothermic reaction, the temperature of the reaction mixture goes up in the reactor as the conversion increases and reaches the final temperature when the reaction is completed. The percentage temperature rise PTR22 measured at the first 22percent of the catalyst loading gives an indication of the conversion in the first 22percent of the catalyst bed. When the catalyst is stable, the conversion in the first 22percent of the catalyst bed is stable and PTR22 remains essentially constant. When the catalyst deactivates, the conversion in the first 22percent of the catalyst bed goes down gradually (while the remainder of the catalyst bed continues to bring the reaction to completion) and the PTR22 goes down. A stable PTR22 therefore indicates that the catalyst bed is stable while a decreasing PTR22 indicates that the catalyst bed is deactivating. [0057] For 68 days with Sigma-Aldrich isopropanol feed, the PTR22 was very stable with a nearly immeasurable average decline rate of less than 0.05percent per day. The isopropanol conversion remained 100percent for the same period of time. These indicate that the MCM-22 family catalyst tested had very high activity and was very stable with the purchased SigmaAldrich isopropanol feed With MCM-22 family catalyst, T= 150 - 210 °C , p= 35253.5Torr , Time, Reagent/catalyst Patent; BADGER LICENSING LLC; BIRKHOFF, Ronald; HWANG, Shyh-Yuan H.; WO2014/8268; (2014); (A1) English View in Reaxys 1 : Example 1 - Alkylation with Purchased Isopropanol [0050] An alkylation test of benzene with isopropanol was carried out in a fixed bed reactor, made from a inch (19 mm) diameter Schedule 40 Stainless Steel 316 pipe with a total length of 34 inches (864 mm). A multi-point thermocouple probe was placed along the center axis of the reactor so that the temperature at various points in the reactor could be be monitored. A storage tank was used for the benzene/isopropanol mixture and a positive displacement pump was used for feeding the benzene/isopropanol mixture into the reactor. The flow rates of the benzene/isopropanol mixture were set by pump settings and monitored by electronic weight scales. The reactor operating conditions were controlled and monitored by an automatic control system. The reactor effluent was cooled to near ambient temperature and then the free water was removed in a decanter. A portion of the reactor effluent, after the free water was removed in the decanter, was circulated back to the reactor inlet by a centrifugal pump to control the temperature rise and the moisture content in the reactor. The feedstock and reactor effluent were analyzed by two Hewlett Packard 5890 Series II Gas Chromatographs, one equipped with a Chrompack CP- Wax 52CB column having an inside diameter of 0.25 mm, film thickness of 0.5 μιη, and length of 60 meters, and the other one equipped with an Agilent DB-1 column having an inside diameter of 0.25 mm, film thickness of 0.5 μιη, and length of 100 meters.

[0051] 30 grams of an MCM-22 family catalyst was loaded into the fixed bed reactor and dried with benzene at 150°C for four days. A feed comprised of 79.6 wt benzene and 20.4 wt isopropanol purchased from Sigma-Aldrich, equivalent to a benzene to isopropanol molar ratio of 3 : 1 , was fed to the reactor at about 75 grams per hour, giving an isopropanol WHSV of 0.5 hr 1. No nitrogen compounds were detected in this purchased isopropanol. The reactor circulation was adjusted to give a moisture content of about 1.0 wt in the reactor effluent. The inlet temperature was 210°C, the reactor pressure was maintained at about 4,700 kPa, and the reaction took place in liquid phase. The isopropanol conversion was 100percent throughout the run. Because the isopropanol conversion was always at or very close to 100percent throughout this example and Examples 3-6, the catalyst stability was also monitored by percent temperature rise at 26percent catalyst loading (PTR26) which is defined below: PTR26 = [ T26 - Tinlet ] / [ Toutlet

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- Tinlet ] x 100percent where Tinlet and Toutiet are the reactor temperatures measured at the inlet and the outlet of the catalyst bed, respectively. T26 is the temperature measured at 26percent of the length from the inlet of the catalyst bed. Because the isopropanol alkylation is an exothermic reaction, the temperature of the reaction mixture goes up in the reactor as the conversion increases and reaches the final temperature when the reaction is completed. The percentage temperature rise PTR26 measured at the first 26percent of the catalyst loading gives an indication of the conversion in the first 26percent of the catalyst bed. When the catalyst is stable, the conversion in the first 26percent of the catalyst bed is stable and PTR FontWeight="Bold" FontSize="10" remains essentially constant. When the catalyst deactivates, the conversion in the first 26percent of the catalyst bed goes down gradually (while the remainder of the catalyst bed continues to bring the reaction to completion) and the PTR26 goes down. A stable PTR FontWeight="Bold" FontSize="10" therefore

indicates that the catalyst bed is stable while a decreasing PTR26 indicates that the catalyst bed is

deactivating. [0052] For 54 days, from 5 to 59 days on-stream with isopropanol feed purchased from Sigma-Aldrich, the PTR FontWeight="Bold" FontSize="10" remained at 100percent. The isopropanol conversion remained at 100percent. This indicates that the MCM-22 family catalyst tested had very high activity and was very stable with the purchased isopropanol feed.

With MCM-22 family catalyst, T= 210 °C , p= 35.2535Torr , Reagent/catalyst Patent; BADGER LICENSING LLC; BIRKHOFF, Ronald; HWANG, Shyh-Yuan H.; WO2014/18515; (2014); (A1) English View in Reaxys

HO

Rx-ID: 846617 View in Reaxys 35/481 Yield 85 %

Conditions & References With sulfuric acid, Time= 3h, T= 80 °C Lipovich, V. G.; Laperdina, T. G.; Latysheva, L. E.; Kalabin, G. A.; J. Gen. Chem. USSR (Engl. Transl.); vol. 52; nb. 2; (1982); p. 284 - 287,246 - 249 View in Reaxys With sulfuric acid, T= 65 °C Ipatieff; Pines; Schmerling; Journal of Organic Chemistry; vol. 5; (1940); p. 253,259 View in Reaxys With boron trifluoride, phosphorus pentoxide Toussaint; Hennion; Journal of the American Chemical Society; vol. 62; (1940); p. 1145 View in Reaxys Patent; du Pont de Nemours and Co.; US2390835; (1940) View in Reaxys With BF3*H3PO4, T= 95 - 97 °C Toptschijew; Jegorowa; Wassilewa; Doklady Akademii Nauk SSSR; vol. 67; (1949); p. 475; ; (1949); p. 7915 View in Reaxys With sulfuric acid, T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys With silica-alumina, T= 330 °C Dolgow; Tscherkasow; Zhurnal Obshchei Khimii; vol. 24; (1954); p. 825; engl. Ausg. S. 825 View in Reaxys With silica-alumina, T= 250 °C Turowa-Poljak et al.; Zhurnal Obshchei Khimii; vol. 29; (1959); p. 3243; engl. Ausg. S. 3207 View in Reaxys

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With boron trifluoride, T= 60 °C McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 470 View in Reaxys

S O

O O

Rx-ID: 10546775 View in Reaxys 36/481 Yield 90 %

Conditions & References With sodium tetrahydroborate, NiCl2((PPh3)P)2, tri-cyclo-hexyl-phosphine in tetrahydrofuran, Time= 14h, T= 20 °C Kogan, Vladimir; Tetrahedron Letters; vol. 47; nb. 43; (2006); p. 7515 - 7518 View in Reaxys

Rx-ID: 23409495 View in Reaxys 37/481 Yield

Conditions & References I.IB :Illustrative Embodiments 1. Illustrative Embodiment I: I (A) Preparation OF HYDROCRACKING Catalyst PdMordenite Catalyst A mixture of 1500 grams of sodium mordenite, (having the following properties: a surface area of 430 square meters per gram; an average crystallite size of around 1 micron; a cyclohexane adsorption uptake of 7.6 cc/g; and a molar silica to alumina ratio of 11. 1), 9000 grams of ammonium nitrate and 15 liters of 1.5 M nitric acid was heated to 50 °C. and stirred for five hours. The solid material was filtered off and washed with 25 liters of deionized water. This treatment of the Mordenite with ammonium nitrate in nitric acid was repeated twice with fresh ammonium nitrate and nitric acid each time. After each treatment the solid material was filtered off and washed with water and dried overnight at 120 °C. Palladium was added to the zeolite to a level of 0.35 percent by weight by treatment with an aqueous solution containing Tetraamine palladium nitrate and an excess of ammonium nitrate prepared by dissolving 6.55 grams of tetramine palladium nitrate in 308 grams of deionized water and adding to this solution 4.92 grams of ammonium nitrate. The palladium solution was then co-mulled with 1083 grams of DEALUMINATED mordenite having an LOI (loss of iginition at 750 °C for 2 hours) of 10.6percent. The palladium- containing mordenite was uniformly mixed and then 338 grams of PSEUDOBOEHMITE alumina (Catapal B which is commercially available from Vista Chemical Company) having an LOI of 28.4percent was added and allowed to mix. The mixture was extruded and the 1.6 mm extrudates were dried in air for 16 hours at 125 °C, and then calcined in flowing air at 500°C. for two hours. The catalyst was crushed and sized to 6-20 mesh particles and then reduced using the procedure as described in IIA below. IB. HYDROCRACKING of Cumene Dimer Using Pd on H-Mordenite Catalyst The bottom stream from a catalytic distillation column, for the catalytic distillation of cumyl alcohol to produce cumene, was distilled to yield a cumene dimer rich mixture that was diluted with cumene and fed into a fixed bed hydrogenation loaded with the acidic palladium on H-Mordenite catalyst as described in I (A) for hydrocracking under the condition as provided in TABLE 1 below. The results are shown in TABLE 2 below. Table 1 Feedrate 33.5 g/hr Reaction Temperature 220°C Pressure 10 bar Hydrogen Flowrate 4 L/Hr Catalyst Weight 33.5 g (before reduction) Table 2 Fixed Bed Cumene Dimers To Cumene Results With Palladium On H-Mordenite Catalyst At 220°C Component Cumene dimers in cumene Fixed Bed Product (FEED) 2,3-Dimethyl-2, 3- 1. 94 0.06 diphenylbutane, (wtpercent) 2methyl-2,4-diphenylpentane, 1. 03 0. 02 (wtpercent) Cumene, (wtpercent) 96. 75 99. 82 Isopropylcyclohexane, (wtpercent) 0.08 0.08 Alpha-Methyl styrene, (wtpercent) 0. 20 0. 02 With hydrogen, palladium on H-mordenite, T= 220 °C , p= 7500.75Torr , Gas phase, Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5351; (2005); (A2) English View in Reaxys III.A :The bottom stream from II (B) (I) above was distilled to yield a cumene dimer rich mixture that was diluted with cumene and fed into a fixed bed hydrogenation loaded with the T-366 catalyst as described in II (A) (i) above for hydrocracking under the condition as provided in TABLE 4 below. The results are shown in TABLE 5 below.

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With hydrogen, hydrogenated copper on silica (T-366), T= 260 °C , p= 7500.75Torr , Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5402; (2005); (A2) English View in Reaxys 3.B :The bottom stream from II (B) (i) above was distilled to yield a cumene dimer rich mixture that was diluted with cumene and fed into a fixed bed hydrogenation loaded with the acidic palladium on H-Mordenite catalyst as described in II (B) (i) above for hydrocracking under the condition as provided in TABLE 6 below. The results are shown in TABLE 7 below.

With hydrogen, palladium on H-Mordenite, T= 220 °C , p= 7500.75Torr , Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5402; (2005); (A2) English View in Reaxys III.IIIB :III. Comparative Example IIIA. Preparation OF HYDROGENATION CATALYST Palladium on Carbon Pressed granules of 0.5 wt. percent of palladium on carbon, available from the Calsicat division of Mallinckrodt Incorporated was mixed with silicon carbide and reduced according the same procedure as described in IIA above. IIIB. HYDROCRACKING OF CUMENE Dimers with Palladium on Carbon Catalyst The bottom stream from a catalytic distillation column, for the catalytic distillation of cumyl alcohol to produce cumene, was distilled to yield a cumene dimer rich mixture that was diluted with cumene and fed into a fixed bed hydrogenation loaded with the acidic palladium on carbon catalyst as described in III (A) for hydrocracking under the condition as provided in TABLE 5 below. The results are shown in TABLE 6 below. Table 5 Feedrate 33.5 g/hr Reaction Temperature 220 °C Pressure 10 bar Hydrogen Flowrate 4 L/Hr Catalyst Weight 33.5 g (before reduction) Table 6 Fixed Bed Cumene Dimers To Cumene Results With Palladium on Carbon Catalyst at 220°C Component Cumene dimers in cumene Fixed Bed Product (FEED) 2,3-Dimethyl-2, 3- 1. 94 0.10 diphenylbutane, (wtpercent) 2-methyl-2,4-diphenylpentane, 1. 03 0. 10 (wtpercent) Cumene, (wtpercent) 96. 75 99. 60 Isopropylcyclohexane, (wtpercent) 0. 08 0.16 Alp11a-Methyl styrene, (wtpercent) 0. 20 0. 04 With hydrogen, 5 Pd/C, T= 220 °C , p= 7500.75Torr , Gas phase, Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5351; (2005); (A2) English View in Reaxys II.IIB :II. Illustrative Embodiment II IIA Preparation of Hydrocracking Catalyst T-366 Catalyst A commercially available copper on silica catalyst, T-366, available from Sud Chemie, having 54 wt. percent of Cu on silica extruded into 3.2 mm extrudate, is further processed using the following procedure for the catalytic cracking experiments. Five grams of Sud Chemie T-366 copper on silica catalyst (3mm tablets) was crushed and sized into 6-20 mesh particles.

The catalyst was mixed with 45 grams of 80 mesh silicon carbide and centered inside a 69 cm long stainless steel reactor tube between beds of 20 mesh SiC and glass wool. The reactor tube had an internal diameter of 1. 5CM. The catalyst was slowly reduced by heating the catalyst particles at a rate of 3°C per minute from 20°C to 180°C while flowing 0.05 wt. percent hydrogen in nitrogen at a rate of 10 L/Hr. The catalyst was allowed to reduce at 180°C for 2 hours and then the hydrogen content in the nitrogen was doubled every 2 hours until the gas was 3.2 wt. percent hydrogen in nitrogen. The catalyst was reduced for a final two-hour period and then cooled while maintaining gas flow. After cooling, the reactor was capped without allowing any air to enter and the gas flow was stopped. The reactor was opened in a nitrogen filled glove box and the catalyst and silicon carbide were separated by screen sieve. IIB. HYDROCRACKING of Cumene Dimers Using T-366 Copper on Silica Catalyst The bottom stream from a catalytic distillation column, for the catalytic distillation of cumyl alcohol to produce cumene, was distilled to yield a cumene dimer rich mixture that was diluted with cumene and fed into a fixed bed hydrogenation loaded with the T-366 catalyst as described in II (A) for hydrocracking under the condition as provided in TABLE 3 below. The results are shown in TABLE 4 below. Table 3 Feedrate 33.5 g/hr Reaction Temperature 260°C Pressure 10 bar Hydrogen Flowrate 4 L/Hr Catalyst Weight 33. 5 g (before reduction) Table 4 Fixed Bed Cumene Dimer To Cumene Results With T-366 Catalyst At 260°C Component Cumene dimers in Fixed Bed Product cumene (FEED) 2,3-Dimethyl-2, 31. 94 0.05 diphenylbutane, (wtpercent) 2-methyl-2,4-diphenylpentane, 1. 03 0. 09 (wtpercent) Cumene, (wtpercent) 96. 75 99. 54 Isopropylcyclohexane, (wtpercent) 0. 08 0.18 alpha-Methyl styrene, (wtpercent) 0. 20 0. 09 With hydrogen, T= 260 °C , p= 7500.75Torr , Gas phase, Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5351; (2005); (A2) English View in Reaxys

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O

O OH

HO

HO

O

OH

Rx-ID: 25047436 View in Reaxys 38/481 Yield

Conditions & References 1 : EXAMPLE 1 EXAMPLE 1 Into a 300-ml stainless steel autoclave were charged 45.6 g (0.30 mole) of methyl 4-hydroxybenzoate, 0.23 g of 5percent palladium-carbon catalyst, and 100 ml of propyl alcohol.

After the air within the autoclave was displaced with nitrogen gas, the reaction mixture was allowed to absorb 0.60 mole of hydrogen at a temperature of 180° C. and a gauge pressure of 20 kg/cm2.

After the reaction mixture was cooled and filtered to remove the catalyst therefrom, the solvent was distilled off to obtain 47.0 g of a reaction mass.

All of the aforesaid reaction mass, 110.0 g of phenol, and 10 ml of 36percent hydrochloric acid were charged into a 300-ml reaction flask, and reacted at 60° C. for 5 hours.

After completion of the reaction, the reaction mixture was poured into 300 ml of benzene, followed by stirring at room temperature for 3 hours.

The precipitate so formed was collected by filtration, washed and then dried to obtain 65.0 g of white crystals.

Next, all of the aforesaid white crystals, 8.2 g of sodium hydroxide, 1.2 g of 5percent palladium-carbon catalyst, 66.0 g of α-methylstyrene, and 300 ml of water were charged into a 500-ml stainless steel autoclave.

After the air within the autoclave was displaced with nitrogen gas, the reaction mixture was heated at 250° C. for 4 hours.

After completion of the reaction, the reaction mixture was cooled.

Since some crystals separated out, 100.0 g of a 20percent aqueous solution of sodium hydroxide was added to the reaction mixture so as to dissolve the crystals.

Thereafter, the reaction mixture was filtered to remove the catalyst therefrom.

After the filtrate was extracted with 300 ml of benzene to recover α-methylstyrene and cumene, diluted hydroxhloric acid was added thereto so as to precipitate 4'-hydroxybiphenyl-4-carboxylic acid.

The crystals so formed were collected by filtration, washed with water, and then dried to obtain 42.4 g of 4'-hydroxybiphenyl-4-carboxylic acid.

Liquid-chromatographic analysis revealed that this product had a purity of 91.2percent, and its yield based on the amount of methyl p-hydroxybenzoate used was 60.2percent.

With hydrogenchloride, propan-1-ol, sodium hydroxide, hydrogen, palladium-carbon catalyst in water, benzene Patent; Mitsui Toatsu Chemicals, Incorporated; US4755617; (1988); (A1) English View in Reaxys OH

Cl

F

F

F

HO

B

F F F

Rx-ID: 33693655 View in Reaxys 39/481 Yield

Conditions & References

72 %, 12 With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride, sodium carbonate in 1,4-dioxane, water, Time= %Chromat. 2h, T= 120 °C , Inert atmosphere, Suzuki-Miyaura coupling Yamamoto, Tetsuya; Yamakawa, Tetsu; Organic Letters; vol. 14; nb. 13; (2012); p. 3454 - 3457 View in Reaxys HO

Rx-ID: 40074637 View in Reaxys 40/481 Yield 70 %, 14 %

Conditions & References With hydrogen in water, Time= 2h, T= 270 °C , p= 13501.4Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017

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View in Reaxys

O

Rx-ID: 40074643 View in Reaxys 41/481 Yield 70 %, 5 %

Conditions & References With hydrogen in water, Time= 3h, T= 270 °C , p= 16501.7Torr Huang, Yao-Bing; Yan, Long; Chen, Meng-Yuan; Guo, Qing-Xiang; Fu, Yao; Green Chemistry; vol. 17; nb. 5; (2015); p. 3010 - 3017 View in Reaxys

Rx-ID: 4756381 View in Reaxys 42/481 Yield

Conditions & References With aluminium trichloride, cobalt(II) chloride, Time= 0.5h, T= 60 °C , other catalysts: AlCl3-NiCl2, AlCl3, AlCl3-NaCl, AlCl3-KCl, AlCl3-CuCl2, various ratios of catalyst components, Product distribution Polubentseva; Duganova; Mikhailenko; Russian Journal of General Chemistry; vol. 66; nb. 4; (1996); p. 614 - 618 View in Reaxys With [Ir(μ-acac-O,O,C3)(acac-O,O)(acac-C3)]2 in water, Time= 0.333333h, T= 180 °C , p= 14701.5Torr , anti-Markovnikov addition Matsumoto, Takaya; Taube, Douglas J.; Periana, Roy A.; Taube, Henry; Yoshida, Hajime; Journal of the American Chemical Society; vol. 122; nb. 30; (2000); p. 7414 - 7415 View in Reaxys With [Ir(μ-acac-O,O,C3)(acac-O,O)(acac-C3)]2, Time= 0.5h, T= 180 °C , p= 7200.72Torr , Product distribution, Further Variations: Catalysts Periana, Roy A.; Liu, Xiang Y.; Bhalla, Gaurav; Chemical Communications; nb. 24; (2002); p. 3000 - 3001 View in Reaxys 3 :The Al2O3-bound MCM-22 catalyst, prepared in Comparative Example 1 as {fraction (1/16)}? extrudates, was crushed and sized to 30-40 mesh. 0.25 g of this catalyst was diluted with sand to 3 cc and charged to an isothermal, down-flow, fixed-bed, ?' o.d. reactor. The catalyst was dried at 125° C. and 1 atm with 100 cc/min of flowing N2 for 2 hours. N2 was turned off. Benzene was fed into the reactor at 60 cc/hr for 1 hr and then reduced to desired WHSV (based on total catalyst weight) while the reactor temperature and pressure were increased to 120° C. and 300 psig, respectively. After reaching 120° C. and 300 psig, propylene (Matheson polymer grade) was introduced from a syringe pump at 3 benzene/propylene molar ratio and the temperature was increased to 130° C. After lining out, liquid products were collected in a cold-trap and analyzed off-line with a Varian 3700 GC. Off-gas was analyzed with an online Carle refinery gas analyzer. Propylene conversion was determined by measuring unreacted propylene relative to feed propylene. Total material balances were 100+-2percent. The experiment was conducted at 130° C. average reactor temperature, 300 psig, 10-60 propylene WHSV, and 3 benzene/propylene molar ratio.

With Al2O3-bound MCM-22 catalyst, T= 130 °C , p= 16274.9Torr , Conversion of starting material Patent; ExxonMobil Oil Corporation; US6919491; (2005); (B1) English View in Reaxys 3 :The binder-free MCM-22 catalyst, prepared in Example 2 as {fraction (1/16)}? extrudates, was crushed and sized to 30-40 mesh. 0.1 g of this catalyst was diluted with sand to 3 cc and charged to an isothermal, down-flow, fixedbed, ?' o.d. reactor. The catalyst was tested with the same procedure described in Comparative Example 3. The experiment was conducted at 130° C. average reactor temperature, 300 psig, 15-100 propylene WHSV, and 3 benzene/propylene molar ratio. Catalyst performance is shown below. Comparison of Catalyst Performance for Liquid Phase Cumene Synthesis FIG. 3 compares catalyst activity for liquid phase cumene synthesis at 130° C. average reactor temperature, 300 psig, 3 benzene/propylene molar ratio with propylene WHSV adjusted between 10 and 100

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h-1. To achieve a constant propylene conversion (e.g., 96percent) at 130° C. average reactor temperature, the binder-free MCM-22 could be operated at 100 propylene WHSV when compared to 40 propylene WHSV with the Al2O3bound catalyst. The catalyst performances for liquid phase cumene synthesis are further compared in Table 3. When operated at 130° C. and 40 propylene WHSV, the binder-free MCM-22 offered 3percent higher propylene conversion than the Al2O3-bound MCM-22. To achieve 96percent propylene conversion at 130deg C., the binder-free MCM-22 can be operated at 100 propylene WHSV vs. 40 propylene WHSV with the Al2O3-bound catalyst. Although cumene,selectivity was somewhat lower with the binder-free MCM-22, the overall alkylation selectivity was higher due to its lower propylene oligomers make. Propylene oligomers are rejected as by-products which reduce net propylene conversion to cumene. The di- and triisopropylbenzene can be converted to cumene in the transalkylator by reacting with benzene.

With MCM-22 Catalyst binder-free, T= 130 °C , p= 16274.9Torr , Conversion of starting material Patent; ExxonMobil Oil Corporation; US6919491; (2005); (B1) English View in Reaxys With C21H26IrNO4, T= 180 °C , Autoclave, Inert atmosphere Bhalla, Gaurav; Bischof, Steven M.; Ganesh, Somesh K.; Liu, Xiang Yang; Jones; Borzenko, Andrey; Tenn III, William J.; Ess, Daniel H.; Hashiguchi, Brian G.; Lokare, Kapil S.; Leung, Chin Hin; Oxgaard, Jonas; Goddard III, William A.; Periana, Roy A.; Green Chemistry; vol. 13; nb. 1; (2011); p. 69 - 81 View in Reaxys With C22H25N2OPt(1+)*C32H12BF24 (1-), Time= 16h, T= 100 °C , p= 5625.56Torr , Inert atmosphere, Catalytic behavior, Kinetics, Reagent/catalyst McKeown, Bradley A.; Gonzalez, Hector Emanuel; Michaelos, Thoe; Gunnoe, T. Brent; Cundari, Thomas R.; Crabtree, Robert H.; Sabat, Michal; Organometallics; vol. 32; nb. 14; (2013); p. 3903 - 3913 View in Reaxys With [(tbpy)2Pt(Ph)(thf)][B(3,5-(CF3)2C6H3)4], Time= 16h, T= 100 °C , p= 6000.6Torr , Inert atmosphere, Catalytic behavior, Time, Reagent/catalyst McKeown, Bradley A.; Prince, Bruce M.; Ramiro, Zoraida; Gunnoe, T. Brent; Cundari, Thomas R.; ACS Catalysis; vol. 4; nb. 5; (2014); p. 1607 - 1615 View in Reaxys With (pypyr)PtPh(SMe2), Time= 120h, T= 100 °C , Inert atmosphere, Glovebox, Sealed tube, Catalytic behavior, Reagent/catalyst Clement, Marie L.; Grice, Kyle A.; Luedtke, Avery T.; Kaminsky, Werner; Goldberg, Karen I.; Chemistry - A European Journal; vol. 20; nb. 52; (2014); p. 17287 - 17291 View in Reaxys

(-)(R)-2-phenyl-propionic acid ethyl ester

H HO

Rx-ID: 7684550 View in Reaxys 43/481 Yield

Conditions & References With copper oxide-chromium oxide, hydrogen, T= 250 °C , p= 110326 - 147102Torr Bowden; Adkins; Journal of the American Chemical Society; vol. 56; (1934); p. 689 View in Reaxys

(v2)

Zn

Rx-ID: 28596356 View in Reaxys 44/481

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Yield

Conditions & References

58 %Chromat.

With iron (III) acetylacetonate, ethylene dibromide in tetrahydrofuran, Time= 0.5h, T= 50 °C , Inert atmosphere Cahiez, Gerard; Foulgoc, Laura; Moyeux, Alban; Angewandte Chemie, International Edition; vol. 48; nb. 16; (2009); p. 2969 - 2972 View in Reaxys

O

Rx-ID: 28687565 View in Reaxys 45/481 Yield

Conditions & References 7 :Example 7; The reaction and analysis were performed in the same manner as Example 6 except for using MCM-22 zeolite (obtainable by compression molding a catalyst prepared according to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001, P225, at 20 MPa followed by classification into 250 to 500 μ) in place of β zeolite. As a result, the acetone conversion rate was 95.6percent, and the selectivity on the basis of acetone was, 7.5percent for a hydrocarbon such as propane, 55.5percent for cumene and 13.8percent for diisopropyl benzene.

With hydrogen, 5percent Re on alumina and MCM-22 zeolite calcined in nitrogen gas at 350C for 1 h and then in hydrogen gas at 400C for 3h, T= 150 °C , Product distribution / selectivity Patent; Mitsui Chemicals, Inc.; EP2103584; (2009); (A1) English View in Reaxys 1 :Reaction was performed in the same manner as in Example 1, except that the 10percent Ag/silica gel catalyst was replaced by 1.0 g of copper chromite (G99b manufactured by Sud-Chemie AG, element mass percent: Cu 35percent, Cr 31percent, Ba 2percent, Mn 3percent). The reaction results are set forth in Table 1. A large amount of propane was produced as a by-product.

With hydrogen, Cr2Cu2O5, T= 175 °C , p= 33753.4Torr Patent; Mitsui Chemicals, Inc.; US2012/4471; (2012); (A1) English View in Reaxys

Br

Br racemate

Rx-ID: 2812309 View in Reaxys 46/481 Yield

Conditions & References

70 %

With 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylamine in tetrahydrofuran, Time= 72h, T= 70 °C Rigby, James H.; Bellemin, Anne-Roberte; Synthesis; nb. 3; (1989); p. 188 - 189 View in Reaxys

(v2)

Zn

Cl

Rx-ID: 2943431 View in Reaxys 47/481 Yield 90 %

Conditions & References With titanium tetrachloride in dichloromethane, Time= 2h, T= 0 °C Reetz, M. T.; Steinbach, R.; Wenderoth, B.; Synthetic Communications; vol. 11; nb. 3; (1981); p. 261 - 266 View in Reaxys

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2H

OH

O

OH racemate HO

2H

Rx-ID: 3399953 View in Reaxys 48/481 Yield

Conditions & References With hydrogen, palladium dihydride in methanol, Yield given Zagorski, Michael G.; Salomon, Robert G.; Journal of the American Chemical Society; vol. 106; nb. 6; (1984); p.

1750 - 1759 View in Reaxys

2H

OH

O

OH racemate HO

2H

Rx-ID: 3399954 View in Reaxys 49/481 Yield

Conditions & References With hydrogen, palladium dihydride in methanol, Yield given Zagorski, Michael G.; Salomon, Robert G.; Journal of the American Chemical Society; vol. 106; nb. 6; (1984); p.

1750 - 1759 View in Reaxys

Rx-ID: 3917109 View in Reaxys 50/481 Yield

Conditions & References With anorthite, T= 40 °C , Yield given. Further byproducts given. Yields of byproduct given. Title compound not separated from byproducts Kolesnikov, I. M.; Grinis, L. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 55; nb. 2; (1982); p. 340 - 343,306 - 309 View in Reaxys With zeolite MCM-22, T= 180 °C , p= 26252.1Torr , Alkylation, Product distribution, Further Variations: Catalysts, Reaction partners, Temperatures Corma; Martinez-Soria; Schnoeveld; Journal of Catalysis; vol. 192; nb. 1; (2000); p. 163 - 173 View in Reaxys 1 : EXAMPLE 1 (COMPARATIVE); Alkylation of Cumene over MCM-22 2 g of MCM-22 ({fraction (1/16)}" extrudates with 35percent alumina binder) were used to alkylate cumene with commercial grade propylene.The catalyst was diluted with about 2 g of sand and charged to a down-flow fixed bed stainless steel reactor having an outside diameter of 3/8".The catalyst was dried at 125° C. and 1 atmosphere pressure with 100 cc/min flowing N2 for 2 hours.While retaining the N2 flow, the reactor pressure was set to 850 psig by a grove loader and the reactor temperature was adjusted to the desired temperature for the first set of alkylation conditions (140° C.).The feed, containing benzene and propylene in the molar ratio stated in Table 1, was introduced to the reactor at the WHSV stated in Table 1.After lining out for 24 hours, liquid products were collected in a cold-trap and analyzed off-line with an HP 5890 gas chromatograph GC. The catalyst was tested at several conditions, with each condition being lined out for 24 hours before collecting a liquid product.Results are shown in Table 1.

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With molecular sieve MCM-22 extrudates with 35percent alumina binder, Time= 24h, T= 140 - 220 °C , p= 46544.6Torr , Product distribution / selectivity Patent; Cheng, Jane Chi-Ya; Weber, William A.; Bryan, Francis S.; US2004/97771; (2004); (A1) English View in Reaxys 1.2 :2. Alkylation ReactionThe catalyst obtained as described above was molded into 1 to 2 mm, and 0.507 g of the catalyst together with 4.3 g of an α alumina sphere (1 mm) (Al2O3) as a diluent was put in a stainless reaction tube having an internal diameter of 10 mm and an external diameter of 12 mm.A catalyst layer was heated to 250° C. for 2 hours under a nitrogen stream at 200 ml/min to calcine the catalyst. After cooled to room temperature, benzene and propylene were passed into the reaction tube at a predetermined pressure in an upflow manner while the catalyst layer was maintained at a predetermined temperature, to perform an alkylation reaction of benzene.In the reaction tube, benzene was passed at 8.5 g/h under nitrogen, propylene was passed at 12.5 Nml/min, and the reaction pressure was maintained at 0.15 MPaG. The hot spot of the catalyst layer was 49.9° C.After 6 hours from initiation of the reaction, the reaction solution was sampled and analyzed by gas chromatography. The propylene conversion was 42.0percent, the cumene selectivity was 77.0percent, and the diisopropylbenzene selectivity was 17.4percent as a total value of three isomers.

With 50 wt.percent Cs1.37H2.63SiW12O40/SiO2 mixed with α-alumina and calcinated at 250 C, Time= 6h, T= 49.9 °C , Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2009/209796; (2009); (A1) English View in Reaxys With MCM-22 zeolite (Si/Al=15), Time= 1h, T= 220 °C Laredo, Georgina C.; Castillo, J. Jesus; Navarrete-Bolanos, Juan; Perez-Romo, Patricia; Lagos, Flavio A.; Applied Catalysis A: General; vol. 413-414; (2012); p. 140 - 148 View in Reaxys

Rx-ID: 23744864 View in Reaxys 51/481 Yield

Conditions & References 1; 1; 2 :Cumyl alcohol is easily converted into α-methyl styrene with activated alumina as a dehydration catalyst.

Examples of hydrogenation of α -methyl styrene obtained by dehydration of cumyl alcohol, are shown below. One hundred grams of a solution composed of 21.5percent by weight of α-methyl styrene and 77.9percent by weight of cumene, and 0.7 g of a supported-type catalyst, 0.05 wtpercent Pd/alumina as a hydrogenation catalyst were charged in an autoclave, and reacted in hydrogen containing CO in amounts shown in Table 1 at 200 °C under 1.0 MPa as a gauge pressure for 30 minutes, respectively. α -methyl styrene conversions (conversion of α -methyl styrene into cumene by hydrogenation) and concentrations of isopropyl cyclohexane(i-PrCH)(produced by nuclear-hydrogenation of cumene) are respectively shown in Table 1.

With carbon monoxide, hydrogen, 0.05 palladium/alumina, Time= 0.5h, T= 200 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1666443; (2006); (A1) English View in Reaxys

S

S

Rx-ID: 29747517 View in Reaxys 52/481 Yield 83 %

Conditions & References With sodium tetrahydroborate, NiII chloride hexahydrate in tetrahydrofuran, methanol, Time= 0.5h, T= 20 °C Khurana, Jitender M.; Magoo, Devanshi; Synthetic Communications; vol. 40; nb. 19; (2010); p. 2908 - 2913 View in Reaxys

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I Cl Mg

Rx-ID: 30159856 View in Reaxys 53/481 Yield

Conditions & References

18 %Chromat.

With N,N,N',N,-tetramethylethylenediamine, ((Me)N2N)Ni-Cl in tetrahydrofuran, Time= 2h, T= 20 °C , Inert atmosphere, Kumada-Corriu-Tamao coupling reaction Vechorkin, Oleg; Proust, Valerie; Hu, Xile; Journal of the American Chemical Society; vol. 131; nb. 28; (2009); p.

9756 - 9766 View in Reaxys Br

Cl Mg

Rx-ID: 30159924 View in Reaxys 54/481 Yield

Conditions & References

11 %Chromat.

With N,N,N',N,-tetramethylethylenediamine, ((Me)N2N)Ni-Cl in tetrahydrofuran, Time= 2h, T= 20 °C , Inert atmosphere, Kumada-Corriu-Tamao coupling reaction Vechorkin, Oleg; Proust, Valerie; Hu, Xile; Journal of the American Chemical Society; vol. 131; nb. 28; (2009); p.

9756 - 9766 View in Reaxys

O

Rx-ID: 847422 View in Reaxys 55/481 Yield

Conditions & References With boron trifluoride O'Connor; Sowa; Journal of the American Chemical Society; vol. 60; (1938); p. 125 View in Reaxys With hydrogen fluoride, T= 20 °C Simons; Archer; Journal of the American Chemical Society; vol. 62; (1940); p. 1623 View in Reaxys With sulfuric acid, T= 40 - 60 °C Wibaut et al.; Recueil des Travaux Chimiques des Pays-Bas; vol. 58; (1939); p. 347; Recueil des Travaux Chimiques des Pays-Bas; vol. 61; (1942); p. 266,267 View in Reaxys

O

O

Rx-ID: 847604 View in Reaxys 56/481 Yield

Conditions & References With aluminium trichloride, Siedetemperatur Bowden; Journal of the American Chemical Society; vol. 60; (1938); p. 646 View in Reaxys With hydrogen fluoride, T= 80 - 100 °C Simons; Archer; Randall; Journal of the American Chemical Society; vol. 61; (1939); p. 1821 View in Reaxys With aluminium trichloride, T= 0 - 25 °C

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Berman; Lowy; Journal of the American Chemical Society; vol. 60; (1938); p. 2596 View in Reaxys

HO

Rx-ID: 9068953 View in Reaxys 57/481 Yield

Conditions & References

54 % Chromat., 29 % Chromat., 13 % Chromat.

With copper(l) iodide, chloro-trimethyl-silane, iodine, lanthanum in acetonitrile, Time= 1h, T= 82 °C

54 % Chromat., 13 % Chromat., 29 % Chromat.

With lanthanum, chloro-trimethyl-silane, iodine, copper(l) iodide in acetonitrile, Time= 1h, T= 82 °C

36 % Chromat., 6 % Chromat., 29 % Chromat.

With lanthanum, chloro-trimethyl-silane, iodine, CoI2 in acetonitrile, Time= 1h, T= 82 °C

Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Tetrahedron Letters; vol. 43; nb. 20; (2002); p. 3689 3691 View in Reaxys

Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Bulletin of the Chemical Society of Japan; vol. 76; nb. 3; (2003); p. 635 - 641 View in Reaxys

Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Bulletin of the Chemical Society of Japan; vol. 76; nb. 3; (2003); p. 635 - 641 View in Reaxys O O

Cl Mg

S O

Rx-ID: 10061410 View in Reaxys 58/481 Yield 61 %

Conditions & References With zirconocene dichloride in tetrahydrofuran, Time= 6h, T= 50 °C Terao, Jun; Begum, Shameem Ara; Oda, Akihiro; Kambe, Nobuaki; Synlett; nb. 11; (2005); p. 1783 - 1786; Art.No: Y01105ST View in Reaxys

Rx-ID: 23744029 View in Reaxys 59/481 Yield

Conditions & References 2 :Example 2; [0045] The catalyst of Example 1 was tested in a down-flow micro-unit for cumene production. The catalyst was crushed to 24-42 mesh and calcined in air at 650° F. before installing the reactor in the micro-unit. The reactor was then pressured up to 600 psig using nitrogen and then lined out at a temperature of 300° F. prior to introducing feed. The feed was an 8/1 volumetric mixture of benzene/propylene, run at a WHSV of 5.7. A 4A mole sieve drier was installed in the feed line to remove any residual water. Samples were taken every three hours using an online gas chromatograph. Results at 40 hours on-stream are shown in Table I, along with results at the same conditions for a commercial prototype Beta catalyst made using conventional synthesis and containing 80percent Beta zeolite bound with alumina. These results show the catalyst of Example 1 to give close to 95percent selectivity to cumene at 100percent propylene conversion.

With catalyst prepared as described in Example 1 with SiO2/Al2O3=17, Time= 40h, T= 148.879 °C , p= 21446.5Torr , Product distribution / selectivity Patent; Miller, Stephen J.; US2003/204121; (2003); (A1) English View in Reaxys

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4 :Example 4; [0053] The catalyst of Example 3 was tested for cumene production using the same method as given in Example 2, except the WHSV was 41.6 to accelerate aging in order to determine catalyst cycle life. The run was considered over when the propylene conversion dropped below 95percent. At 40 hours on-stream, cumene selectivity was 92percent, and was 94percent at 122 hours. The cycle life with this catalyst was 131 hours.

With catalyst prepared as described in Example 3 with SiO2/Al2O3=17, T= 148.879 °C , p= 21446.5Torr , Product distribution / selectivity Patent; Miller, Stephen J.; US2003/204121; (2003); (A1) English View in Reaxys Example 4; [0053] The catalyst of Example 3 was tested for cumene production using the same method as given in Example 2, except the WHSV was 41.6 to accelerate aging in order to determine catalyst cycle life. The run was considered over when the propylene conversion dropped below 95percent. At 40 hours on-stream, cumene selectivity was 92percent, and was 94percent at 122 hours. The cycle life with this catalyst was 131 hours.

With commercial Beta zeolite extrudate containing 80 wt. percent Beta zeolite and 20percent wt. percent alumina binder, T= 148.879 °C , p= 21446.5Torr , Product distribution / selectivity Patent; Miller, Stephen J.; US2003/204121; (2003); (A1) English View in Reaxys 2 :Example 2; [0045] The catalyst of Example 1 was tested in a down-flow micro-unit for cumene production. The catalyst was crushed to 24-42 mesh and calcined in air at 650° F. before installing the reactor in the micro-unit. The reactor was then pressured up to 600 psig using nitrogen and then lined out at a temperature of 300° F. prior to introducing feed. The feed was an 8/1 volumetric mixture of benzene/propylene, run at a WHSV of 5.7. A 4A mole sieve drier was installed in the feed line to remove any residual water. Samples were taken every three hours using an online gas chromatograph. Results at 40 hours on-stream are shown in Table I, along with results at the same conditions for a commercial prototype Beta catalyst made using conventional synthesis and containing 80percent Beta zeolite bound with alumina. These results show the catalyst of Example 1 to give close to 95percent selectivity to cumene at 100percent propylene conversion.

With commercial catalyst with SiO2/Al2O3=25, Time= 40h, T= 148.879 °C , p= 21446.5Torr , Product distribution / selectivity Patent; Miller, Stephen J.; US2003/204121; (2003); (A1) English View in Reaxys With H-BASF-acid(30) catalyst, T= 149.84 °C , p= 30003Torr , Inert atmosphere, Autoclave Van Laak, Adri N.C.; Sagala, Sophia L.; Zecevic, Jovana; Friedrich, Heiner; De Jongh, Petra E.; De Jong, Krijn P.; Journal of Catalysis; vol. 276; nb. 1; (2010); p. 170 - 180 View in Reaxys With zeolite Beta (Si/Al=30), Time= 8h, T= 220 °C Laredo, Georgina C.; Castillo, J. Jesus; Navarrete-Bolanos, Juan; Perez-Romo, Patricia; Lagos, Flavio A.; Applied Catalysis A: General; vol. 413-414; (2012); p. 140 - 148 View in Reaxys

HO

Rx-ID: 23755686 View in Reaxys 60/481 Yield

Conditions & References 1; 1 :The catalyst A of 3 m-thick as a first layer and the catalyst B of 1.2 m-thick as a second layer were packed in a reactor having an inner diameter of 4 mm. The first layer and second layer were heated to 230 °C and 190°C, respectively, and 0.1 liter/minute of hydrogen and 1.6 g/minute of a cumene solution having a cumyl alcohol concentration of 23 percent by weight under a pressure of 4 MPa-G, were simultaneously fed to the reactor, continuously. After the reaction of 106 hours, a cumyl alcohol conversion was 99.8percent and a selectivity of a cumene dimer (hydrogenated product of an α-methyl styrene dimer) was 0.9percent. Further, a concentration of α-methyl styrene in cu-

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mene obtained was less than 0.01 percent by weight.; The catalyst B of 0.1 m-thick as a first layer, the catalyst A of 0.2 m-thick as a second layer, the catalyst B of 0.4 m-thick as a third layer, the catalyst A of 0.4 m-thick as a fourth layer, the catalyst B of 0.4 m-thick as a fifth layer, the catalyst A of 2.4 m-thick as a sixth layer and the catalyst B of 0.4 m-thick as a seventh layer (catalyst A: 3 m-thick in total, catalyst B: 1. 3 m-thick in total) were packed in a reactor having an inner diameter of 4 mm OE. The first and second layers, the third to fifth layers, and the sixth and sevens layers were heated to 180°C, 200°C and 230°C, respectively, and 0.1 normal liter/minute of hydrogen and 1.6 g/ minute of a cumene solution having a cumyl alcohol concentration of 23 percent by weight under a pressure of 4 MPa-G, were simultaneously fed to the reactor, continuously. After the reaction of 88 hours, a cumyl alcohol conversion was 99.9percent and a selectivity of a cumene dimer (hydrogenated product of an α-methyl styrene dimer) was 0.2percent. Further, a concentration of α-methyl styrene in cumene obtained was less than 0.01 percent by weight.

With hydrogen, aluminum oxide, 0.05 palladium/alumina, Time= 88 - 106h, T= 180 - 230 °C , p= 30003Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1666442; (2006); (A1) English View in Reaxys Br

(v2)

Zn

Rx-ID: 39925875 View in Reaxys 61/481 Yield 57 %

Conditions & References With (2-phenylethyl)diphenylphosphane, iron(II) chloride in toluene, Time= 14h, T= 45 °C , Inert atmosphere, Negishi Coupling Brown, Caleb A.; Nile, Terence A.; Mahon, Mary F.; Webster, Ruth L.; Dalton Transactions; vol. 44; nb. 27; (2015); p. 12189 - 12195 View in Reaxys in benzene-d6, Time= 0.166667h, T= 20 °C , Inert atmosphere, Glovebox Dunsford, Jay J.; Clark, Ewan R.; Ingleson, Michael J.; Angewandte Chemie, International Edition; vol. 54; nb.

19; (2015); p. 5688 - 5692; Angewandte Chemie; vol. 127; nb. 19; (2015); p. 5780 - 5784,5 View in Reaxys

H Br

Rx-ID: 40007785 View in Reaxys 62/481 Yield 73 %

Conditions & References With 1-phenyl-1-propyne, n-butyl-magnesium chloride, copper dichloride in tetrahydrofuran, Time= 24h, T= 25 °C , Schlenk technique, Inert atmosphere Iwasaki, Takanori; Imanishi, Reiko; Shimizu, Ryohei; Kuniyasu, Hitoshi; Terao, Jun; Kambe, Nobuaki; Journal of Organic Chemistry; vol. 79; nb. 18; (2014); p. 8522 - 8532 View in Reaxys F O O

FF

F F

S O F

F F

F

Rx-ID: 2615301 View in Reaxys 63/481 Yield

Conditions & References With hydrogen, palladium on activated charcoal in methanol, p= 760Torr , Ambient temperature, Yield given Subramanian, L. R.; Martinez, A. Garcia; Fernandez A. Herrera; Alvarez, R. Martinez; Synthesis; nb. 6; (1984); p. 481 - 485 View in Reaxys

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O C

Cl

O

Cl Cl

O

Cl

Rx-ID: 3287558 View in Reaxys 64/481 Yield

Conditions & References With Os(III) chloride in benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys With Ir(III) chloride in benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys

diisoproyl sulfate Rx-ID: 6416610 View in Reaxys 65/481 Yield

Conditions & References With boron trifluoride McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys With aluminium trichloride, T= 70 °C Kane; Lowy; Journal of the American Chemical Society; vol. 58; (1936); p. 2605 View in Reaxys

O F F

O F

Rx-ID: 9536974 View in Reaxys 66/481 Yield 89 %

Conditions & References With (Ph)2SiH2, Time= 15h, T= 130 °C Kim, Joong-Gon; Cho, Dae Hyan; Jang, Doo Ok; Tetrahedron Letters; vol. 45; nb. 15; (2004); p. 3031 - 3033 View in Reaxys

I Br

Rx-ID: 29075178 View in Reaxys 67/481 Yield 79 %Chromat., 20 %Chromat., 14 %Chromat.

Conditions & References Stage 1: With n-butyllithium in tetrahydrofuran, hexane, Time= 0.166667h, T= -78 °C , Inert atmosphere, Negishi coupling reaction Stage 2: With zinc(II) chloride in tetrahydrofuran, hexane, T= -78 - 20 °C , Inert atmosphere, Negishi coupling reaction Stage 3: With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride in tetrahydrofuran, hexane, Time= 2h, T= 60 °C , Inert atmosphere, Negishi coupling reaction Liu, Qiang; Lan, Yu; Liu, Jing; Li, Gang; Wu, Yun-Dong; Lei, Aiwen; Journal of the American Chemical Society; vol. 131; nb. 29; (2009); p. 10201 - 10210 View in Reaxys

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O

HO

Rx-ID: 29485900 View in Reaxys 68/481 Yield

Conditions & References With Cl2Ru((rac)-Binap)(BIMe)2, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 6h, T= 19.84 °C , p= 3800.26Torr Praetorius, Jeremy M.; Wang, Ruiyao; Crudden, Cathleen M.; Organometallics; vol. 29; nb. 3; (2010); p. 554 561 View in Reaxys

HO

HO

Rx-ID: 37387462 View in Reaxys 69/481 Yield

Conditions & References With carbon dioxide, 5 palladium on charcoal, hydrogen in methanol, Time= 2h, T= 49.84 °C , p= 15001.5Torr , Autoclave, Green chemistry, Pressure Lin, Hsin-Wei; Yen, Clive H.; Hsu, Han; Tan, Chung-Sung; RSC Advances; vol. 3; nb. 38; (2013); p. 17222 17227 View in Reaxys

O C

Cl

O

Cl Cl

O

Cl

Rx-ID: 3287567 View in Reaxys 70/481 Yield

Conditions & References With Ir(III) chloride in benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys With Os(III) chloride in benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys O O

S O

Rx-ID: 5109499 View in Reaxys 71/481 Yield 56 % Chromat.

Conditions & References With n-butyl-magnesium chloride, zirconocene dichloride in tetrahydrofuran, Time= 2h, T= 50 °C Terao, Jun; Watanabe, Tsunenori; Saito, Koyu; Kambe, Nobuaki; Sonoda, Noboru; Tetrahedron Letters; vol.

39; nb. 50; (1998); p. 9201 - 9204 View in Reaxys

HO

HO

Rx-ID: 37387463 View in Reaxys 72/481 Yield

Conditions & References With 5 palladium on charcoal, hydrogen, acetic acid in water, Time= 1h, T= 49.84 °C , p= 7500.75Torr , pH= 3.6, Autoclave, Green chemistry Lin, Hsin-Wei; Yen, Clive H.; Hsu, Han; Tan, Chung-Sung; RSC Advances; vol. 3; nb. 38; (2013); p. 17222 17227

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View in Reaxys

H O

O

Rx-ID: 2071794 View in Reaxys 73/481 Yield

Conditions & References

17 %, 2.8 %, 1.3 %, 30 %

With sodium lauryl sulfate in water, Irradiation, Title compound not separated from byproducts

30 %, 17 %, 2.8 %, 1.3 %

With sodium lauryl sulfate in water, Irradiation, further detergents, Quantum yield, Product distribution

30 %, 30 %, 2.0 %, 1%

With trimethylhexadecylammonium chloride in water, T= 20 - 25 °C , Irradiation, cage effect, Quantum yield, Product distribution

Turro, J. Nicholas; Mattay, Jochen; Tetrahedron Letters; vol. 21; nb. 19; (1980); p. 1799 - 1802 View in Reaxys

Turro, J. Nicholas; Mattay, Jochen; Tetrahedron Letters; vol. 21; nb. 19; (1980); p. 1799 - 1802 View in Reaxys

Turro, Nicholas J.; Mattay, Jochen; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4200 4204 View in Reaxys 22 %, 2.2 %, 0.8 %, 23 %

With trimethylhexadecylammonium chloride in water, Irradiation, Title compound not separated from byproducts Turro, J. Nicholas; Mattay, Jochen; Tetrahedron Letters; vol. 21; nb. 19; (1980); p. 1799 - 1802 View in Reaxys

Se

HSe

Rx-ID: 2340064 View in Reaxys 74/481 Yield 32 %, 20 %

Conditions & References With sulfuric acid in chloroform, Time= 0.2h, T= 20 °C Clarembeau, M.; Krief, A.; Tetrahedron Letters; vol. 25; nb. 33; (1984); p. 3625 - 3628 View in Reaxys

Rx-ID: 10817674 View in Reaxys 75/481 Yield

Conditions & References 3; 4 :The present example illustrates the use of a material prepared according to Example 1 as catalyst in the alkylation of benzene with propylene.[0025] A sample with ratio τIV/Tnι = 12, prepared according Example 1 , was pelletized, selecting a particle size between 0.25 and 0.42 mm, for carrying out the reaction. The zeolite (0.75 g) was diluted with silicon carbide (0.59- 0.84 mm) to give a final SiC/zeolite ratio of 2.8 by weight. The diluted catalyst was placed in a tubular steel reactor 1 cm in diameter, and it was calcined in an air stream following the method described in Example 2. Next, the temperature was lowered to the reaction temperature of 125°C in a stream of N2, the flow of N2 was stopped and benzene was supplied until the pressure reached 3.5 MPa. At this point the reactor was switched off for feed of a mixture of benzene (400 μl) and propylene (90 μl), at a benzene/propylene molar ratio of 3.5, through a parallel line until a constant composition was achieved, and then the feed was again passed through the reactor, this being regarded as the start of the reaction.The results for propylene conversion are presented in Figure 2, and are compared with those obtained in the same conditions with a commercial zeolite BETA (Zeolyst CP81 1) with ratio Si/Al = 13. The distribution of products obtained with ITQ-33 and with BETA at different reaction times is compared in Tables 5 and 6, respectively.Table 5: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mol"1, WHSV prop = 12 h"\\ P = 3.5 MPa obtained with zeolite ITQ-33 <n="14"/>Table 6: Selec-

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tivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mor1, WHSV prop = 12 h"1, P = 3.5 MPa obtained with zeolite BETA.[0026] The results in Figure 2 clearly show that zeolite ITQ-33, as claimed in this patent, is more active than the commercial zeolite BETA, maintaining a degree of conversion of propylene greater than 95percent at 8 hours of reaction, whereas the conversion obtained with zeolite BETA at 8 hours of reaction is of the order of 55percent. Comparing Tables 5 and 6, it can be seen that the selectivity for the unwanted product NPB obtained with ITQ-33 is less than 0.01percent, and the selectivity for products other than alkylation products (others) is less than that obtained with zeolite BETA. The di- and trialkylated products, obtained in higher proportion with zeolite ITQ-33 could be converted to cumene in the associated transalkylation units. <n="15"/>Example 4: Use of the zeolitic component ITQ-33 in the alkylation of benzene with propylene; effect of space velocity[0027] This example shows the influence of the space velocity (WHSV) (24 h"1) on the conversion and selectivity for the alkylation of benzene with propylene using the same catalysts as in Example 3, with the other reaction conditions the same as in Example 3.Table 7: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mor, WHSV prop = 24 h -I, n P - = 3.5 MPa obtained with zeolite ITQ-33Table 8: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mol 1, WHSV prop = 24 h"1, P = 3.5 MPa obtained with zeolite BETA.The results presented in Tables 7 and 8 show that at this higher space velocity, the differences in activity between zeolite ITQ-33 and zeolite BETA are even greater than at a space velocity of 12 h"1, the zeolite according to the present patent being much more active, while maintaining, for this zeolite, low selectivities for NPB <n="16"/>and for products different from those obtained by alkylation of benzene with propylene (others).

With zeolite ITQ-33, Time= 0.5 - 8h, T= 125 °C , p= 26252.6Torr , Product distribution / selectivity Patent; UNIVERSIDAD POLITECNICA DE VALENCIA; CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS; WO2008/14904; (2008); (A1) English View in Reaxys 3; 4 :The present example illustrates the use of a material prepared according to Example 1 as catalyst in the alkylation of benzene with propylene.[0025] A sample with ratio τIV/Tnι = 12, prepared according Example 1 , was pelletized, selecting a particle size between 0.25 and 0.42 mm, for carrying out the reaction. The zeolite (0.75 g) was diluted with silicon carbide (0.59- 0.84 mm) to give a final SiC/zeolite ratio of 2.8 by weight. The diluted catalyst was placed in a tubular steel reactor 1 cm in diameter, and it was calcined in an air stream following the method described in Example 2. Next, the temperature was lowered to the reaction temperature of 125°C in a stream of N2, the flow of N2 was stopped and benzene was supplied until the pressure reached 3.5 MPa. At this point the reactor was switched off for feed of a mixture of benzene (400 μl) and propylene (90 μl), at a benzene/propylene molar ratio of 3.5, through a parallel line until a constant composition was achieved, and then the feed was again passed through the reactor, this being regarded as the start of the reaction.The results for propylene conversion are presented in Figure 2, and are compared with those obtained in the same conditions with a commercial zeolite BETA (Zeolyst CP81 1) with ratio Si/Al = 13. The distribution of products obtained with ITQ-33 and with BETA at different reaction times is compared in Tables 5 and 6, respectively.Table 5: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mol"1, WHSV prop = 12 h"\\ P = 3.5 MPa obtained with zeolite ITQ-33 <n="14"/>Table 6: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mor1, WHSV prop = 12 h"1, P = 3.5 MPa obtained with zeolite BETA.[0026] The results in Figure 2 clearly show that zeolite ITQ-33, as claimed in this patent, is more active than the commercial zeolite BETA, maintaining a degree of conversion of propylene greater than 95percent at 8 hours of reaction, whereas the conversion obtained with zeolite BETA at 8 hours of reaction is of the order of 55percent. Comparing Tables 5 and 6, it can be seen that the selectivity for the unwanted product NPB obtained with ITQ-33 is less than 0.01percent, and the selectivity for products other than alkylation products (others) is less than that obtained with zeolite BETA. The di- and trialkylated products, obtained in higher proportion with zeolite ITQ-33 could be converted to cumene in the associated transalkylation units. <n="15"/>Example 4: Use of the zeolitic component ITQ-33 in the alkylation of benzene with propylene; effect of space velocity[0027] This example shows the influence of the space velocity (WHSV) (24 h"1) on the conversion and selectivity for the alkylation of benzene with propylene using the same catalysts as in Example 3, with the other reaction conditions the same as in Example 3.Table 7: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mor, WHSV prop = 24 h -I, n P - = 3.5 MPa obtained with zeolite ITQ-33Table 8: Selectivity in the alkylation of benzene with propylene at 125°C, B/P = 3.5 mol.mol 1, WHSV prop = 24 h"1, P = 3.5 MPa obtained with zeolite BETA.The results presented in Tables 7 and 8 show that at this higher space velocity, the differences in activity between zeolite ITQ-33 and zeolite BETA are even greater than at a space velocity of 12 h"1, the zeolite according to the present patent being much more active, while maintaining, for this zeolite, low selectivities for NPB <n="16"/>and for products different from those obtained by alkylation of benzene with propylene (others).

With Zeolyst CP811, Time= 0.5 - 8h, T= 125 °C , p= 26252.6Torr , Product distribution / selectivity

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Patent; UNIVERSIDAD POLITECNICA DE VALENCIA; CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS; WO2008/14904; (2008); (A1) English View in Reaxys

Rx-ID: 23572129 View in Reaxys 76/481 Yield

Conditions & References 5 :0.5 g of Al2O3-bound MCM-22 catalyst, prepared in Comparative Example 1 as {fraction (1/16)}'' extrudates, was chopped to {fraction (1/16)}'' length. The catalyst was diluted with sand to 3 cc and charged to an isothermal, downflow, fixed-bed, 3/8'' o.d. reactor. The catalyst was dried at 125° C. and 1 atm with 100 cc/min flowing N2 for 2 hours.

N2 was turned off and reactor pressure was set to 300 psig by a grove loader. The feed (75.0 wt. percent benzene, 8.3 wt. percent m-diisopropylbenzene and 16.7 wt. percent p-diisopropylbenzene) was fed into the reactor at 60 cc/hr for 1 hour and then at 4 total WHSV (based on total catalyst weight). The reactor temperature was then increased to 200° C. After lining out, liquid products were collected in a cold-trap and analyzed off-line with an HP 5890 GC. The catalyst was further tested at 210° C. and 220° C. under otherwise identical conditions. Total material balances were 100+-2percent.

With Al2O3-bound MCM-22, T= 203 °C , p= 16274.9Torr , Conversion of starting material Patent; ExxonMobil Oil Corporation; US6919491; (2005); (B1) English View in Reaxys 5 :1.0 g of binder-free MCM-22 catalyst, prepared in Example 1 as 1/6'' extrudates, was chopped to {fraction (1/16)}'' length. The catalyst was tested at 180° C., 190° C., and 200° C. with the same procedure described in Comparative Example 5. Catalyst performance is compared with that of Al2O3-bound MCM-22. Comparison of Catalyst Performance for Liquid Phase Cumene Synthesis Via Benzene/Diisopropylbenzene Transalkylation FIG. 5 compares catalyst activity for liquid phase cumene synthesis via benzene/diisopropylbenzene transalkylation at 300 psig, 4 total WHSV, and 3:1 benzene/diisopropylbenzene weight ratio. The catalyst performances for benzene/diisopropylbenzene transalkylation are tabulated in Table 5. At 36percent diisopropylbenzene conversion, binder-free MCM-22 can be operated at 190° C. vs. 203° C. with the Al2O3-bound MCM-22. At 200° C., binder-free MCM-22 had 67percent higher diisopropylbenzene conversion (59.3percent vs. 35.6percent) when compared with Al2O3-bound MCM-22.

With MCM-22 binder-free, T= 190 - 200 °C , p= 16274.9Torr , Conversion of starting material Patent; ExxonMobil Oil Corporation; US6919491; (2005); (B1) English View in Reaxys 1 :Two grams of a zeolite beta catalyst comprising 80 wt.percent of hydrogen form (H-form) of beta zeolite crystal and 20 wt.percent alumina (Al2O3) cylindrical extrudates (chopped to 1/16" [1.59mm] length) was used for transalkylation of the feed described in Table 1. The zeolite beta catalyst was dried off-line at 3920F (2000C) at atmospheric pressure (100 kPa) with 100 cc/min flowing N2 for 2 hours. The zeolite beta catalyst was diluted with approximately 2.6 grams of sand per gram of catalyst and charged to an isothermal, down-flow, 3/8" [9.5" mm] outside diameter fixed bed reactor. The reactor was heated to 356°F (18O0C) under flowing nitrogen. The feed described in Table 1 was introduced into the reactor (based on total catalyst weight) and the reactor pressure was set to 300 psig (2170 kPa) by a grove loader. Weight hourly space velocity (WHSV) was set to achieve approximately 50percent total DIPB conversion. The beta zeolite reached approximately 50percent DIPB conversion at 16 WHSV. After lining out weight hourly space velocity, the total product was vaporized and sent to an on-line HP 5890 GPC. Relative activity based on a first order reaction rate constant, cumene selectivity and impurity-make for the catalyst were determined and are shown in Table 2.

With zeolite β catalyst, Time= 16h, T= 179.99 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2006/107462; (2006); (A1) English View in Reaxys 2 :To prepare the P-Beta catalyst, 50 grams of sample comprising 80 wt.percent of hydrogen form (H-form) beta zeolite crystal and 20 wt.percent alumina (Al2O3 1/20" (1.27 mm) quadrulobe extrudate was impregnated to incipient wetness with an aqueous solution of ammonium hydrogen phosphate prepared by dissolving 0.43 grams of ammonium hydrate phosphate in 30 cc of distilled water. The P-Beta was then calcined at 10000F (538°C) with a 10 hour

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hold at full air. The P-Beta was then dried off-line at 3920F (2000C) at atmospheric pressure (100 kPa) with 100 cc/min flowing N2 for 2 hours. The total phosphorus content of the catalyst was 0.02 wt.percent based on the total weight of the catalyst. Two (2.0) grams of the P-Beta extrudates (chopped to 1/16" [1.59 mm] length) were used for transalkylation of the feed described in Table 1. The P-Beta was diluted with approximately 2.6 grams of sand per gram of catalyst and charged to an isothermal, down-flow, 3/8" [9.5 mm] outside diameter fixed bed reactor. The EPO <DP n="14"/>reactor was heated to 3560F (1800C) under flowing nitrogen. The feed described in Table 1, was introduced into the reactor (based on total catalyst weight) and reactor pressure was set to 300 psig (2170 kPa) by a grove loader. Weight hourly space velocity (WHSV) was set to achieve approximately 50percent total DIPB conversion. P-Beta reached approximately 50percent DIPB conversion at 72 WHSV. After lining out WHSV, the total product was vaporized and sent to an on-line HP 5890 GPC. Relative activity based on a first order reaction rate constant, cumene selectivity and impurity-make for the catalyst were determined and are also shown in Table 2.

With P-β catalyst, Time= 72h, T= 179.99 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2006/107462; (2006); (A1) English View in Reaxys

Cl

H

Mg

Br

Rx-ID: 39005171 View in Reaxys 77/481 Yield

Conditions & References

56 %, 10 %

With 1-phenyl-1-propyne, copper dichloride in tetrahydrofuran, Time= 24h, T= 25 °C , Schlenk technique, Inert atmosphere Iwasaki, Takanori; Imanishi, Reiko; Shimizu, Ryohei; Kuniyasu, Hitoshi; Terao, Jun; Kambe, Nobuaki; Journal of Organic Chemistry; vol. 79; nb. 18; (2014); p. 8522 - 8532 View in Reaxys

Rx-ID: 40973756 View in Reaxys 78/481 Yield

Conditions & References With mixture of 7 percent carbon-supported platinum and silica, Time= 2h, T= 300 °C , p= 750.075Torr Alotaibi, Abdullah; Bayahia, Hossein; Kozhevnikova, Elena F.; Kozhevnikov, Ivan V.; ACS Catalysis; vol. 5; nb.

9; (2015); p. 5512 - 5518 View in Reaxys

O

O P

O

O

Rx-ID: 847205 View in Reaxys 79/481 Yield

Conditions & References With aluminium trichloride, T= 0 - 15 °C Berman; Lowy; Journal of the American Chemical Society; vol. 60; (1938); p. 2596 View in Reaxys

Rx-ID: 847358 View in Reaxys 80/481 Yield

Conditions & References With phosphoric acid, T= 450 °C

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Ipatieff; Komarewsky; Pines; Journal of the American Chemical Society; vol. 58; (1936); p. 918; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1526 View in Reaxys H Ti

Cl

(v4) Cl

O

Rx-ID: 2682398 View in Reaxys 81/481 Yield

Conditions & References

93 %

in dichloromethane, Time= 3h, T= -30 °C Reetz, Manfred T.; Kyung, Suk-Hun; Chemische Berichte; vol. 120; (1987); p. 123 - 124 View in Reaxys

Rx-ID: 3287570 View in Reaxys 82/481 Yield

Conditions & References With ruthenium trichloride, carbon monoxide in methanol, benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys With Rhodium trichloride, carbon monoxide in methanol, benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys With carbon monoxide, platinum (II) chloride in methanol, benzene, Time= 20h, T= 90 °C , p= 11400Torr , Yield given. Yields of byproduct given Johnson, Thomas J.; Baldwin, Thomas F.; Journal of Organic Chemistry; vol. 45; nb. 1; (1980); p. 140 - 142 View in Reaxys With hydrogen, T= 34 °C , p= 100Torr , Irradiation Attina, Marina; Cacace, Fulvio; Giacomello, Pierluigi; Journal of the American Chemical Society; vol. 102; nb.

14; (1980); p. 4768 - 4772 View in Reaxys With ethane, oxygen, Time= 2h, T= 30 °C , Irradiation, Product distribution, Further Variations: Reagents, Temperatures Chiavarino, Barbara; Crestoni, Maria Elisa; Fokin, Andrey A.; Fornarini, Simonetta; Chemistry - A European Journal; vol. 7; nb. 13; (2001); p. 2916 - 2921 View in Reaxys

O Cl

N N

Rx-ID: 8797674 View in Reaxys 83/481 Yield

Conditions & References With aluminium trichloride, T= 25 °C , Friedel-Crafts reaction Moss; Fede; Yan; Journal of the American Chemical Society; vol. 122; nb. 40; (2000); p. 9878 - 9879 View in Reaxys

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F

Mg Br

Rx-ID: 33679120 View in Reaxys 84/481 Yield

Conditions & References With C37H30OP2, ZnCl2*TMEDA, Ni(acac)2 in tetrahydrofuran, Time= 13h, T= 0 - 70 °C , Inert atmosphere Nakamura, Yuki; Yoshikai, Naohiko; Ilies, Laurean; Nakamura, Eiichi; Organic Letters; vol. 14; nb. 13; (2012); p.

3316 - 3319 View in Reaxys

Si

Si Si

O

HO

Rx-ID: 34246199 View in Reaxys 85/481 Yield

Conditions & References With 1 Au/TiO2 in ethyl acetate, Time= 1.5h, T= 55 °C , Overall yield = 82 percent Gryparis, Charis; Stratakis, Manolis; Chemical Communications (Cambridge, United Kingdom); vol. 48; nb. 87; (2012); p. 10751 - 10753,3 View in Reaxys

Cl

Rx-ID: 847372 View in Reaxys 86/481 Yield

Conditions & References With hydrogenchloride, T= 235 °C Simons; Hart; Journal of the American Chemical Society; vol. 66; (1944); p. 1309,1310; Journal of the American Chemical Society; vol. 69; (1947); p. 979 View in Reaxys

HO

HO

O

Rx-ID: 23426136 View in Reaxys 87/481 Yield

Conditions & References II.B.ii :The reduced Pd-Mordenite catalyst, prepared by the procedure of Illustrative Embodiment II (A) (ii) above, were loaded into the reflux zone of a thick walled 31 cm long Vigreux column with an internal diameter of 1.5 cm while inside a nitrogen filled glove box. The same procedures described in II (A (I) and II (A) (II) above were followed for the set-up and operation of a catalytic distillation operation. The results are provided in TABLE 3 below. As shown, the top product stream produced, after removal of water, had a purity of cumene of >99. 6 wt. percent. No measurable cumyl alcohol (<0. 1 wt. percent) was found in the cumene product. When desired, the bottoms can be withdrawn, optionally distilled to remove lighter boiling compounds (which can be recycled back to the catalytic distillation reactor) and then optionally diluted with fresh cumene or cumene product and sent to a fixed bed hydrogenation reactor to make additional cumene as illustrated in Illustrative Embodiment III below.

With hydrogen, palladium on H-Mordenite, p= 750.075 - 7500.75Torr , Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5402; (2005); (A2) English View in Reaxys

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Rx-ID: 25832063 View in Reaxys 88/481 Yield

Conditions & References 1; 3; 6 :Example 1 (Comparative)Sec-butylbenzene synthesis with MCM-22 and single-step addition of 1- butene[0064] A sample of fresh MCM-22 catalyst with a nominal composition of 80percent zeolite and 20percent Versal 300 alumina, extruded to 1/16 inch (1.6 mm) diameter cylinder form, was dried at 26O0C for a minimum of 2 hours before testing. 0.5 grams of catalyst (containing 0.4 grams of zeolite) was loaded <n="18"/>between two 0.25-inch layers of inert, 8-grit quartz particles that had previously been dried at 121 °C until loaded into the stationary sample basket. 150 grams of reagent grade benzene was added to a 600-ml batch autoclave reactor. The sample basket assembly was installed in the autoclave reactor and sealed. The batch reactor was evacuated and purged twice with N2 to ensure the elimination of air from the head space. The batch reactor was then pressured to about 200 psig (1480 kPa) with N2 to ensure proper sealing and absence of leaks. Pressure was reduced to about 50 psig (446 kPa) and about 100 psig (791 kPa) of N2 was used to quantitatively deliver 25 grams of reagent grade 1-butene from a transfer vessel into the batch reactor. The benzene to 1-butene ratio was 6:1 by weight and 4.3:1 by mole.[0065] Reactor contents were mixed at 1000 rpm with a vertically positioned impeller located in the center of the stationary sample basket. The reactor was heated to 160°C in about 20 minutes using a programmable autoclave controller to maintain constant ramp rate and temperature. After reaching temperature, the reactor pressure was increased between 600 and 700 psig (4746-5537 kPa) by adding more N2 to the system. Reaction time-zero was recorded from the point at which temperature and pressure targets (160°C, 600-700 psig) are attained and stable. The reaction period for this evaluation was 5 hours. Samples (1 cc each) were taken at 1-hour increments for GC analysis. At the end of the reaction period, the run was discontinued, the reactor cooled to ambient conditions and the total liquid product recovered for GC analysis.[0066] Product analysis by GC was based on the assumption that composition of light components in the vapor phase was identical to those dissolved in liquid phase. The analysis was performed using an HP 6890 GC equipped with a DB-I column (6OM, 0.25mm ID, 1 micro liter film thickness) and an FID detector. A 0.2 micro liter portion of the product was injected onto the column and the following temperature program was used to perform the analysis: injection with 2-minute hold at -20°C, ramp at 8°C/min to 2750C, hold at 2750C for 35 minutes. Response factors were used to convert GC area-based data to actual composition in the product. Butene conversion was determined by measuring unreacted butene <n="19"/>relative to feed butene. Data obtained from the evaluation of Example 1 catalyst are reported in Table 1. Table 1. MCM-22 with Single-Step Addition of 1 -Butene in a Batch ReactorHours on Stream 1.0 2.0 3.0 4.0 5.0Feed QzICA= Weight ratio 6.0 6.0 6.0 6.0 6.0Feed Bz/C4= Molar ratio 4.3 4.3 4.3 4.3 4.3Butene Conversion, percent 72.4 83.7 90.9 94.9 97.1Product Selectivity. wtpercent iButane 0.058 0.051 0.046 0.041 0.039 n-Butane 0.229 0.193 0.173 0.153 0.143C5-C7 0.169 0.139 0.132 0.124 0.135C8= 1.669 1.498 1.319 1.163 1.128Cg- 11 0.131 0.096 0.076 0.086 0.079Ci2= + C10-C11 Aromatics 0.112 0.105 0.122 0.113 0.131C13-15 0.063 0.066 0.065 0.093 0.082Cumene 0.016 0.015 0.015 0.018 0.018 t-Butylbenzene 0.034 0.035 0.038 0.042 0.046 i-Butylbenzene * 0.000 0.000 0.000 0.000 0.000 s-Butylbenzene 90.113 90.703 91.050 91.089 91.279 n-Butylbenzene 0.011 0.015 0.013 0.015 0.014Di-butylbenzene 7.012 6.591 6.459 6.636 6.526Tri-butylbenzene 0.355 0.299 0.353 0.381 0.349Heavies 0.028 0.194 0.138 0.045 0.031Sum 100.0 100.0 100.0 100.0 100.0 s-Butvlbenzene (BB) Puritv, percent t-BB/all BB, percent 0.038 0.038 0.042 0.046 0.050 i-BB*/all BB, percent 0.000 0.000 0.000 0.000 0.000 s-BB/all BB, percent 99.950 99.945 99.944 99.937 99.935 n-BB/all BB, percent 0.012 0.016 0.015 0.017 0.015Sum, percent 100.0 100.0 100.0 100.0 100.0Di-BB/s-BB Wt Ratio, percent 7.8 7.3 7.1 7.3 7.1All samples collected at 1600C, 600-700 psig with 150 g of benzene and 25 g of 1-butene. * iButylbenzene less than 0.5percent in total butylbenzene not detectable with GC used. Example 3Sec-butylbenzene synthesis with MCM-22 and multi-staged addition of equal amounts of 1-butene[0068] A further 0 5 gram sample of the dπed MCM-22 catalyst used in Example 1 was loaded between two 0 25-inch layers of inert, 8-grit quartz particles that were previously dπed at 121°C until loaded into the stationary sample basket 150 grams of reagent grade benzene was added to a 600 ml batch autoclave reactor The sample basket assembly was installed on the body of the autoclave reactor and sealed The batch reactor was evacuated and purged twice with N2 to ensure the elimination of air from the head space The batch reactor <n="21"/>was then pressured to about 200 psig (1480 kPa) with N2 to ensure proper sealing and absence of leaks. Pressure was reduced to about 50 psig (446 kPa) and about 100 psig (791 kPa) of N2 was used to quantitatively deliver 5 grams of reagent grade 1 -butene from a transfer vessel into the batch reactor. [0069] Reactor contents were mixed at 1000 rpm with a vertically positioned impeller located in the center of the stationary sample basket. The reactor was heated to 160°C in about 20 minutes using a programmable autoclave controller to maintain constant ramp rate and temperature. After reaching temperature, the reactor pressure was increased between 600 and 700 psig ( 4746-5537 kPa)by adding more N2 to the system. Reaction time zero was recorded from the point at which temperature and pressure targets (160°C, 600-700 psig) are attained and stable. At the end of 1-hour, a 1-cc sample was taken from the reactor. Another 5 grams of reagent grade 1 -butene was quantitatively delivered from a transfer vessel into the batch reactor. This step- wise sampling

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and 5 gram 1 -butene addition procedure was followed until a total of 5 increments (including the initial 5 gram charge) of 1 -butene were added to the reactor. The final benzene to 1- butene ratio was 6:1 by weight and 4.3:1 by mole. The total reaction period for this evaluation was 5 hours. At the end of the reaction period, the run was discontinued, the reactor cooled to ambient conditions and the total liquid product recovered GC analysis. Incremental samples were also evaluated.[0070] Product analysis by GC and data analysis were identical to those described in Example 1. Data obtained from the evaluation of Example 3 catalyst are reported in Table 3. <n="22"/>Table 3.

MCM-22 with Multi-Staged Addition of 1-Butene in a Batch ReactorHours on Stream 1 0 2 0 3 0 4 0 5 0Benzene Weight, g 150 150 150 150 150Butene Weight, g 5 10 15 20 25Feed Bz/C4= Weight Ratio 30 0 15 0 10 0 7 5 6 0Feed Bz/C4= Molar Ratio 21 5 10 7 7 2 5 4 4 3Butene Conversion, percent 94 7 95 5 95 9 95 8 96 6Product Selectivity. wtpercent ι-Butane 0 048 0 040 0 046 0 040 0 036 n-Butane 0 167 0 132 0 158 0 136 0 124C5-C7 0 442 0 233 0 204 0 141 0 109C8= 0 721 0 397 0 322 0 290 0 287Cg- 11 0 035 0 015 0 025 0 037 0 028Ci2= + C10-C11 Aromatics 0 069 0 038 0 033 0 035 0 042C13-15 0 024 0 015 0 022 0 039 0 037Cumene 0 157 0 064 0 023 0 016 0 012 tButylbenzene 0 064 0 063 0 061 0 059 0 057 i-Butylbenzene * 0 000 0 000 0 000 0 000 0 000 s-Butylbenzene 95 317 95 699 94 853 94 101 93 268 n-Butylbenzene 0 011 0 012 0 012 0 009 0 010Di-butylbenzene 2 729 3 162 4 083 4 912 5 771Tri-butylbenzene 0 183 0 121 0 131 0 172 0 197Heavies 0 033 0 008 0 026 0 014 0 022Sum 100 0 100 0 100 0 100 0 100 0 s-Butylbenzene (BB) Puπtv. percent t-BB/all BB, percent 0 068 0 066 0 064 0 063 0 061 iBBVall BB, percent 0 000 0 000 0 000 0 000 0 000 s-BB/all BB, percent 99 921 99 921 99 923 99 928 99 929 nBB/all BB, percent 0 012 0 013 0 013 0 009 0 010Sum, percent 100 0 100 0 100 0 100 0 100 0Di-BB/s-BB Wt Ratio, percent 2 9 3 3 4 3 5 2 6 2All samples collected at 1600C, 600-700 psig * i-Butylbenzene less than 0 5percent in total butylbenzene not detectable with GC usedExample 6: Comparison of Batch Reactor Results[0073] Table 6 compares batch reactor data of Examples 1 to 5 collected at 5 hours reaction time. When operated with a single-step addition of 1 -butene,MCM-22 and MCM-49 catalysts produced sec-butylbenzene with 91percent selectivity.When operated with multi-staged addition of 1 -butene to reach the same final benzene/1 -butene molar ratio of 4.3:1, MCM-22 and MCM-49 catalysts improved sec-butylbenzene selectivity to 93-94percent. Multi-staged addition also provided a 3- fold reduction of butene oligomers, and a reduction of di-butylbenzenes and tri- butylbenzenes. <n="25"/>Table 6. Comparison of Batch Reactor Results at the End of RunMode of Butene Addition Single-Step Addition Multi-Staged (5x 5 g) AdditionExample Example 1 Example 2 Example 3 Example 4 Example 5Jet-milledCatalyst MCM-22 MCM-49 MCM-22 MCM-49 MCM-49Benzene (Bz) Weight, g 150 150 150 150 150Total Butene (C4 =) Weight, g 25 25 5 x 5 5 x 5 5 x 5Total Feed Bz/C4= Weight Ratio 6.0 6.0 6.0 6.0 6.0Total Feed Bz/C4= Molar Ratio 4.3 4.3 4.3 4.3 4.3Butene Conversion, percent 97.1 95.3 96.6 96.8 93.1Product Selectivitv. wtpercent i-Butane 0.039 0.041 0.036 0.038 0.037 n-Butane 0.143 0.138 0.124 0.131 0.134C5-C7 0.135 0.128 0.109 0.105 0.081C8= 1.128 1.068 0.287 0.273 0.247Cg- 11 0.079 0.086 0.028 0.034 0.053Ci2= + C10-C11 Aromatics 0.131 0.114 0.042 0.036 0.036C13-15 0.082 0.090 0.037 0.037 0.035Cumene 0.018 0.017 0.012 0.008 0.010 t-Butylbenzene 0.046 0.043 0.057 0.058 0.055 i-Butylbenzene * 0.000 0.000 0.000 0.000 0.000 s-Butylbenzene 91.279 91.391 93.268 93.513 94.432 n-Butylbenzene 0.014 0.013 0.010 0.009 0.012Di-butylbenzene 6.526 6.486 5.771 5.547 4.681Tri-butylbenzene 0.349 0.356 0.197 0.184 0.163Heavies 0.031 0.028 0.022 0.026 0.024Sum 100.0 100.0 100.0 100.0 100.0 sButylbenzene (BB) Purity, percent t-BB/all BB, percent 0.050 0.047 0.061 0.062 0.058 i-BB7all BB, percent 0.000 0.000 0.000 0.000 0.000 s-BB/all BB, percent 99.935 99.938 99.929 99.928 99.929 n-BB/all BB, percent 0.015 0.015 0.010 0.010 0.013Sum, percent 100.00 100.00 100.00 100.00 100.00Di-BB/s-BB Wt Ratio, percent 7.1 7.1 6.2 5.9 5.0 All samples collected at 1600C, 600-700 psig, and 5 hours reaction time.* i-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0074] It is to be appreciated that at a 6: 1 benzene/ 1 -butene weight ratio (4.3 molar ratio), the 1-butene concentration is 14.3 wtpercent (1/7) if all of the feed 1- butene mixes with all of the feed benzene instantaneously upon addition. Given the relatively slow reaction rates and fast stirring, this is a reasonable approximation with a well-stirred autoclave reactor, and can be approached in a fixed bed reactor with adequate feed distribution nozzles at each feed injection level. The local concentrations would be higher with nonideal mixing. For a <n="26"/>fixed bed system, there will normally be two or more catalyst beds, preferably with a separate olefin feed injection zone upstream of at least two of these beds. Within each zone, there may be a single nozzle for introduction of olefins into the bulk flowing mixture, or preferably multiple nozzles. [0075] When the same amount of butene was added stepwise (5-steps as in Examples 3-5) with nearly complete conversion of butene in between additions (92-97percent butene conversion as in Examples 3-5), the maximum olefin concentration would be 2.9 wtpercent (20percent x 1/7). In a fixed bed reactor with essentially steady state operation, having multiple feed injection points is more or less the equivalent of multiple feed addition events to a batch reactor.

With MCM-22 zeolitic catalyst, Time= 1 - 5h, T= 160 °C , p= 31029.7 - 36201.3Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93357; (2007); (A1) English View in Reaxys 2; 4; 5; 6 :Example 2 (Comparative) Sec-Butylbenzene synthesis using MCM-49 with single-step addition of 1- Butene[0067] The process of Example 1 was repeated but using a fresh MCM-49 catalyst with a nominal composition

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of 80percent zeolite and 20percent Versal 300 alumina, extruded to 1/16 inch cylinder form. Data are reported in Table 2. <n="20"/>Table 2. MCM-49 with Single-Step Addition of 1-Butene in a Batch ReactorHours on Stream 1 0 2 0 3 0 4 0 5 0Feed Bz/C4= Weight ratio 6 0 6 0 6 0 6 0 6 0Feed Bz/C4= Molar ratio 4 3 4 3 4 3 4 3 4 3Butene Conversion, percent 70 8 82 2 89 0 93 2 95 3Product Selectivity. wtpercent ι-Butane 0 058 0 045 0 041 0 039 0 041 n-Butane 0 203 0 154 0 139 0 133 0 138C5-C7 0 187 0 146 0 130 0 115 0 128C8= 1 484 1 302 1 201 1 078 1 068C9-11 0 117 0 112 0 094 0 089 0 086Ci2= + C10-C11 Aromatics 0 115 0 112 0 100 0 103 0 114C13-15 0 082 0 070 0 065 0 077 0 090Cumene 0 011 0 012 0 014 0 015 0 017 t-Butylbenzene 0 036 0 036 0 038 0 041 0 043 iButylbenzene * 0 000 0 000 0 000 0 000 0 000 s-Butylbenzene 90 296 90 872 91 464 91 368 91 391 n-Butylbenzene 0 012 0 015 0 014 0 013 0 013Di-butylbenzene 6 999 6 723 6 360 6 564 6 486Tπ-butylbenzene 0 368 0 354 0 314 0 340 0 356Heavies 0 032 0 047 0 026 0 026 0 028Sum 100 0 100 0 100 0 100 0 100 0 s-Butvlbenzene (BB) Puπtv. percent t-BB/all BB, percent 0 040 0 040 0 041 0 045 0 047 i-BBVall BB, percent 0 000 0 000 0 000 0 000 0 000 sBB/all BB, percent 99 947 99 944 99 943 99 941 99 938 n-BB/all BB, percent 0 013 0 016 0 015 0 014 0 015Sum, percent 100 0 100 0 100 0 100 0 100 0Di-BB/s-BB Wt Ratio, percent 7 8 7 4 7 0 7 2 7 1All samples collected at 160°C, 600-700 psig with 150 g of benzene and 25 g of 1 -butene* i-Butylbenzene less than 0 5percent in total butylbenzene not detectable with GC used Example 4Sec-butylbenzene synthesis with MCM-49 and multi-staged addition of equal amounts of 1-butene [0071 J The evaluation protocol of Example 3 was repeated but using the MCM-49 catalyst of Example 2 The results are summarized in Table 4 <n="23"/>Table 4. MCM-49 with Multi-Staged Addition of 1-Butene in a Batch ReactorHours on Stream 1.0 2.0 3.0 4.0 5.0Benzene Weight, g 150 150 150 150 150Butene Weight, g 5 10 15 20 25Feed Bz/C4= Weight Ratio 30.0 15.0 10.0 7.5 6.0Feed Bz/C4= Molar Ratio 21.5 10.7 7.2 5.4 4.3C4= Conv percent 92.9 94.4 94.9 95.1 96.8Product Selectivity, wtpercent i-Butane 0.041 0.046 0.043 0.045 0.038 n-Butane 0.150 0.166 0.144 0.147 0.131C5-C7 0.485 0.258 0.164 0.120 0.105C8= 0.650 0.446 0.326 0.318 0.273Cg11 0.045 0.046 0.042 0.030 0.034Ci2= + C10-C11 Aromatics 0.043 0.046 0.042 0.036 0.036C13-15 0.028 0.028 0.027 0.034 0.037Cumene 0.024 0.018 0.012 0.008 0.008 t-Butylbenzene 0.068 0.062 0.063 0.061 0.058 i-Butylbenzene * 0.000 0.000 0.000 0.000 0.000 s-Butylbenzene 96.331 95.693 95.206 94.362 93.513 n-Butylbenzene 0.011 0.018 0.010 0.011 0.009Di-butylbenzene 1.991 3.007 3.775 4.663 5.547Tri-butylbenzene 0.115 0.148 0.124 0.151 0.184Heavies 0.019 0.018 0.022 0.017 0.026Sum 100.0 100.0 100.0 100.0 100.0 s-Butvlbenzene (BB) Puritv. percent t-BB/all BB, percent 0.071 0.065 0.066 0.064 0.062 i-BB7all BB, percent 0.000 0.000 0.000 0.000 0.000 sBB/all BB, percent 99.918 99.917 99.923 99.925 99.928 n-BB/all BB, percent 0.011 0.019 0.011 0.011 0.010Sum, percent 100.00 100.00 100.00 100.00 100.00Di-BB/s-BB Wt Ratio, percent 2.1 3.1 4.0 4.9 5.9All samples collected at 1600C, 600-700 psig. * i-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.

Example 5Sec-butylbenzene synthesis with jet-milled MCM-49 and multi-staged addition of equal amounts of 1-butene [0072] A sample of fresh MCM-49 was jet milled and then extruded with Versal 200 alumina into a 1/20 inch (1.3 mm) quadailobe catalyst with a nominal composition of 60percent zeolite and 40percent alumina. 0.667 g of catalyst (containing 0.4 grams of zeolite) was loaded into the batch reactor and the evaluation protocol of Example 3 was repeated. Data are reported in Table 5. <n="24"/>Table 5. Jet-Milled MCM-49 with Multi-Staged Addition of 1Butene in a BatchReactorHours on Stream 1.0 2.0 3.0 4.0 5.0Benzene Weight, g 150 150 150 150 150Butene Weight, g 5 10 15 20 25Feed Bz/C4= Weight Ratio 30.0 15.0 10.0 7.5 6.0Feed BzJCA= Molar Ratio 21.5 10.7 7.2 5.4 4.3Butene Conversion, percent 92.4 93.1 93.7 93.2 93.1Product Selectivity. wtpercent i-Butane 0.051 0.044 0.038 0.040 0.037 n-Butane 0.197 0.157 0.136 0.145 0.134C5-C7 0.439 0.254 0.162 0.101 0.081C8= 0.751 0.325 0.261 0.251 0.247C9-11 0.195 0.069 0.054 0.050 0.053 + C10-C11 Aromatics 0.030 0.034 0.031 0.036 0.036C13-15 0.022 0.028 0.024 0.030 0.035Cumene 0.027 0.019 0.012 0.010 0.010 t-Butylbenzene 0.064 0.062 0.059 0.057 0.055 i-Butylbenzene * 0.000 0.000 0.000 0.000 0.000 s-Butylbenzene 95.479 95.827 95.428 94.937 94.432 n-Butylbenzene 0.016 0.015 0.013 0.012 0.012Di-butylbenzene 2.294 2.914 3.621 4.159 4.681Tri-butylbenzene 0.138 0.121 0.138 0.154 0.163Heavies 0.297 0.130 0.024 0.017 0.024Sum 100.0 100.0 100.0 100.0 100.0 s-Butvlbenzene (BB) Puritv. percent t-BB/all BB, percent 0.067 0.064 0.061 0.060 0.058 i-BB7all BB, percent 0.000 0.000 0.000 0.000 0.000 s-BB/all BB, percent 99.916 99.920 99.925 99.927 99.929 n-BB/all BB, percent 0.016 0.015 0.014 0.013 0.013Sum, percent 100.0 100.0 100.0 100.0 100.0Di-BB/s-BB Wt Ratio, percent 2.4 3.0 3.8 4.4 5.0All samples collected at 1600C, 600-700 psig. * i-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.Example 6: Comparison of Batch Reactor Results[0073] Table 6 compares batch reactor data of Examples 1 to 5 collected at 5 hours reaction time. When operated with a single-step addition of 1 -butene,MCM-22 and MCM-49 catalysts produced sec-butylbenzene with 91percent selectivity.When operated with multi-staged addition of 1 -butene to reach the same final benzene/1 -butene molar ratio of 4.3:1, MCM-22 and MCM-49 catalysts improved secbutylbenzene selectivity to 93-94percent. Multi-staged addition also provided a 3- fold reduction of butene oligomers, and a reduction of di-butylbenzenes and tri- butylbenzenes. <n="25"/>Table 6. Comparison of Batch Reactor Results at the End of RunMode of Butene Addition Single-Step Addition Multi-Staged (5x 5 g) AdditionExample Example 1 Example 2 Example 3 Example 4 Example 5Jet-milledCatalyst MCM-22 MCM-49 MCM-22 MCM-49 MCM-49Benzene (Bz) Weight, g 150 150 150 150 150Total Butene (C4 =) Weight, g 25 25 5 x 5 5 x 5 5 x 5Total Feed Bz/C4= Weight Ratio 6.0 6.0 6.0 6.0 6.0Total Feed Bz/C4= Molar Ratio 4.3 4.3 4.3 4.3 4.3Butene Conversion, percent 97.1 95.3 96.6 96.8 93.1Product Selectivitv. wtpercent i-Butane 0.039 0.041 0.036 0.038 0.037 n-Butane 0.143 0.138 0.124 0.131 0.134C5-C7 0.135 0.128 0.109 0.105 0.081C8= 1.128 1.068 0.287 0.273 0.247Cg- 11 0.079 0.086 0.028

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0.034 0.053Ci2= + C10-C11 Aromatics 0.131 0.114 0.042 0.036 0.036C13-15 0.082 0.090 0.037 0.037 0.035Cumene 0.018 0.017 0.012 0.008 0.010 t-Butylbenzene 0.046 0.043 0.057 0.058 0.055 i-Butylbenzene * 0.000 0.000 0.000 0.000 0.000 s-Butylbenzene 91.279 91.391 93.268 93.513 94.432 n-Butylbenzene 0.014 0.013 0.010 0.009 0.012Di-butylbenzene 6.526 6.486 5.771 5.547 4.681Tri-butylbenzene 0.349 0.356 0.197 0.184 0.163Heavies 0.031 0.028 0.022 0.026 0.024Sum 100.0 100.0 100.0 100.0 100.0 s-Butylbenzene (BB) Purity, percent t-BB/all BB, percent 0.050 0.047 0.061 0.062 0.058 i-BB7all BB, percent 0.000 0.000 0.000 0.000 0.000 s-BB/all BB, percent 99.935 99.938 99.929 99.928 99.929 n-BB/all BB, percent 0.015 0.015 0.010 0.010 0.013Sum, percent 100.00 100.00 100.00 100.00 100.00Di-BB/s-BB Wt Ratio, percent 7.1 7.1 6.2 5.9 5.0 All samples collected at 1600C, 600-700 psig, and 5 hours reaction time.* i-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.

[0074] It is to be appreciated that at a 6: 1 benzene/ 1 -butene weight ratio (4.3 molar ratio), the 1-butene concentration is 14.3 wtpercent (1/7) if all of the feed 1- butene mixes with all of the feed benzene instantaneously upon addition. Given the relatively slow reaction rates and fast stirring, this is a reasonable approximation with a well-stirred autoclave reactor, and can be approached in a fixed bed reactor with adequate feed distribution nozzles at each feed injection level. The local concentrations would be higher with non-ideal mixing. For a <n="26"/>fixed bed system, there will normally be two or more catalyst beds, preferably with a separate olefin feed injection zone upstream of at least two of these beds. Within each zone, there may be a single nozzle for introduction of olefins into the bulk flowing mixture, or preferably multiple nozzles. [0075] When the same amount of butene was added stepwise (5-steps as in Examples 3-5) with nearly complete conversion of butene in between additions (92-97percent butene conversion as in Examples 3-5), the maximum olefin concentration would be 2.9 wtpercent (20percent x 1/7). In a fixed bed reactor with essentially steady state operation, having multiple feed injection points is more or less the equivalent of multiple feed addition events to a batch reactor.

With MCM-49 zeolitic catalyst, Time= 1 - 5h, T= 160 °C , p= 31029.7 - 36201.3Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93357; (2007); (A1) English View in Reaxys 1; 3 :Example 1 (Comparative)Sec-butylbenzene synthesis with MCM-22 and single-step addition of 1- butene[0069] A sample of fresh MCM-22 catalyst with a nominal composition of 80percent zeolite and 20percent Versal 300 alumina, extruded to 1/16 inch (1.6 mm) diameter cylinder form, was dried at 260°C for a minimum of 2 hours before testing. 0.5 grams of catalyst (containing 0.4 grams of zeolite) was loaded between two 0.25-inch layers of inert, 8-grit quartz particles that had previously been dried at 121 °C until loaded into the stationary sample basket. 150 grams of reagent grade benzene was added to a 600-ml batch autoclave reactor. The sample basket assembly was installed in the autoclave reactor and sealed. The batch reactor was evacuated and purged twice with N2 to ensure the elimination of air from the head space. The batch reactor was then pressured to about 200 psig (1480 kPa) with N2 to ensure proper sealing and absence of leaks. Pressure was reduced to about 50 psig (446 kPa) and about 100 psig (791 kPa) of N2 was used to quantitatively deliver 25 grams of reagent grade 1-butene from a transfer vessel into the batch reactor. The benzene to 1-butene ratio was 6:1 by weight and 4.3:1 by mole. <n="20"/>[0070] Reactor contents were mixed at 1000 rpm with a vertically positioned impeller located in the center of the stationary sample basket. The reactor was heated to 160°C in about 20 minutes using a programmable autoclave controller to maintain constant ramp rate and temperature. After reaching temperature, the reactor pressure was increased to between 600 and 700 psig (4750-5540 kPa) by adding more N2 to the system. Reaction time-zero was recorded from the point at which temperature and pressure targets (160°C, 600-700 psig) are attained and stable. The reaction period for this evaluation was 5 hours. Samples (1 cc each) were taken at 1-hour increments for GC analysis. At the end of the reaction period, the run was discontinued, the reactor cooled to ambient conditions and the total liquid product recovered for GC analysis.[0071] Product analysis by GC was based on the assumption that composition of light components in the vapor phase was identical to those dissolved in liquid phase. The analysis was performed using an HP 6890 GC equipped with a DB-I column (6OM, 0.25mm ID, 1 micro liter film thickness) and an FID detector. A 0.2 micro liter portion of the product was injected onto the column and the following temperature program was used to perform the analysis: injection with 2-minute hold at -20°C, ramp at 8°C/min to 275°C, hold at 275°C for 35 minutes. Response factors were used to convert GC area-based data to actual composition in the product. Butene conversion was determined by measuring unreacted butene relative to feed butene. Data obtained from the evaluation of Example 1 catalyst are reported in Table 1.; Example 3Sec-butylbenzene synthesis with MCM-22 and multi-staged addition of equal amounts of 1-butene [0073] A further 0.5 gram sample of the dried MCM-22 catalyst used in Example 1 was loaded between two 0.25-inch layers of inert, 8-grit quartz particles that were previously dried at 121°C until loaded into the stationary sample basket. 150 grams of reagent grade benzene was added to a 600 ml batch autoclave reactor. The sample basket assembly was installed on the body of the autoclave reactor and sealed. The batch reactor was evacuated and purged twice <n="23"/>with N2 to ensure the elimination of air from the head space. The batch reactor was then pressured to about 200 psig (1480 kPa) with N2 to ensure proper sealing and absence of leaks. Pressure was reduced to about 50 psig (446 kPa) and about 100 psig (791 kPa) of N2 was used to

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quantitatively deliver 5 grams of reagent grade 1-butene from a transfer vessel into the batch reactor.[0074] Reactor contents were mixed at 1000 rpm with a vertically positioned impeller located in the center of the stationary sample basket. The reactor was heated to 16O0C in about 20 minutes using a programmable autoclave controller to maintain constant ramp rate and temperature. After reaching temperature, the reactor pressure was increased to 600 and 700 psig (4750-5540 kPa) by adding more N2 to the system. Reaction time zero was recorded from the point at which temperature and pressure targets (160°C, 600-700 psig) are attained and stable. At the end of 1-hour, a 1-cc sample was taken from the reactor. Another 5 grams of reagent grade 1-butene was quantitatively delivered from a transfer vessel into the batch reactor. This step-wise sampling and 5 gram 1-butene addition procedure was followed until a total of 5 increments (including the initial 5 gram charge) of 1-butene were added to the reactor. The final benzene to 1-butene ratio was 6:1 by weight and 4.3:1 by mole. The total reaction period for this evaluation was 5 hours.

At the end of the reaction period, the run was discontinued, the reactor cooled to ambient conditions and the total liquid product recovered GC analysis. Incremental samples were also evaluated.[0075] Product analysis by GC and data analysis were identical to those described in Example 1. Data obtained from the evaluation of Example 3 catalyst are reported in Table 3.

With MCM-22, Time= 1.33333 - 5.33333h, T= 160 °C , p= 5931.67 - 36961.4Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93358; (2007); (A1) English View in Reaxys 2; 4; 5 :Example 2 (Comparative)Sec-Butylbenzene synthesis using MCM-49 with single-step addition of 1-Butene [0072] The process of Example 1 was repeated but using a fresh MCM-49 catalyst with a nominal composition of 80percent zeolite and 20percent Versal 300 alumina, extruded to 1/16 inch cylinder form. Data are reported in Table 2.; Example 4Sec-butylbenzene synthesis with MCM-49 and multi-staged addition of equal amounts of 1-butene[0076] The evaluation protocol of Example 3 was repeated but using the MCM-49 catalyst of Example 2. The results are summarized in Table 4.; Example 5Sec-butylbenzene synthesis with jet-milled MCM-49 and multi-staged addition of equal amounts of 1-butene[0077] A sample of fresh MCM-49 was jet milled and then extruded with Versal 200 alumina into a 1/20 inch (1.3 mm) quadrulobe catalyst with a nominal composition of 60percent zeolite and 40percent alumina. 0.667 g of catalyst (containing 0.4 grams of zeolite) was loaded into the batch reactor and the evaluation protocol of Example 3 was repeated. Data are reported in Table 5.

With MCM-49, Time= 1.33333 - 5.33333h, T= 160 °C , p= 5931.67 - 36961.4Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93358; (2007); (A1) English View in Reaxys

13C

H 13C

O

O

Rx-ID: 2834975 View in Reaxys 89/481 Yield 41 %, 41 %, 1.4 %, 0.7 %

Conditions & References With trimethylhexadecylammonium chloride in water, T= 20 - 25 °C , Irradiation, isotope effect, cage effect, Quantum yield Turro, Nicholas J.; Mattay, Jochen; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4200 4204 View in Reaxys

Rx-ID: 3917105 View in Reaxys 90/481

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Yield

Conditions & References With aluminosilicate, T= 70 °C , effect of the composition and amount of catalysts, reaction time and temperature, Rate constant, Product distribution Kolesnikov; Zaitseva; Journal of applied chemistry of the USSR; vol. 58; nb. 4 pt 1; (1985); p. 754 - 760 View in Reaxys 1; 2 :EXAMPLE 1; Reaction of Propylene with Benzene; Benzene and propylene were reacted over the CP 786 catalyst at the conditions outlined in Table 2. Complete conversion of the propylene was observed. The results of the testing are presented in Table 2. The product obtained was found to contain a significant amount of di-isopropyl benzenes isomers, such as 1,2 di-isopropyl benzene, (1,2-DIPB) 1,3 di-isopropyl benzene, (1,3-DIPB) and 1,4 di-isopropyl benzene (1,4-DIPB) and even some 1,3,5-tri-isopropyl benzene, (1,3,5-TIPB); EXAMPLE 2; Reaction of Propylene with Benzene; A higher concentration of propylene, (2.013 wt. percent) than used in Example 1 was reacted with benzene over the CP 786 catalyst at similar conditions outlined in Table 3. Complete conversion of the propylene was observed. The results of the testing are presented in Table 3. The product obtained was found to contain higher 15 amounts of the di-isopropyl benzenes isomers and 1,3,5-tri-isopropyl benzene; The total moles of di- and tri- propyl benzene in the product (0.00124) is the data point at the right end of line Y, and the data point at the right end of line X. With zeolite beta CP 786 catalyst, T= 132 - 133 °C , p= 15757.7 - 15809.5Torr , Product distribution / selectivity Patent; Murray, Brendan Dermot; Mysore, Narayana; Yaeger, James William; US2006/178544; (2006); (A1) English View in Reaxys

OH

Rx-ID: 21236788 View in Reaxys 91/481 Yield

Conditions & References Reaction Steps: 2 1: 92 percent / triethylamine / diethyl ether / Ambient temperature 2: H2 / 10percent Pd-C / methanol / 760 Torr / Ambient temperature With hydrogen, triethylamine, palladium on activated charcoal in methanol, diethyl ether Subramanian, L. R.; Martinez, A. Garcia; Fernandez A. Herrera; Alvarez, R. Martinez; Synthesis; nb. 6; (1984); p. 481 - 485 View in Reaxys

C10, C11 and others

triisopropylbenzenes Rx-ID: 23225167 View in Reaxys 92/481

Yield 37.0 %, 1.5 %, 0.7 %, 3.3 %

Conditions & References 1 :Example 1 Comparative Example 1 shows the results of a base case with the traditional transalkylator feed in a 2:1 weight ratio of benzene to DIPB. The feed composition was 65.9 wt. percent benzene, 30.9 wt. percent metaDIPB, 1.8 wt. percent ortho-DIPB, and 0.4 wt. percent para-DIPB. The reaction was conducted at a WHSV of 1 with a feed rate of 2 grams per hour and a temperature of 405° F. (207° C.). The effluent composition is shown in Table 1.

It can be seen that the effluent was primarily benzene and cumene with 3.3 wt. percent para-DIPB. With MCM-22 zeolite, T= 207 °C , Product distribution / selectivity Patent; Clark, Michael C.; Cimini, Ronald J.; Cheng, Jane C.; Stern, David L.; Buchanan, John Scott; US2005/75523; (2005); (A1) English View in Reaxys

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Rx-ID: 23225168 View in Reaxys 93/481 Yield 1.0 - 9.9 %, 3.3 15.2 %, 1.2 - 14.5 %, 0.4 1.4 %

Conditions & References 1 :In this experiment, p-DIPB was synthesized by utilizing the technique of this invention. In the procedure used, 142 g (195 cc) of silica alumina catalyst, consisting of 90percent silica and 10percent alumina, was loaded into a 24 long 1.0OD (0.83 ID) 316 stainless steel tube. The catalyst bed was positioned for optimal heating within the reactor by supporting and retaining the bed on inert packing. The reactor was heated externally with hot-oil spiral-wound heat tracing (0.25 OD tubing). A m-DIPB stream (consisting of 98.5percent m-DIPB, 0.6percent o-DIPB, 0.2percent pDIPB, with the balance being m-, o-, and p-ethylcumenes) was fed to the reactor at a rate of 4.0 g/minute, resulting in a space velocity of 1.7 WHSV's. Pressure was maintained at 700 psig by a back pressure controller. The reactor was heated to 392° F. and the contents were allowed to come to steady state. Sample No.1 was collected and analyzed by GC. The temperature was then raised to 419° F. and the contents were allowed to come to steady state.

Sample No.2 was collected and analyzed by GC. The temperature was then raised to 455° F. and the contents were allowed to come to steady state. Sample No.3 was collected and analyzed by GC. The results are reported in the table below. In the catalyst loading procedure used, a stainless steel screen was positioned at the bottom of the reactor. Then about -1/4 of glass wool was packed next on top of the screen, followed by the catalyst. Finally, about 10 cc of glass chips were loaded on top of the catalyst bed, followed by another plug of glass wool. The feed stream was fed with vertical downflow and was operated liquid-full. , T= 199.99 - 234.99 °C , p= 36961.4Torr , Product distribution / selectivity Patent; Bennett, Ronald Quentin; Goodwin, Jeffrey Alan; Rich, Jonathan David; US2005/75522; (2005); (A1) English View in Reaxys

Rx-ID: 23228080 View in Reaxys 94/481 Yield 2.6 - 11.4 %, 8.3 28.1 %, 0.1 - 0.4 %, 2.9 15.4 %, 1.3 - 1.8 %

Conditions & References 2 :In this experiment, m-DIPB was synthesized utilizing the technique of this invention. In the procedure used, 142 grams (195 cc) of silica alumina catalyst, consisting of 90percent silica and 10percent alumina, was loaded into a 24 long 1.0 OD (0.83 ID) 316 stainless steel tube. The catalyst bed was positioned for optimal heating within the reactor by supporting and retaining the bed on inert packing. The reactor was heated externally with hot-oil spiral-wound heat tracing (0.25 OD tubing). p-DIPB stream (consisting of 99.4percent p-DIPB, 0.1percent m-DIPB, with the balance being various hexylbenzene isomers) was fed to the reactor at 4.0 g/minute, resulting in a space velocity of 1.7 WHSV's. Pressure was maintained at 700 psig by a back pressure controller. The reactor was heated to 392° F. and the contents were allowed to come to steady state. Sample No.1 was collected and analyzed by GC. The temperature was then raised to 419° F. and the contents were allowed to come to steady state. Sample No.2 was collected and analyzed by GC. The temperature was then raised to 455° F. and the contents were allowed to come to steady state. Sample No.3 was collected and analyzed by GC. The results are reported in the table below. In the catalyst loading procedure used, a stainless steel screen was positioned at the bottom of the reactor. Then about -1/4 of glass wool was packed next on top of the screen, followed by the catalyst. Finally, about 10 cc of glass chips were loaded on top of the catalyst bed, followed by another plug of glass wool. The feed stream was fed with vertical downflow and was operated liquid-full. , T= 199.99 - 234.99 °C , p= 36961.4Torr , Product distribution / selectivity

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Patent; Bennett, Ronald Quentin; Goodwin, Jeffrey Alan; Rich, Jonathan David; US2005/75522; (2005); (A1) English View in Reaxys

HO

HO

O

Rx-ID: 23426134 View in Reaxys 95/481 Yield

Conditions & References II.B.i :The 6-20 mesh particles of reduced T-366 catalyst, prepared by the procedure of Illustrative Embodiment II (A) (i), were loaded into the reflux zone of a thick walled 31 cm long Vigreux column with an internal diameter of 1.5 cm while inside a nitrogen filled glove box. A small, piece of glass wool was used to support the catalyst particles. The column was attached to a thick walled 250 ml round bottom flask which served as the bottom segment of the reactor for catalytic distillation. Hydrogen gas was added via a regulator to the apparatus to maintain a pressure between 1 and 10 bar. The flow rate was adjusted to maintain twice the amount of hydrogen required for the reaction stoichiometry. 50 grams of 2-phenyl-2-propanol (cumyl alcohol) from Avacado Chemical was added to the 250 mL flask which contained a magnetic stir bar at the bottom of the round bottom flask. The flask containing the cumyl alcohol was lowered into a heater and then the temperature was raised until the liquid refluxed in the Vigreux column containing the catalyst. Lower boiling cumene and water were distilled out from the top of the column. Additional cumyl alcohol was continually added with a slight molar excess of hydrogen to replace the amount of cumyl alcohol that was converted to cumene and distilled off. The cumene product easily separated from the denser water phase. It was optionally dried further with 3A molecular sieves. The results are provided in TABLE 2 below. As shown, the top product stream produced, (after removal of the water), had a purity of cumene of >99.5 wt. percent. No measurable cumyl alcohol (<0. 1 wt. percent) was found in the cumene product. When desired, the bottoms can be removed, optionally diluted with cumene and sent to a fixed bed hydrogenation reactor to make additional cumene.

With hydrogen, hydrogenated copper on silica (T-366), p= 750.075 - 7500.75Torr , Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5402; (2005); (A2) English View in Reaxys

Rx-ID: 23831758 View in Reaxys 96/481 Yield

Conditions & References 3 :EXAMPLE 3; According to the Invention; In the presence of a catalyst for alkylation of benzene, the light reformate that is described in Example 2 is brought into contact, in a first zone, with all of the dry gas that is produced by the catalytic cracking unit of Example 1 (or 8.1 t/h of dry gas and 20.4 t/h of light reformate).The molar flow rates at the inlet of the alkylation zone are as follows:Dry hydrogen gas: 162 kmol/hEthylene: 50 kmol/hPropylene: 12.9 kmol/ hBenzene: 74.5 kmol/hThe alkylation process is carried out in a reactor that contains a catalyst that contains 80percent by weight of Y zeolite and 20percent by weight of alumina, and whose Si/Al (silica/alumina) molar ratio is equal to 20, at a temperature of 270° C. and under a pressure of 0.5 MPa, whereby the PPH (expressed in terms of gram of benzene/gram of catalyst/hour) is 0.4 h-1.Under these conditions, the conversion of the ethylene and the propylene is close to 100percent. At the outlet of the alkylation zone, the following molar flow rates are finally obtained:Ethylene: 0Propylene: 0Benzene: 19.5 kmol/h or 1.52 t/hAlkylated aromatic compounds (ethylbenzene, diethylbenzene, cumene, diisopropylbenzene): 55 kmol/h or 6.23 t/h.The flow rate of reformate at the outlet of the alkylation zone, comprising the alkylated aromatic compounds and benzene that has not reacted, is equal to 22.34 t/h.In contrast, a flow rate of 6.158 t/h of dry gas that contains hydrogen (324 kg/h of H2) and from which olefins are largely removed, is recovered. This dry gas is used according to this example to carry out a partial hydrogenation of the aromatic compounds that are contained in the naphtha fraction that is described in Example 2. In other words, in a second zone, the hydrogenation of a portion of the aromatic compounds of said naphtha is carried out by the hydrogen that is contained in the dry gas that is recovered at the outlet of the alkylation zone.The hydrogenation is carried out in the presence of a catalyst for hydrogenation of aromatic compounds with an Ni base that rests on an alumina with a specific surface area of 130 m2/g and a pore volume that is equal to 1.04 cc/g (cubic centimeter per gram).

The nickel content is 20percent by weight expressed in Ni oxide (NiO), whereby the metal is deposited by an impregnation stage of a mineral precursor (nickel nitrate). The catalyst is then dried and calcined at high temperature so as to transform the metallic precursors into oxide particles that are finally reduced under a hydrogen flow at 350° C. for 2 hours. The hydrogenation reaction is carried out at a temperature of 130° C. and a pressure of 0.6 MPa, whereby

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the hourly volumetric flow rate is 8 h-1 relative to the liquid feedstock.The flow rates by mass of the reagents at the inlet of the hydrogenation zone are:Naphtha: 111.8 t/h (including 15.65 t/h of aromatic compounds)Dry gas flow rate: 6.158 t/h (containing 324 kg/h of hydrogen)Under the conditions that are described above, the conversion of the hydrogen is essentially equal to 99percent.At the outlet of the hydrogenation zone,a gas fraction that contains the lightest elements, i.e., primarily hydrogen that has not reacted (1.6 kmol/h) and the hydrocarbons that contain 1 to 4 carbon atoms and other compounds with a flow rate of 5.83 t/h, a liquid fraction that consists of hydrogenated naphtha with a flow rate of 112.12 t/h including 94.13 kmol/h of aromatic compounds and 53.47 kmol/h of naphthenes are obtained. , T= 270 °C , p= 3750.38Torr , Conversion of starting material Patent; Institut Francais du Petrole; US7081558; (2006); (B2) English View in Reaxys

E

Rx-ID: 23831760 View in Reaxys 97/481 Yield

Conditions & References 6; 7 :EXAMPLE 6; Reaction of a 4:1 Molar Blend of Propylene and trans-2-Butene with Benzene; An olefin blend of 80percent propylene and 20percent trans-2-butene (on a molar basis) was reacted over the CP 786 catalyst at the conditions outlined in Table 7. Complete conversion of the C3/C4 olefins was observed. Sec-butyl benzene and cumene were formed in high selectivity with a smaller amount of di- and tri-alkyl benzenes produced than when a similar number of moles of only propylene were used (Example 2). The total amount of moles of di- and tri-alkyl benzenes produced per 100 g of product was 0.00074 moles. This was at least 38percent less than the predicted amount (approximately 0.001 moles) based on interpolation from the amounts produced using the same number of moles of propylene or trans-2-butene only (see FIG. 1); EXAMPLE 7; Reaction of a 1:4 Molar Blend of Propylene and trans-2-Butene with Benzene; An olefin blend of 20percent propylene and 80percent trans-2-Butene (on a molar basis) was reacted over the CP 786 catalyst at the conditions outlined in Table 8. Complete conversion of the C3/C4 olefins was again observed. Sec-butyl benzene and cumene were formed in high selectivity with a smaller amount of di- and tri-alkyl benzenes produced than when a similar number of moles of only propylene were used (Example 2).

The total amount of moles of di- and tri-alkyl benzenes produced per 10 g of product was 0.00026 moles. This was at least 53percent less than the predicted amount (0.0004 moles) based on interpolation from the amounts produced using the same number of moles of propylene or trans-2-butene only (see FIG. 1).

With zeolite beta CP 786 catalyst, T= 133 °C , p= 15654.3Torr , Conversion of starting material Patent; Murray, Brendan Dermot; Mysore, Narayana; Yaeger, James William; US2006/178544; (2006); (A1) English View in Reaxys

crushed scrap tires Rx-ID: 27958320 View in Reaxys 98/481 Yield

Conditions & References With synthetic air, T= 450 °C , Formation of xenobiotics Conesa, Juan A.; Martin-Gullon; Font; Jauhiainen; Environmental Science and Technology; vol. 38; nb. 11; (2004); p. 3189 - 3194 View in Reaxys T= 450 °C , Formation of xenobiotics Conesa, Juan A.; Martin-Gullon; Font; Jauhiainen; Environmental Science and Technology; vol. 38; nb. 11; (2004); p. 3189 - 3194 View in Reaxys

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O –O

F

S

F +N

F

O

Rx-ID: 28554683 View in Reaxys 99/481 Yield

Conditions & References With ammonia, sodium in tetrahydrofuran, Time= 0.0833333h, T= -78 °C , regioselective reaction Paras, Nick A.; Simmons, Bryon; MacMillan, David W.C.; Tetrahedron; vol. 65; nb. 16; (2009); p. 3232 - 3238 View in Reaxys

O

Rx-ID: 28687567 View in Reaxys 100/481 Yield

Conditions & References 1 :Example 1; 2.0 g of a 5percent Re carbon catalyst (manufactured by NE Chemcat Co.) and 2.0 g of β zeolite (classified into 250 to 500 μ after compression molding at 20 MPa, manufactured by Shokubai Kasei Co., Ltd.) were mixed homogenously, and then fed into a quartz glass reactor having a diameter of 3 cm and a length of 40 cm and calcined in a nitrogen gas stream of 30 ml/min at 500°C for 1 hr, and then subjected to reduction treatment in a hydrogen gas stream of likewise 30 ml/min at 500°C for 1 hr. In the hydrogen gas stream, the temperature was decreased to 160°C, and then a mixed solution of benzene and acetone (benzene/acetone (molar ratio) = 5/1) was passed through at a rate of 2. 3 ml/min. A resulting product was collected by cooling an outlet. One to two hours after the reaction start, the resulting product was analyzed by a gas chromatography. All of acetone was disappeared, and cumene, m-diisopropyl benzene and p-diisopropyl benzene were generated in amounts of 95percent on the basis of the amount of acetone fed. The generation of cyclohexane was not found at all.

With hydrogen, 5percent Re carbon catalyst and β zeolite calcined in a nitrogen gas stream at 500C for 1 hr and and then subjected to reduction treatment in a hydrogen gas stream at 500C for 1 h, T= 160 °C , Product distribution / selectivity Patent; Mitsui Chemicals, Inc.; EP2103584; (2009); (A1) English View in Reaxys

HO

O

HO

O

Rx-ID: 38846036 View in Reaxys 101/481 Yield

Conditions & References 4.8.1. General method General procedure: To a solution of vanadium catalyst in chloroform (1.5 mL) was added cumene hydroperoxide (80 percent by weight). The mixture was heated for 1 min to 60oC and treated ata temperature of 20oC with chloroform (1.5 mL). The reaction mixture was stirred 72oh at 20oC and filtrated through a pad of neutral aluminum oxide. Lipophilic products were washed with ethyl acetate (5mL) from the pad of aluminum oxide. The eluate wa streated with triphenylphosphine and the solution stirred for 5 min.

With [VO(N-salicylidene 2-aminophenolate)(OEt)]EtOH in chloroform, Time= 72h, T= 20 - 60 °C , Catalytic behavior, Reagent/catalyst Amberg, Matthias; Dönges, Maike; Stapf, Georg; Hartung, Jens; Tetrahedron; vol. 70; nb. 34; (2014); p. 5321 5331 View in Reaxys

H N

H N O

Rx-ID: 3916905 View in Reaxys 102/481

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Yield

Conditions & References

100 %

With aluminium trichloride, Time= 3.5h, Ambient temperature Chung, Kun Hoe; Kim, Jae Nyoung; Ryu, Eung K.; Tetrahedron Letters; vol. 35; nb. 18; (1994); p. 2913 - 2914 View in Reaxys

HO

Rx-ID: 4033059 View in Reaxys 103/481 Yield

Conditions & References

53 %, 4 %, With sodium tetrahydroborate, (5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride, oxygen in ethanol, ben34 % zene, Time= 1h, Ambient temperature Takeuchi, Masayuki; Kano, Koji; Bulletin of the Chemical Society of Japan; vol. 67; nb. 6; (1994); p. 1726 - 1733 View in Reaxys

O

O

Rx-ID: 4116161 View in Reaxys 104/481 Yield

Conditions & References

24 % Chromat.

With formic acid, tri-ruthenium(0)dodecacarbonyl in benzene, Time= 6h, T= 200 °C Kondo, Teruyuki; Kajiya, Satoshi; Tantayanon, Supawan; Watanabe, Yoshihisa; Journal of Organometallic Chemistry; vol. 489; nb. 1-2; (1995); p. 83 - 92 View in Reaxys

O

cymene

O

Rx-ID: 11713230 View in Reaxys 105/481 Yield

Conditions & References Reaction Steps: 3 1: 78 percent / diethyl ether 2: diatomite PD-400 / 370 - 380 °C / in vapor phase 3: 6.7 percent Chromat. / H2 / calcium hexaammoniate / 2 h / 170 - 200 °C With diatomite PD-400, hydrogen, calcium hexaammine in diethyl ether Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys Reaction Steps: 3 1: 78 percent / diethyl ether 2: diatomite PD-400 / 370 - 380 °C / in vapor phase 3: 6.7 percent Chromat. / H2 / calcium hexaammoniate / 2 h / 170 - 200 °C With diatomite PD-400, hydrogen, calcium hexaammine in diethyl ether Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys

O

Rx-ID: 28687566 View in Reaxys 106/481

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Yield

Conditions & References 3 :Example 3; The reaction was performed in the same manner as Example 1 except that 0.5 percent Pt sulfided carbon catalyst (manufactured by NE Chemcat Co.) was used in place of 2.0 g of a 5percent Re carbon catalyst (manufactured by NE Chemcat Co.). One to two hours after the reaction start, the resulting product was analyzed by a gas chromatography. Cumene, m-diisopropyl benzene and p-diisopropyl benzene were generated in amounts of 10percent, and cyclohexane was generated in an amount of 6percent, on the basis of the amount of acetone fed.

With hydrogen, 0.5 percent Pt sulfided carbon catalyst and β zeolite calcined in a nitrogen gas stream at 500C for 1 hr and and then subjected to reduction treatment in a hydrogen gas stream at 500C for 1 h, T= 160 °C , Product distribution / selectivity Patent; Mitsui Chemicals, Inc.; EP2103584; (2009); (A1) English View in Reaxys

Rx-ID: 31525823 View in Reaxys 107/481 Yield

Conditions & References With ZSM-5/MCM-48, Time= 0.00555556h, T= 350 °C , p= 760.051Torr , fluidized-bed reactor Odedairo; Balasamy; Al-Khattaf; Journal of Molecular Catalysis A: Chemical; vol. 345; nb. 1-2; (2011); p. 21 - 36 View in Reaxys

Rx-ID: 31525824 View in Reaxys 108/481 Yield

Conditions & References With Y-zeolite, Time= 0.00555556h, T= 400 °C , p= 760.051Torr , fluidized-bed reactor Odedairo; Balasamy; Al-Khattaf; Journal of Molecular Catalysis A: Chemical; vol. 345; nb. 1-2; (2011); p. 21 - 36 View in Reaxys I Br Mg

Rx-ID: 31679705 View in Reaxys 109/481 Yield 69 %Spectr.

Conditions & References With C20H26Cl2FeN4 in tetrahydrofuran, Time= 0.666667h, T= 20 °C , Inert atmosphere Xue, Fei; Zhao, Jin; Hor, T. S. Andy; Dalton Transactions; vol. 40; nb. 35; (2011); p. 8935 - 8940 View in Reaxys

62 %Spectr.

With C18H22ClN3Ni, Kumada Cross-Coupling, Reagent/catalyst Perez Garcia, Pablo M.; Di Franco, Thomas; Epenoy, Alexandre; Scopelliti, Rosario; Hu, Xile; ACS Catalysis; vol. 6; nb. 1; (2016); p. 258 - 261 View in Reaxys

O

Rx-ID: 1990025 View in Reaxys 110/481

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Yield 54 %, 12 %

Conditions & References With para-dicyanobenzene in methanol, acetonitrile, Time= 6h, Irradiation Bardi, Luca; Fasani, Elisa; Albini, Angelo; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 5; (1994); p. 545 - 550 View in Reaxys

HO

Rx-ID: 2011785 View in Reaxys 111/481 Yield 28 %, 57 %

Conditions & References With triphenyl phosphite, tetraethylammonium bromide in acetonitrile, constant current electrolysis, 25 mA Maeda, Hatsuo; Maki, Toshihide; Eguchi, Kaoru; Koide, Takashi; Ohmori, Hidenobu; Tetrahedron Letters; vol.

35; nb. 24; (1994); p. 4129 - 4132 View in Reaxys

Cl

Rx-ID: 4614459 View in Reaxys 112/481 Yield 23.9 %, 76.1 %

Conditions & References With sodium naphthalenide in tetrahydrofuran, T= 25 °C , Product distribution, Mechanism Denney, Donald B.; Denney, Dorothy Z.; Fenelli, Steven P.; Tetrahedron; vol. 53; nb. 15; (1997); p. 5397 - 5402 View in Reaxys

61 %, 32 %

With dipotassium hydrogenphosphate, benzaldehyde, silver nitrate, zinc in water, Time= 1h, T= 30 °C Bieber, Lothar W.; Storch, Elisabeth C.; Malvestiti, Ivani; Da Silva, Margarete F.; Tetrahedron Letters; vol. 39; nb. 51; (1998); p. 9393 - 9396 View in Reaxys

acetic acid isoproyl ester Rx-ID: 6416607 View in Reaxys 113/481 Yield

Conditions & References With boron trifluoride McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

diisopropylbenzene Rx-ID: 22960925 View in Reaxys 114/481 Yield

Conditions & References With Zeolite Y, T= 121 - 177 °C , p= 7600.51 - 38002.6Torr , Industry scale Patent; UOP LLC; US6339179; (2002); (B1) English View in Reaxys

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Rx-ID: 23913548 View in Reaxys 115/481 Yield

Conditions & References A 1 inch diameter reactor was filled with two beds of five feet each of beta zeolite catalyst. The reactor was configured such that there were two olefin injection points, one under each bed. The olefin feed (propylene or butylene) lines were set up so that either could go to either feed point. Fresh benzene was fed to the reactor as the entire reflux stream. The column was operated in a liquid continuous distillation. The reactor was operated first with propylene feed only to both beds and then through one bed only. Then butylene was fed to one bed only. Propylene was then added to both beds and finally both olefins were fed through both beds. The bottoms products from the combined feeds were collected and distilled in an Oldershaw column and the heavy cuts (to simulate benzene stripping) were analyzed by gas chromatography. Temperatures in the bed ranged from about 265 to 340° F. The overhead pressure was maintained at 75 psig. The analysis of the heavy Oldershaw cuts are shown below in TABLE I. With Beta zeolite, T= 129.434 - 171.101 °C , p= 4638.76Torr , Product distribution / selectivity Patent; CATALYTIC DISTILLATION TECHNOLOGIES; US2006/211901; (2006); (A1) English View in Reaxys

Rx-ID: 25668127 View in Reaxys 116/481 Yield

Conditions & References 1 :A 0.5 gram sample of an MCM-22 catalyst (65 wtpercent MCM-22/35percent alumina binder) was used for the alkylation of benzene with butene-2. The catalyst was in the form of a 1.6mm (1/16") diameter cylindrical extradate and was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16"). The catalyst was dried at 125°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr for 1 hour and then reduced to desired WHSV while the reactor pressure was increased to 300 psig (2170 kPa). 2-butene (mixture of cis and trans) was introduced from a syringe pump at a 3:1 benzene/butene molar ratio and the reactor temperature was ramped to 160°C at 5°C/min. Liquid product was collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Stable operation with 95percent+ butene conversion was obtained at butene flow rate of 1.5 WHSV. Catalyst performance at 10 and 13 days on stream are shown in the Table 2.

With MCM-22 (65 wtpercent MCM-22/ 35percent alumina binder), Time= 240 - 312h, T= 160 °C , p= 16274.9Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15825; (2006); (A1) English View in Reaxys 2 :The process of Example 1 was repeated but with the MCM-22 catalyst being replaced by 0.5 gm of a zeolite beta catalyst (65 wtpercent beta/35percent alumina binder), again with the catalyst being in the form of a 1.6mm (1/16") diameter cylindrical extrudate. Catalyst performance at 1, 3 and 5 days on stream are shown in the Table 2. Data in Table 2 show that MCM-22 catalyst was highly active and selective for the production of sec-butylbenzene without producing a measurable quantity of iso-butylbenzene and very low quantities of tert-butylbenzene. MCM-22 was also quite stable with no sign of deactivation during the 13-day test cycle. Zeolite beta showed good initial activity. Although it deactivated rapidly as a result of butene oligomer formation, zeolite beta produced sec-butylbenzene without producing measurable quantities of iso-butylbenzene. Zeolite beta produced low quantities of tert-butylbenzene, albeit not as low as MCM-22. When compared at 95+percent conversion, MCM-22 was about 8percent more selective than zeolite beta for sec-butylbenzene production.

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With zeolite beta (65 wtpercent beta/ 35percent alumina binder), Time= 24 - 120h, T= 160 °C , p= 16274.9Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15825; (2006); (A1) English View in Reaxys

Z

E

Rx-ID: 25672028 View in Reaxys 117/481 Yield

Conditions & References 4 :The process of Example 3 was repeated but with the MCM-22 catalyst being replaced by 1.6 gm of a solid phosphoric acid (SPA catalyst, commercially available from UOP). The catalyst was sized to 14-24 mesh and loaded to the reactor in a glove bag with nitrogen purge. Representative data are shown in Table 3.; Data in Table 3 show that the MCM-22 catalyst was much more active, selective, and stable than the SPA catalyst. When compared at 80-86percent conversion, MCM-22 is at least 7-times more active than the SPA. MCM-22 is also highly selective for sec-butylbenzene production with much lower tendency than SPA to form butene oligomers. MCM-22 was stable during the 11-day test cycle without any indication of deactivation. Sec-butylbenzene purity is also superior with the MCM-22 catalyst. SPA was active for this reaction but deactivated rapidly with time on stream. Its overall performance was poor compared to the performance of MCM-22.

With solid phosphoric acid (SPA), Time= 18.96 - 66.96h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 5 :The process of Example 3 was repeated but with the MCM-22 catalyst replaced by a) 0.5 gm of MCM-49-A, b) 0.6 gm of MCM-49-B, and c) 0.5 gm of MCM-49-C. The catalyst information and experimental sequence for each run are provided below.MCM-49-B: 1/20" quadrulobe extrudate with 60 percent MCM-49/40percent Versal 200 alumina binder, cut to 1/20" length. The catalyst was on stream for 4 days at 2.7 WHSV of butene with 98percent conversion, 1 day at 8 WHSV with 97 percent conversion, 0.5 days at 12 WHSV with 93percent conversion, 1.6 days at 2.7 WHSV with 98percent conversion, 0.3 days at 19.2 WHSV with 86percent conversion, and followed by 0.7 days at 2.7 WHSV again with 98 percent conversion. Representative data are shown in Table 4. The data in Table 4 shows that MCM-49 catalysts are much more active, selective and stable than solid phosphoric acid in catalyzing the formation of sec-butylbenzene from benzene and ethylene With 60percent MCM-49/40percent Versal 200 alumina binder, Time= 96 - 170.4h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 3 :A 1.0 gram sample of the same MCM-22 catalyst (65 percent MCM-22/35percent alumina binder) as used in Example 1 was used for the alkylation of benzene with 2-butene. The catalyst was in the form of a 1.6 mm (1/16") diameter cylindrical extrudate, chopped to 1/16" length, and was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr for 1 hour and then reduced to desired WHSV while the reactor pressure was increased to 300 psig (2170 kPa). Butene feed (57.1percent cis-butene, 37.8percent trans-butene, 2.5percent n-butane, 0.8percent isobutene and 1-butene, and 1.8percent others) was introduced from a syringe pump at a 3:1 benzene/butene molar ratio, and this ratio was kept constant for the entire run. The reactor temperature was ramped to 160°C at 2°C/ min. Liquid products were collected at reactor conditions of 160°C and 300 psig in a cold-trap and analyzed off line.

2-Butene conversion was determined by measuring unreacted 2-butene relative to feed 2-butene.The catalyst was on stream for 4 days at 1.6 WHSV of butene with 97percent 2-butene conversion, 2 days at 4.8 WHSV with 95per-

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cent conversion, then 1 day at 7.2 WHSV with 86percent conversion, and followed by 4 days again at 1.6 WHSV with 97percent conversion. No deactivation was detected during the 11-day test cycle. Representative data are shown in Table 3.; Data in Table 3 show that the MCM-22 catalyst was much more active, selective, and stable than the SPA catalyst. When compared at 80-86percent conversion, MCM-22 is at least 7-times more active than the SPA. MCM-22 is also highly selective for sec-butylbenzene production with much lower tendency than SPA to form butene oligomers. MCM-22 was stable during the 11-day test cycle without any indication of deactivation. Sec-butylbenzene purity is also superior with the MCM-22 catalyst. SPA was active for this reaction but deactivated rapidly with time on stream. Its overall performance was poor compared to the performance of MCM-22.

With 65 wtpercent MCM-22 / 35percent alumina binder, Time= 91.2 - 259.2h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 5 :The process of Example 3 was repeated but with the MCM-22 catalyst replaced by a) 0.5 gm of MCM-49-A, b) 0.6 gm of MCM-49-B, and c) 0.5 gm of MCM-49-C. The catalyst information and experimental sequence for each run are provided below.MCM-49-C: 1/20" quadrulobe extrudate with 80 percent MCM-49/20 percent alumina binder, cut to 1/20" length. The MCM-49 crystal was jet-milled prior to extrusion with alumina (Jet Mill grinds aggregated zeolite crystal by rubbing and colliding them each other through blowing high-speed jet stream emitted from several pieces of grinding nozzles into the material layer in the grinding chamber). The catalyst was on stream for 5 days at 3.2 WHSV of butene with 98percent 2-butene conversion, 1.1 days at 9.6 WHSV with 97 percent conversion, 4 day at 3.2 WHSV with 98percent conversion, 0.4 days at 23 WHSV with 89 percent conversion, and followed by 3 days at 3.2 WHSV again with 98 percent conversion. Representative data are shown in Table 4. The data in Table 4 shows that MCM-49 catalysts are much more active, selective and stable than solid phosphoric acid in catalyzing the formation of sec-butylbenzene from benzene and ethylene.

With 80percent MCM-49/20percent alumina binder, Time= 120 - 324h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 5 :The process of Example 3 was repeated but with the MCM-22 catalyst replaced by a) 0.5 gm of MCM-49-A, b) 0.6 gm of MCM-49-B, and c) 0.5 gm of MCM-49-C. The catalyst information and experimental sequence for each run are provided below:MCM-49-A: 1/20" quadrulobe extrudate with 80percent MCM-49/20percent alumina binder, cut to 1/20" length. The catalyst was on stream for 6 days at 3.2 WHSV of butene with 96percent 2-butene conversion, 0.8 days at 9.6 WHSV with 88 percent conversion, 0.6 day at 14.4 WHSV with 85percent conversion, and followed by 3 days at 3.2 WHSV again with 95 percent conversion.Representative data are shown in Table 4. The data in Table 4 shows that MCM-49 catalysts are much more active, selective and stable than solid phosphoric acid in catalyzing the formation of sec-butylbenzene from benzene and ethylene.

With 80percent MCM-49/20percent alumina binder, Time= 144 - 235.2h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys

Z

E

Rx-ID: 25672030 View in Reaxys 118/481 Yield

Conditions & References 7 :The procedure of Example 6 was followed except the MCM-22 catalyst was replaced with 0.5 gm of catalyst MCM-49-B mentioned at Example 5. Catalyst MCM-49-B was on stream for 3 days at 3.2 WHSV of butene with

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96percent conversion, 0.7 days at 9.6 WHSV with 83 percent conversion, and followed by 3 days at 3.2 WHSV again with 95 percent conversion. Representative data is given in Table 6.

With 60percent MCM-49/40percent Versal 200 alumina binder, Time= 55.2 - 144h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 6 :A 1.0 gram sample of the same MCM-22 catalyst (65 percent MCM-22/35percent alumina binder) as used in Example 1 was used for the alkylation of benzene with a butene feed. The process of Example 3 was repeated but with the feed being replaced by a new feed with the following composition: 53.4percent cis-butene, 41.2percent transbutene, 4.6percent isobutene, 0.5percent butadiene, 0.1percent n-butane and 0.2percent others. [0068] The catalyst was on stream for 6 days at 1.6 WHSV of butene with 98percent> 2-butene conversion, 1 day at 4.8 WHSV with 80percent conversion, 1 day at 7.2 WHSV with 62percent conversion, then followed by 4 days again at 1.6 WHSV with 97percent conversion. Representative data are shown in Table 5 below.; Data in Table 5 show that the MCM-22 catalyst was effective for sec-butylbenzene production using a 2-butene feed with 4.6percent isobutene and 0.5percent butadiene. The presence of 0.5percent butadiene caused no significant deactivation of MCM-22 during the 12day test cycle. The presence of 4.6percent isobutene in butene feed resulted less than 2percent tert-butylbenzene formation in the combined butylbenzene fraction after initial lineout. The increased butene oligomer formation is caused by increased isobutene which oligomerizes more readily than it undergoes alkylation with benzene.

With 65 wtpercent MCM-22 / 35percent alumina binder, Time= 18.96 - 282.96h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys

Mg Cl Cl

Rx-ID: 661604 View in Reaxys 119/481 Yield

Conditions & References With diethyl ether Ellingboe; Fuson; Journal of the American Chemical Society; vol. 55; (1933); p. 2960,2965 View in Reaxys

O

O S

O

O

Rx-ID: 847199 View in Reaxys 120/481 Yield

Conditions & References With boron trifluoride McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

O

O

Rx-ID: 847584 View in Reaxys 121/481 Yield

Conditions & References With boron trifluoride McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

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Cl

Cl

O

Cl O

Rx-ID: 847710 View in Reaxys 122/481 Yield

Conditions & References With boron trifluoride McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

O

Rx-ID: 847887 View in Reaxys 123/481 Yield

Conditions & References With boron trifluoride O'Connor; Sowa; Journal of the American Chemical Society; vol. 60; (1938); p. 125 View in Reaxys

E

E

Rx-ID: 4186163 View in Reaxys 124/481 Yield

Conditions & References

93 %, 85 %

With 9,10-dihydro-anthracene in toluene, Time= 16h, T= 246.9 °C , thermolysis; activation parameters ΔG(excit.), ΔH(excit.), ΔS(excit.), half-life; other termperatures, Kinetics, Thermodynamic data Herberg, Clemens; Verevkin, Sergej P.; Noelke, Margot; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Liebigs Annalen; nb. 3; (1995); p. 515 - 522 View in Reaxys

HO

O

Rx-ID: 5048190 View in Reaxys 125/481 Yield

Conditions & References

89 % With Amberlite IRA-400, borohydride form, copper(II) sulfate in methanol, Time= 1h, T= 65 °C , Reduction Chromat., 11 % Chro- Sim, Tae Bo; Yoon, Nung Min; Bulletin of the Chemical Society of Japan; vol. 70; nb. 5; (1997); p. 1101 - 1107 View in Reaxys mat.

paraformaldehyde O O

HO

O

Rx-ID: 6675314 View in Reaxys 126/481 Yield

Conditions & References With RhH2(O2COH)(P(i-Pr)3)2 in tetrahydrofuran, Time= 20h, T= 120 °C , Yield given. Further byproducts given.

Yields of byproduct given. Title compound not separated from byproducts Okano, Tamon; Kobayashi, Teruyuki; Konishi, Hisatoshi; Kiji, Jitsuo; Tetrahedron Letters; vol. 23; nb. 47; (1982); p. 4967 - 4968

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View in Reaxys

paraformaldehyde

HO

O O

Rx-ID: 7176821 View in Reaxys 127/481 Yield

Conditions & References With RhH2(O2COH)(P(i-Pr)3)2 in tetrahydrofuran, Time= 20h, T= 120 °C , Yield given. Further byproducts given.

Yields of byproduct given. Title compound not separated from byproducts Okano, Tamon; Kobayashi, Teruyuki; Konishi, Hisatoshi; Kiji, Jitsuo; Tetrahedron Letters; vol. 23; nb. 47; (1982); p. 4967 - 4968 View in Reaxys

O

N

O

N

Rx-ID: 10138183 View in Reaxys 128/481 Yield

Conditions & References With thiophenol in benzene, T= 150 °C , Kinetics Engel; Pan; Ying; Alemany; Journal of the American Chemical Society; vol. 123; nb. 16; (2001); p. 3706 - 3715 View in Reaxys

C10, C11 and others

triisopropylbenzenes Rx-ID: 23225169 View in Reaxys 129/481

Yield 0.02 %, 2.31 %, 0.77 %, 2.45 %, 25.67 %

Conditions & References 13 :Example 13 Example 10 was repeated using a commercially available ZSM-12 catalyst prepared in the same manner as the MCM-22. Again, the feed was DIPB-only with the composition being 89.7 wt. percent meta-DIPB, 5.1 wt. percent ortho-DIPB, and 1.1 wt. percent para-DIPB. The reaction was conducted at a WHSV of 1 with a feed rate of 2 grams per hour. The temperature was held constant at 405° F. (207° C.). The effluent composition at 4.5 days is shown in Table 1. It was noted that the ZSM-12 in the isomerization reaction showed signs of aging during the testing, whereas the MCM-22 did not show any signs of aging within one to three weeks of testing at different conditions.

With ZSM-12 zeolite, T= 207 °C , Product distribution / selectivity Patent; Clark, Michael C.; Cimini, Ronald J.; Cheng, Jane C.; Stern, David L.; Buchanan, John Scott; US2005/75523; (2005); (A1) English View in Reaxys

0.5 - 0.8 %, 1.8 2.7 %, 8.1 - 14.3 %, 8.1 - 17.0 %, 23.0 26.7 %

10; 11; 12 :Examples 10 Through 12 Examples 10 through 12 show the results of a DIPB-only feed to the same MCM-22 catalyst. These examples represent an alternative embodiment of the goal of removing feed benzene from the system. The feed composition was 89.7 wt. percent meta-DIPB, 5.1 wt. percent ortho-DIPB, and 1.1 wt. percent para-DIPB. The reaction was conducted at WHSVs of 1, 2, and 4, respectively, with corresponding feed rates of 2, 4, and 8 grams per hour, respectively. The temperature was held constant at 405° F. (207° C.). The effluent compositions are shown in Table 1. At equivalent temperature and WHSV, the DIPB feed results in a higher rate of m-DIPB conversion. At equivalent WHSV, m-DIPB is converted at twice the rate of the base case shown in Example 1. TIPB production is higher relative to Example 1. The formation of TIPB relative to m-DIPB converted can be reduced by

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operating the reactor at higher WHSV. Examples 11 and 12 demonstrate the effect of increasing WHSV to reduce TIBP production relative to m-DIPB converted (decrease from 48 to 38 to 29percent with increase of WHSV from 1 to 2 to 4). Although TIPB formation is much higher than in the base case, other experimental results suggest TIPB formation can be reduced further by decreasing temperature.

With MCM-22 zeolite, T= 207 °C , Product distribution / selectivity Patent; Clark, Michael C.; Cimini, Ronald J.; Cheng, Jane C.; Stern, David L.; Buchanan, John Scott; US2005/75523; (2005); (A1) English View in Reaxys

Rx-ID: 25047438 View in Reaxys 130/481 Yield

Conditions & References I : Cumene: Despite the decrease in hydrogenation of alpha-methylstyrene to isopropyl cyclohexane, the hydrogenation to cumene remains high, indicating that selectivity of the catalyst is improving.

Patent; Engelhard Minerals and Chemicals Corporation; US4257877; (1981); (A1) English View in Reaxys

Z

E

Rx-ID: 25832066 View in Reaxys 131/481 Yield

Conditions & References 1 :Example 1 (Comparative)Sec-Butylbenzene synthesis using MCM-49 at 160°C[0054] A 0.5 gram sample of an MCM-49 catalyst (1.3 mm [1/20"] quadrulobe extrudate of 60 percent MCM-49/40percent Versal 200 alumina binder, cut to 1.3 mm [1/20"] length) was used for the alkylation of benzene with a mixed butene feed having the following composition: 53.4percent cis-butene, 41.2percent trans- butene, 4.6percent isobutene, 0.5percent butadiene, 0.1percent n-butane and 0.2percent others. The catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until the reactor pressure increased to 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr (6.67 WHSV) and the mixed butene feed was introduced from a syringe pump at 2.57 cc/hr. The reactor temperature was adjusted to 160°C. Feed benzene/butene molar ratio was maintained at 3:1 for the entire run. Liquid product was collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. The MCM-49 was on stream for 3 days at 3.2 WHSV of butene with 96percent conversion, 1 day at 9.6 WHSV with 80-83percent conversion, and 3 days at 3.2 WHSV with 95percent conversion. Relative activity of MCM-49 based on first-order butene conversion was 1.1. Representative data are shown in Table 1. <n="17"/>Table 1. sec-Butylbenzene Production with MCM-49 and Mixed Butene Feed at160°CDays on Stream 2.3 3.2 5.3Butene WHSV, h'1 3.2 9.6 3.22-Butene Conv, percent 96.1 83.0 95.5Isobutene Conv, percent 97.7 67.2 92.8Butadiene Conv, percent 100.0 100.0 100.0Product Selectivity, wtpercent i-C4 0.041 0.032 0.028C5-C7 0.527 0.503 0.583C8 and C12 (butene oligomers) 7.688 9.732 8.185Cumene 0.128 0.144 0.127 t-Butylbenzene 1.849 0.849 1.240 iso-Butylbenzene* 0.000 0.008 0.012 sec-Butylbenzene 82.977 84.284 84.720 n-Butylbenzene 0.062 0.059 0.068Di-butylbenzene 5.431 3.878 4.273Tri-butylbenzene 1.079 0.429 0.629Heavies 0.218 0.082 0.134Sum 100.0 100.0 100.0Butylbenzene Composition, percent t-Butylbenzene 2.179 0.996 1.441 iso-Butylbenzene* 0.000 0.010 0.013 sec-Butylbenzene 97.749 98.925 98.467 n-Butylbenzene 0.073 0.069 0.078Sum 100.0 100.0 100.0* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.

With MCM-49 zeolitic catalyst, Time= 76.8 - 127.2h, T= 160 °C , p= 16276.6Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93361; (2007); (A1) English

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View in Reaxys 3 :A 1.0 gram sample of an MCM-22 catalyst (65 wtpercent MCM-22/35percent alumina binder) was used for the alkylation of benzene with Raffinate-2 type feed. This is the same catalyst used in Example 1. The Raffinate-2 type feed is a synthetic blend with the following composition: 53.4percent cis-butene, 41.2percent trans- butene, 4.6percent isobutene, 0.5percent butadiene, 0.1percent n-butane and 0.2percent others. The catalyst was in the form of a 1.6 mm (1/16") diameter cylindrical extrudate and was diluted with sand to 3 cc and loaded into an isothermal, downflow, fixed- bed, tubular reactor having an outside diameter of 4.76 mm (3/16"). The catalyst was dried at 1500C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached the desired 300 psig (2170 kPa). Benzene flow was then reduced <n="20"/>to 7.63 cc/hr (6.67 WHSV) and Raffinate-2 type feed was introduced from a syringe pump at 2.57 cc/hr (1.6 WHSV). The reactor temperature was adjusted to 160°C. Feed benzene/butene molar ratio was maintained at 3:1 for the entire run. Liquid product was collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. The catalyst was on stream for 6 days at 1.6 WHSV of butene with 98percent 2-butene conversion, 1 day at 4.8 WHSV with 80percent conversion, 1 day at 7.2 WHSV with 62percent conversion, and followed by 4 days again at 1.6 WHSV with 97percent conversion. Representative data are shown in Table 3. [0066] Table 3 shows that MCM-22 catalyst was effective for sec- butylbenzene production using a Raffnate-2 type feed. The 0.5percent butadiene in butene feed had no significant effect on MCM-22 stability during the 12-day test cycle. The 4.6percent isobutene in butene feed increased by-product formation. After initial lineout, selectivity measured at 97-98percent 2-butene conversion was 8percent for butene oligomers, 1.2-1.5percent for t-butylbenzene, and 83percent for sec-butylbenzene. This was a significant change when compared to results in Table 1 using the same catalyst and 2-butene feed. Selectivity measured with 2-butene feed at 97-98percent 2- butene conversion was 1-2 percent for butene oligomers, 0.1-0.2percent for t-butylbenzene, and 89-91percent for sec-butylbenzene. The use of Raffinate-2 type feed resulted in a 50percent activity drop for MCM-22.

With MCM-22, Time= 18.96 - 282.96h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93362; (2007); (A1) English View in Reaxys 4 :The process of Example 3 was repeated but with the MCM-22 catalyst replaced by 0.5 gm of MCM-49 catalyst used in Example 2. The MCM-49 was on stream for 3 days at 3.2 WHSV of butene with 96percent conversion, 1 day at 9.6 WHSV with 80-83percent conversion, and 3 days at 3.2 WHSV with 95percent conversion. Representative data are shown in Table 4.[0068] Table 4 shows that MCM-49 catalyst was also effective for sec- butylbenzene production using a Raffinate-2 type feed. The 0.5percent butadiene in the feed had no significant effect on MCM-49 stability during the 7-day test cycle. The 4.6percent isobutene in butene feed increased by-product formation. Selectivity measured at 96percent 2-butene conversion was 8percent for butene oligomers, 1.2-1.8percent for t-butylbenzene, and 83-85percent for sec-butylbenzene. This is a significant change when compared to results in Table 2 using the same MCM-49 catalyst and 2- butene feed. Selectivity measured with 2-butene feed at 97percent 2-butene conversion was 1.5 percent for butene oligomers, 0.1percent for t-butylbenzene, and 92percent for sec- butylbenzene. The use of Raffinate-2 type feed resulted in a 50percent activity drop for MCM-49.

With MCM-49, Time= 55.2 - 127.2h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93362; (2007); (A1) English View in Reaxys Br

Br Mg

Rx-ID: 31679713 View in Reaxys 132/481 Yield 65 %Spectr.

Conditions & References With C20H26Cl2FeN4 in tetrahydrofuran, Time= 0.666667h, T= 20 °C , Inert atmosphere Xue, Fei; Zhao, Jin; Hor, T. S. Andy; Dalton Transactions; vol. 40; nb. 35; (2011); p. 8935 - 8940 View in Reaxys

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H

H

Rx-ID: 35949459 View in Reaxys 133/481 Yield 43 %Spectr.

Conditions & References With [Ir(6-Neo)(COD)Cl] in ethanol, Time= 1h, p= 3750.38Torr Dunsford, Jay J.; Tromp, Dorette S.; Cavell, Kingsley J.; Elsevier, Cornelis J.; Kariuki, Benson M.; Dalton Transactions; vol. 42; nb. 20; (2013); p. 7318 - 7329 View in Reaxys 2H

2H

2H 2H 2H

2H

Rx-ID: 39590629 View in Reaxys 134/481 Yield

Conditions & References With anhydrous iron chloride, LiAlD4 in tetrahydrofuran, Time= 2h, T= -78 - 20 °C , Inert atmosphere Gieshoff, Tim N.; Villa, Matteo; Welther, Alice; Plois, Markus; Chakraborty, Uttam; Wolf, Robert; Jacobi Von Wangelin, Axel; Green Chemistry; vol. 17; nb. 3; (2015); p. 1408 - 1413 View in Reaxys

Rx-ID: 679753 View in Reaxys 135/481 Yield

Conditions & References With sulfuric acid, T= 65 °C Ipatieff; Pines; Schmerling; Journal of Organic Chemistry; vol. 5; (1940); p. 253,259 View in Reaxys

Rx-ID: 1832229 View in Reaxys 136/481 Yield 49.7 % Chromat., 11.7 % Chromat., 6.7 % Chromat., 3.2 %

Conditions & References With hydrogen, calcium hexaammine, Time= 2h, T= 170 - 200 °C , Further byproducts given Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys

HO

O

HO

Rx-ID: 8671548 View in Reaxys 137/481 Yield 17 %

Conditions & References With montmorillonite clay, sulfuric acid, Time= 3h, T= 180 °C McPhail, Kerry L.; Rivett, Douglas E.A.; Lack, David E.; Davies-Coleman, Michael T.; Tetrahedron; vol. 56; nb.

47; (2000); p. 9391 - 9396 View in Reaxys

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E

Rx-ID: 9188405 View in Reaxys 138/481 Yield

Conditions & References With hydrogen, platinum on silica, T= 499.85 °C , p= 3750.3Torr , Kinetics, Product distribution, Further Variations: Catalysts Djega-Mariadassou; Toppi; Le Peltier; Thomas; Travers; Sayag; Brodzki; Journal of Catalysis; vol. 210; nb. 2; (2002); p. 431 - 444 View in Reaxys

Z

E

Rx-ID: 25672029 View in Reaxys 139/481 Yield

Conditions & References 1 :A 0.5 gram sample of an MCM-22 catalyst (65 wtpercent MCM-22/35percent alumina binder) was used for the alkylation of benzene with butene-2. The catalyst was in the form of a 1.6mm (1/16") diameter cylindrical extrudate and was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16"). The catalyst was dried at 125°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr for 1 hour and then reduced to desired WHSV while the reactor pressure was increased to 300 psig (2170 kPa). 2-butene (mixture of cis and trans) was introduced from a syringe pump at a 3:1 benzene/butene molar ratio and the reactor temperature was ramped to 160°C at 5°C/min. Liquid product was collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Stable operation with 95percent+ butene conversion was obtained at butene flow rate of 1.5 WHSV. Catalyst performance at 10 and 13 days on stream are shown in Table 2.; Data in Table 2 show that MCM-22 catalyst was highly active and selective for the production of sec-butylbenzene without producing a measurable quantity of iso-butylbenzene and very low quantities of tert-butylbenzene.

MCM-22 was also quite stable with no sign of deactivation during the 13-day test cycle. Zeolite beta showed good initial activity. Although it deactivated rapidly as a result of butene oligomer formation, zeolite beta produced sec-butylbenzene without producing measurable quantities of iso-butylbenzene. Zeolite beta produced low quantities of tert-butylbenzene, albeit not as low as MCM-22. When compared at 95+percent conversion, MCM-22 was about 8percent more selective than zeolite beta for sec-butylbenzene production.

With 65 wtpercent MCM-22 / 35percent alumina binder, Time= 240 - 312h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys 2 :The process of Example 1 was repeated but with the MCM-22 catalystbeing replaced by 0.5 gm of a zeolite beta catalyst (65 wtpercent beta/35percent alumina binder), again with the catalyst being in the form of a 1.6mm (1/16") diameter cylindrical extrudate. Catalyst performance at 1, 3 and 5 days on stream are shown in Table 2.; Data in Table 2 show that MCM-22 catalyst was highly active and selective for the production of sec-butylbenzene without producing a measurable quantity of iso-butylbenzene and very low quantities of tert-butylbenzene. MCM-22 was also quite stable with no sign of deactivation during the 13-day test cycle. Zeolite beta showed good initial activity. Although it deactivated rapidly as a result of butene oligomer formation, zeolite beta produced sec-butylbenzene without producing measurable quantities of iso-butylbenzene. Zeolite beta produced low quantities of tert-butylbenzene, albeit not as low as MCM-22. When compared at 95+percent conversion, MCM-22 was about 8percent more selective than zeolite beta for sec-butylbenzene production.; Data in Table 2 show that MCM-22 catalyst was highly active and selective for the production of sec-butylbenzene without producing a measurable quantity of iso-butylbenzene and very low quantities of tert-butylbenzene. MCM-22 was also quite stable with no sign of deactivation during the 13-day test cycle. Zeolite beta showed good initial activity. Although it deactivated rapidly as a result of butene oligomer formation, zeolite beta produced sec-butylbenzene without producing measurable quantities of iso-butyl-

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benzene. Zeolite beta produced low quantities of tert-butylbenzene, albeit not as low as MCM-22. When compared at 95+percent conversion, MCM-22 was about 8percent more selective than zeolite beta for sec-butylbenzene production.

With 65percent wtpercent beta/35percent alumina binder, Time= 24 - 120h, T= 160 °C , p= 16276.6Torr , Continuous process, Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; EXXONMOBIL CHEMICAL LIMITED; WO2006/15826; (2006); (A1) English View in Reaxys

Z

E

Rx-ID: 25832065 View in Reaxys 140/481 Yield

Conditions & References 1; 2 :Example 2Sec-Butylbenzene synthesis using MCM-49 at 1300C[0055] The process of Example 1 was repeated but using a 2.0 gram sample of the MCM-49 catalyst used in Example 1 and with the reactor temperature being adjusted to 130°C and kept at 130°C for the entire run. The catalyst was on stream for 8 days at 0.8 WHSV of butene with 94percent+ 2-butene conversion, 1 day at 2.4 WHSV with 69-72percent conversion. Relative activity of MCM-49 based on first-order butene conversion was 0.2. Representative data are shown in Table 2. <n="18"/>Table 2. secButylbenzene Production with MCM-49 and Mixed Butene Feed at130°CDays on Stream 4.8 6.8 8.8Butene WHSV, h'1 0.8 0.8 2.42-Butene Conv, percent 96.3 95.7 71.3Isobutene Conv, percent 94.9 93.8 62.9Butadiene Conv, percent 100.0 100.0 100.0Product Selectivity, wtpercent i-C4 0.008 0.004 0.004C5-C7 0.311 0.289 0.311C8 and Ci2 (butene oligomers) 7.328 7.313 10.574Cumene 0.030 0.028 0.072 t-Butylbenzene 0.403 0.358 0.212 iso-Butylbenzene* 0.000 0.000 0.000 sec-Butylbenzene 89.306 89.177 86.167 n-Butylbenzene 0.044 0.043 0.054Di-butylbenzene 2.290 2.500 2.344Tri-butylbenzene 0.253 0.261 0.222Heavies 0.027 0.027 0.040Sum 100.0 100.0 100.0Butvlbenzene Composition, percent t-Butylbenzene 0.449 0.399 0.245 iso-Butylbenzene* 0.000 0.000 0.000 sec-Butylbenzene 99.502 99.553 99.692 n-Butylbenzene 0.049 0.048 0.063Sum 100.0 100.0 100.0 * iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0056] The data in Tables 1 and 2 show that the MCM-49 catalyst effectively alkylated benzene with the mixed butene feed with improved sec-butylbenzene selectivity when operated at 130°C, as compared with operation at 160°C. Table 3 provides a head-to-head comparison to demonstrate this improvement using data collected at 1600C (Table 1) and data collected at 130°C (Table 2). At comparable 2-butene conversion of 96percent, operating MCM-49 at 1300C vs. 1600C shows clear advantages: secbutylbenzene selectivity improved from 83-85percent to 89percent; whereas all by-product selectivities decreased. <n="19"/>Table 3. Comparison of MCM-49 Performance with Mixed Butene Feed atDifferent TemperaturesTemperature 1600C 1600C 1300C 1300CDays on Stream 2.3 5.3 4.8 6.8Butene WHSV, h"1 3.2 3.2 0.8 0.82-Butene Conv, percent 96.1 95.5 96.3 95.7Isobutene Conv, percent 97.7 92.8 94.9 93.8Butadiene Conv, percent 100.0 100.0 100.0 100.0Product Selectivity, wtpercent i-C4 0.041 0.028 0.008 0.004C5-C7 0.527 0.583 0.311 0.289C8 and Cu (butene oligomers) 7.688 8.186 7.328 7.313Cumene 0.128 0.127 0.030 0.028 t-Butylbenzene 1.849 1.240 0.403 0.358 isoButylbenzene* 0.000 0.000 0.000 0.000 sec-Butylbenzene 82.977 84.730 89.306 89.177 n-Butylbenzene 0.062 0.068 0.044 0.043Di-butylbenzene 5.431 4.273 2.290 2.500Tri-butylbenzene 1.079 0.629 0.253 0.261Heavies 0.218 0.134 0.027 0.027Sum 100.0 100.0 100.0 100.0Butylbenzene Composition, percent t-Butylbenzene 2.179 1.441 0.449 0.399 iso-Butylbenzene* 0.000 0.000 0.000 0.000 sec-Butylbenzene 97.749 98.480 99.502 99.553 n-Butylbenzene 0.073 0.079 0.049 0.048Sum 100.0 100.0 100.0 100.0* i iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.Example 1 (Comparative)Sec-Butylbenzene synthesis using MCM-49 at 160°C[0054] A 0.5 gram sample of an MCM-49 catalyst (1.3 mm [1/20"] quadrulobe extrudate of 60 percent MCM-49/40percent Versal 200 alumina binder, cut to 1.3 mm [1/20"] length) was used for the alkylation of benzene with a mixed butene feed having the following composition: 53.4percent cis-butene, 41.2percent trans- butene, 4.6percent isobutene, 0.5percent butadiene, 0.1percent n-butane and 0.2percent others. The catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until the reactor pressure increased to 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr (6.67 WHSV) and the mixed butene feed was introduced from a syringe pump at 2.57 cc/hr. The reactor temperature was adjusted to 160°C. Feed benzene/butene molar ratio was maintained at 3:1 for the entire run. Liquid product was collected in a cold-trap and analyzed off line. Butene

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conversion was determined by measuring unreacted butene relative to feed butene. The MCM-49 was on stream for 3 days at 3.2 WHSV of butene with 96percent conversion, 1 day at 9.6 WHSV with 80-83percent conversion, and 3 days at 3.2 WHSV with 95percent conversion. Relative activity of MCM-49 based on first-order butene conversion was 1.1. Representative data are shown in Table 1. <n="17"/>Table 1. sec-Butylbenzene Production with MCM-49 and Mixed Butene Feed at160°CDays on Stream 2.3 3.2 5.3Butene WHSV, h'1 3.2 9.6 3.22-Butene Conv, percent 96.1 83.0 95.5Isobutene Conv, percent 97.7 67.2 92.8Butadiene Conv, percent 100.0 100.0 100.0Product Selectivity, wtpercent i-C4 0.041 0.032 0.028C5-C7 0.527 0.503 0.583C8 and C12 (butene oligomers) 7.688 9.732 8.185Cumene 0.128 0.144 0.127 t-Butylbenzene 1.849 0.849 1.240 iso-Butylbenzene* 0.000 0.008 0.012 sec-Butylbenzene 82.977 84.284 84.720 n-Butylbenzene 0.062 0.059 0.068Di-butylbenzene 5.431 3.878 4.273Tri-butylbenzene 1.079 0.429 0.629Heavies 0.218 0.082 0.134Sum 100.0 100.0 100.0Butylbenzene Composition, percent t-Butylbenzene 2.179 0.996 1.441 iso-Butylbenzene* 0.000 0.010 0.013 sec-Butylbenzene 97.749 98.925 98.467 n-Butylbenzene 0.073 0.069 0.078Sum 100.0 100.0 100.0* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.

With MCM-49 zeolitic catalyst, Time= 55.2 - 211.2h, T= 130 - 160 °C , p= 16276.6Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93361; (2007); (A1) English View in Reaxys 3 :Example 3Sec-Butylbenzene synthesis using MCM-22 at Different Temperatures[0057] A 1.0 gram sample of an MCM-22 catalyst (1.6 mm [1/16"] diameter cylindrical extrudate of 65 wtpercent MCM-22/35percent alumina binder cut to 1.6 mm[1/16"] length) was used for the alkylation of benzene with the mixed butene feed of Example 1 and according to the process of Example 1 (reactor temperature of160°C). The catalyst was on stream for 6 days at 1.6 WHSV of butene with 98percent2-butene conversion, 1 day at 4.8 WHSV with 80percent conversion, 1 day at 7.2 WHSV with 62percent conversion, and followed by 4 days again at 1.6 WHSV with97percent conversion. Representative data are shown in Table 4. Relative activity ofMCM-22 based on first-order butene conversion was 0.5.[0058] A 2.3 gram sample of the same MCM-22 catalyst (65 percent MCM-22/35percent alumina binder) was used for the alkylation of benzene with the mixed butene <n="20"/>feed of Example 1 and according to the process of Example 2 (reactor temperature of 130°C). The MCM-22 catalyst was on stream for 4 days at 0.43 WHSV of butene with 94percent+ 2-butene conversion. Relative activity of MCM-22 based on first-order butene conversion was 0.1. Representative data are shown in Table 4, from which it will be seen that the sec-butylbenzene selectivity of the MCM-22 catalyst improved (from about 83 wtpercent to about 84 wtpercent) when operated at 130°C as compared with operation at 160°C.Table 4. Comparison of MCM-22 Performance with Mixed Butene Feed atDifferent TemperaturesTemperature 1600C 1600C 130°C 1300CDays on Stream 5.79 9.8 1.8 2.8Butene WHSV, h 1 1.6 1.6 0.43 0.432-Butene Conv, percent 98.4 96.9 95.9 95.2Isobutene Conv, percent 96.8 93.7 99.5 98.6Butadiene Conv, percent 100.0 100.0 100.0 100.0Product Selectivity, wtpercent i-C4 0.034 0.027 0.016 0.012C5-C7 0.467 0.556 0.464 0.478C8 and Ci 2 (butene oligomers) 7.746 7.916 8.211 8.806Cumene 0.189 0.196 0.048 0.048 t-Butylbenzene 1.521 1.267 0.839 0.613 isoButylbenzene* 0.000 0.000 0.000 0.000 sec-Butylbenzene 83.282 83.453 84.228 84.312 n-Butylbenzene 0.055 0.060 0.074 0.079Di-butylbenzene 5.580 5.465 4.727 4.507Tri-butylbenzene 0.926 0.837 0.985 0.806Heavies 0.200 0.224 0.407 0.339Sum 100.0 100.0 100.0 100.0Butvlbenzene Composition, percent t-Butylbenzene 1.792 1.494 0.985 0.721 iso-Butylbenzene* 0.000 0.000 0.000 0.000 sec-Butylbenzene 98.143 98.435 98.928 99.186 n-Butylbenzene 0.064 0.071 0.087 0.093Sum 100.0 100.0 100.0 100.0* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.

With MCM-22 zeolitic catalyst, Time= 43.2 - 235.2h, T= 130 - 160 °C , p= 16276.6Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93361; (2007); (A1) English View in Reaxys

Rx-ID: 28440800 View in Reaxys 141/481

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Yield

Conditions & References 2 :Example 2: Sec-Butylbenzene Production Using MCM-22 Catalyst and 2-Butene Feed [0046] A 1.0 gram sample of the same MCM-22 catalyst (65 percent MCM-22/35percent alumina binder) as used in Example 1 was used for the alkylation of benzene with 2-butene. The catalyst was in the form of a 1.6 mm (l/16inch) diameter cylindrical extrudate, chopped to 1.6 mm (l/16inch) length, and was diluted with sand to 3 cc and loaded into an isothermal, downflow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16inch). The catalyst was dried at 1500C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached the desired 2068 kPag (300 psig). Benzene flow was then reduced to 7.63 cc/hr (6.67 WHSV). Butene feed (99.28percent 2-butene, 0.39percent n-butane, 0.15percent isobutene, and 0.18percent others) was introduced from a syringe pump at 2.57 cc/hr (1.6 WHSV). Feed benzene/butene molar ratio was maintained at 3 : 1 for the entire run. The reactor temperature was adjusted to 1600C. Liquid products were collected at reactor conditions of 1600C and 2068 kPag (300 psig) in a cold-trap and analyzed off line. 2-Butene conversion was determined by measuring unreacted 2-butene relative to feed 2-butene. The catalyst was on stream for 4 days at 1.6 WHSV of butene with 97percent 2-butene conversion, 2 days at 4.8 WHSV with 95percent conversion, then 1 day at 7.2 WHSV with 86percent conversion, and followed by 4 days again at 1.6 WHSV with 97percent conversion. No deactivation was detected during the 11 -day test cycle. Representative data are shown in Table 4. Relative activity of MCM-22 based on first-order butene conversion was 1.0. <n="15"/>Table 4* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0047] The results in Table 4 show that, with a 2butene feed containing only 0.15percent isobutene, MCM-22 is effective in alkylating benzene at 95percent+ 2-butene conversion with a selectivity to sec -butylbenzene in excess of 90percent.

With 65 percent MCM-22/35percent Versal 300 alumina, Time= 91.2 - 259.2h, T= 160 °C , p= 16274.9Torr , Conversion of starting material Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2009/55227; (2009); (A1) English View in Reaxys 3 :Example 3: Sec-Butylbenzene Production Using MCM-49 Catalysts and 2-Butene Feed [0048] The process of Example 2 was repeated but with the MCM-22 catalyst replaced by 0.6 gm of MCM-49. The 1.3 mm (1/20 inch) quadrulobe extrudate with 60 percent MCM- 49/40percent Versal 200 alumina binder was cut to 1.3 mm (1/20 inch) length.

The catalyst was on stream for 4 days at 2.7 WHSV of butene with 97-98percent butene conversion, 1 day at 8 WHSV with 97 percent conversion, 0.5 days at 12 WHSV with 93percent conversion, 1.6 days at 2.7 WHSV with 98percent conversion, 0.3 days at 19.2 WHSV with 86percent conversion, and followed by 0.7 days at 2.7 WHSV again with 98 percent conversion. Relative activity of MCM-49 based on first-order butene conversion was 2.4. Representative data are shown in Table 5. <n="16"/>Table 5* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0049] The results in Table 5 show that, with a 2-butene feed containing only 0.15percent isobutene, MCM-49 is effective in alkylating benzene at 95percent+ 2-butene conversion with a selectivity to sec -butylbenzene in excess of 92percent.

With 60 percent MCM-49/40percent Versal 300 alumina, Time= 91.2 - 259.2h, T= 150 °C , p= 16274.9Torr , Conversion of starting material Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2009/55227; (2009); (A1) English View in Reaxys

OH

Rx-ID: 29263411 View in Reaxys 142/481 Yield

Conditions & References 1 :Example 1; [0040] An alkylation test of benzene with isopropanol and propylene was carried out in a fixed bed reactor, made from a percent inch (19 cm) diameter Schedule 40 Stainless Steel 316 pipe with a total length of 34 inches (864 cm). A storage tank was used for the benzene/isopropanol mixture and another tank was used for propylene. A positive displacement pump was used for feeding the benzene/isopropanol mixture into the reactor and another positive displacement pump was used for feeding propylene into the reactor. The flow rates of the benzene/ isopropanol mixture and propylene were set by pump settings and monitored by electronic weight scales. The reactor operating conditions were controlled and monitored by an automatic control system. A portion of the reactor effluent was circulated back to the reactor inlet by a centrifugal pump to control 13the temperature rise across the catalyst bed. The feedstock and reactor effluent were analyzed by two Hewlett Packard 5890 Series II Gas Chromatographs, one equipped with a Chrompack CP-Wax 52CB column having an inside diameter of 0.25 mm, film thickness of 0.5 μm, and length of 60 meters, and the other one equipped with an Agilent HP-PONA column having an

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inside diameter of 0.20 mm, film thickness of 0.5 μm, and length of 50 meters.[0041] 60 grams of an MCM-22 catalyst was loaded into the fixed bed reactor. Before the benzene/isopropanol mixture was introduced into the reactor, the feed to the reactor consisted of pure benzene and propylene and the catalyst performance was stable. The propylene feed weight hourly space velocity (WHSV) was 0.5 hr"1, the feed benzene to propylene ratio was 1.2:1 molar, and the reactor inlet temperature was 1280C. The reactor circulation was adjusted to control the temperature rise across the catalyst bed below 200C. As shown in Figure 1 , after the pure benzene feed was replaced with a mixture consisting of 1 wtpercent isopropanol and 99 wtpercent benzene and the reactor inlet temperature adjusted to 147°C, the Cumene/(Isopropanol+Propylene) selectivity went down slightly and stabilized at a lower level than before, due to a slight increase in the production of polyisopropylbenzenes. The Aromatics/(Isopropanol+Propylene) selectivity remained essentially unchanged throughout the test, as shown in Figure 1. No gradual or rapid aging as shown in the examples of US PAT No. 6,512,153 was observed. The propylene conversion was 100percent and the isopropanol conversion was 99percent. The moisture level in the reactor was about 20 ppm with the benzene feed and about 2,100 ppm with the benzene/isopropanol mixture. The corresponding isopropanol WHSV was 0.01 and the isopropanol to propylene molar ratio in the reactor feed was 2:98.

With MCM-22, T= 128 - 147 °C , Product distribution / selectivity Patent; BADGER LICENSING, LLC; HWANG, Shyh-Yuan, Henry; JOHNSON, Dana, E.; PETERS, Joseph, C.; CHI, Chung-Ming; FALLON, Kevin, J.; DEMERS, Francis, A.; WO2010/42314; (2010); (A1) English View in Reaxys

O

O

Rx-ID: 34664311 View in Reaxys 143/481 Yield

Conditions & References With copper chromite, hydrogen, Time= 1h, T= 150 °C , p= 22502.3Torr , Temperature Shutkina; Ponomareva; Ivanova; Petroleum Chemistry; vol. 53; nb. 1; (2013); p. 20 - 26 View in Reaxys With copper chromite, hydrogen, Time= 1h, T= 170 °C , p= 750.075Torr , Pressure Shutkina; Ponomareva; Ivanova; Petroleum Chemistry; vol. 53; nb. 1; (2013); p. 20 - 26 View in Reaxys 2H

2H 2H

2H

2

H

2 H 2

H 2H

2H

Rx-ID: 39590627 View in Reaxys 144/481 Yield

Conditions & References With anhydrous iron chloride, LiAlD4 in tetrahydrofuran, Time= 2h, T= -78 - 20 °C , Inert atmosphere Gieshoff, Tim N.; Villa, Matteo; Welther, Alice; Plois, Markus; Chakraborty, Uttam; Wolf, Robert; Jacobi Von Wangelin, Axel; Green Chemistry; vol. 17; nb. 3; (2015); p. 1408 - 1413 View in Reaxys

racemate

Rx-ID: 435672 View in Reaxys 145/481 Yield

Conditions & References With hydrogen, T= 350 - 360 °C , beim Leiten ueber Nickel Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

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T= 600 °C , beim Leiten ueber Kupfer Sabatier; Mailhe; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 929 View in Reaxys

T-4

T-4

Rx-ID: 1832230 View in Reaxys 146/481 Yield

Conditions & References

49.7 % Chromat., 11.7 % Chromat., 6.7 % Chromat., 5.7 % Chromat.

O

With hydrogen, calcium hexaammine, Time= 2h, T= 170 - 200 °C , Further byproducts given Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys

N

S

O

Rx-ID: 2037444 View in Reaxys 147/481 Yield 29 % Spectr., 30 % Spectr., 31 % Spectr., 9 % Spectr.

Conditions & References With sodium thiomethoxide in N,N,N',N',N'',N''-hexamethylphosphoric triamide, T= 90 °C , Product distribution Tanner, Dennis D.; Blackburn, Edward V.; Diaz, Gilberto E.; Journal of the American Chemical Society; vol. 103; nb. 6; (1981); p. 1557 - 1559 View in Reaxys

H 14 3 C

14

CH 3

racemate

14

CH 3

racemate

Rx-ID: 2063327 View in Reaxys 148/481 Yield

Conditions & References With potassium-sodium, [14C]-methyl iodide, 1.) glyme, triglyme, 0 deg C, 3 h, Yield given. Multistep reaction. Further byproducts given. Yields of byproduct given. Title compound not separated from byproducts Collins, Clair J.; Hombach, Hans-Peter; Maxwell, Brian; Woody, Madge C.; Benjamin, Ben M.; Journal of the American Chemical Society; vol. 102; nb. 2; (1980); p. 851 - 853 View in Reaxys

O N

NH

Rx-ID: 2937781 View in Reaxys 149/481 Yield

Conditions & References With water, T= 30 °C , p= 706Torr , Irradiation, effect of the presence of water, appparent rel. reaction rates, Product distribution, Mechanism Cacace, Fulvio; Ciranni, Giovanna; Giacomello, Pierluigi; Journal of the American Chemical Society; vol. 104; nb. 8; (1982); p. 2258 - 2261 View in Reaxys

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O HO

O

HO

HO

O

O

Rx-ID: 3117018 View in Reaxys 150/481 Yield

Conditions & References With 2,6-di-tert-butyl-4-methyl-phenol in acetone, T= -18 °C , Arrhenius parameters; other temperatures, reagents ratio, Rate constant, Thermodynamic data, Mechanism Pryor, William A.; Ohto, Norio; Church, Daniel F.; Journal of the American Chemical Society; vol. 104; nb. 21; (1982); p. 5813 - 5814 View in Reaxys

H N

N

O

Rx-ID: 3739080 View in Reaxys 151/481 Yield

Conditions & References With water, T= 30 °C , p= 705Torr , Irradiation, effect of the presence of water, appparent rel. reaction rates, Product distribution, Mechanism Cacace, Fulvio; Ciranni, Giovanna; Giacomello, Pierluigi; Journal of the American Chemical Society; vol. 104; nb. 8; (1982); p. 2258 - 2261 View in Reaxys

O

Cl

Cl

O

O

O

Rx-ID: 3832727 View in Reaxys 152/481 Yield

Conditions & References

0.8 %, 3.6 %, 0.63 g, 41.8 %

With aluminium trichloride in tetrachloromethane, Time= 1.5h, T= -2 - 0 °C , Further byproducts given. Title compound not separated from byproducts Grebenyuk, A. D.; Zavizion, E. M.; Rusin, A. N.; Bengard, Z. V.; Journal of Organic Chemistry USSR (English Translation); vol. 19; (1983); p. 811 - 814; Zhurnal Organicheskoi Khimii; vol. 19; nb. 5; (1983); p. 916 - 919 View in Reaxys

O

N O

Rx-ID: 4615867 View in Reaxys 153/481 Yield 8.8 %, 91.2 %

Conditions & References With sodium naphthalenide in tetrahydrofuran, T= 25 °C , Product distribution, Mechanism Denney, Donald B.; Denney, Dorothy Z.; Fenelli, Steven P.; Tetrahedron; vol. 53; nb. 15; (1997); p. 5397 - 5402 View in Reaxys

85 % Chromat., 2 % Chromat.

With potassium hydroxide, mercury in ethanol, T= 20 °C , pH= 13, Electrolysis, Reduction Chan-Shing, Elisa Soazara; Boucher, Denys; Lessard, Jean; Canadian Journal of Chemistry; vol. 77; nb. 5-6; (1999); p. 687 - 694 View in Reaxys

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O

O

Rx-ID: 5268422 View in Reaxys 154/481 Yield

Conditions & References With air, T= 120 °C , Thermolysis, Oxidation Mcgraw, Gerald W.; Hemingway, Richard W.; Ingram Jr., Leonard L.; Canady, Catherine S.; Mcgraw, William B.; Environmental Science and Technology; vol. 33; nb. 22; (1999); p. 4029 - 4033 View in Reaxys

tetra methyl tin Br

Rx-ID: 6416614 View in Reaxys 155/481 Yield

Conditions & References

77 % Chromat.

With (Et2)Pd(bpy), Time= 113h, T= 60 °C , in presence of fumaronitrile Sustmann, Reiner; Lau, Juergen; Zipp, Manfred; Tetrahedron Letters; vol. 27; nb. 43; (1986); p. 5207 - 5210 View in Reaxys

N N

N

N

N N N

Grignard reagent, R'=i-Pr

O

N OH

Rx-ID: 6674708 View in Reaxys 156/481 Yield

Conditions & References

7.5 %, 75 %

With [1,3-bis(diphenylphosphino) propane] dichloronickel(II) in diethyl ether, Heating Johnstone, Robert A.W.; McLean, W. Neil; Tetrahedron Letters; vol. 29; nb. 43; (1988); p. 5553 - 5556 View in Reaxys

O

O

Rx-ID: 8945421 View in Reaxys 157/481 Yield

Conditions & References in carbon dioxide, T= 50 °C , p= 320330Torr , UV-irradiation, Product distribution, Further Variations: Pressures, Solvents Tanko; Pacut; Journal of the American Chemical Society; vol. 123; nb. 24; (2001); p. 5703 - 5709 View in Reaxys

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Rx-ID: 22834150 View in Reaxys 158/481 Yield

Conditions & References With zeolite beta diluted with sand, T= 180 °C , p= 16276.6Torr , 60 cc/hr for 1 h then 2.0, 2,2 and 2.4 feed weight hourly space velocity relates to catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys With 1:1 coextruded mixt. of TEA-mordenite and MCM-22 mol. sieve diluted with sand, T= 180 °C , p= 16276.6Torr , 3.0 total weight hourly space velocity relates to total catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys With 1:1 mixt. of TEA-mordenite and MCM-22 mol. sieve diluted with sand, T= 180 °C , p= 16276.6Torr , 3.0 total weight hourly space velocity relates to total catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys With 1:1 mixt. of zeolite β and TEA-mordenite diluted with sand, T= 180 °C , p= 16276.6Torr , 3.0 total weight hourly space velocity relates to total catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys With MCM-22 molecular sieve diluted with sand, T= 180 °C , p= 16276.6Torr , 2.0, and 1.1 feed weight hourly space velocity related to total catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys With TEA-mordenite diluted with sand, T= 180 °C , p= 16276.6Torr , 4.0, 5.3 and 6.3 total weight hourly space velocity relates to total catalyst weight Patent; EXXONMOBIL CHEMICAL PATENTS, INC.; WO2002/8159; (2002); (A1) English View in Reaxys

E

Rx-ID: 23831759 View in Reaxys 159/481 Yield

Conditions & References 5 :EXAMPLE 5; Reaction of a 1:1 Molar Blend of Propylene and trans-2-Butene with Benzene; An olefin blend of 50percent propylene and 50percent trans-2-butene (on a molar basis) was reacted over the CP 786 catalyst at the conditions outlined in Table 6. Complete conversion of the C3/C4 olefins was observed. The results of the testing are presented in Table 6. Sec-Butyl Benzene and cumene were formed in high selectivity with a smaller amount of diand tri-alkyl benzenes than expected. Due to the fact that a mixture of olefins was used, the product did contain some di-alkyl benzene species containing both a C3 and a C4 chain in the product.

With zeolite beta CP 786 catalyst, T= 133 °C , p= 15654.3Torr , Product distribution / selectivity

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Patent; Murray, Brendan Dermot; Mysore, Narayana; Yaeger, James William; US2006/178544; (2006); (A1) English View in Reaxys

E

Z

Rx-ID: 25832064 View in Reaxys 160/481 Yield

Conditions & References 7; 8 :Example 7Sec-butylbenzene synthesis with jet-milled MCM-49 in fixed-bed reactor at3:1 benzene/2-butene molar ratio[0076] 0.4 g of the jet-milled MCM-49 catalyst of Example 5 (but cut to 1/16 inch [1.6 mm] length) was used for alkylation of benzene with 2-butene in a fixed- bed reactor. The catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached the desired 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr. 2-Butene feed (57.1percent cis- butene, 37.8percent trans-butene, 2.5percent n-butane, 0.8percent isobutene and 1 -butene, and 1.8percent others) was introduced from a syringe pump at 2.57 cc/hr. Feed benzene/butene molar ratio was maintained at 3:1 for the entire run. The reactor temperature was adjusted to 160°C. Liquid products were collected at reactor conditions of 160°C and 300 psig (2170 kPa) in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Representative data are shown in Table 7. <n="27"/>Example 8Sec-butylbenzene synthesis with jet-milled MCM-49 in fixed-bed reactor at6:1 benzene/2-butene molar ratio[0077] The process of Example 7 was repeated but using 0.6 g of the jet- milled MCM-49 catalyst of Example 5 (cut to 1/16 inch [1.6 mm] length) and with the feed benzene/butene molar ratio being maintained at 6:1 for the entire run (benzene at 11.47 cc/hr and butene at 1.93 cc/hour). Representative data are also shown in Table 7.Table 7 sec-Butylbenzene Production with Jet-Milled MCM-49 in Fixed-bedReactorExample Example 7 Example 8Feed Bz/C4= Weight Ratio 3 1 6 1Feed Bz/C4= Molar Ratio 4 2 1 8 4 1Days on Stream 1 8 2 8 6 8 7 8Butene WHSV, h 1 4 0 4 0 2 0 2 0Benzene WHSV, h 1 16 7 16 7 16 7 16 7Butene Conversion, percent 96 30 95 41 97 41 97 33Product Selectivity, wt percent ι-Butane 0 003 0 003 0 000 0 000 n-Butane 0 000 0 000 0 000 0 000C5-C7 0 055 0 059 0 099 0 107C8= 0 443 0 865 0 466 0 474C9-11 0 019 0 042 0 016 0 033Ci2= + C10-C11 Aromatics 0 157 0 135 0 066 0 073C13-15 0 158 0 166 0 062 0 071Cumene 0 243 0 251 0 156 0 159 t-Butylbenzene 0 093 0 078 0 078 0 068 i-Butylbenzene * 0 000 0 000 0 000 0 000 s-Butylbenzene 92 547 93 054 96 257 96 244 n-Butylbenzene 0 013 0 009 0 011 0 010Di-butylbenzene 5 546 5 040 2 667 2 620Tri-butylbenzene 0 405 0 287 0 113 0 125Heavies 0 320 0 013 0 010 0 016Sum 100 000 100 000 100 000 100 000 s-Butvlbenzene (BB) Puπtv, percent t-BB/all BB, percent 0 100 0 084 0 081 0 071 ι-BB7all BB, percent 0 000 0 000 0 000 0 000 s-BB/all BB, percent 99 886 99 907 99 909 99 919 n-BB/all BB, percent 0 014 0 009 0 011 0 011Sum, percent 100 00 100 00 100 00 100 00Di-BB/s-BB Wt Ratio, percent 6 0 5 4 2 8 2 7All samples collected at 160°C and 300 psig * iso-Butylbenzene less than 0 5percent in total butylbenzene is not detectable with oui GC <n="28"/>[0078] When operated at 3:1 benzene/2 -butene molar ratio (or 4.2:1 weight ratio), the 2-butene concentration is 18.9 wtpercent (1/5.3) if 2-butene mixes with benzene instantaneously. At this benzene/2-butene molar ratio, the MCM-49 catalyst produced sec-butylbenzene with 93percent selectivity. [0079] When operated at 6:1 benzene/2-butene molar ratio (or 8.4:1 weight ratio), the 2-butene concentration is 10.6 wtpercent (1/9.4) if 2-butene mixes with benzene instantaneously. At this benzene/2-butene molar ratio, the MCM-49 catalyst produced sec-butylbenzene with 96percent selectivity. By-products such as butene oligomers and di-butylbenzenes and tri-butylbenzenes were reduced by about 50percent. Thus reducing local concentration of butene in the fixed-bed reactor has a positive impact on secbutylbenzene selectivity.

With MCM-49 zeolitic catalyst, Time= 43.2 - 187.2h, T= 160 °C , p= 15514.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93357; (2007); (A1) English View in Reaxys

HO

HO

O

O

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O

O

O

O

OH

HO

O

Rx-ID: 27897452 View in Reaxys 161/481 Yield

Conditions & References 4 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit in the form of a reactor with a volume of 12 mL, equipped with a circulation loop to mix the reaction mass and a water jacket to maintain the assigned temperature. To prepare the catalyst, a reactor with a volume of 10 μL was used, and sulfuric acid and phenol were fed by pumps to the reactor. Catalyst and feedstock were fed to the stream of reaction mass at the input to the reactor. The composition of the feedstock is shown in Table 1. Sulfuric acid was also fed to the catalyst synthesis reactor at a rate of 3 μL/h, phenol was fed at a rate of 6 μL/h, which corresponds to a concentration in the reaction medium of 0.02 wt. percent, and the holding time in the reactor was 70 minutes at a temperature of 45° C. The rate at which the feedstock was fed to the CHP decomposition reactor was 27 mL/h. The rate of circulation of the reaction mass was 500 mL/h. The temperature in the reactor was maintained at 75° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the CHP decomposition reactor was cooled to room temperature and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2.; Example 2; CHP decomposition was carried out in the same equipment as in Example 1, but the reactor for synthesis of the catalytic system had a volume of 20 μL, and a mixture having the composition shown in Table 3 was used as feedstock.The feedstock was fed to the reactor at a rate of 10 mL/h, concentrated (96percent) sulfuric acid was fed at a rate of 1.1 μL/h, which corresponded to a concentration of 0.02 wt. percent, and phenol for mixing with sulfuric acid was fed at a rate of 0.9 μL/h, which corresponded to a sulfuric acid/phenol ratio of 2:1. The mixture of phenol and sulfuric acid was held for 600 minutes at a temperature of 20° C. The circulation rate of the reaction mixture was 200 mL/h, and the temperature in the reactor was 70° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4).

With sulfuric acid, phenol in water, T= 85 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys

HO

HO

O

O

O

O

O

O

OH

HO O

Rx-ID: 27897454 View in Reaxys 162/481 Yield

Conditions & References 1 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit consisting of two reactors: the first stage was a CHP decomposition reactor that had a volume of 12 mL and was equipped with a circulation loop, and the second stage reactor was a displacement reactor that had a volume of 7 mL. The reaction mass from the first stage reactor was partially fed to the second reactor and partially returned to the input of the first reactor, thus accomplishing its circulation. Catalyst and feedstock, the composition of which is shown in Table 1, were fed to the stream of reaction mass at the input to the first stage reactor. The catalyst was prepared by mixing concentrated sulfuric acid with phenol, which were fed by two pumps into a constant-temperature reactor with a capacity of 10 μL, from which the mixture was directed to the CHP decomposition reactor. The feedstock having the composition shown in Table 1, as well as a catalyst obtained directly by mixing concentrated sulfuric acid at a rate of 1 μL/h and phenol at a rate of 9 μL/h (ratio 1:5), were fed to the CHP decomposition reactor, and the mixture was kept for 60 minutes at a temperature of 50° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4). This feed corresponds to a sulfuric acid concentration of 0.007 wt. percent in the reaction medium. The rate of circulation of the reaction mass was 500 mL/h. The temperature in the reactor was kept at a level of 40° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the first stage reactor was diluted

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with acetone supplied at a rate of 8 mL/h, and was fed to the second stage reactor heated to a temperature of 125° C. The stream emerging from the second stage reactor was cooled and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2.

With sulfuric acid, phenol in water, T= 40 - 125 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English View in Reaxys

Z

E

Rx-ID: 28440798 View in Reaxys 163/481 Yield

Conditions & References 4 :Example 4: Sec-Butylbenzene Production with MCM-22 Catalyst and Raffinate-2 Type Feed[0050] A 1.0 gram sample of the MCM-22 catalyst (65 wtpercent MCM-22/35percent alumina binder) from Example 1 was used for the alkylation of benzene with Raffinate-2 type feed. The Raffinate-2 type feed was a synthetic blend with the following weight composition: 53.43percent cis-butene, 41.29percent trans-butene, 4.54percent isobutene, 0.48percent butadiene, 0.09percent 1- butene, 0.09percent n-butane, and 0.1percent others. The catalyst was in the form of a 1.6 mm (l/16inch) diameter cylindrical extrudate and was diluted with sand to 3 cc and loaded into an isothermal, downflow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16inch). The catalyst was dried at 1500C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until <n="17"/>reactor pressure reached the desired 2068 kPag (300 psig). Benzene flow was then reduced to 7.63 cc/hr (6.67 WHSV) and Raffinate-2 type feed was introduced from a syringe pump at 2.57 cc/hr (1.6 WHSV). The reactor temperature was adjusted to 1600C. Feed benzene/butene molar ratio was maintained at 3: 1 for the entire run. Liquid product was collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. The catalyst was on stream for 6 days at 1.6 WHSV of butene with 98percent 2-butene conversion, 1 day at 4.8 WHSV with 80percent conversion, 1 day at 7.2 WHSV with 62percent conversion, and followed by 4 days again at 1.6 WHSV with 97percent conversion. Representative data are shown in Table 6. Relative activity of MCM-22 based on first-order butene conversion was 0.5.Table 6* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0051] Table 6 shows that the MCM-22 catalyst was effective for sec -butylbenzene production using a Raffinate-2 type feed. The 0.5percent butadiene in butene feed had no significant effect on MCM-22 stability during the 12-day test cycle. However, the 4.5percent <n="18"/>isobutene in the butene feed increased by-product formation. After initial lineout, selectivity measured at 97-98percent 2-butene conversion was 8percent for butene oligomers, 1.2-1.5percent for t- butylbenzene, and 83percent for sec-butylbenzene. This was a significant change when compared to results in Table 4 using the same catalyst and 2-butene feed. Selectivity measured with 2- butene feed at 97-98percent 2-butene conversion was 1-2 percent for butene oligomers, 0.1-0.2percent for t- butylbenzene, and 89-91percent for sec-butylbenzene.

The use of Raffinate-2 type feed resulted a 50percent activity drop for MCM-22.

With 65 percent MCM-22/35percent Versal 300 alumina, Time= 18.96 - 282.96h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2009/55227; (2009); (A1) English View in Reaxys

Rx-ID: 30175497 View in Reaxys 164/481 Yield

Conditions & References With H-BASF-at catalyst, T= 149.84 °C , p= 30003Torr , Inert atmosphere, Autoclave

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Van Laak, Adri N.C.; Sagala, Sophia L.; Zecevic, Jovana; Friedrich, Heiner; De Jongh, Petra E.; De Jong, Krijn P.; Journal of Catalysis; vol. 276; nb. 1; (2010); p. 170 - 180 View in Reaxys With CP814N CY catalyst, T= 149.84 °C , p= 30003Torr , Inert atmosphere, Autoclave Van Laak, Adri N.C.; Sagala, Sophia L.; Zecevic, Jovana; Friedrich, Heiner; De Jongh, Petra E.; De Jong, Krijn P.; Journal of Catalysis; vol. 276; nb. 1; (2010); p. 170 - 180 View in Reaxys

Rx-ID: 32381371 View in Reaxys 165/481 Yield

Conditions & References With meso-macroporous aluminosilicate, T= 350 °C Yang, Xiao-Yu; Tian, Ge; Chen, Li-Hua; Li, Yu; Rooke, Joanna C.; Wei, Ying-Xu; Liu, Zhong-Min; Deng, Zhao; Van Tendeloo, Gustaaf; Su, Bao-Lian; Chemistry - A European Journal; vol. 17; nb. 52; (2011); p. 14987 - 14995 View in Reaxys With hierarchically porous zeolite ZSM-11, T= 399.84 °C , Temperature Song, Wen; Liu, Zhiting; Liu, Liping; Skov, Anne Ladegaard; Song, Nan; Xiong, Guang; Zhu, Kake; Zhou, Xinggui; RSC Advances; vol. 5; nb. 39; (2015); p. 31195 - 31204 View in Reaxys

O

O

OH

Rx-ID: 34664310 View in Reaxys 166/481 Yield

Conditions & References With copper chromite, hydrogen, Time= 1h, T= 135 °C , p= 22502.3Torr , Temperature Shutkina; Ponomareva; Ivanova; Petroleum Chemistry; vol. 53; nb. 1; (2013); p. 20 - 26 View in Reaxys

I H 14 3 C

H 14 3 C

14CH

3

racemate

14CH

3

racemate

Rx-ID: 1848985 View in Reaxys 167/481 Yield

Conditions & References With potassium-sodium, 1.) glyme, triglyme, 0 deg C, 3 h, Yield given. Multistep reaction. Further byproducts given.

Yields of byproduct given. Title compound not separated from byproducts Collins, Clair J.; Hombach, Hans-Peter; Maxwell, Brian; Woody, Madge C.; Benjamin, Ben M.; Journal of the American Chemical Society; vol. 102; nb. 2; (1980); p. 851 - 853 View in Reaxys

O O

S

HO

Rx-ID: 2041508 View in Reaxys 168/481 Yield

Conditions & References With sulfuric acid, T= 150 °C , sealed tube, various H2SO4 concentration, Kinetics, Rate constant

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Krylov E. N.; Pelevina, M. B.; Journal of Organic Chemistry USSR (English Translation); vol. 21; nb. 10; (1985); p.

1983 - 1987; Zhurnal Organicheskoi Khimii; vol. 21; nb. 10; (1985); p. 2166 - 2171 View in Reaxys With phosphoric acid, T= 150 °C , various H3PO4 concentration, Rate constant Krylov E. N.; Radzyun, O. S.; Journal of Organic Chemistry USSR (English Translation); vol. 21; nb. 10; (1985); p.

1987 - 1991; Zhurnal Organicheskoi Khimii; vol. 21; nb. 10; (1985); p. 2171 - 2176 View in Reaxys With perchloric acid, T= 150 °C , other concentration of HClO4, Rate constant Krylov, E. N.; Mironova, O. A.; Journal of Organic Chemistry USSR (English Translation); vol. 21; (1985); p. 1901 1904; Zhurnal Organicheskoi Khimii; vol. 21; nb. 10; (1985); p. 2077 - 2081 View in Reaxys With water in sulfuric acid, T= 110 - 150 °C , khydrolysis, Eact, Rate constant, Thermodynamic data Krylov, E. N.; Savel'eva, G. M.; J. Gen. Chem. USSR (Engl. Transl.); vol. 52; nb. 5; (1982); p. 957 - 961,833 - 836 View in Reaxys

tetra methyl tin Br

Rx-ID: 6416618 View in Reaxys 169/481 Yield

Conditions & References With (Et2)Pd(bpy), Time= 114h, T= 60 °C , in presence of fumaronitrile Sustmann, Reiner; Lau, Juergen; Zipp, Manfred; Tetrahedron Letters; vol. 27; nb. 43; (1986); p. 5207 - 5210 View in Reaxys

cymene HO

Rx-ID: 11713091 View in Reaxys 170/481 Yield

Conditions & References Reaction Steps: 2 1: diatomite PD-400 / 370 - 380 °C / in vapor phase 2: 6.7 percent Chromat. / H2 / calcium hexaammoniate / 2 h / 170 - 200 °C With diatomite PD-400, hydrogen, calcium hexaammine Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys Reaction Steps: 2 1: diatomite PD-400 / 370 - 380 °C / in vapor phase 2: 6.7 percent Chromat. / H2 / calcium hexaammoniate / 2 h / 170 - 200 °C With diatomite PD-400, hydrogen, calcium hexaammine Bazyl'chik, V. V.; Journal of Organic Chemistry USSR (English Translation); vol. 18; nb. 10; (1982); p. 1847 - 1851; Zhurnal Organicheskoi Khimii; vol. 18; nb. 10; (1982); p. 2099 - 2103 View in Reaxys

Z

E

Rx-ID: 25832061 View in Reaxys 171/481

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Yield

Conditions & References 1 :A 1.0 gram sample of MCM-22 catalyst (65 percent MCM-22/35percent alumina binder) was used for the alkylation of benzene with 2-butene. The catalyst was in the form of a 1.6 mm (1/16") diameter cylindrical extrudate, chopped to 1/16" length, and was diluted with sand to 3 cc and loaded into an isothermal, down- flow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16"). The catalyst was dried at 1500C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached the desired 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr (6.67 WHSV) and a butene feed (57.1percent cis-butene, 37.8percent trans-butene, 2.5percent n-butane, 0.8percent isobutene and 1 butene, and 1.8percent others) was introduced from a syringe pump at 2.57 cc/hr (1.6 WHSV). Feed benzene/ butene molar ratio was maintained at 3 : 1 for the entire run and the reactor temperature was adjusted to 160°C. Liquid products were collected at reactor conditions of 1600C and 300 psig (2170 kPa) in a cold-trap and analyzed off line. 2-Butene conversion was determined by measuring unreacted 2-butene relative to feed 2-butene. The catalyst was on stream for 4 days at 1.6 WHSV of butene with 97percent 2-butene conversion, 2 days at 4.8 WHSV with 95percent conversion, then 1 day at 7.2 WHSV with 86percent conversion, and followed by 4 days again at 1.6 WHSV with 97percent conversion. Representative data are shown in Table 1.

With MCM-22, Time= 91.2 - 259.2h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93362; (2007); (A1) English View in Reaxys 2 :The process of Example 1 was repeated but with the MCM-22 catalyst replaced by 0.6 gm of MCM-49 catalyst (1/20" quadralobe extrudate with 60 percentMCM-49/40percent Versal 200 alumina binder cut to 1/20" length). The catalyst was on stream for 4 days at 2.7 WHSV of butene with 97-98percent butene conversion, 1 day at 8 WHSV with 97 percent conversion, 0.5 days at 12 WHSV with 93percent conversion, 1.6 days at 2.7 WHSV with 98percent conversion, 0.3 days at 19.2 WHSV with 86percent conversion, and followed by 0.7 days at 2.7 WHSV with 98 percent conversion. Representative data are shown in Table 2.

With MCM-49, Time= 24 - 189.6h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93362; (2007); (A1) English View in Reaxys

Z

E

Rx-ID: 25896730 View in Reaxys 172/481 Yield

Conditions & References 7; 8 :Example 7Sec-butylbenzene synthesis with jet-milled MCM-49 in fixed-bed reactor at3:1 benzene/2-butene molar ratio [0081] 0.4 g of the jet-milled MCM-49 catalyst of Example 5 (but cut to 1/16 inch [1.6 mm] length) was used for alkylation of benzene with 2-butene in a fixed- bed reactor. The catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cc/min flowing nitrogen for 2 hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached the desired 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr. 2-Butene feed (57.1percent cis- butene, 37.8percent trans-butene, 2.5percent n-butane, 0.8percent isobutene and 1 -butene, and 1.8percent others) was introduced from a syringe pump at 2.57 cc/hr. Feed benzene/butene molar ratio was maintained at 3:1 for the entire run. The reactor temperature was adjusted to 160°C. Liquid products were collected at reactor conditions of 160°C and 300 psig (2170 kPa) in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Representative data are shown in Table 7.; Example 8Sec-butylbenzene synthesis with jet-milled MCM-49 in fixed-bed reactor at6:1 benzene/2-butene molar ratio[0082] The process of Example 7 was repeated but using 0.6 g of the jetmilled MCM-49 catalyst of Example 5 (cut to 1/16 inch [1.6 mm] length) and with the feed benzene/butene molar ratio being maintained at 6:1 for the entire run (benzene at 11.47 cc/hr and butene at 1.93 cc/hour). Representative data are also shown in Table 7. [0083] When operated at 3:1 benzene/2 -butene molar ratio (or 4.2:1 weight ratio), the 2-butene concentration is 18.9 wtpercent (1/5.3) if 2-butene mixes with benzene instantaneously. At this ben-

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zene/2-butene molar ratio, the MCM-49 catalyst produced sec-butylbenzene with 93percent selectivity. [0084] When operated at 6:1 benzene/2-butene molar ratio (or 8.4:1 weight ratio), the 2-butene concentration is 10.6 wtpercent (1/9.4) if 2-butene mixes with benzene instantaneously. At this benzene/2-butene molar ratio, the MCM-49 catalyst produced sec-butylbenzene with 96percent selectivity. By-products such as butene oligomers and di-butylbenzenes and tri-butylbenzenes were reduced by about 50percent. Thus reducing local concentration of butene in the fixedbed reactor has a positive impact on sec-butylbenzene selectivity.

With MCM-49, Time= 43.2 - 187.2h, T= 160 °C , p= 16274.9Torr , Product distribution / selectivity Patent; EXXONMOBIL CHEMICAL PATENTS INC.; EXXONMOBIL CHEMICAL LIMITED; WO2007/93358; (2007); (A1) English View in Reaxys

Rx-ID: 25937073 View in Reaxys 173/481 Yield

Conditions & References With hierarchical zeolite, Time= 3h, T= 349.84 °C , Product distribution, Further Variations: Reagents, time Lei, Qian; Zhao, Tianbo; Li, Fengyan; Zhang, Ling; Wang, Yue; Chemical Communications; nb. 16; (2006); p.

1769 - 1771 View in Reaxys With ZSM-5, T= 399.84 °C , Inert atmosphere Koo, Jeong-Boon; Jiang, Nanzhe; Saravanamurugan, Shunmugavel; Bejblova, Martina; Musilova, Zuzana; Cejka, Jiri; Park, Sang-Eon; Journal of Catalysis; vol. 276; nb. 2; (2010); p. 327 - 334 View in Reaxys With ZSM-5/MCM-48, Time= 0.00555556h, T= 400 °C , p= 760.051Torr , fluidized-bed reactor Odedairo; Balasamy; Al-Khattaf; Journal of Molecular Catalysis A: Chemical; vol. 345; nb. 1-2; (2011); p. 21 - 36 View in Reaxys With aluminosilicate nanospheres, Time= 0.0333333h, T= 300 °C , Inert atmosphere, Kinetics, Catalytic behavior, Reagent/catalyst Choi, Youngbo; Yun, Yang Sik; Park, Hongseok; Park, Dae Sung; Yun, Danim; Yi, Jongheop; Chemical Communications; vol. 50; nb. 57; (2014); p. 7652 - 7655 View in Reaxys

H

Rx-ID: 27853562 View in Reaxys 174/481 Yield

Conditions & References 2 :EXAMPLE 2; Tests were carried out with a hydrocarbon composition feed that comprised 66 weight percent benzene and 34 percent by weight of 2-methyl-hexane. Propylene was present in the feed in varied amounts, i.e., the propylene to benzene mole ratio was 1.0; 0.5; and 0.25. The test was conducted by passing the feed over a MCM-22 catalyst at a temperature of 130° C. and at a pressure sufficient to maintain the benzene in the liquid phase. Results of the tests are shown in FIG. 6 through FIG. 8. FIG. 6, which plots the degree of 2-methylhexane isomerization to 3methylhexane, shows the practice of the present disclosure results in minimal isomerization of 2-methylhexane to 3methylhexane. FIG. 7, which plots the amount of n-propylbenzene impurity at various space velocities, shows that the amount of n-propylbenzene formation was not significantly changed by space velocity. FIG. 8, which plots cumene selectivity versus benzene conversion, shows that the practice of the present disclosure results in both high benzene conversion and high cumene selectivity.

With MCM-22, T= 130 °C , Liquid phase, Product distribution / selectivity

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Patent; Brown, Stephen Harold; US2008/194890; (2008); (A1) English View in Reaxys

Z

E

Rx-ID: 28440799 View in Reaxys 175/481 Yield

Conditions & References 5 :Example 5: Sec-Butylbenzene Production with MCM-49 Catalyst and Raffinate-2 Type Feed[0052] The process of Example 4 was repeated but with the MCM-22 catalyst replaced by 0.5 gm of MCM-49. This is the same catalyst used in Example 2. The 1.3 mm (1/20 inch) quadrulobe extrudate with 60percent MCM-49/40percent Versal 200 alumina binder was cut to 1.3 mm (1/20 inch) length. The MCM-49 was on stream for 3 days at 3.2 WHSV of butene with 96percent conversion, 1 day at 9.6 WHSV with 80-83percent conversion, and 3 days at 3.2 WHSV with 95percent conversion. Representative data are shown in Table 7. Relative activity of MCM-49 based on first-order butene conversion was 1.1. <n="19"/>Table 7* iso-Butylbenzene less than 0.5percent in total butylbenzene not detectable with GC used.[0053] Table 7 shows that MCM-49 catalyst was also effective for sec -butylbenzene production using a Raffinate-2 type feed. The 0.5percent butadiene in butene feed had no significant effect on MCM-49 stability during the 7-day test cycle. Again, however, the 4.5percent isobutene in the butene feed increased by-product formation.

Selectivity measured at 96percent 2- butene conversion was 8percent for butene oligomers, 1.2-1.8percent for t-butylbenzene, and 83-85percent for sec -butylbenzene. This is a significant change when compared to results in Table 5 using the same MCM-49 catalyst and 2-butene feed. Selectivity measured with 2-butene feed at 97percent 2-butene conversion was 1.5 percent or less for butene oligomers, 0.1percent for t-butylbenzene, and 92percent for sec butylbenzene. The use of Raffinate-2 type feed resulted a 50percent activity drop for MCM-49.

With 60 percent MCM-49/40percent Versal 300 alumina, Time= 55.2 - 127.2h, T= 160 °C , p= 16274.9Torr , Conversion of starting material Patent; EXXONMOBIL CHEMICAL PATENTS INC.; WO2009/55227; (2009); (A1) English View in Reaxys

2-butene liquid

Rx-ID: 28488708 View in Reaxys 176/481 Yield

Conditions & References 2 :A MCM-22 catalyst with a nominal composition of 80 wt. percent MCM-22 crystal and 20percent Versal 300 alumina was prepared according to the same preparation procedure described in Example 1 with a MCM-22 molecular sieve. The mixture was pelletized and sized to 14-24 mesh particles. A 0.202 g of this sized catalyst was used for sBB production, following the same procedure described in Example 1. Data were collected at 160° C., 2170 kPa-a, and 3:1 benzene/butene molar ratio with butene flow adjusted to 8, 24, 48 then 8 hr-1 WHSV. First-order rate constant based on butene conversion and total catalyst weight was 82.8 hr-1 for this catalyst. Representative data at 94percent butene conversions are shown in Table 1. Representative data at 82percent butene conversions are shown in Table 2.

With MCM-22 molecular sieve, Time= 72h, T= 160 °C , Conversion of starting material Patent; Roth, Wieslaw J.; Cheng, Jane C.; Kalyanaraman, Mohan; Kerby, Michael C.; Helton, Terry E.; US2009/163753; (2009); (A1) English View in Reaxys 3 :A MCM-22 catalyst with a nominal composition of 80 wt. percent MCM-22 crystal and 20percent Versal 300 alumina was prepared according to the same preparation procedure described in Example 1 with a MCM-22 molecular

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sieve. The mixture was pelletized and sized to 14-24 mesh particles. A 0.202 g of this sized catalyst was used for sBB production, following the same procedure described in Example 1. Data were collected at 160° C., 2170 kPa-a, and 3:1 benzene/butene molar ratio with butene flow adjusted to 8, 24, 48 then 8 hr-1 WHSV. First-order rate constant based on butene conversion and total catalyst weight was 82.8 hr-1 for this catalyst. Representative data at 94percent butene conversions are shown in Table 1. Representative data at 82percent butene conversions are shown in Table 2.

With MCM-49 molecular sieve, Time= 72h, T= 160 °C , Conversion of starting material Patent; Roth, Wieslaw J.; Cheng, Jane C.; Kalyanaraman, Mohan; Kerby, Michael C.; Helton, Terry E.; US2009/163753; (2009); (A1) English View in Reaxys

2-butene liquid

Rx-ID: 28488709 View in Reaxys 177/481 Yield

Conditions & References 1 :An EMM-10 catalyst was prepared by slurrying a mixture consisting of 80percent by weight of EMM-10 and 20percent by weight of alumina (Vesral-300) in ammonium nitrate. The solution was then filtered, washed and dried at 120° C. The dried catalyst mixture was placed in a muffle and ramped up in temperature in a flow of air to a maximum of 538° C. The mixture was then pelletized and sized to 14-24 mesh particles. A 0.101 g of this sized catalyst was used for alkylation of benzene with 2-butene in a fixed-bed reactor. The catalyst was diluted with sand to 3 ml and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm. The catalyst was dried for 2 hours at 150° C. and 101 kpa-a with 100 ml/min flowing nitrogen. Nitrogen was turned off and benzene was fed to the reactor at 60 ml/hr until reactor pressure reached 2170 kPa-a. Benzene flow was then reduced to 7.63 ml/hr and temperature was adjusted to 160° C. 2-Butene liquid feed (48.66 wt. percent cis-butene, 51.07 wt. percent trans-butene, 0.05 wt. percent n-butane, 0.21 wt. percent isobutene and 1-butene, and 0.01 wt. percent others) was introduced using a syringe pump at 2.57 ml/hr or 16 hr-1 WHSV. Feed benzene/butene molar ratio was 3:1. Liquid products were collected in a cold-trap (25° C. and 101.3 kPa-a) and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Data were collected at 16 then 48 hr-1 WHSV on butene at 160° C., 2170 kPa-a, and 3:1 benzene/butene molar ratio. First-order rate constant based on butene conversion and total catalyst weight was 80.2 hr-1 for this catalyst. Representative data at 95percent butene conversions are shown in Table 1. Representative data at 82percent butene conversions are shown in Table 2.

With EMM-10 molecular sieve, Time= 115.2h, T= 160 °C , Conversion of starting material Patent; Roth, Wieslaw J.; Cheng, Jane C.; Kalyanaraman, Mohan; Kerby, Michael C.; Helton, Terry E.; US2009/163753; (2009); (A1) English View in Reaxys

racemate

Rx-ID: 435611 View in Reaxys 178/481 Yield

Conditions & References With hydrogen, T= 350 - 360 °C , beim Leiten ueber Nickel Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

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Rx-ID: 435908 View in Reaxys 179/481 Yield

Conditions & References With hydrogen, T= 350 - 360 °C , beim Leiten ueber Nickel Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

HO

O

Rx-ID: 1579338 View in Reaxys 180/481 Yield

Conditions & References

12 %, 54 %

With para-dicyanobenzene in acetonitrile, Time= 6h, Irradiation Bardi, Luca; Fasani, Elisa; Albini, Angelo; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 5; (1994); p. 545 - 550 View in Reaxys

Si

Si

Si

Si

Rx-ID: 1895064 View in Reaxys 181/481 Yield

Conditions & References With oxygen, T= 37.5 °C , p= 760Torr , Irradiation, var. reagents; other phenyltrimethylsilane, Product distribution, Mechanism Attina', Marina; Cacace, Fulvio; Ricci, Andreina; Journal of the American Chemical Society; vol. 113; nb. 16; (1991); p. 5937 - 5942 View in Reaxys

Cl HO

Rx-ID: 4516116 View in Reaxys 182/481 Yield

Conditions & References With hydrogen, palladium on activated charcoal in ethanol, T= 50 °C , var. solv.: isooctane, Product distribution Marques, Carlos Alberto; Selva, Maurizio; Tundo, Pietro; Gazzetta Chimica Italiana; vol. 126; nb. 6; (1996); p.

317 - 328 View in Reaxys

H

copper oxide-chromium oxide

O O

(R)-2-phenyl-propanol-(1) Rx-ID: 8286290 View in Reaxys 183/481

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Yield

Conditions & References T= 250 °C , p= 110326 - 147102Torr , Hydrogenation Bowden; Adkins; Journal of the American Chemical Society; vol. 56; (1934); p. 689 View in Reaxys

Si

Si

Si HO

Si N H

Rx-ID: 8559666 View in Reaxys 184/481 Yield

Conditions & References

99 % Chromat., 16 % Chromat., 11 % Chromat.

With ammonia, iron(III) chloride, sodium amide, Time= 0.0333333h, T= 20 °C , Decomposition, Substitution, Title compound not separated from byproducts Sun, Guang-Ri; He, Jin-Bao; Zhu, Hua-Jie; Pittman Jr., Charles U.; Synlett; nb. 5; (2000); p. 619 - 622 View in Reaxys

Rx-ID: 8749818 View in Reaxys 185/481 Yield

Conditions & References With HMCM-41 aluminosilicate, T= 250 °C , Product distribution, Further Variations: Temperatures, Reagents, aluminosilicate pretreatment Zhang, Zongtao; Han; Zhu, Lei; Wang, Runwei; Yu, Yi; Qiu, Shilun; Zhao, Dongyuan; Xiao, Feng-Shou; Angewandte Chemie - International Edition; vol. 40; nb. 7; (2001); p. 1258 - 1262 View in Reaxys

O O

Rx-ID: 38295131 View in Reaxys 186/481 Yield

Conditions & References With 1,4-dioxane, palladium on activated charcoal, T= 160 °C Zhou, Xiaoyuan; Mitra, Joyee; Rauchfuss, Thomas B.; ChemSusChem; vol. 7; nb. 6; (2014); p. 1623 - 1626 View in Reaxys

S

Rx-ID: 38342624 View in Reaxys 187/481 Yield

Conditions & References With sodium tetrahydroborate, water, [Ni(O2CCH3)2]*4H2O, [C4C1Pyrr][CF3SO3] in octane, Time= 0.833333h, T= 10 - 30 °C , p= 760.051Torr , Catalytic behavior Shu, Chenhua; Sun, Tonghua; Guo, Qingbin; Jia, Jinping; Lou, Ziyang; Green Chemistry; vol. 16; nb. 8; (2014); p. 3881 - 3889 View in Reaxys

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O

Rx-ID: 40597978 View in Reaxys 188/481 Yield

Conditions & References Reaction Steps: 2 1.1: n-butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C 1.2: -78 - 20 °C 2.1: C21H30Si; C18H15FP(1+)*C24H20B(1-); bromobenzene-d5 / 24 h / 100 °C / 3040.2 Torr / |Schlenk technique; |Inert atmosphere; |Cooling with liquid nitrogen With n-butyllithium, bromobenzene-d5, C21H30Si, C18H15FP(1+)*C24H20B(1-) in tetrahydrofuran, hexane Vom Stein, Thorsten; Perz, Manuel; Dobrovetsky, Roman; Winkelhaus, Daniel; Caputo, Christopher B.; Stephan, Douglas W.; Angewandte Chemie - International Edition; vol. 54; nb. 35; (2015); p. 10178 - 10182; Angew.

Chem.; vol. 54; (2015); p. 10178 - 10182,5 View in Reaxys

Br Mg

Rx-ID: 42040362 View in Reaxys 189/481 Yield

Conditions & References Reaction Steps: 2 1: diethyl ether; tetrahydrofuran / 0.5 h / |Inert atmosphere 2: iron(II) chloride; (2-phenylethyl)diphenylphosphane / toluene / 14 h / 45 °C / |Inert atmosphere With (2-phenylethyl)diphenylphosphane, iron(II) chloride in tetrahydrofuran, diethyl ether, toluene, 2: |Negishi Coupling Brown, Caleb A.; Nile, Terence A.; Mahon, Mary F.; Webster, Ruth L.; Dalton Transactions; vol. 44; nb. 27; (2015); p. 12189 - 12195 View in Reaxys O

O OH

Rx-ID: 294292 View in Reaxys 190/481 Yield

Conditions & References With potassium hydroxide, T= 250 - 300 °C Koslow; Fedoseew; Olifson; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 259,263; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 1919 View in Reaxys

Rx-ID: 435728 View in Reaxys 191/481 Yield

Conditions & References T= 479 °C , p= 600174Torr , Pyrolysis Ipatieff et al.; Journal of the American Chemical Society; vol. 75; (1953); p. 3323,3324 View in Reaxys

HS

Rx-ID: 846983 View in Reaxys 192/481

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Yield

Conditions & References With copper(II) pyrophosphate, T= 300 - 425 °C Patent; Pure Oil Co.; US2409080; (1944) View in Reaxys

OH

Rx-ID: 847813 View in Reaxys 193/481 Yield

Conditions & References With hydrogenchloride, aluminium trichloride, T= 50 °C Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys

HO

Rx-ID: 847891 View in Reaxys 194/481 Yield

Conditions & References With hydrogenchloride, aluminium trichloride, T= 50 °C Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys

Rx-ID: 848022 View in Reaxys 195/481 Yield

Conditions & References With silica-alumina, T= 400 °C Patent; Koppers Co.; US2589057; (1948) View in Reaxys

Rx-ID: 1981168 View in Reaxys 196/481 Yield

Conditions & References With zeolite (type 13 NaHX) in pentane, benzene, T= 260.1 °C , p= 18751.5 - 150012Torr , catalyst deactiv. and reactiv. in dependence on pressure, Kinetics, Product distribution Tiltscher; Wolf; Schelschshorn; Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics; vol. 88; nb. 9; (1984); p. 897 - 900 View in Reaxys

Rx-ID: 2007642 View in Reaxys 197/481

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Yield

Conditions & References With hydrogen, Chromatron W, platinum in gas, T= 40 °C , other temperatures (100 deg C, 200 deg C); hydrogenolysis of cyclopropane derivatives, effect of the nature of substituent on the product ratio; deuterolysis; reaction chromato-mass spectrometry for studiyng of cyclopropane compounds Mikaya, A. I.; Medvedkova, L. P.; Zaikin, V. G.; Vdovin, V. M.; Kamyshova, A. A.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 32; nb. 5; (1983); p. 1066 - 1068; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 5; (1983); p. 1181 - 1184 View in Reaxys

O S O

O

Rx-ID: 4854868 View in Reaxys 198/481 Yield 94 % Chromat.

Conditions & References With scandium tris(trifluoromethanesulfonate), Time= 1.5h, T= 80 °C Kotsuki, Hiyoshizo; Oshisi, Takeshi; Inoue, Motoshi; Synlett; nb. 3; (1998); p. 255 - 256 View in Reaxys

94 % Chromat.

With trifluorormethanesulfonic acid, Time= 1.5h, T= 80 °C Kotsuki, Hiyoshizo; Ohishi, Takeshi; Inoue, Motoshi; Kojima, Tomoyuki; Synthesis; nb. 4; (1999); p. 603 - 606 View in Reaxys With Cs2,6PW, Time= 1.5h, T= 89.85 °C , Friedel-Crafts reaction, Product distribution, Further Variations: Catalysts Molnar; Beregszaszi; Fudala; Lentz; Nagy; Konya; Kiricsi; Journal of Catalysis; vol. 202; nb. 2; (2001); p. 379 386 View in Reaxys

Rx-ID: 8736375 View in Reaxys 199/481 Yield

Conditions & References With H-MFI-300 + Zr2Fe, T= 349.85 °C , p= 760Torr , Alkylation, Product distribution, Further Variations: Catalysts, Temperatures Smirnov, Andrei V.; Mazin, Evgenii V.; Yuschenko, Valentina V.; Knyazeva, Elena E.; Nesterenko, Sergei N.; Ivanova, Irina I.; Galperin, Leonid; Jensen, Robert; Bradley, Steven; Journal of Catalysis; vol. 194; nb. 2; (2000); p. 266 - 277 View in Reaxys With 0.31 percent Pt-modified HZSM-5 zeolites, Time= 8h, Reagent/catalyst Alotaibi, Abdullah; Bayahia, Hossein; Kozhevnikova, Elena F.; Kozhevnikov, Ivan V.; ACS Catalysis; vol. 5; nb.

9; (2015); p. 5512 - 5518 View in Reaxys

Rx-ID: 28225724 View in Reaxys 200/481 Yield

Conditions & References With C19H26N2PtS, Time= 21.2h, T= 110 °C , Inert atmosphere Luedtke, Avery T.; Goldberg, Karen I.; Angewandte Chemie - International Edition; vol. 47; nb. 40; (2008); p. 7694 - 7696

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View in Reaxys With (3,5-dimethyl-2-(2-pyridyl)pyrrolide)PtPh(SMe2), Time= 120h, T= 100 °C , Inert atmosphere, Glovebox, Sealed tube, Catalytic behavior, Reagent/catalyst Clement, Marie L.; Grice, Kyle A.; Luedtke, Avery T.; Kaminsky, Werner; Goldberg, Karen I.; Chemistry - A European Journal; vol. 20; nb. 52; (2014); p. 17287 - 17291 View in Reaxys

Rx-ID: 35772945 View in Reaxys 201/481 Yield Ca. 10 %Chromat., Ca. 70 %Chromat.

Conditions & References With diethyl ether, tris(pentafluorophenyl)-borane, hydrogen in dichloromethane-d2, Time= 24h, T= 20 °C , p= 60804.1Torr , Catalytic behavior Hounjet, Lindsay J.; Bannwarth, Christoph; Garon, Christian N.; Caputo, Christopher B.; Grimme, Stefan; Stephan, Douglas W.; Angewandte Chemie - International Edition; vol. 52; nb. 29; (2013); p. 7492 - 7495; Angew.

Chem.; vol. 125; nb. 29; (2013); p. 7640 - 7643,4 View in Reaxys

Rx-ID: 41958517 View in Reaxys 202/481 Yield

Conditions & References With ZSM-5, Time= 2.5h, T= 380 °C , p= 37503.8Torr , Inert atmosphere Guo, Aijun; Wu, Chongchong; He, Peng; Luan, Yingqi; Zhao, Lulu; Shan, Wenpo; Cheng, Wei; Song, Hua; Catalysis Science and Technology; vol. 6; nb. 4; (2016); p. 1201 - 1213 View in Reaxys

Rx-ID: 170500 View in Reaxys 203/481 Yield

Conditions & References T= 400 - 460 °C , p= 308913Torr Pines; Arrigo; Journal of the American Chemical Society; vol. 79; (1957); p. 4958,4965 View in Reaxys

Cl

Rx-ID: 847368 View in Reaxys 204/481 Yield 24 % Chromat.,

Conditions & References With aluminium trichloride, Time= 0.333333h, Heating, degree of isomerization of the alkyl chain, Product distribution

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76 % Chromat.

Zakharkin, L. I.; Anikina, E. V.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 36; nb. 2; (1987); p. 327 - 330; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 2; (1987); p. 367 - 371 View in Reaxys With aluminium amalgam Diuguid; Journal of the American Chemical Society; vol. 63; (1941); p. 3527 View in Reaxys With aluminium trichloride Konowalow; Bulletin de la Societe Chimique de France; vol. <3> 16; (1896); p. 864 View in Reaxys Konowalow; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 27; (1895); p. 457 864; Jahresbericht ueber die Fortschritte der Chemie und Verwandter Theile Anderer Wissenschaften; (1895); p. 1514 View in Reaxys

Mg Br HO

Rx-ID: 2012066 View in Reaxys 205/481 Yield

Conditions & References With DTPP-F6, Yield given. Multistep reaction Kubota, Toshio; Miyashita, Satoshi; Kitazume, Tomoya; Ishikawa, Nobuo; Journal of Organic Chemistry; vol.

45; nb. 25; (1980); p. 5052 - 5057 View in Reaxys

HO

Rx-ID: 3923373 View in Reaxys 206/481 Yield

Conditions & References With sodium tetrahydroborate, oxygen, cobalt-salen complex in ethylene glycol dimethyl ether, isopropyl alcohol, Time= 16h, Ambient temperature, other catalysts, Mechanism, Product distribution Okamoto, Tadashi; Oka, Shinzaburo; Journal of Organic Chemistry; vol. 49; nb. 9; (1984); p. 1589 - 1594 View in Reaxys

Rx-ID: 9778778 View in Reaxys 207/481 Yield

Conditions & References With aluminum oxide, tin(ll) chloride, Time= 5h, T= 500 °C , p= 3750.3Torr , Product distribution, Further Variations: Reagents Toppi, Stephanie; Thomas, Cyril; Sayag, Celine; Brodzki, Dominique; Fajerwerg, Katia; Le Peltier, Fabienne; Travers, Christine; Djega-Mariadassou, Gerald; Journal of Catalysis; vol. 230; nb. 2; (2005); p. 255 - 268 View in Reaxys

Cl

Cl

Rx-ID: 1441383 View in Reaxys 208/481 Yield

Conditions & References With aluminium trichloride

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Ransley,D.L.; Journal of Organic Chemistry; vol. 31; (1966); p. 3595 - 3599 View in Reaxys With aluminium trichloride Ransley,D.L.; Journal of Organic Chemistry; vol. 31; (1966); p. 3595 - 3599 View in Reaxys

HO

O

Rx-ID: 2017881 View in Reaxys 209/481 Yield

Conditions & References With bis(acetylacetonato)(phenanthroline)zinc in various solvent(s), T= 120 °C , effect of the catalyst and the temperature, Thermodynamic data, Kinetics Kozlov, S. K.; Potekhin, V. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 58; nb. 4; (1985); p. 870 - 872,791 - 793 View in Reaxys With ethyl 3-(2',3'-epoxypropyl)-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate in chlorobenzene, T= 110 °C , Inert atmosphere, Kinetics, Reagent/catalyst Zamanova; Kurbanova; Rzaeva; Farzaliev; Allakhverdiev; Russian Journal of Applied Chemistry; vol. 83; nb. 2; (2010); p. 293 - 296 View in Reaxys

O

HO

Rx-ID: 3384376 View in Reaxys 210/481 Yield

Conditions & References With hydrogen, copperchromium (KGA-43), T= 80 - 100 °C , p= 15200 - 22800Torr , Product distribution, Kinetics Ziyatdinov, A. Sh.; Stepanenko, V. V.; Chernykh, I. S.; E. B. Leonova; Pisarenko, V. N.; Kafarov, V. V.; J. Appl.

Chem. USSR (Engl. Transl.); vol. 61; nb. 3; (1988); p. 565 - 571,506 - 511 View in Reaxys

N

N

Rx-ID: 3774645 View in Reaxys 211/481 Yield

Conditions & References With thiophenol in chlorobenzene, T= 55 °C , various pressure, also with DBNO and cumene; activation volumes; efficiency of radical production, Rate constant, Mechanism, Product distribution Neuman, Robert C.; Amrich, Michael J.; Journal of Organic Chemistry; vol. 45; nb. 23; (1980); p. 4629 - 4636 View in Reaxys

N

N

Rx-ID: 3774647 View in Reaxys 212/481 Yield

Conditions & References in chlorobenzene, T= 55 °C , p= 760Torr , various pressure, Product distribution Neuman, Robert C.; Amrich, Michael J.; Journal of Organic Chemistry; vol. 45; nb. 23; (1980); p. 4629 - 4636

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View in Reaxys

Rx-ID: 4459505 View in Reaxys 213/481 Yield

Conditions & References With Zeolite β, T= 150 °C , p= 22501.8Torr , other olefin as alkylating agent, other zeolyte as catalyst, influence of Si/Al ratio in catalyst, var. temp., var. pressure values, liquid phase alkylation, Product distribution, Mechanism Bellussi, G.; Pazzuconi, G.; Perego, C.; Girotti, G.; Terzoni, G.; Journal of Catalysis; vol. 157; nb. 1; (1995); p.

227 - 234 View in Reaxys

NE

N

Rx-ID: 8905082 View in Reaxys 214/481 Yield

Conditions & References in decane, T= 101.37 °C , Kinetics, Product distribution, Further Variations: Temperatures Engel; Pan; Ying; Alemany; Journal of the American Chemical Society; vol. 123; nb. 16; (2001); p. 3706 - 3715 View in Reaxys

Bi

Rx-ID: 26841086 View in Reaxys 215/481 Yield

Conditions & References With hydrogenchloride Gillmeister, A.; Ber. Dtsch. Chem. Ges.; vol. 30; (1897); p. 2843 - 2850 ; (from Gmelin) View in Reaxys With HCl vol. Bi: Org.Verb.; 1.3.3.2.6.1, page 82 - 86 ; (from Gmelin) View in Reaxys

O

HO

O

HO

Rx-ID: 27742538 View in Reaxys 216/481 Yield

Conditions & References 1 :Example 1; According to the method described in the specification, an oxidization reaction solution (1) containing 31percent by weight of cumene hydroperoxide was obtained by oxidizing cumene with an oxygen-containing gas (air) in an oxidation step. An epoxidation reaction solution (2) containing mainly propylene oxide, cumyl alcohol, unreacted propylene, and cumene was obtained by passing the oxidization reaction solution and propylene through a reactor filled with a titanium-containing silicon oxide catalyst in an epoxidation step. The unreacted propylene (3) was separated and removed from the resulting reaction solution (2) to obtain a reaction solution (4) after recovering propylene. The reaction solution (4) after recovering propylene was used in the following Example 3 and Comparative Example 1.First, the reaction solution (4) after recovering propylene was separated into a fraction of a solution (5) containing mainly cumyl alcohol and cumene and a fraction containing mainly propylene oxide in a propylene oxide

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purification step, and then the fraction containing mainly <n="27"/>propylene oxide was distilled with a plurality of distillation columns including extraction and distillation so as to satisfy product quality to obtain a propylene oxide product. Regarding the fraction of the solution (5) containing mainly cumyl alcohol and cumene, cumyl alcohol was subjected to a dehydration reaction and a hydrogenation reaction in a hydrogenation step to obtain cumene, which was recycled to the oxidization step.Fig. 1 is a schematic flow chart described in the specification.

With titanium-containing silicon dioxide, Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; WO2008/123384; (2008); (A1) English View in Reaxys Rx-ID: 41958516 View in Reaxys 217/481 Yield

Conditions & References With Ag–Zn/ZSM-5, Time= 2.5h, T= 380 °C , p= 37503.8Torr , Inert atmosphere Guo, Aijun; Wu, Chongchong; He, Peng; Luan, Yingqi; Zhao, Lulu; Shan, Wenpo; Cheng, Wei; Song, Hua; Catalysis Science and Technology; vol. 6; nb. 4; (2016); p. 1201 - 1213 View in Reaxys

C

Rx-ID: 41958520 View in Reaxys 218/481 Yield

Conditions & References With ZSM-5, Time= 2.5h, T= 380 °C , p= 37503.8Torr Guo, Aijun; Wu, Chongchong; He, Peng; Luan, Yingqi; Zhao, Lulu; Shan, Wenpo; Cheng, Wei; Song, Hua; Catalysis Science and Technology; vol. 6; nb. 4; (2016); p. 1201 - 1213 View in Reaxys O OH

Rx-ID: 280906 View in Reaxys 219/481 Yield

Conditions & References With methyllithium, calcium carbonate Gerhardt; Cahours; Annales de Chimie (Cachan, France); vol. <3> 1; (1841); p. 87; Justus Liebigs Annalen der Chemie; vol. 38; (1841); p. 88 View in Reaxys With barytes Gerhardt; Cahours; Annales de Chimie (Cachan, France); vol. <3> 1; (1841); p. 87; Justus Liebigs Annalen der Chemie; vol. 38; (1841); p. 88 View in Reaxys

Rx-ID: 1546614 View in Reaxys 220/481

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Yield

Conditions & References With hydrogen, K doped ZnO, Time= 2h, T= 299.9 °C , p= 1500.1Torr , other temp., differently modified ZnO2; initial rate of hydrogenation, Product distribution Kijenski, Jacek; Bulletin de l'Academie Polonaise des Sciences, Serie des Sciences Chimiques; vol. 29; nb. 5-6; (1981); p. 225 - 230 View in Reaxys

Br

Rx-ID: 2943993 View in Reaxys 221/481 Yield

Conditions & References With tetramethylstannane, (FMD)Pd(bpy), Time= 15h, T= 60 °C , catalytic activity of fumaronitril palladium(0), Product distribution Sustmann, Reiner; Lau, Juergen; Zipp, Manfred; Tetrahedron Letters; vol. 27; nb. 43; (1986); p. 5207 - 5210 View in Reaxys

Cl –

Rx-ID: 3148793 View in Reaxys 222/481 Yield

Conditions & References in gas, T= 26 °C , p= 0 - 0.3Torr , Equilibrium constant French, M. A.; Ikuta, S.; Kebarle, P.; Canadian Journal of Chemistry; vol. 60; (1982); p. 1907 - 1918 View in Reaxys

Rx-ID: 3917107 View in Reaxys 223/481 Yield

Conditions & References T= 313 °C , p= 75006Torr , Further byproducts given. Title compound not separated from byproducts Kolesnikov, I. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 60; nb. 11; (1987); p. 2504 - 2510,2316 - 2322 View in Reaxys

Rx-ID: 3917395 View in Reaxys 224/481 Yield

Conditions & References With aluminum tri-bromide, 2-methyl propane, 1,2,2-trifluoro-trichloroethane, Time= 16h, T= 50 °C , Yield given. Further byproducts given. Yields of byproduct given. Title compound not separated from byproducts Miethchen, Ralf; Roehse, Carola; Kroeger, Carl-Friedrich; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 24; nb. 4; (1984); p. 145 - 146 View in Reaxys

O

O

F

S

F

F

O

Rx-ID: 3917450 View in Reaxys 225/481

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Yield

Conditions & References in pentane, Time= 16h, Ambient temperature, Yield given Aubert, Corinne; Begue, Jean-Pierre; Synthesis; nb. 8; (1985); p. 759 - 760 View in Reaxys

Z

Rx-ID: 4501130 View in Reaxys 226/481 Yield

Conditions & References With (E)-7-methyl-3,5,6-octatrien-1-yne in benzene-d6, T= 37 °C , reaction half-life Wang, Kung K.; Wang, Zhongguo; Sattsangi, Prem D.; Journal of Organic Chemistry; vol. 61; nb. 4; (1996); p.

1516 - 1517 View in Reaxys

OH HO

S OO

Rx-ID: 5801868 View in Reaxys 227/481 Yield

Conditions & References T= 65 °C Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys Grosse; Ipatieff; Journal of Organic Chemistry; vol. 2; (1937); p. 447,450 View in Reaxys Ipatieff; Pines; Corson; Journal of the American Chemical Society; vol. 60; (1938); p. 577,578 View in Reaxys Ipatieff; Pines; Schmerling; Journal of Organic Chemistry; vol. 5; (1940); p. 253,259 View in Reaxys

sodium

Rx-ID: 5806895 View in Reaxys 228/481 Yield

Conditions & References T= 290 °C , p= 128714Torr , Hydrieren des Reaktionsprodukts an Platin Mark; Pines; Journal of the American Chemical Society; vol. 78; (1956); p. 5946,5947 View in Reaxys T= 287 °C , p= 128714Torr , Hydrieren des Reaktionsprodukts Mark; Pines; Journal of the American Chemical Society; vol. 78; (1956); p. 5946,5947 View in Reaxys

<α-hydroxy-isoproyl>-benzene Rx-ID: 6416606 View in Reaxys 229/481 Yield

Conditions & References With ethanol, ammonia, sodium

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Birch; Journal of the Chemical Society; (1945); p. 809,812; Journal and Proceedings of the Royal Society of New South Wales; vol. 83; (1949); p. 245,249 View in Reaxys

cymene Rx-ID: 6683228 View in Reaxys 230/481 Yield

Conditions & References With aluminium trichloride, benzene Wheeler; Chem. Zentralbl.; vol. 89; nb. II; (1918); p. 617 View in Reaxys Boedtker; Halse; Bulletin de la Societe Chimique de France; vol. <4> 19; (1916); p. 447 View in Reaxys

α.β-diphenyl-propane Rx-ID: 7043280 View in Reaxys 231/481 Yield

Conditions & References With aluminium trichloride Silva; Bulletin de la Societe Chimique de France; vol. <2> 44; (1885); p. 417 View in Reaxys Bodroux; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 155 View in Reaxys

HO

H2 HO

Rx-ID: 7076703 View in Reaxys 232/481 Yield

Conditions & References

24 %, 5 %, With methanol, Europium chloride, Time= 3h, Irradiation 2 %, 50 % Ishida, Akito; Toki, Susumu; Takamuku, Setsuo; Chemistry Letters; (1985); p. 893 - 896 View in Reaxys

S

nickel /kieselguhr

Rx-ID: 7449734 View in Reaxys 233/481 Yield

Conditions & References T= 350 °C , p= 51485.6Torr , Hydrogenation Pines; Postl; Journal of the American Chemical Society; vol. 79; (1957); p. 1769 View in Reaxys

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NE

HS

N

S

S S

Rx-ID: 8890290 View in Reaxys 234/481 Yield

Conditions & References in N-dodecane, benzene-d6, Time= 8h, T= 112.9 °C , Product distribution, Further Variations: Reaction partners Engel; Pan; Ying; Alemany; Journal of the American Chemical Society; vol. 123; nb. 16; (2001); p. 3706 - 3715 View in Reaxys HS

Rx-ID: 286590 View in Reaxys 235/481 Yield

Conditions & References T= 425 °C , Leiten ueber Chrom(VI)-oxyd-Aluminiumoxyd Hansch; Blondon; Journal of the American Chemical Society; vol. 70; (1948); p. 1561 View in Reaxys

Cl

O

Rx-ID: 317769 View in Reaxys 236/481 Yield

Conditions & References With aluminium trichloride, benzene Rothstein; Saville; Journal of the Chemical Society; (1949); p. 1946,1949 View in Reaxys

HO

Rx-ID: 2016232 View in Reaxys 237/481 Yield

Conditions & References With potassium hydroxide, sodium hypophosphite, N,N-dimethyl-aniline; compound with sulfur trioxide, palladium dichloride, Yield given. Multistep reaction Davydov, D. V.; Beletskaya, I. P.; Russian Chemical Bulletin; vol. 42; nb. 3; (1993); p. 573 - 575; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 3; (1993); p. 605 - 606 View in Reaxys N

N

H

H

H

H

racemate

Rx-ID: 2478877 View in Reaxys 238/481 Yield 72 % Chromat.,

Conditions & References With triethylamine in benzene-d6, Time= 1h, T= 150 °C Klaerner, Frank-Gerrit; Glock, Volker; Hemmes, Jan-Luiken; Chemische Berichte; vol. 123; nb. 9; (1990); p.

1869 - 1879

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28 % Chromat.

View in Reaxys

28 % Chromat., 72 % Chromat.

With triethylamine in benzene-d6, Time= 1h, T= 150 °C , deuterium isotope effect; other temperature, other solvent C6H6, Rate constant, Mechanism, Kinetics Klaerner, Frank-Gerrit; Glock, Volker; Hemmes, Jan-Luiken; Chemische Berichte; vol. 123; nb. 9; (1990); p.

1869 - 1879 View in Reaxys

OH O

S O

Rx-ID: 3038678 View in Reaxys 239/481 Yield

Conditions & References With water in sulfuric acid, T= 110 - 150 °C , khydrolysis, Eact, Rate constant, Thermodynamic data Krylov, E. N.; Savel'eva, G. M.; J. Gen. Chem. USSR (Engl. Transl.); vol. 52; nb. 5; (1982); p. 957 - 961,833 - 836 View in Reaxys O O

H N

O

O

NH

Rx-ID: 3456589 View in Reaxys 240/481 Yield

Conditions & References With Thiokresol in 1,3,5-trimethyl-benzene, T= 190 °C , Yield given. Yields of byproduct given Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys With Thiokresol in 1,3,5-trimethyl-benzene, T= 144.5 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Kinetics, Thermodynamic data Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys O O

O

N

N

O

Rx-ID: 3456791 View in Reaxys 241/481 Yield

Conditions & References With Thiokresol in 1,3,5-trimethyl-benzene, T= 143 °C , Yield given. Yields of byproduct given Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys With Thiokresol in 1,3,5-trimethyl-benzene, T= 116.1 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Kinetics, Thermodynamic data Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys

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O O

O

N

O

N

Rx-ID: 3457025 View in Reaxys 242/481 Yield

Conditions & References With Thiokresol in 1,3,5-trimethyl-benzene, T= 170 °C , Yield given. Yields of byproduct given Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys With Thiokresol in 1,3,5-trimethyl-benzene, T= 104.2 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Kinetics, Thermodynamic data Schulze, Rainer; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p.

1031 - 1038 View in Reaxys

N

N

Rx-ID: 3774648 View in Reaxys 243/481 Yield

Conditions & References With silica surface, T= 55 °C , energy data (ΔH(excit.), ΔS(excit.)); also photolysis at 25 deg C; labeling studies, Kinetics, Mechanism, Rate constant Leffler, J. E.; Zupancic, J. J.; Journal of the American Chemical Society; vol. 102; nb. 1; (1980); p. 259 - 267 View in Reaxys

Rx-ID: 3917103 View in Reaxys 244/481 Yield

Conditions & References

67.0 %, 23.4 %

With aluminium trichloride, Time= 1h, T= 75 °C , other molar ratio, Product distribution Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

C H

O

CH

O OH

OH

Rx-ID: 5198701 View in Reaxys 245/481 Yield

Conditions & References With di-tert-butyl peroxide in various solvent(s), T= 26.85 °C , Photolysis, products were determined by spectr. methods, radical generation, Product distribution, Kinetics, Activation energy, Further Variations: Reagents, Temperatures

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Jackson, Leon; Walton, John C.; Tetrahedron Letters; vol. 40; nb. 38; (1999); p. 7019 - 7021 View in Reaxys

11-iodo-1-isopropyl-benzene Rx-ID: 7024728 View in Reaxys 246/481 Yield

Conditions & References With hydrogen iodide, acetic acid, zinc Klages; Chemische Berichte; vol. 35; (1902); p. 2649; Chemische Berichte; vol. 39; (1906); p. 2591 View in Reaxys O

waste stream Rx-ID: 23075110 View in Reaxys 247/481 Yield

Conditions & References 1 : Example 1 A waste stream was obtained from the acetone purification stage of the Hock process comprising 2 wt-percent low boiling hydrocarbons, 11 wt-percent acetone, 68 wt-percent water, 10 wt-percent mesityl oxide and 9 wt-percent high boiling hydrocarbons and continuously fed to the middle section of a first distillation column as shown in Fig. 1.

Based on 1000 parts by weight of waste stream the waste stream was continuously separated into 150 parts by weight of a head product stream consisting essentially of acetone and containing only traces of low boiling hydrocarbons and into 713 parts by weight of a bottom stream consisting essentially of water and some high boiling hydrocarbons. A side stream was removed from the first distillation column and fed to an decanter, wherein the aqueous phase and the organic phase was separated. The aqueous phase was recycled to the first column and 279 parts by weight organic phase based on 1000 parts by weight of the waste stream comprising 7 wt-percent low boiling hydrocarbons, 36 wt-percent mesityl oxide, 25 wt-percent acetone and 32 wt-percent high boiling hydrocarbons was continuously fed to a middle section of a second distillation column. The organic phase was continuously separated in 65 parts by weight of a head product stream consisting essentially of acetone, in 25 parts by weight of an upper side stream comprising 80 wt-percent low boiling hydrocarbons and 20 wt-percent acetone, 47 parts by weight of a bottom stream comprising high boiling hydrocarbons i.a. cumene and 142 parts by weight of a lower side stream comprising 70 wt-percent mesityl oxide, 25 wt-percent high boiling hydrocarbons and 5 wt-percent acetone, all parts by weight being based on 1000 parts by weight of the initial waste stream. With upper side stream benzene was quantitatively removed from the waste stream. The lower side stream was continuously recycled to a lower portion of the first distillation column, where the mesityl oxide was converted to acetone as described above. As can be seen from this example valuable components like acetone, mesityl oxide converted to acetone and cumene can be economically recovered from a waste stream using the process of the present invention. , Purification / work up Patent; INEOS Phenol GmbH and Co. KG; EP1380561; (2004); (A1) English View in Reaxys

Li

Rx-ID: 31255765 View in Reaxys 248/481 Yield

Conditions & References Reaction Steps: 2 1: diethyl ether in diethyl ether vol. Sn: Org.Verb.2; 1.1.2.11, page 339 - 345 View in Reaxys

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F

F

F

F

F

BH–

F F F F

F F

FF

F

F

P+ F

F

Rx-ID: 35848566 View in Reaxys 249/481 Yield

Conditions & References Time= 24h, T= 20 °C Greb, Lutz; Tussing, Sebastian; Schirmer, Birgitta; Ona-Burgos, Pascual; Kaupmees, Karl; Lokov, Maert; Leito, Ivo; Grimme, Stefan; Paradies, Jan; Chemical Science; vol. 4; nb. 7; (2013); p. 2788 - 2796 View in Reaxys

C

Rx-ID: 41958519 View in Reaxys 250/481 Yield

Conditions & References With Ag–Zn/ZSM-5, Time= 2.5h, T= 380 °C , p= 37503.8Torr , Industrial scale, Reagent/catalyst Guo, Aijun; Wu, Chongchong; He, Peng; Luan, Yingqi; Zhao, Lulu; Shan, Wenpo; Cheng, Wei; Song, Hua; Catalysis Science and Technology; vol. 6; nb. 4; (2016); p. 1201 - 1213 View in Reaxys I Br

Rx-ID: 58110 View in Reaxys 251/481 Yield

Conditions & References With sodium Jacobsen; Chemische Berichte; vol. 8; (1875); p. 1260 View in Reaxys Br

Br–+Mg

Rx-ID: 772917 View in Reaxys 252/481 Yield

Conditions & References With diethyl ether, iron(III) chloride Vavon; Mottez; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 218; (1944); p.

557 View in Reaxys

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O

O S

O

OH

Rx-ID: 847178 View in Reaxys 253/481 Yield

Conditions & References T= 70 °C Andrejew; Meschtscherjakow; Petrow; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 19; (1946); p. 705; ; (1947); p. 5279 View in Reaxys

Rx-ID: 2113807 View in Reaxys 254/481 Yield

Conditions & References With lithium, 1) THF, Yield given. Multistep reaction. Yields of byproduct given Maercker, Adalbert; Berkulin, Willi; Schiess, Peter; Angewandte Chemie; vol. 95; nb. 3; (1983); p. 248 - 251 View in Reaxys

O

N

O

O

Rx-ID: 3917133 View in Reaxys 255/481 Yield

Conditions & References With methane, oxygen, sulphur(VI) hexafluoride, T= 37.5 °C , p= 720Torr , Irradiation, Product distribution Attina, Marina; Cacace, Fulvio; Gazzetta Chimica Italiana; vol. 118; nb. 4; (1988); p. 241 - 248 View in Reaxys

Rx-ID: 3923090 View in Reaxys 256/481 Yield

Conditions & References in diphenylether, T= 300 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Thermodynamic data, Mechanism, Kinetics Ruechardt, Christoph; Gerst, Matthias; Noelke, Margot; Angewandte Chemie; vol. 104; nb. 11; (1992); p. 1516 1518 View in Reaxys in diphenylether, T= 270 °C , further temperatures; further p-substituted α-methylstyrene; (2)H-labeling experiments, Rate constant, Mechanism, Thermodynamic data Gerst, Matthias; Ruechardt, Christoph; Tetrahedron Letters; vol. 34; nb. 48; (1993); p. 7733 - 7736 View in Reaxys in diphenylether, T= 270 - 320 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Rate constant, Thermodynamic data Friebolin, Heike; Roers, Rolf; Ebenhoch, Jochen; Gerst, Matthias; Ruechardt, Christoph; Liebigs Annales; nb.

2; (1997); p. 385 - 389 View in Reaxys

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N

N

N

N

Rx-ID: 4585674 View in Reaxys 257/481 Yield

Conditions & References With para-thiocresol in 1,3,5-trimethyl-benzene, T= 210 °C , other solvents and temp.; ΔH(excit.), ΔS(excit.), ΔG(excit.), Kinetics, Thermodynamic data Welle, Frank M.; Verevkin, Sergey P.; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Liebigs Annales; nb. 1; (1997); p. 155 - 163 View in Reaxys

Cl Al Cl

Cl

HO

Rx-ID: 5957230 View in Reaxys 258/481 Yield

Conditions & References T= 0 °C , bei laengerem Erwaermen auf 80-95grad Norris; Sturgis; Journal of the American Chemical Society; vol. 61; (1939); p. 1413,1416 View in Reaxys Potts; Dodson; Journal of the American Chemical Society; vol. 61; (1939); p. 2553 View in Reaxys Huston; Fox; Binder; Journal of Organic Chemistry; vol. 3; (1938); p. 252 View in Reaxys Zukerwanik; Zhurnal Obshchei Khimii; vol. 5; (1935); p. 117,120; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 2896 View in Reaxys

Cl

amalgamated aluminium Rx-ID: 6416608 View in Reaxys 259/481

Yield

Conditions & References T= 20 °C Diuguid; Journal of the American Chemical Society; vol. 63; (1941); p. 3527 View in Reaxys

di-isopropylbenzenes Rx-ID: 6727903 View in Reaxys 260/481 Yield

Conditions & References With octamethylpentachlorotrialuminocyclotetrasiloxane, Time= 0.25h, T= 110 °C , p= 9000.7Torr , var. reaction times, Rate constant Kolesnikov, I. M.; Russian Journal of Physical Chemistry; vol. 55; nb. 8; (1981); p. 1121 - 1123; Zhurnal Fizicheskoi Khimii; vol. 55; (1981); p. 1970 - 1974 View in Reaxys

F

H

Rx-ID: 6801008 View in Reaxys 261/481

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Yield

Conditions & References T= 0 °C , in fluessiger Phase Patent; du Pont de Nemours and Co.; US2423470; (1938) View in Reaxys Simons; Archer; Journal of the American Chemical Society; vol. 60; (1938); p. 2953 View in Reaxys

OH HO

S OO

1.3(and 1.4)-diisopropyl-benzene

Rx-ID: 7047308 View in Reaxys 262/481 Yield

Conditions & References T= 30 - 40 °C Newton; Journal of the American Chemical Society; vol. 65; (1943); p. 320 View in Reaxys Wunderly; Slanina; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1008 View in Reaxys Slanina; Nieuwland; Journal of the American Chemical Society; vol. 57; (1935); p. 1547 View in Reaxys Ipatieff; Corson; Pines; Journal of the American Chemical Society; vol. 58; (1936); p. 919,921; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1519,1523 View in Reaxys

potassium

Rx-ID: 7154743 View in Reaxys 263/481 Yield

Conditions & References T= 180 °C Pines; Schaap; Journal of the American Chemical Society; vol. 80; (1958); p. 4378,4380 View in Reaxys

chromium (III)-oxide-aluminium oxide catalyst Rx-ID: 7919124 View in Reaxys 264/481 Yield

Conditions & References T= 500 °C Pines; Marechal; Journal of the American Chemical Society; vol. 77; (1955); p. 2819,2821 View in Reaxys

platinum / aluminium oxide Rx-ID: 7919125 View in Reaxys 265/481

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Yield

Conditions & References T= 330 °C Pines; Marechal; Journal of the American Chemical Society; vol. 77; (1955); p. 2819,2821 View in Reaxys

Rx-ID: 22960923 View in Reaxys 266/481 Yield

Conditions & References With zeolite beta; cerium promoted, T= 310 °C , p= 28443.9Torr , Super critical phase, Product distribution / selectivity Patent; Kelly, Kevin P.; Butler, James R.; US2004/68151; (2004); (A1) English View in Reaxys With silicate, T= 380 - 425 °C , p= 15514.9 - 20686.5Torr , Product distribution / selectivity Patent; Butler, James R.; Kelly, Kevin P.; US2004/68152; (2004); (A1) English View in Reaxys With zeolite beta; lanthanum modified, T= 310 °C , p= 28443.9Torr , benzene in super critical phase, Product distribution / selectivity Patent; Butler, James R.; Kelly, Kevin P.; US2004/68152; (2004); (A1) English View in Reaxys

Rx-ID: 33132167 View in Reaxys 267/481 Yield

Conditions & References With propane, 2-methyl propane, 1,2-dimethylethane Kudryashov; Perevezentsev; Ryabov; Shchegoleva; Sirotkin; Petroleum Chemistry; vol. 52; nb. 1; (2012); p. 60 - 64 View in Reaxys

O

O

Rx-ID: 847605 View in Reaxys 268/481 Yield

Conditions & References With aluminium trichloride Kurssanow; Selwin; Zhurnal Obshchei Khimii; vol. 9; (1939); p. 2173,2176; Chem. Zentralbl.; vol. 111; nb. I; (1940); p. 3242 View in Reaxys 1

1

1

1

Rx-ID: 1784378 View in Reaxys 269/481 Yield

Conditions & References T= 335 °C , -ΔGo, Thermodynamic data Meot-Ner (Mautner), Michael; Journal of the American Chemical Society; vol. 104; nb. 1; (1982); p. 5 - 10

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View in Reaxys

SiH

Si+

C+

Rx-ID: 1896774 View in Reaxys 270/481 Yield

Conditions & References T= 24.9 °C , ΔG(excit.)298, ΔS(excit.), ΔH(excit.), Thermodynamic data, Equilibrium constant, Rate constant Shin, Seung Koo; Beauchamp, J. L.; Journal of the American Chemical Society; vol. 111; nb. 3; (1989); p. 900 906 View in Reaxys

O O

N

N

N

N

O

O N

N O

O O O O

O N

O

O O

O

O

N O

Rx-ID: 1963371 View in Reaxys 271/481 Yield

Conditions & References in dichloromethane, Irradiation, solvent and salt effect, Product distribution Masnovi, J. M.; Kochi, J. K.; Journal of the American Chemical Society; vol. 107; nb. 26; (1985); p. 7880 - 7893 View in Reaxys O N

O

O O O O

N

N

N

N

O

O O

O N

O

O O

O N N O

O

Rx-ID: 1963402 View in Reaxys 272/481 Yield

Conditions & References in dichloromethane, Irradiation, solvent and salt effect, Product distribution Masnovi, J. M.; Kochi, J. K.; Journal of the American Chemical Society; vol. 107; nb. 26; (1985); p. 7880 - 7893 View in Reaxys

O

O

HO

O

Rx-ID: 1990023 View in Reaxys 273/481 Yield

Conditions & References With Cs/Na/K alloy, multistep reaction: 1.) THF, -75 deg C, 2 h, rate of cleavage relative to bibenzyl, Product distribution Grovenstein, Erling; Bhatti, Amjad M.; Quest, Dean E.; Sengupta, Dibyendu; VanDerveer, Don; Journal of the American Chemical Society; vol. 105; nb. 20; (1983); p. 6290 - 6299 View in Reaxys

Rx-ID: 2866632 View in Reaxys 274/481

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Yield

Conditions & References

44.8 %

With aluminium trichloride, Time= 1h, T= 75 °C , other molar ratio, Product distribution Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

HC

Rx-ID: 3923150 View in Reaxys 275/481 Yield

Conditions & References With 1,2-dihydroanthracene in diphenylether, T= 200 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), also with D4-DHA, Kinetics, Thermodynamic data, Mechanism Gerst, Matthias; Ruechardt, Christoph; Chemische Berichte; vol. 126; nb. 4; (1993); p. 1039 - 1046 View in Reaxys

O

O

O O

Rx-ID: 4159177 View in Reaxys 276/481 Yield

Conditions & References With 9,10-dihydro-anthracene in diphenylether, T= 280 °C , Mechanism Noelke, Margot; Verevkin, Sergej P.; Beckhaus, Hans-Dieter; Ruechardt, Christoph; Liebigs Annalen; nb. 1; (1995); p. 41 - 52 View in Reaxys

Cl

OH

1.4(?)-diisopropyl-benzene

S OH O

O

Rx-ID: 5801872 View in Reaxys 277/481 Yield

Conditions & References T= 0 - 10 °C Rueggeberg; Cushing; Cook; Journal of the American Chemical Society; vol. 68; (1946); p. 192 View in Reaxys

Cl

O Al

O S

Cl

O

Cl

O

Rx-ID: 6416595 View in Reaxys 278/481 Yield

Conditions & References T= 25 - 70 °C Kane; Lowy; Journal of the American Chemical Society; vol. 58; (1936); p. 2605 View in Reaxys

O

O F

H

Rx-ID: 6416598 View in Reaxys 279/481

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Yield

Conditions & References T= 100 °C Simons; Archer; Randall; Journal of the American Chemical Society; vol. 61; (1939); p. 1821 View in Reaxys

Cl Fe Cl

(v3)

Cl

Rx-ID: 6416603 View in Reaxys 280/481 Yield

Conditions & References T= 20 °C Potts; Carpenter; Journal of the American Chemical Society; vol. 61; (1939); p. 663 View in Reaxys F

2H

OH

B

deuterio-isopropyl-benzenene

F

F

Rx-ID: 7073330 View in Reaxys 281/481 Yield

Conditions & References T= 0 °C , Deuterium-Isotopeneffekt Russell; Journal of the American Chemical Society; vol. 81; (1959); p. 2017,2018 View in Reaxys

potassium

Rx-ID: 7980993 View in Reaxys 282/481 Yield

Conditions & References T= 190 °C Pines; Schaap; Journal of the American Chemical Society; vol. 80; (1958); p. 4378,4380 View in Reaxys

Rx-ID: 23228631 View in Reaxys 283/481 Yield

Conditions & References 1; 2; 3; 4 :In a system such as that illustrated in FIG. 1, a portion of the effluent 14 is drawn off as dilute ethylene stream 14a which is totally condensed to produce a liquid equivalent to the amount of ethylene required for ethylbenzene production and is sent to ethylbenzene plant 16 as a liquid stream 14b. The remaining stream 14c is sent to the ethylene fractionator 14 as a vapor. This case reduces the feed to the ethylene fractionator 17. Energy is saved in the ethylene fractionator 17 but partly lost in the form of lower recuperation from ethane recycle and in the form of higher reflux requirements in the deethanizer 11 to reduce the propylene content of the deethanizer overhead (dilute ethylene). Propylene content of the dilute ethylene must be sufficiently low to prevent the excessive formation of cumene in the ethylbenzene unit. Cumene, if formed, will be present as an impurity in the ethylbenzene product and is typically limited to 500 ppm or less. The purity of the ethylene feed 14b in this case is about 80 mol percent to about 83 mol percent. The operating cost savings for a 950,000 kta ethylene plant combined with a 550,00 kta ethylbenzene plant are estimated to be about USD560,000 per annum at current energy price levels.; EXAMPLE 2; In a system such as that illustrated in FIG. 2, the effluent 24 is sent to condenser 25 where it is partially condensed. The liquid equivalent to the amount of ethylene required for ethylbenzene production is sent to the ethylbenzene plant 26 via line 24a. The chilled but uncondensed portion of the effluent 24 is sent to the ethylene fractionator as a vapor via line 24b. In this case the feed to the ethylene fractionator is both reduced as well as enriched. Energy is saved in the ethylene fractionator but is partly lost in the form of lower recuperation from ethane recycle and in the form of higher reflux requirements in the deethanizer 21 to reduce the propylene content of the deethanizer overhead (dilute ethyl-

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ene). The purity of the ethylene feed 24a to the ethylbenzene plant 16 in this case is about 72 mol percent to about 78 mol percent. The purity level is expected to cause reduced steam production in the ethylbenzene plant. However, without considering the impact in the ethylbenzene plant the savings in operating costs for a 950,000 kta ethylene plant combined with a 550,000 kta ethylbenzene plant are estimated to be about USD580,000 per annum at current energy price levels.; EXAMPLE 3; In a system such as that illustrated in FIG. 3, the entire effluent 34 from the acetylene converter 33 is sent to the ethylene fractionator 37 and the dilute ethylene feed to the ethylbenzene plant 36 is drawn off via stream 35 as a vapor from the stripping portion of the ethylene fractionator 37. Energy is saved in the ethylene fractionator 37 but is partly lost in the form of lower recuperation from ethane recycle and in the form of a higher reflux requirements in the deethanizer 31 to reduce the propylene content of the deethanizer overhead (dilute ethylene). The purity of the dilute ethylene stream 35 is about 60 mol percent to about 65 mol percent. The purity level is expected to cause reduced steam production in the ethylbenzene plant. However, without considering the impact in the ethylbenzene plant the savings in operating cost for a 950,000 kta ethylene plant combined with a 550,000 kta ethylbenzene plant are estimated to be about USD850,000 per annum at current energy price levels.; EXAMPLE 4; In system such as that illustrated in FIG. 4, the entire effluent 44 from the acetylene converter 43 is sent to the ethylene fractionator 47 and the dilute ethylene feed to the ethylbenzene plant 46 is drawn off via stream 45 as a liquid from the rectification portion of the ethylene fractionator 47. Energy is saved in the ethylene fractionator 47 but is partly lost in the form of lower recuperation from ethane recycle. A higher reflux requirement in the deethanizer is not needed for this case since the side-draw is taken above the feed where propylene concentration is already sufficiently low. The purity of the dilute ethylene stream 45 is about 82 mol percent to about 85 mol percent.

This case produces the highest purity of dilute ethylene feed and has no significant impact in the ethylbenzene plant.

The savings in operating cost for a 950,000 kta ethylene plant combined with a 550,000 kta ethylbenzene plant are estimated to be about USD780.000 per annum at current energy price levels. , Product distribution / selectivity Patent; Hildreth, James M.; Dukandar, Kerman Nariman; Venner, Ronald M.; US2005/54888; (2005); (A1) English View in Reaxys

Rx-ID: 40970643 View in Reaxys 284/481 Yield

Conditions & References

12.5 %

With mixture of unreduced aluminium-platinum-rhenium and H form of zeolite Y, T= 320 °C , Flow reactor, Catalytic behavior, Temperature, Reagent/catalyst Abasov; Isayeva; Babayeva; Agayeva; Ibragimov; Tagiyev; Rustamov; Russian Journal of Applied Chemistry; vol. 88; nb. 5; (2015); p. 787 - 795; Zh. Prikl. Khim. (S.-Peterburg, Russ. Fed.); vol. 88; nb. 5; (2015); p. 744 - 752,9 View in Reaxys With 7 percent carbon-supported platinum (top) and 25 percent silica-supported H4SiW12O40 (bottom) containing 0.7 percent of Pt two-bed catalyst, Time= 15h, Reagent/catalyst, Temperature Alotaibi, Abdullah; Bayahia, Hossein; Kozhevnikova, Elena F.; Kozhevnikov, Ivan V.; ACS Catalysis; vol. 5; nb.

9; (2015); p. 5512 - 5518 View in Reaxys

N

N

Rx-ID: 3311256 View in Reaxys 285/481 Yield

Conditions & References in hexane, Irradiation, other solvents, Quantum yield, Rate constant Lewis; Reddy; Bassani; Schneider; Gahr; Journal of the American Chemical Society; vol. 116; nb. 2; (1994); p.

597 - 605 View in Reaxys

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Br

Rx-ID: 3735609 View in Reaxys 286/481 Yield

Conditions & References

42.7 %, 9.2 %

With aluminium trichloride, Time= 1h, T= 20 °C , other molar ratio, other temperature, Product distribution Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

O

Cl

Cl

O

O

O

Rx-ID: 3832725 View in Reaxys 287/481 Yield

Conditions & References

17.7 %, 14.9 %, 0.82 g, 1.6 %, 1.5 %

F

With aluminium trichloride in tetrachloromethane, Time= 6h, T= -4 - 0 °C , other temperature, other time; various molar ratios; other solvent, Product distribution, Rate constant Grebenyuk, A. D.; Zavizion, E. M.; Rusin, A. N.; Bengard, Z. V.; Journal of Organic Chemistry USSR (English Translation); vol. 19; (1983); p. 811 - 814; Zhurnal Organicheskoi Khimii; vol. 19; nb. 5; (1983); p. 916 - 919 View in Reaxys

Br

H

copper Rx-ID: 5806889 View in Reaxys 288/481

Yield

Conditions & References T= 80 °C Simons; Archer; Journal of the American Chemical Society; vol. 60; (1938); p. 2953 View in Reaxys

HO

C

C, CO, CO2

O

Rx-ID: 6210792 View in Reaxys 289/481 Yield

Conditions & References

15.5 %, 25.0 %, 1.5 %, 1.0 %, 1.1 %, 1.0 %

O

With Cs exchanged copper doped zeolite 13X, T= 400 °C , p= 760Torr , The catalytic system was optimized vs. the catalyst preparation, basicity and promoters. Effect of nature and flow-rate of the flow gas on the yield and product ratio was also studied, Product distribution, Mechanism Lacroix, C.; Deluzarche, A.; Kiennemann, A.; Boyer, A.; Journal de Chimie Physique et de Physico-Chimie Biologique; vol. 81; nb. 7/8; (1984); p. 481 - 486 View in Reaxys

O

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C

CO2, CO

O

Rx-ID: 6211624 View in Reaxys 290/481 Yield

Conditions & References

18.6 %, 30.1 %, 1.8 %, 3.0 %, 0.8 %, 0.7 %

With Cs exchanged boron doped zeolite 13X, T= 400 - 450 °C , p= 760Torr , The catalytic system was optimized vs. the nature of the exchanged cation, the promoters and the catalyst preparation. Effect of toluene/methylal ratio, temperature, nature and flow-rate of the flow gas on the yield and product ratio was also studied, Product distribution, Kinetics Lacroix, C.; Deluzarche, A.; Kiennemann, A.; Boyer, A.; Journal de Chimie Physique et de Physico-Chimie Biologique; vol. 81; nb. 7/8; (1984); p. 473 - 480 View in Reaxys

F

Br

H

Rx-ID: 6674707 View in Reaxys 291/481 Yield

Conditions & References T= 80 °C Simons; Archer; Journal of the American Chemical Society; vol. 60; (1938); p. 2953 View in Reaxys

OH HO

P OH O

Rx-ID: 6674724 View in Reaxys 292/481 Yield

Conditions & References T= 450 °C Ipatieff; Komarewsky; Pines; Journal of the American Chemical Society; vol. 58; (1936); p. 918; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1526 View in Reaxys

Cl Al

Cl

O

Cl

O

Rx-ID: 7043281 View in Reaxys 293/481 Yield

Conditions & References T= 60 °C Bowden; Journal of the American Chemical Society; vol. 60; (1938); p. 646 View in Reaxys

O

O

hydrofluoric acid

O

O

Rx-ID: 7061729 View in Reaxys 294/481 Yield

Conditions & References T= 80 - 100 °C Simons; Archer; Randall; Journal of the American Chemical Society; vol. 61; (1939); p. 1821 View in Reaxys

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Rx-ID: 10226728 View in Reaxys 295/481 Yield

Conditions & References With silica-supported tantalum hydride, Time= 60h, T= 250 °C , Product distribution, Further Variations: Pressures Kimura, Takumi; Kawai, Kiyohiko; Fujitsuka, Mamoru; Majima, Tetsuro; Chemical Communications; nb. 12; (2004); p. 1438 - 1439 View in Reaxys

Rx-ID: 25940980 View in Reaxys 296/481 Yield

Conditions & References

76.5 % Chromat., 17.3 % Chromat., 3.7 % Chromat.

With ITQ-33 zeolite, T= 124.84 °C , p= 26252.6Torr , Kinetics, Further Variations: Catalysts Moliner, Manuel; Diaz-Cabanas, Maria J.; Fornes, Vicente; Martinez, Cristina; Corma, Avelino; Journal of Catalysis; vol. 254; nb. 1; (2008); p. 101 - 109 View in Reaxys

Rx-ID: 33132166 View in Reaxys 297/481 Yield

Conditions & References With propane, 2-methyl propane, 1,2-dimethylethane Kudryashov; Perevezentsev; Ryabov; Shchegoleva; Sirotkin; Petroleum Chemistry; vol. 52; nb. 1; (2012); p. 60 - 64 View in Reaxys

Br

Rx-ID: 2866630 View in Reaxys 298/481 Yield

Conditions & References

23.6 %

With aluminium trichloride, Time= 1h, T= 20 °C , other molar ratio, other temperaure, Product distribution Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

Cl

Cl

OH Al

H

Cl

Cl

Rx-ID: 5801869 View in Reaxys 299/481 Yield

Conditions & References Huston; Hsieh; Journal of the American Chemical Society; vol. 58; (1936); p. 439 View in Reaxys Huston; Kaye; Journal of the American Chemical Society; vol. 64; (1942); p. 1576,1578 View in Reaxys

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Zukerwanik; Zhurnal Obshchei Khimii; vol. 5; (1935); p. 117,120; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 2896 View in Reaxys entsteht auch ein Gemisch isomerer Diisopropylbenzole Zukerwanik; Tokarewa; Zhurnal Obshchei Khimii; vol. 5; (1935); p. 764; Chem. Zentralbl.; vol. 108; nb. I; (1937); p.

578 View in Reaxys

F

OH

B

P2O5

F

F

Rx-ID: 5806184 View in Reaxys 300/481 Yield

Conditions & References Vermillion; Hill; Journal of the American Chemical Society; vol. 67; (1945); p. 2209 View in Reaxys Toptschijew; Jegorowa; Wassiljewa; Doklady Akademii Nauk SSSR; vol. 67; p. 475; ; (1949); p. 7916 View in Reaxys Toussaint; Hennion; Journal of the American Chemical Society; vol. 62; (1940); p. 1145 View in Reaxys reagiert analog mit Chlorbenzol, o-Dichlorbenzol und Brombenzol Vermillion; Hill; Journal of the American Chemical Society; vol. 67; (1945); p. 2209 View in Reaxys Hennion; Pieronek; Journal of the American Chemical Society; vol. 64; (1942); p. 2751 View in Reaxys

O F

H

Rx-ID: 6676550 View in Reaxys 301/481 Yield

Conditions & References T= 20 °C Simons; Archer; Journal of the American Chemical Society; vol. 62; (1940); p. 1623 View in Reaxys Simons; Archer; Journal of the American Chemical Society; vol. 62; (1940); p. 1623 View in Reaxys

F

H

Rx-ID: 7047310 View in Reaxys 302/481 Yield

Conditions & References T= 10 - 25 °C , in fluessiger Phase Calcott; Tinker; Weinmayr; Journal of the American Chemical Society; vol. 61; (1939); p. 1010,1014 View in Reaxys

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I H 14 3 C

H 14 3 C

14CH

14CH

3

racemate

3

racemate

Rx-ID: 1848986 View in Reaxys 303/481 Yield

Conditions & References With potassium-sodium, multistep reaction; analogous reaction with water quench (instead of (14)CH3I); possibility of sp2-sp3 carbon-carbon bonds cleavage, Product distribution Collins, Clair J.; Hombach, Hans-Peter; Maxwell, Brian; Woody, Madge C.; Benjamin, Ben M.; Journal of the American Chemical Society; vol. 102; nb. 2; (1980); p. 851 - 853 View in Reaxys

Br

Rx-ID: 2855624 View in Reaxys 304/481 Yield

Conditions & References

18.6 %, 2.7 %

With aluminium trichloride, Time= 1h, T= 20 °C , other molar ratio, other temperature, Product distribution Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

OH

Rx-ID: 4360326 View in Reaxys 305/481 Yield

Conditions & References With zeolite NCL-1, Time= 1h, T= 229.9 °C , var. Si/Al ratio in zeolite; var. temperature; effect of feed ratio, weight hourly space velocity, and time on stream, Product distribution Sasidharan, M.; Reddy, K. Ramesh; Kumar, Rajiv; Journal of Catalysis; vol. 154; nb. 2; (1995); p. 216 - 221 View in Reaxys

Rx-ID: 4724712 View in Reaxys 306/481 Yield

Conditions & References With aluminium trichloride in benzene, Time= 2h, T= 40 °C , other catalysts: AlCl3/SiO2, AlCl3-MnCl2/SiO2, other reaction time, Product distribution, Mechanism Polubentseva; Duganova; Mikhailenko; Russian Journal of General Chemistry; vol. 66; nb. 4; (1996); p. 607 - 613

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View in Reaxys

Cl

Cl

OH Al

H

Cl

Cl

Rx-ID: 5809573 View in Reaxys 307/481 Yield

Conditions & References T= 90 - 100 °C Norris; Sturgis; Journal of the American Chemical Society; vol. 61; (1939); p. 1413,1416 View in Reaxys

Cl Al

Cl

Cl

Cl

Rx-ID: 6674706 View in Reaxys 308/481 Yield

Conditions & References Silva; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 321 View in Reaxys Konowalow; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 27; (1895); p. 457; Bulletin de la Societe Chimique de France; vol. <3> 16; (1896); p. 864 View in Reaxys T= -6 °C , sowie bei +35grad, Product distribution Ipatieff; Pines; Schmerling; Journal of Organic Chemistry; vol. 5; (1940); p. 253,259 View in Reaxys Ipatieff; Pines; Schmerling; Journal of Organic Chemistry; vol. 5; (1940); p. 253,259 View in Reaxys

alkanes, alkenes, alkylbenzenes, alkenylbenzenes Rx-ID: 6726068 View in Reaxys 309/481 Yield

Conditions & References With water, T= 535 °C , p= 187515Torr , var. of reagent, pressure, temp., time, further with D2O, Product distribution, Mechanism Kruse, Andrea; Ebert; Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics; vol. 100; nb. 1; (1996); p. 80 - 83 View in Reaxys

diisopropylbenzene Rx-ID: 6727904 View in Reaxys 310/481 Yield 2.4 %

Conditions & References With amorphous aluminosilicate, Time= 3h, T= 20 °C , zirconosilicate, zeolite-containing aluminosilicate and zirconosilicate catalysts, 40 and 60 deg C, Product distribution

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Panchenkov, G. M.; Kolesnikov, I. M.; Mel'nikov, V. B.; Russian Journal of Physical Chemistry; vol. 54; nb. 3; (1980); p. 416 - 417; Zhurnal Fizicheskoi Khimii; vol. 54; nb. 3; (1980); p. 733 - 735 View in Reaxys

Cl Al

Cl

Cl

Rx-ID: 7044201 View in Reaxys 311/481 Yield

Conditions & References T= 30 - 40 °C Newton; Journal of the American Chemical Society; vol. 65; (1943); p. 320 View in Reaxys

(v5)

(v5) (v5) (v5) (v5)

(v5) (v12) Cr (v5)

(v5)(v5)(v5) (v5) (v5)

Rx-ID: 26529851 View in Reaxys 312/481 Yield

Conditions & References byproducts: C6H6; decompn. in vac.,bomb tube Sorokin, Yu. A.; Petukhov, G. G.; Journal of General Chemistry USSR (English Translation); (1965); p. 2123 2125 ; (from Gmelin) View in Reaxys byproducts: C6H6; decompn. in vac.,bomb tube vol. Cr: Org.Verb.; 1.6.2.1.2, page 331 - 347 ; (from Gmelin) View in Reaxys

O–

OH O

+Sn

Sn

Cl OO

O

Cl OO

Rx-ID: 26700736 View in Reaxys 313/481 Yield

Conditions & References Kinetics Eaborn, C.; Waters, J. A.; Journal of the Chemical Society; (1961); p. 542 - 547 ; (from Gmelin) View in Reaxys Kinetics vol. Sn: Org.Verb.2; 1.1.2.11, page 339 - 345 ; (from Gmelin) View in Reaxys

(v1)

O

O

Rx-ID: 29668655 View in Reaxys 314/481

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Yield

Conditions & References With 2,2'-azo-bisisobutyronitrile, T= 60 °C , Kinetics, Reagent/catalyst Zamanova; Kurbanova; Rzaeva; Farzaliev; Allakhverdiev; Russian Journal of Applied Chemistry; vol. 83; nb. 2; (2010); p. 293 - 296 View in Reaxys

Rx-ID: 40970642 View in Reaxys 315/481 Yield

Conditions & References

11.2 %, 6.4 With mixture of unreduced aluminium-platinum-rhenium and H form of zeolite Y, T= 350 °C , Flow reactor, Catalytic % behavior, Temperature Abasov; Isayeva; Babayeva; Agayeva; Ibragimov; Tagiyev; Rustamov; Russian Journal of Applied Chemistry; vol. 88; nb. 5; (2015); p. 787 - 795; Zh. Prikl. Khim. (S.-Peterburg, Russ. Fed.); vol. 88; nb. 5; (2015); p. 744 - 752,9 View in Reaxys

O

Cl N

N

N

N N

N

N

NH

N

N

Cl

O

Rx-ID: 2741512 View in Reaxys 316/481 Yield

Conditions & References in dimethyl sulfoxide, T= 100 °C , Product distribution Shmelev, L. V.; Stopnikova, M. N.; Poponova, R. V.; Kessenikh, A. V.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 3; (1985); p. 347 - 354; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 3; (1985); p. 413 - 420 View in Reaxys O

N

O Cl N

N N

N

N

N

NH

N

N

Cl

N

N O

O

Rx-ID: 2742606 View in Reaxys 317/481 Yield

Conditions & References in dimethyl sulfoxide, T= 100 °C , Product distribution Shmelev, L. V.; Stopnikova, M. N.; Poponova, R. V.; Kessenikh, A. V.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 3; (1985); p. 347 - 354; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 3; (1985); p. 413 - 420 View in Reaxys

C

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Rx-ID: 3536844 View in Reaxys 318/481 Yield

Conditions & References With oxygen, yttrium(III) oxide, CaO, lithium oxide, T= 699.9 °C , perdeuterated toluene and benzaldehyde as reactants, Product distribution, Mechanism Osada, Yo; Ogasawara, Sadao; Fukushima, Takakazu; Shikada, Tsutomu; Ikariya, Takao; Journal of the Chemical Society, Chemical Communications; nb. 20; (1990); p. 1434 - 1436 View in Reaxys

I

Rx-ID: 3916886 View in Reaxys 319/481 Yield

Conditions & References With carbon, Time= 20h, T= 20 °C , var. solid surfaces, time, and temp.; or isopropyl bromide, Product distribution Ibatullin, U. G.; Petrushina, T. F.; Shits, O. V.; Journal of Organic Chemistry USSR (English Translation); vol. 27; nb. 9.1; (1991); p. 1673 - 1674; Zhurnal Organicheskoi Khimii; vol. 27; nb. 9; (1991); p. 1900 - 1902 View in Reaxys

Rx-ID: 3917106 View in Reaxys 320/481 Yield

Conditions & References With aluminosilicates, T= 39.9 °C , p= 75006Torr , temperature, volume flow rate, molar ratio, nature of the catalyst, Product distribution Kolesnikov, I. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 60; nb. 11; (1987); p. 2504 - 2510,2316 - 2322 View in Reaxys HO

O –O

Na +

S

OH

O

HO

Rx-ID: 4260879 View in Reaxys 321/481 Yield

Conditions & References With sodium hydroxide, sodium hypochlorite in water, Time= 0.75h, Ambient temperature, Irradiation, other aromatic sulfonic acids; var. concentration of alkali, Product distribution, Mechanism Kimura; Ogata; Bulletin of the Chemical Society of Japan; vol. 56; nb. 2; (1983); p. 471 - 473 View in Reaxys

Cl

amalgamated aluminium Rx-ID: 6416609 View in Reaxys 322/481 Yield

Conditions & References Diuguid; Journal of the American Chemical Society; vol. 63; (1941); p. 3527

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View in Reaxys

HO

HO

H2 HO

Rx-ID: 6728541 View in Reaxys 323/481 Yield

Conditions & References

50 %, 24 %, 5 %, 2 %

With Europium chloride, Time= 3h, Irradiation, investigation of reactions with CD3OH and CH3OD between var. conditions, Product distribution, Mechanism Ishida, Akito; Toki, Susumu; Takamuku, Setsuo; Chemistry Letters; (1985); p. 893 - 896 View in Reaxys

50 %, 5 %, With Europium chloride, Time= 3h, Irradiation 2 %, 24 % Ishida, Akito; Toki, Susumu; Takamuku, Setsuo; Chemistry Letters; (1985); p. 893 - 896 View in Reaxys

polyalkylbenzene Rx-ID: 6730780 View in Reaxys 324/481 Yield

Conditions & References

91.5 %

Heating, synthesis by chemorectification, Product distribution Makar'in, V. V.; Utkin, O. V.; J. Appl. Chem. USSR (Engl. Transl.); vol. 57; nb. 8; (1984); p. 1894 - 1896,1759 - 1761 View in Reaxys

H3PO4-kieselguhr

polyisopropyl-benzene Rx-ID: 6730810 View in Reaxys 325/481 Yield

Conditions & References T= 200 - 280 °C , p= 5148.6 - 44130.5Torr Patent; Universal Oil Prod. Co.; US2382318; (1942) View in Reaxys

O

O S

O

OH

F B

F

F

Rx-ID: 6801009 View in Reaxys 326/481 Yield

Conditions & References aehnlich verlaeuft die Reaktion in Gegenwart von AlCl3 Nasarowa; Zukerwanik; Zhurnal Obshchei Khimii; vol. 18; p. 433; ; (1948); p. 7238 View in Reaxys Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1008 View in Reaxys

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F

H

Rx-ID: 7044200 View in Reaxys 327/481 Yield

Conditions & References T= 35 - 38 °C , Produkt 5: 3-tert.-Butyl-1-isopropyl-benzol; Produkt 6: 4-tert.-Butyl-1-isopropyl-benzol Condon; Matuszak; Journal of the American Chemical Society; vol. 70; (1948); p. 2539,2540 View in Reaxys

OH

Raney nickel HO

Rx-ID: 7980955 View in Reaxys 328/481 Yield

Conditions & References Zderic et al.; Journal of the American Chemical Society; vol. 79; (1957); p. 1696 View in Reaxys Bonner et al.; Journal of the American Chemical Society; vol. 80; (1958); p. 4732,4735 View in Reaxys

O

Rx-ID: 10205745 View in Reaxys 329/481 Yield

Conditions & References in benzene, Photolysis, Quantum yield Veerman, Marcel; Resendiz, Marino J. E.; Garcia-Garibay, Miguel A.; Organic Letters; vol. 8; nb. 12; (2006); p.

2615 - 2617 View in Reaxys

di-isopropyl benzene Rx-ID: 22842186 View in Reaxys 330/481 Yield

Conditions & References 2 With trifluoromethanesulphonic acid/silica gel, T= 80 - 110 °C , Product distribution / selectivity Patent; Haldor Topsoe A/S; EP1184360; (2002); (A1) English View in Reaxys

tri-isopropyl benzene Rx-ID: 22842187 View in Reaxys 331/481 Yield

Conditions & References 2 With trifluoromethanesulphonic acid/silica gel, T= 80 - 110 °C , Product distribution / selectivity

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Patent; Haldor Topsoe A/S; EP1184360; (2002); (A1) English View in Reaxys

O SiH SiH

Si O Si

O

Si

O

O

Si

Si

O

O Si

O

Si

Si

O

Si Si O

O

Si Si

O Si

O O

Si

O Si

Si

O

Si

Si O

O

Si O

Si O

SiH O

Si O

Si

O

Si

Si

O

Si O

Si SiH

SiH

O

Si O

O

Si O

O

Si O

SiH

O

Rx-ID: 28772763 View in Reaxys 332/481 Yield

Conditions & References With [Pd(MeCOD)Cl2] De Vekki; Skvortsov; Russian Journal of General Chemistry; vol. 79; nb. 4; (2009); p. 762 - 777 View in Reaxys

Mg Cl

O

Cl

Rx-ID: 171750 View in Reaxys 333/481 Yield

Conditions & References Ellingboe; Fuson; Journal of the American Chemical Society; vol. 55; (1933); p. 2960,2965 View in Reaxys

O

O O

Rx-ID: 1753374 View in Reaxys 334/481 Yield

Conditions & References in diphenylether, T= 300 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Thermodynamic data, Mechanism, Kinetics Ruechardt, Christoph; Gerst, Matthias; Noelke, Margot; Angewandte Chemie; vol. 104; nb. 11; (1992); p. 1516 1518 View in Reaxys

HO

O

O

HO

Rx-ID: 2017892 View in Reaxys 335/481 Yield 0.49 %, 0.041 %, 0.26 %, 0.54 %

Conditions & References With acetone, F-4SK, Time= 60h, Heating, varied CHP content in org. mixture; purified or technical CHP; experiments in the presence of H2SO4 or KU-23/10-60 cation-exchange resin (without F-4SK), Product distribution Etlis; Beshenova; Semenova; Shomina; Dreiman; Balaev; Journal of applied chemistry of the USSR; vol. 59; nb.

3 pt 2; (1986); p. 551 - 555 View in Reaxys

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O O

O O

Rx-ID: 2051822 View in Reaxys 336/481 Yield

Conditions & References

48 % Chromat., 5 % Chromat., 1 % Chromat.

Time= 0.75h, T= 750 °C , p= 0.05Torr , Product distribution Cadogan, J. I. G.; Hickson, Clare L.; McNab, Hamish; Journal of Chemical Research, Miniprint; nb. 10; (1983); p.

2247 - 2273 View in Reaxys

Br

Rx-ID: 2855921 View in Reaxys 337/481 Yield

Conditions & References

11.6 %, 7.6 With aluminium trichloride, Time= 1h, T= 20 °C , other molar ratio, other temperature, Product distribution %, 12.0 % Polubentseva, M. F.; Zemskov, V. V.; Arkhipov, V. A.; Lipovich, V. G.; J. Gen. Chem. USSR (Engl. Transl.); vol.

54; nb. 9; (1984); p. 2098 - 2103,1874 - 1878 View in Reaxys

N

N H

Rx-ID: 3305437 View in Reaxys 338/481 Yield

Conditions & References in hexane, Irradiation, Rate constant, Mechanism Lewis, Frederick D.; Bassani, Dario M.; Reddy, G. Dasharatha; Journal of Organic Chemistry; vol. 58; nb. 23; (1993); p. 6390 - 6393 View in Reaxys in hexane, Irradiation, Title compound not separated from byproducts Lewis, Frederick D.; Bassani, Dario M.; Reddy, G. Dasharatha; Journal of Organic Chemistry; vol. 58; nb. 23; (1993); p. 6390 - 6393 View in Reaxys in hexane, Irradiation Lewis, Frederick D.; Bassani, Dario M.; Reddy, G. Dasharatha; Journal of Organic Chemistry; vol. 58; nb. 23; (1993); p. 6390 - 6393 View in Reaxys

Rx-ID: 3918748 View in Reaxys 339/481 Yield 23.48 %, 13.79 %,

Conditions & References With BaCl2, Time= 0.00694444h, T= 475 °C , flow system, other hydrocarbons investigated, Product distribution

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9.01 %, 8.53 %, 7.99 %, 5.86 %

Kolesov, S. V.; Ivanova, S. R.; Tsadkin, M. A.; Berlin, Al. Al.; Minsker, K. S.; Enikolopyan, N. S.; Doklady Chemistry; vol. 302; (1988); p. 289 - 291; Dokl. Akad. Nauk SSSR Ser. Khim.; vol. 302; nb. 5; (1988); p. 1119 - 1122 View in Reaxys

HO

Rx-ID: 3923371 View in Reaxys 340/481 Yield

Conditions & References With lithium triethylborohydride, other reagents, rel. rates, Product distribution Brown, Herbert C.; Kim, Suk-Choong; Journal of Organic Chemistry; vol. 49; nb. 6; (1984); p. 1064 - 1071 View in Reaxys

HO

Rx-ID: 4296794 View in Reaxys 341/481 Yield

Conditions & References

8 % Turnov., 4 % Turnov.

With Tisial-4C, T= 160 °C , also toluene and xylene isomers; other C2, C3 and C4 aliphatic alcohols; var. catalysts; in temp. range from 160 to 240 deg C, Product distribution, Mechanism Sabu, K. R.; Rao, K. V. C.; Nair, C. G. R.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 33; nb. 11; (1994); p. 1053 - 1061 View in Reaxys

N H

N

Rx-ID: 4560022 View in Reaxys 342/481 Yield

Conditions & References in various solvent(s), T= 260 - 300 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Rate constant, Thermodynamic data Friebolin, Heike; Roers, Rolf; Ebenhoch, Jochen; Gerst, Matthias; Ruechardt, Christoph; Liebigs Annales; nb.

2; (1997); p. 385 - 389 View in Reaxys

O

O O

Rx-ID: 4560028 View in Reaxys 343/481 Yield

Conditions & References in various solvent(s), T= 285 - 315 °C , ΔG(excit.), ΔH(excit.), ΔS(excit.), Rate constant, Thermodynamic data Friebolin, Heike; Roers, Rolf; Ebenhoch, Jochen; Gerst, Matthias; Ruechardt, Christoph; Liebigs Annales; nb.

2; (1997); p. 385 - 389 View in Reaxys

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OH

Rx-ID: 5012925 View in Reaxys 344/481 Yield

Conditions & References With H-(Al)ZSM-5, T= 246.9 °C , various catalysts, Product distribution Cejka, Jiri; Zilkova, Nadezda; Sponer, Judit E.; Wichterlova, Blanka; Collection of Czechoslovak Chemical Communications; vol. 63; nb. 11; (1998); p. 1769 - 1780 View in Reaxys

Br

gallium (III)-bromide Rx-ID: 5806890 View in Reaxys 345/481

Yield

Conditions & References Smoot; Brown; Journal of the American Chemical Society; vol. 78; (1956); p. 6249 View in Reaxys

Cl

O Al

O

Cl

Cl

Rx-ID: 6416597 View in Reaxys 346/481 Yield

Conditions & References Bowden; Journal of the American Chemical Society; vol. 60; (1938); p. 646 View in Reaxys

O

O

F

O

F

B

S O

F

Rx-ID: 6416599 View in Reaxys 347/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

O

F B

F

F

Rx-ID: 6416600 View in Reaxys 348/481 Yield

Conditions & References O'Connor; Sowa; Journal of the American Chemical Society; vol. 60; (1938); p. 125 View in Reaxys

F O

O

B

F

F

Rx-ID: 6416601 View in Reaxys 349/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

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O

O

F B

F

F

Rx-ID: 6416602 View in Reaxys 350/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

O

ZnCl2-aluminium oxide

hydrogen

Rx-ID: 6566092 View in Reaxys 351/481 Yield

Conditions & References T= 250 - 300 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2410553; (1944) View in Reaxys

O

ZnCl2-silicon dioxide

hydrogen

Rx-ID: 6566093 View in Reaxys 352/481 Yield

Conditions & References T= 250 - 300 °C , p= 73550.8Torr Patent; Universal Oil Prod. Co.; US2410553; (1944) View in Reaxys

hydrogen

Cl

Cl

Cl

Cl

Rx-ID: 6683239 View in Reaxys 353/481 Yield

Conditions & References T= 360 °C , p= 36775.4Torr , Produkt5:Menthan Arnold; Lennartz; Chemische Berichte; vol. 80; (1947); p. 554,556,557 View in Reaxys Wagner-Jauregg; Justus Liebigs Annalen der Chemie; vol. 488; (1931); p. 184 View in Reaxys

O

polyisopropyl-benzene

S HO

O

Rx-ID: 6730809 View in Reaxys 354/481 Yield

Conditions & References T= 50 - 75 °C , p= 2206.5Torr Proell; Adams; Industrial and Engineering Chemistry; vol. 41; (1949); p. 2217,2220 View in Reaxys

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F HO

B

P2O5

F

F

polyisopropyl-benzene Rx-ID: 6730814 View in Reaxys 355/481 Yield

Conditions & References Toussaint; Hennion; Journal of the American Chemical Society; vol. 62; (1940); p. 1145 View in Reaxys Patent; du Pont de Nemours and Co.; US2390835; (1940) View in Reaxys

Cl

amalgamated aluminium Rx-ID: 7043282 View in Reaxys 356/481

Yield

Conditions & References Diuguid; Journal of the American Chemical Society; vol. 63; (1941); p. 3527 View in Reaxys OH OH

Raney nickel HO

HO

Rx-ID: 7981233 View in Reaxys 357/481 Yield

Conditions & References Zderic et al.; Journal of the American Chemical Society; vol. 79; (1957); p. 1696 View in Reaxys Bonner; Greenlee; Journal of the American Chemical Society; vol. 81; (1959); p. 2122,2125 View in Reaxys

O SiH SiH

Si O Si

O

Si

Si

O

Si Si O

O

Si

Si

SiH O

Si

Si

Si

O

O Si

O

Si

SiH O

O

Si O

Si O

Si O

Si SiH

SiH

O

O

O Si

O

O Si

Si O

Si

Si

O

Si

Si O

O

O Si

O

Si

O

O

O

O

Si

Si O

Si O

SiH

O

Si

Rx-ID: 28772764 View in Reaxys 358/481 Yield

Conditions & References With tris (triphenylphosphine)rhodium(I) chloride De Vekki; Skvortsov; Russian Journal of General Chemistry; vol. 79; nb. 4; (2009); p. 762 - 777 View in Reaxys

O Si

Si O

Rx-ID: 223808 View in Reaxys 359/481

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Yield

Conditions & References T= 125 °C , Zeitlicher Verlauf Hahn; Metzinger; Makromolekulare Chemie; vol. 21; (1956); p. 113,114,118 View in Reaxys T= 135 °C , Zeitlicher Verlauf Hahn; Metzinger; Makromolekulare Chemie; vol. 21; (1956); p. 113,114,118 View in Reaxys T= 140 °C , Zeitlicher Verlauf Hahn; Metzinger; Makromolekulare Chemie; vol. 21; (1956); p. 113,114,118 View in Reaxys

N

N

Rx-ID: 2044542 View in Reaxys 360/481 Yield

Conditions & References

58 % Chromat., 39 % Chromat., 4 % Chromat., 12 % Chromat.

Time= 0.416667h, T= 800 °C , p= 0.005Torr , Product distribution, Mechanism Cadogan, J. I. G.; Hickson, Clare L.; McNab, Hamish; Journal of Chemical Research, Miniprint; nb. 10; (1983); p.

2247 - 2273 View in Reaxys

N H

N

Rx-ID: 2108267 View in Reaxys 361/481 Yield

Conditions & References

20 % Chromat., 42 % Chromat., 4 % Chromat., 7 % Chromat.

Time= 0.333333h, T= 800 °C , p= 0.005Torr , Product distribution, Mechanism Cadogan, J. I. G.; Hickson, Clare L.; McNab, Hamish; Journal of Chemical Research, Miniprint; nb. 10; (1983); p.

2247 - 2273 View in Reaxys

N

N

Rx-ID: 2173284 View in Reaxys 362/481 Yield 56 % Chromat., 44 % Chromat., 6 % Chromat., 2 % Chromat.

Conditions & References Time= 0.5h, T= 800 °C , p= 0.005 - 0.01Torr , Product distribution, Mechanism Cadogan, J. I. G.; Hickson, Clare L.; McNab, Hamish; Journal of Chemical Research, Miniprint; nb. 10; (1983); p.

2247 - 2273 View in Reaxys

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Rx-ID: 3917114 View in Reaxys 363/481 Yield 14.7 %, 0.4 %, 2.1 %, 1.1 %, 0.5 %

Conditions & References With A-45 zeolite, T= 200 °C , var. ratio of reactants, oth. temperature, effect of size of catalyst particles, Product distribution, Rate constant, Mechanism Kafarov, V. V.; Pisarenko, V. N.; Mortikov, E. S.; Manukyan, S. N.; Shvets, A. F.; et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 53; nb. 6; (1980); p. 1351 - 1358,1079 - 1085 View in Reaxys

Rx-ID: 4506236 View in Reaxys 364/481 Yield

Conditions & References

7 %, 0.6 % With decationized ferrisilicate, T= 249.9 °C , var. treatment of catalyst, Product distribution, Mechanism Vishnetskaya; Loginov; Ivanova; Romanovskii; Romannikov; Russian Journal of Physical Chemistry A; vol. 70; nb. 1; (1996); p. 72 - 75 View in Reaxys

F HO

B

F

F

Rx-ID: 6674192 View in Reaxys 365/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 470 View in Reaxys

C8-dimer of 1,3-butadiene (trace) Rx-ID: 6726771 View in Reaxys 366/481 Yield 6.9 % Turnov., 4.8 % Turnov., 2.6 % Turnov., 2.4 % Turnov.,

Conditions & References With zirconium oxide, Time= 17h, T= 199.9 °C , other temperatures; also with NH3 and CO2 poisoned ZrO2, Product distribution, Mechanism Suzuka, Hiroyasu; Hattori, Hideshi; Bulletin of the Chemical Society of Japan; vol. 64; nb. 4; (1991); p. 1332 1335 View in Reaxys

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1.8 % Turnov.

F HO

B

F

F

polyisopropyl-benzene Rx-ID: 6730811 View in Reaxys 367/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 470 View in Reaxys

O

O

F

S O

B

O

F

F

polyisopropyl-benzene Rx-ID: 6730812 View in Reaxys 368/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

O

O

F B

F

F

Rx-ID: 7018208 View in Reaxys 369/481 Yield

Conditions & References neben anderen Polyisopropylbenzolen McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

hydrogen

platinum / aluminium silicate-catalyst

Rx-ID: 7043294 View in Reaxys 370/481 Yield

Conditions & References T= 450 °C , p= 36775.4Torr Nowikow et al.; Doklady Akademii Nauk SSSR; vol. 97; (1954); p. 463,466; ; (1954); p. 14170 View in Reaxys

O

OH

zinc dust Cl

Rx-ID: 7067051 View in Reaxys 371/481 Yield

Conditions & References T= -10 °C

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Brown; Mighton; Senkus; Journal of Organic Chemistry; vol. 3; (1938); p. 62,72 View in Reaxys

Cl

Cl

O

F B

Cl

F

F

O

polyisopropylbenzenene Rx-ID: 7085044 View in Reaxys 372/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

O

O

F

O

F

B

S O

F

polyisopropylbenzene Rx-ID: 7085045 View in Reaxys 373/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

O

F B

F

F

Rx-ID: 7156127 View in Reaxys 374/481 Yield

Conditions & References O'Connor; Sowa; Journal of the American Chemical Society; vol. 60; (1938); p. 125 View in Reaxys

O

1 mol BF3

Rx-ID: 7253495 View in Reaxys 375/481 Yield

Conditions & References Monacelli; Hennion; Journal of the American Chemical Society; vol. 63; (1941); p. 1722 View in Reaxys

OH

Rx-ID: 9207374 View in Reaxys 376/481 Yield

Conditions & References With zeolite H-beta-15, T= 209.85 °C , Product distribution, Further Variations: Catalysts, Temperatures Gnanapragasam; Krishnasamy; Mohan; Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry; vol. 40; nb. 9; (2001); p. 947 - 952

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View in Reaxys

O B

H

O

O

O

B

B O

B

O

O

B

O

O

O

Rx-ID: 10335746 View in Reaxys 377/481 Yield

Conditions & References With Rh(acac)(Ph2PCC-t-Bu)2 in benzene-d6, Time= 18h, Product distribution, Further Variations: Catalysts Vogels, Christopher M.; Decken, Andreas; Westcott, Stephen A.; Canadian Journal of Chemistry; vol. 84; nb. 2; (2006); p. 146 - 153 View in Reaxys

O

O S

O

O

F B

F

F

polyisopropylbenzene Rx-ID: 10600472 View in Reaxys 378/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1205 View in Reaxys

N

N

H 2N

Rx-ID: 3721082 View in Reaxys 379/481 Yield 34 % Chromat., 7 % Chromat., 7 % Chromat., 60 % Chromat., 2 % Chromat.

Conditions & References Time= 0.333333h, T= 800 °C , p= 0.001 - 0.005Torr , Product distribution, Mechanism Cadogan, J. I. G.; Hickson, Clare L.; McNab, Hamish; Journal of Chemical Research, Miniprint; nb. 10; (1983); p.

2247 - 2273 View in Reaxys

Rx-ID: 3882575 View in Reaxys 380/481 Yield

Conditions & References With aluminum tri-bromide, 2-methyl propane, 1,2,2-trifluoro-trichloroethane, Time= 10h, T= 36 °C , Product distribution

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Miethchen, Ralf; Roehse, Carola; Kroeger, Carl-Friedrich; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 24; nb. 4; (1984); p. 145 - 146 View in Reaxys

Z

Rx-ID: 3917025 View in Reaxys 381/481 Yield

Conditions & References

14.6 %, 1.7 %

With specimen (II), T= 40 °C , Product distribution Kolesnikov, I. M.; Grinis, L. M.; Russian Journal of Physical Chemistry; vol. 54; nb. 2; (1980); p. 276 - 277; Zhurnal Fizicheskoi Khimii; vol. 54; nb. 2; (1980); p. 480 - 482 View in Reaxys

Rx-ID: 3917165 View in Reaxys 382/481 Yield

Conditions & References With aluminum tri-bromide, Time= 16h, T= 22 °C , Product distribution Miethchen, Ralf; Roehse, Carola; Kroeger, Carl-Friedrich; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 24; nb. 4; (1984); p. 145 - 146 View in Reaxys

HO

Rx-ID: 4812641 View in Reaxys 383/481 Yield

Conditions & References With β-Zeolite, T= 224.9 °C Das; Bhat; Halgeri; Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry; vol. 35; nb. 8; (1996); p. 690 - 692 View in Reaxys

F

OH

B

F

F

polyisopropylbenzene

Rx-ID: 6218747 View in Reaxys 384/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 470 View in Reaxys

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Cl Mg Cl

O

Cl

H

racem. 2.3-diphenyl-butane H

Cl

Rx-ID: 6731120 View in Reaxys 385/481 Yield

Conditions & References Ellingboe; Fuson; Journal of the American Chemical Society; vol. 55; (1933); p. 2960,2965 View in Reaxys

triisopropylbenzenes

Rx-ID: 6731915 View in Reaxys 386/481 Yield

Conditions & References With aluminium silicates, T= 40 °C , other catalyst, Product distribution Kolesnikov, I. M.; Grinis, L. M.; Russian Journal of Physical Chemistry; vol. 54; nb. 2; (1980); p. 260 - 262; Zhurnal Fizicheskoi Khimii; vol. 54; nb. 2; (1980); p. 459 - 460 View in Reaxys

HO

O

Cl Al

Cl

HO

Cl

Rx-ID: 7020791 View in Reaxys 387/481 Yield

Conditions & References Smith; Journal of the American Chemical Society; vol. 56; (1934); p. 717,718; Journal of the American Chemical Society; vol. 59; (1937); p. 899 View in Reaxys

F O

B

O

F

F

Rx-ID: 7047115 View in Reaxys 388/481 Yield

Conditions & References McKenna; Sowa; Journal of the American Chemical Society; vol. 59; (1937); p. 1204 View in Reaxys

HO

Cl Al

Cl

HO

Cl

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petroleum ether

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OH

2-methyl-1.1-diphenyl-propene-(1) OH

Rx-ID: 7439492 View in Reaxys 389/481 Yield

Conditions & References Huston; Jackson; Journal of the American Chemical Society; vol. 63; (1941); p. 541 View in Reaxys

Cl +

Mg

O

Cl

Cl –

H

racemic 2.3-diphenyl-butane H

Cl

Rx-ID: 8286593 View in Reaxys 390/481 Yield

Conditions & References Ellingboe; Fuson; Journal of the American Chemical Society; vol. 55; (1933); p. 2960,2965 View in Reaxys

O

O Br–+Mg

S O

O

Rx-ID: 183035 View in Reaxys 391/481 Yield

Conditions & References With diethyl ether Bert; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 176; (1923); p. 840; Bulletin de la Societe Chimique de France; vol. <4> 37; (1925); p. 1259 View in Reaxys Bert; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 176; (1923); p. 840; Bulletin de la Societe Chimique de France; vol. <4> 37; (1925); p. 1259 View in Reaxys

Z

Rx-ID: 3917024 View in Reaxys 392/481 Yield 14.0 %, 1.5 %, 0.6 %

Conditions & References With specimen (I), T= 40 °C , Product distribution Kolesnikov, I. M.; Grinis, L. M.; Russian Journal of Physical Chemistry; vol. 54; nb. 2; (1980); p. 276 - 277; Zhurnal Fizicheskoi Khimii; vol. 54; nb. 2; (1980); p. 480 - 482 View in Reaxys

Cl

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Rx-ID: 3917102 View in Reaxys 393/481 Yield

Conditions & References With silica-alumina or zeolite Al silicate, Time= 5h, T= 25 - 65 °C , Irradiation, the reaction was studied also without irradiation, Mechanism, Product distribution Kolesnikov, I. M.; Mamedova S. L.; J. Appl. Chem. USSR (Engl. Transl.); vol. 53; nb. 8; (1980); p. 1812 1818,1379 - 1384 View in Reaxys

Cl Cl

Rx-ID: 3917359 View in Reaxys 394/481 Yield

Conditions & References T= 25 °C , ΔH, ΔS, Thermodynamic data Nesterova, T. N.; Rozhnov, A. M.; Malova, T. N.; Kovzel, E. N.; Journal of Chemical Thermodynamics; vol. 17; nb.

7; (1985); p. 649 - 656 View in Reaxys

OH

Rx-ID: 4691714 View in Reaxys 395/481 Yield

Conditions & References With H-(Al)ZSM-5, Time= 1.58333h, T= 196.9 °C , various substrates under different reaction conditions, Product distribution, Kinetics Cejka, Jiri; Zilkova, Nadezda; Wichterlova, Blanka; Collection of Czechoslovak Chemical Communications; vol.

61; nb. 8; (1996); p. 1115 - 1130 View in Reaxys

Rx-ID: 4921021 View in Reaxys 396/481 Yield

Conditions & References With aluminium trichloride, hydrochloric ether, Time= 1h, T= 125 °C , alkylation of benzene with alkanes (2-methylbutane, n-pentane) in the presence of promoted aluminum chloride and AlCl3/SiO2; effect of various promoters (Br2, C2H5Cl, CCl4, Ph3CCl); proposed mechanism, Product distribution Polubentseva; Pikerskii; Duganova; Chenets; Russian Journal of General Chemistry; vol. 67; nb. 10; (1997); p.

1613 - 1617 View in Reaxys

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OH F

H

Rx-ID: 5809926 View in Reaxys 397/481 Yield

Conditions & References bei Raumtemperatur Simons; Archer; Journal of the American Chemical Society; vol. 62; (1940); p. 1623 View in Reaxys

HO

OH

F

S OO

F

B

F

Rx-ID: 6676551 View in Reaxys 398/481 Yield

Conditions & References Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1007 View in Reaxys Slanina; Nieuwland; Journal of the American Chemical Society; vol. 57; (1935); p. 1547 View in Reaxys

F B

F

HO

F

Rx-ID: 6676552 View in Reaxys 399/481 Yield

Conditions & References Wunderly; Sowa; Nieuwland; Journal of the American Chemical Society; vol. 58; (1936); p. 1007 View in Reaxys Slanina; Nieuwland; Journal of the American Chemical Society; vol. 57; (1935); p. 1547 View in Reaxys

hydrogen

nickel

cymene Rx-ID: 7073128 View in Reaxys 400/481

Yield

Conditions & References T= 350 - 360 °C Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

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platinum/charcoal Rx-ID: 7154742 View in Reaxys 401/481 Yield

Conditions & References T= 325 - 350 °C Sopow; Zhurnal Obshchei Khimii; vol. 25; (1955); p. 2082,2087; engl. Ausg. S. 2035, 2040 View in Reaxys

hydrogen

nickel

cymene

menthane(?)

Rx-ID: 7455344 View in Reaxys 402/481 Yield

Conditions & References T= 350 - 360 °C , beim Ueberleiten Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

hydrogen

nickel

cymene Rx-ID: 8273615 View in Reaxys 403/481

Yield

Conditions & References T= 350 - 360 °C , beim Ueberleiten Sabatier; Gaudion; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 168; (1919); p. 671 View in Reaxys

C

Rx-ID: 1870040 View in Reaxys 404/481 Yield

Conditions & References T= 25 °C , ΔGHI, Thermodynamic data Ben-Naim, A.; Wilf, J.; Journal of Physical Chemistry; vol. 84; nb. 6; (1980); p. 583 - 586 View in Reaxys

Rx-ID: 3917104 View in Reaxys 405/481 Yield 17.5 % Chromat., 1.9 % Chromat., 0.2 % Chromat.,

Conditions & References With aluminosilicate (15percent Al2O3), T= 40 °C , other catalysts (Ga, In, Mg, La silicates), Product distribution Kolesnikov, I. M.; Grinis, L. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 55; nb. 1; (1982); p. 87 - 91,77 - 80 View in Reaxys

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0.9 % Chromat.

Rx-ID: 3917108 View in Reaxys 406/481 Yield

Conditions & References With metal oxide-aluminosilicate, T= 40 °C , various metal oxides in the catalyst, Product distribution Kolesnikov, I. M.; Grinis, L. M.; J. Appl. Chem. USSR (Engl. Transl.); vol. 55; nb. 2; (1982); p. 340 - 343,306 - 309 View in Reaxys

Rx-ID: 3917396 View in Reaxys 407/481 Yield

Conditions & References With aluminum tri-bromide, Time= 16h, T= 22 °C , further temp.: 50 deg C, reaction in the presence of Freon 113 and (or) isobutane, Product distribution Miethchen, Ralf; Roehse, Carola; Kroeger, Carl-Friedrich; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 24; nb. 4; (1984); p. 145 - 146 View in Reaxys

C

Rx-ID: 5142925 View in Reaxys 408/481 Yield

Conditions & References T= 428.85 - 510.85 °C , Rate constant Dorrestijn, Edwin; Mulder, Peter; Journal of the Chemical Society. Perkin Transactions 2; nb. 4; (1999); p. 777 780 View in Reaxys

OH

80 percent sulfuric acid

1.2.4-triisopropyl-benzene(?)

Rx-ID: 5806185 View in Reaxys 409/481 Yield

Conditions & References T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys

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Br

n-propylbenzene, butylbenzenes Rx-ID: 6217515 View in Reaxys 410/481 Yield

Conditions & References With aluminium trichloride, Time= 4h, T= 40 °C , other catalysts: AlCl3-CoCl2-H2O, AlCl3-FeSO4-H2O, AlCl3Fe2(SO4)3-H2O, AlCl3-CuSO4-H2O, AlCl3-CuSO4, AlCl3-CuSO4-EtCl, AlCl3/SiO2, AlCl3-CuSO4-SiO2, AlCl3-CoCl2/ SiO2, AlCl3-MnCl2/SiO2, other temperature, other reaction time, various reactants ratio, Product distribution, Mechanism Polubentseva; Duganova; Mikhailenko; Russian Journal of General Chemistry; vol. 66; nb. 4; (1996); p. 607 - 613 View in Reaxys

Rx-ID: 6416594 View in Reaxys 411/481 Yield 97.18 %

Conditions & References IV : EXAMPLE IV The alkylation and transalkylation reactions yield 97.18 percent of cumene.

Patent; Union Oil Company of California; US4459426; (1984); (A1) English View in Reaxys Jeffery,E.A. et al.; Australian Journal of Chemistry; vol. 27; (1974); p. 2569 - 2576 View in Reaxys Huthmacher,K. et al.; Chemische Berichte; vol. 108; (1975); p. 2947 - 2954 View in Reaxys Kornblum,N. et al.; Journal of the American Chemical Society; vol. 101; (1979); p. 647 - 657 View in Reaxys Zymalkowski,F. et al.; Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft; vol. 302; (1969); p. 272 - 284 View in Reaxys Brewster,J.H. et al.; Journal of Organic Chemistry; vol. 29; (1964); p. 110 - 115 View in Reaxys Ransley,D.L.; Journal of Organic Chemistry; vol. 31; (1966); p. 3595 - 3599 View in Reaxys Ciganek,E.; Journal of Organic Chemistry; vol. 34; (1969); p. 1923 - 1930 View in Reaxys Gaudemar-Bardone,F.; Gaudemar,M.; Synthesis; (1979); p. 463 - 465 View in Reaxys Irwin; McQuillin; Tetrahedron Letters; (1968); p. 1937 View in Reaxys Grandberg et al.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 15; (1979); p.

501,502,505,506; Khimiya Geterotsiklicheskikh Soedinenii; vol. 15; (1979); p. 620 View in Reaxys Nagai et al.; Kogyo Kagaku Zasshi; vol. 69; (1966); p. 669,672,673; ; vol. 66; nb. 85708 View in Reaxys Shelton et al.; Canadian Journal of Chemistry; vol. 46; (1968); p. 1149 View in Reaxys Foeldeak et al.; Acta Physica et Chemica; vol. 10; (1964); p. 41,54 View in Reaxys Staviskii; Levin; J. Appl. Chem. USSR (Engl. Transl.); vol. 49; (1976); p. 1830,1841 View in Reaxys Posner; Brunelle; Journal of Organic Chemistry; vol. 38; (1973); p. 2747,2752 View in Reaxys Cabiddu et al.; Annali di Chimica (Rome, Italy); vol. 60; (1970); p. 580,582,583,585

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View in Reaxys Sugi; Mitsui; Bulletin of the Chemical Society of Japan; vol. 42; (1969); p. 2984,2988 View in Reaxys Andersen; Fenton; Journal of Organic Chemistry; vol. 29; (1964); p. 3270 View in Reaxys Kennedy; Journal of Organic Chemistry; vol. 35; (1970); p. 532 View in Reaxys Friedman; Berger; Journal of the American Chemical Society; vol. 82; (1960); p. 5758 View in Reaxys Herault et al.; Bulletin de la Societe Chimique de France; (1970); p. 400,401-405 View in Reaxys Minatschew et al.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); (1957); p. 1241; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1957); p. 1218 View in Reaxys Zukerwanik; Juldaschew; J. Gen. Chem. USSR (Engl. Transl.); vol. 33; (1963); p. 3497,3429 View in Reaxys Minsker et al.; Neftekhimiya; vol. 17; (1977); p. 697,164 View in Reaxys Sosnovsky et al.; Synthesis; (1971); p. 142 View in Reaxys Patent; Brit. Petrol. Co. Ltd.; DE2127481; (1970); ; vol. 76; nb. 72190d; (1972) View in Reaxys Patent; BASF; DE2039591; (1970); ; vol. 76; nb. 112862h; (1972) View in Reaxys Mortikow et al.; Neftekhimiya; vol. 16; (1976); p. 543; ; vol. 85; nb. 192254; (1976) View in Reaxys ZUL'FUGAROV ZG; BAKHSHI-ZADE AA; ZUL'FUGAROV LSH; SMIRNOVA NA; PIS'MAN II; Kinetics and Catalysis; vol. 10; nb. 4 pt 2; (1969); p. 749 - 751 View in Reaxys Olah; Surya Prakash; Synthesis; (1978); p. 397 View in Reaxys Khattab et al.; Egyptian Journal of Chemistry; vol. 21; (1978); p. 295,297 View in Reaxys Rabinovich et al.; Kinetika i Kataliz; vol. 9; (1968); p. 365 View in Reaxys Graham; Slaugh; Tetrahedron Letters; (1971); p. 787 View in Reaxys Itoh et al.; Tetrahedron Letters; (1979); p. 4751,4753 View in Reaxys Kulicki; Zeszyty Naukowe Politechniki Slaskiej, Chemia; vol. 36; (1967); p. 1 View in Reaxys Romanovskii et al.; Kinetika i Kataliz; vol. 9; (1968); p. 1143 View in Reaxys Patent; Aries; US2930819; (1960); ; vol. 54; nb. 16428cd; (1960) View in Reaxys Julia; Joigny; Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques; vol. 270; (1970); p. 1308 View in Reaxys Patent; Zoi et al.; SU691440; (1979); Ref. Zh., Khim.; vol. 12; nb. N99P; (1980) View in Reaxys Morita et al.; Kogyo Kagaku Zasshi; vol. 71; (1968); p. 1492,1493-1495 View in Reaxys Hasegawa et al.; Kogyo Kagaku Zasshi; vol. 74; (1971); p. 903,904,905 View in Reaxys Alberola; Borque; Anales de Quimica (1968-1979); vol. 70; (1974); p. 882 View in Reaxys Patent; FEDOTOV et al.; SU622801; (1978); Ref. Zh., Khim.; vol. 8; nb. N125P; (1979) View in Reaxys Lipovich et al.; J. Gen. Chem. USSR (Engl. Transl.); vol. 45; (1975); p. 2507,2461,2462-2464 View in Reaxys Okamura; Takei; Tetrahedron Letters; (1979); p. 3425,3427

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View in Reaxys Shimada et al.; Nippon Kagaku Kaishi; (1972); p. 616,617, 618 View in Reaxys Posner; Brunelle; Tetrahedron Letters; (1973); p. 935,936 View in Reaxys Jones; Journal of Labelled Compounds; vol. 4; (1968); p. 197,203 View in Reaxys Isidorov et al.; Doklady Chemistry; vol. 205; (1972); p. 595,596; Dokl. Akad. Nauk SSSR Ser. Khim.; vol. 205; (1972); p. 585 View in Reaxys Panchenkov et al.; Russian Journal of Physical Chemistry; vol. 47; (1973); p. 280; ; p. 488 View in Reaxys Botteghi et al.; Journal of Organometallic Chemistry; vol. 161; (1978); p. 197,199,203 View in Reaxys Posner; Brunelle; Tetrahedron Letters; (1972); p. 293,294 View in Reaxys Yamamoto et al.; Chemistry Letters; (1974); p. 849,850,851 View in Reaxys Mazonski et al.; Zeszyty Naukowe Politechniki Slaskiej, Chemia; vol. 13; (1963); p. 49,50 View in Reaxys Ando; Ikeno; Tetrahedron Letters; (1979); p. 4941 View in Reaxys Schenderowa et al.; Azerbaidzhanskii Khimicheskii Zhurnal; vol. 2; (1967); p. 65; ; vol. 68; nb. 49188; (1968) View in Reaxys Yamamoto et al.; Journal of the American Chemical Society; vol. 100; (1978); p. 2474 View in Reaxys Dolansky et al.; Collection of Czechoslovak Chemical Communications; vol. 38; (1973); p.

3823,3824,3825,3826,3827 View in Reaxys Kulicki; Zeszyty Naukowe Politechniki Slaskiej, Chemia; vol. 30; (1966); p. 23 View in Reaxys Hopfinger et al.; Zeszyty Naukowe Politechniki Slaskiej, Chemia; vol. 39; (1967); p. 105,107,108 View in Reaxys Kozorezov et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 45; (1972); p. 398,393 View in Reaxys Mamedaliew et al.; Doklady - Akademiya Nauk Azerbaidzhanskoi SSR; vol. 19; nb. 1; (1963); p. 13,16; ; vol. 59; nb. 6279g; (1963) View in Reaxys Goosen; Taljaard; Journal of the South African Chemical Institute; vol. 28; (1975); p. 196,200,201,205,207,210 View in Reaxys Schmerling; Journal of the American Chemical Society; vol. 97; (1975); p. 6134 View in Reaxys Kozorezov; Lazareva; J. Appl. Chem. USSR (Engl. Transl.); vol. 48; (1975); p. 168,163 View in Reaxys Minatschew et al.; Neftekhimiya; vol. 13; (1973); p. 407,114 View in Reaxys Heesing; Peppmoeller; Zeitschrift fuer Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, Biochemie, Biophysik, Biologie; vol. 23; (1968); p. 1325 View in Reaxys Olah et al.; Journal of the American Chemical Society; vol. 86; (1964); p. 1046,1048 View in Reaxys Zukerwanik; Chakimow; J. Gen. Chem. USSR (Engl. Transl.); vol. 32; (1962); p. 1296,1272 View in Reaxys Radsewentschuk; J. Appl. Chem. USSR (Engl. Transl.); vol. 35; (1962); p. 2538,2433; ; vol. 59; nb. 2673; (1963) View in Reaxys Kosoresow; Nowoshilowa; Neftekhimiya; vol. 8; (1968); p. 858,276 View in Reaxys Yamaguchi et al.; Nippon Kagaku Zasshi; vol. 81; (1960); p. 789; ; vol. 56; nb. 403; (1962) View in Reaxys Kolesnikov et al.; Russian Journal of Physical Chemistry; vol. 53; (1979); p. 1716; ; p. 2982 View in Reaxys

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Krylova et al.; High Energy Chemistry; vol. 6; (1972); p. 138; ; p. 157 View in Reaxys Gribble et al.; Synthesis; (1977); p. 172 View in Reaxys Pis'man et al.; Doklady Chemistry; vol. 179; (1968); p. 338; Doklady Akademii Nauk SSSR; vol. 179; (1968); p.

1117 View in Reaxys Minatschew et al.; Neftekhimiya; vol. 6; (1966); p. 47,1 View in Reaxys Minatschew et al.; Neftekhimiya; vol. 5; (1965); p. 676,678; ; vol. 64; nb. 3256; (1965) View in Reaxys Minatschew et al.; Neftekhimiya; vol. 6; (1966); p. 53,55; ; vol. 64; nb. 19452; (1966) View in Reaxys Bestmann; Klein; Tetrahedron Letters; (1966); p. 6181,6184 View in Reaxys Weyenberg; Journal of Organic Chemistry; vol. 30; (1965); p. 3236,3237 View in Reaxys Rudkowskii; Imjanitow; J. Appl. Chem. USSR (Engl. Transl.); vol. 35; (1962); p. 2719,2608; ; vol. 59; nb. 2689; (1963) View in Reaxys Schuikin; Posdnjak; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); (1957); p. 713; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1957); p. 697; ; nb. 2772; (1958) View in Reaxys Koelewijn; Berger; Recueil des Travaux Chimiques des Pays-Bas; vol. 93; (1974); p. 63,65 View in Reaxys Salesskaja; Remisowa; J. Gen. Chem. USSR (Engl. Transl.); vol. 34; (1964); p. 3168,3215 View in Reaxys Plate; Kikot; J. Gen. Chem. USSR (Engl. Transl.); vol. 32; (1962); p. 1828,1810 View in Reaxys Jurjew; Ssawossina; J. Gen. Chem. USSR (Engl. Transl.); vol. 29; (1959); p. 432,433; ; nb. 21721; (1959) View in Reaxys Patent; Am. Cyanamid Co.; US2694095; (1951); ; nb. 3524; (1955) View in Reaxys Jaouen et al.; Journal of the Chemical Society, Chemical Communications; (1975); p. 813 View in Reaxys Simanow; Nemzow; J. Gen. Chem. USSR (Engl. Transl.); vol. 32; (1962); p. 2914,2868 View in Reaxys Slaugh; Raley; Journal of the American Chemical Society; vol. 84; (1962); p. 2640,2641, 2643 View in Reaxys Petrow et al.; Doklady Akademii Nauk SSSR; vol. 79; (1951); p. 811,812 View in Reaxys Pines; Pillai; Journal of the American Chemical Society; vol. 82; (1960); p. 2921,2924 View in Reaxys Alekseewa et al.; Zhurnal Fizicheskoi Khimii; vol. 34; (1960); p. 726,727; ; p. 344 View in Reaxys Granoth et al.; Journal of Organic Chemistry; vol. 41; (1976); p. 3682,3685 View in Reaxys Alberola et al.; Anales de Quimica (1968-1979); vol. 65; (1969); p. 493,504 View in Reaxys Saveant; Binh; Journal of Organic Chemistry; vol. 42; (1977); p. 1242,1243,1245 View in Reaxys Okada; Hashimoto; Kogyo Kagaku Zasshi; vol. 70; (1967); p. 2152,2153, 2155 View in Reaxys Zalesskaja; Lavrova; Zhurnal Organicheskoi Khimii; vol. 4; (1968); p. 2070,1999 View in Reaxys Rey et al.; Tetrahedron Letters; (1968); p. 3583 View in Reaxys Normant et al.; Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques; vol.

266; (1968); p. 124 View in Reaxys

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Joffe; Stoljarow; Journal fuer Praktische Chemie (Leipzig); vol. 36; (1967); p. 92 View in Reaxys Irwin; McQuillin; Tetrahedron Letters; (1968); p. 2195 View in Reaxys Janickin; Vdovcova; Journal of Organic Chemistry USSR (English Translation); vol. 3; (1967); p. 738; Zhurnal Organicheskoi Khimii; vol. 3; (1967); p. 774 View in Reaxys Rummel et al.; Journal fuer Praktische Chemie (Leipzig); vol. 37; (1968); p. 206,212 View in Reaxys 4 : EXAMPLE 4) 375 kg/h of residues are taken off from the reactor and mixed with 200 kg/h of a mixture of compounds whose boiling point is above 250° C. and which come from the preparation of cumene.

Patent; Rhodia Chimie; US6464838; (2002); (B1) English View in Reaxys 1 : Example 1 Example 1 Cumene was oxidized with air at 70-115° C. in the presence of sodium carbonate, followed by oil-water separation and concentrating to prepare the product of cumene oxidation, which had the following composition: Patent; Mitsui Chemicals, Inc.; US5998677; (1999); (A1) English View in Reaxys 1 : Transalkylation to Produce Cumene Transalkylation to Produce Cumene Reactant feed is a mixture of distilled heavies from a cumene production and recycled benzene.

Patent; The Dow Chemical Company; US5198595; (1993); (A1) English View in Reaxys The effluent from transalkylator 42 then passes to a distillation and recovery system (for example as described with reference to FIG. 1) to recover cumene, benzene, propane and DIPB and TIPB and heavy ends.

Patent; Lummus Crest, Inc.; US5003119; (1991); (A1) English View in Reaxys 4 : Cumene Synthesis over Zeolite SSZ-25 EXAMPLE 4 Cumene Synthesis over Zeolite SSZ-25 This example was carried out in the same manner as Example 3 except that propylene was fed instead of ethylene and the reaction pressure was 600 psig.

The propylene feed rate was 1.5 mL of liquid per hour. WHSV was 5.7 with a benzene to propylene molar ratio of 7.8.

The cumene synthesis results are shown in Table 5.

Patent; Chevron Research and Technology Company; US5149894; (1992); (A1) English View in Reaxys 120%

1 : EXAMPLE 1 EXAMPLE 1 Benzene (60 g, 0.77 mole), diisopropylbenzene (12.5 g, 0.077 mole consisting of the ortho-, meta-, and para-isomers in the proportion of 1:2.8:0) and hydrogen ion-exchanged Wyoming bentonite (A) (5 g) were added to a 150 ml stainless steel autoclave fitted with a magnetic stirrer.

The autoclave was sealed, charged to 20 bar with nitrogen and stirred (400 rpm) at 230° C. for 2.5 hours when a maximum pressure of 45 bar was obtained.

On cooling, gaseous products were vented off, and the catalyst and liquid products removed.

The liquid products (68.0 g) contained benzene (52.6 g), cumene (11.1 g) and diisopropylbenzene (2.6 g) as major products.

The diisopropylbenzene product consisted of the ortho-, meta- and para-isomers in the proportion of trace: 3.0:1.

Cumene was made in a 120percent molar yield from reactant diisopropylbenzene at a selectivity of 76percent, assuming two molecules of cumene are produced from the reaction of one molecule of diisopropylbenzene.

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Patent; The British Petroleum Company P.L.C.; US4599470; (1986); (A1) English View in Reaxys 82.4% w/w Comparison Test 1 The diisopropylbenzene product consisted of the ortho-, meta- and para-isomers in the proportion of 1:2.8:0.

The total recovery of liquid products was 92percent w/w, the recovery of unchanged diisopropylbenzene was 82.4percent w/w and the yield of cumene was 20.6percent molar based on reactant diisopropyl benzene.

Patent; The British Petroleum Company P.L.C.; US4599470; (1986); (A1) English View in Reaxys III : EXAMPLE III EXAMPLE III Cumene is produced from benzene and propylene in accordance with the procedure of Example II with the following exception: the catalyst in the two alkylation reactors contain 1.12 weight percent lithium.

The alkylation and transalkylation reactions yield 99.52 molar percent of cumene.

Patent; Union Oil Company of California; US4459426; (1984); (A1) English View in Reaxys IV : EXAMPLE IV EXAMPLE IV Benzene is alkylated with propylene to produce cumene by following the procedure of Example II with the following exception: the catalyst in the two alkylation reactors contain 4.3 weight percent barium.

Patent; Union Oil Company of California; US4459426; (1984); (A1) English View in Reaxys V : EXAMPLE V EXAMPLE V Benzene is alkylated with propylene to produce cumene by following the procedure of Example II with the following exception: the catalyst in the transalkylation reactor contains 0.74 weight percent calcium.

Substantially the same results are obtained using the above catalyst in the transalkylation reaction.

Patent; Union Oil Company of California; US4459426; (1984); (A1) English View in Reaxys 15 : EXAMPLE 15 EXAMPLE 15 Propylene was bubbled through a 154° F benzene solution containing a quantity of the ZSM-35 zeolite prepared in Example 1 in the ratio of 10 grams of benzene per gram of zeolite catalyst.

Cumene was produced at the hourly rate of 14 grams per 100 grams of zeolite ZSM-35 catalyst.

Patent; Mobil Oil Corporation; US4070407; (1978); (A1) English View in Reaxys 13 : EXAMPLE 13 The alkylate has the following composition as determined by chromatographic analysis, per cent: Conversion of propylene to isopropylbenzene is 80percent.

Patent; Seidov; Nadyr M. O.; Dalin; Mark A.; Bakhshi-Zade; Amir-Mamed A. O.; Kyazimov; Sabir M. O.; Kuliev; Tair A. O.; Lobkina; Valentina V.; Reitman; Gennady A.; Pshik; Julia N.; Kasumov; Kasum G. O.; US4155944; (1979); (A1) English View in Reaxys 15 : EXAMPLE 15 EXAMPLE 15 Propylene was bubbled through a 68° C. benzene solution containing a quantity of the ZSM-35 zeolite prepared in Example 1 in the ratio of 10 grams of benzene per gram of zeolite catalyst.

Cumene was produced at the hourly rate of 14 grams per 100 grams of zeolite ZSM-35 catalyst.

Patent; Mobil Oil Corporation; US4136128; (1979); (A1) English

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View in Reaxys 21 : EXAMPLE 21 EXAMPLE 21 In this experiment, propylene was bubbled through a 68° C. benzene solution containing a quantity of the ZSM-38 zeolite prepared in Example 3 in the ratio of 10 grams of benzene per gram of zeolite catalyst.

Cumene was produced at the hourly rate of 95 grams per 100 grams of catalyst.

Patent; Mobil Oil Corporation; US4136128; (1979); (A1) English View in Reaxys 4 : EXAMPLE 4 (comparative) EXAMPLE 4 (comparative) An alkylation test of benzene with propylene to give cumene is carried out using a catalyst based on beta zeolite and the experimental apparatus described in example 1.

Patent; Enichem S.p.A.; ENITECNOLOGIE S.p.A.; EP1068898; (2001); (A2) English View in Reaxys 4 : Example 4 Example 4 In a similar manner to that described in Example 1 and 3 a solution containing 2 parts by weight of silver neononanoate for each part of cumene is prepared.

Patent; Scientific Design Company Inc.; EP236025; (1987); (A2) English View in Reaxys 7 : Example 7 Example 7 Cumene synthesis via benzene/polyisopropylbenzene transalkylation over a 1:1 MCM-22 and beta catalyst mixture 1.0 g of MCM-22 and 1.0 g of beta, as described in Examples 2 and 3, were mixed thoroughly and used for transalkylation.

The catalyst mixture was diluted with sand to 5.5 cm3 and charged to the reactor.

The same procedure described in Example 2 was followed to start the run.

Patent; ExxonMobil Chemical Patents Inc.; EP1218324; (2004); (B1) English View in Reaxys 27 : Typical Procedure for Example 23 to Example 38 General procedure: The 50 mg 1percent Pd-MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 10 mE/mm in the methanol (10 mE) with constant stirring at mentioned temperature. To this solution was added 0.5 g of various substrates as given in table 2. The reaction was continued for specified time. The samples were collected intermittently and analyzed by GC and GCMS. The product was also confirmed by FTIR analysis which shows absence ofolefinic CrrrC bond frequency. The reaction conditions and results are given in table 2.

With hydrogen in methanol, Time= 12h, T= 20 °C Patent; Council of Scientific and Industrial Research; Umbarkar, Shubhangi Bhalchandra; Dongare, Mohan Keraba; Acham, Vaibhav Ravindrakumar; US2015/239821; (2015); (A1) English View in Reaxys 48 %Spectr.

General procedure: Under nitrogen, complex 1(6.1 mg, 10.0 tmol) and H[BAr’4].(Et2O)2 (10.1 mg, 10.0 jtmol) were dissolved in THF (2.0 mL) in a thick-walled glass vessel equipped with a TEFLON stopper and a stir bat Styrene (52.0 mg, 0.5 mmol) and Hg (606 mg, 3 mmol) were then added and hexamethylbenzene (0.1 mmol) was also added as internal standard. The bottle was degas sed by freeze-pump-thaw and charged with 1 atm of hydrogen gas.

The resulting solution was stirred at 25° C. for 24 hours, afier which time the reaction mixture was exposed to air and diluted with dichloromethane. GC analysis revealed quantitative conversion to ethylbenzene.

With [H(OEt2)2]+[[3,5-(CF3)2C6H3]4B]-, (bis[(2-dicyclohexylphosphino)ethyl]amine)cobalt(II)(CH2SiMe3), hydrogen, mercury in tetrahydrofuran-d8, Time= 48h, T= 80 °C , p= 3040.2Torr , Temperature, Pressure, Reagent/catalyst Patent; LOS ALAMOS NATIONAL SECURITY, LLC; Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.; US2015/336862; (2015); (A1) English View in Reaxys

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O

O

KO H

OH

Rx-ID: 7159749 View in Reaxys 412/481 Yield

Conditions & References T= 250 - 300 °C Koslow; Fedoseew; Olifson; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 259,263; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 1919 View in Reaxys

OH

O

O

O

H

Rx-ID: 560119 View in Reaxys 413/481 Yield

Conditions & References T= 200 °C Sopow; Zhurnal Obshchei Khimii; vol. 25; (1955); p. 2082,2087; engl. Ausg. S. 2035, 2040 View in Reaxys

E

Rx-ID: 3917115 View in Reaxys 414/481 Yield

Conditions & References p= 14Torr , Ambient temperature, variation of pressure, O2 (4-10 torr), gas phase, labelled with tritium, Product distribution, Mechanism Colosimo, M.; Speranza, M.; Cacace, F.; Ciranni, G.; Tetrahedron; vol. 40; nb. 23; (1984); p. 4873 - 4884 View in Reaxys

OH

Cl

ZnCl2

H

Rx-ID: 5801871 View in Reaxys 415/481 Yield

Conditions & References T= 140 - 160 °C Zukerwanik; Zhurnal Obshchei Khimii; vol. 17; (1947); p. 1005,1006; ; (1948); p. 4541 View in Reaxys

Cl Al

Cl

Cl

Cl

Rx-ID: 6416596 View in Reaxys 416/481 Yield

Conditions & References T= 80 °C Boedtker; Bulletin de la Societe Chimique de France; vol. <3> 25; (1901); p. 851 View in Reaxys

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HO

80 percent sulfuric acid

Rx-ID: 6675343 View in Reaxys 417/481 Yield

Conditions & References T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys

aluminium silicate Rx-ID: 7066932 View in Reaxys 418/481 Yield

Conditions & References T= 490 °C , Pyrolysis Georgiew; Kasanskii; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1959); p. 491; engl. Ausg. S. 463 View in Reaxys

E

Rx-ID: 3287569 View in Reaxys 419/481 Yield

Conditions & References p= 10Torr , Ambient temperature, variation of pressure, O2 (4-10 torr) , gas phase, labelled with tritium, Product distribution, Mechanism Colosimo, M.; Speranza, M.; Cacace, F.; Ciranni, G.; Tetrahedron; vol. 40; nb. 23; (1984); p. 4873 - 4884 View in Reaxys

HO

Rx-ID: 3916885 View in Reaxys 420/481 Yield

Conditions & References With catalyst 10, variation of temp., examination of reaction time, Product distribution Coughlan, Brendan; Carroll, William M.; Nunan, John; Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases; vol. 79; (1983); p. 327 - 342 View in Reaxys

OH

HO HO

S OO

Rx-ID: 6675341 View in Reaxys 421/481

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Yield

Conditions & References T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys

OH HO

OH

S OO

Rx-ID: 6675342 View in Reaxys 422/481 Yield

Conditions & References T= 65 °C Meyer,H.; Bernhauer; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 728 View in Reaxys

Cl Al

Cl

Cl

Rx-ID: 6676549 View in Reaxys 423/481 Yield

Conditions & References T= 20 °C , untersucht wurde die Anfangsgeschwindigkeit der Reaktion auch bei 60grad und 80grad Babin et al.; ; nb. 11; (1958); p. 28; ; (1959); p. 16026 View in Reaxys T= 40 °C , untersucht wurde die Anfangsgeschwindigkeit der Reaktion auch bei 50grad und 60grad Beltrame; Chimica e l'Industria (Milan, Italy); vol. 40; (1958); p. 906 View in Reaxys

SiO2-Al2O3 Rx-ID: 6801015 View in Reaxys 424/481 Yield

Conditions & References bei hoeheren Temperaturen und Drucken Patent; Universal Oil Prod.Co.; US2448160; (1946) View in Reaxys Patent; Phillips Petr.Co.; US2408167; (1942) View in Reaxys Patent; Phillips Petr.Co.; US2419599; (1944) View in Reaxys O'Kelly; Kellett; Plucker; Industrial and Engineering Chemistry; vol. 39; (1947); p. 154,157 View in Reaxys

nickel-aluminium oxide catalyst Rx-ID: 7066969 View in Reaxys 425/481

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Yield

Conditions & References T= 425 °C Chromow et al.; Doklady Akademii Nauk SSSR; vol. 96; (1954); p. 1175,1177; ; (1955); p. 8827 View in Reaxys

Cl

Cl

Al

H

zinc cyanide

Cl

Cl

HO

Rx-ID: 7154745 View in Reaxys 426/481 Yield

Conditions & References T= 0 °C , spaeter Erwaermen auf 50grad Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys O OH

H

O

H

NiO

Rx-ID: 7446750 View in Reaxys 427/481 Yield

Conditions & References T= 340 °C , unter Druck Ipatieff et al.; Bulletin de la Societe Chimique de France; (1951); p. 259,268 View in Reaxys

-1

N S

N+

O

F F (v6) F F P F F

N+ S

N

Rx-ID: 9746832 View in Reaxys 428/481 Yield

Conditions & References in acetonitrile-D3, Photolysis, Product distribution Shukla, Deepak; Liu, Guanghua; Dinnocenzo, Joseph P.; Farid, Samir; Canadian Journal of Chemistry; vol. 81; nb. 6; (2003); p. 744 - 757 View in Reaxys

I

I

Rx-ID: 2856672 View in Reaxys 429/481 Yield

Conditions & References Time= 24h, Irradiation, addition of Et3N, other alkyl iodides, var. solvents, other arenes, Product distribution, Mechanism Kurz, Michael E.; Noreuil, Tim; Seebauer, Joe; Cook, Stephanie; Geier, Douglas; et al.; Journal of Organic Chemistry; vol. 53; nb. 1; (1988); p. 172 - 177 View in Reaxys

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O N O

E

Rx-ID: 3917214 View in Reaxys 430/481 Yield

Conditions & References With aluminium trichloride, 2 h, room temp., 55 deg C, various periods of time, Product distribution, Mechanism Bonvino, V.; Casini, G.; Ferappi, M.; Cingolani, G. M.; Pietroni, B. R.; Tetrahedron; vol. 37; (1981); p. 615 - 620 View in Reaxys

H3PO4-BF3 Rx-ID: 6801012 View in Reaxys 431/481 Yield

Conditions & References auch in fluessiger Phase bei Raumtemperatur oder wenig erhoehter Temperatur Pauschkin; Toptschijew; Ssergatschewa; Doklady Akademii Nauk SSSR; vol. 64; p. 81; ; (1949); p. 4638 View in Reaxys Patent; Phillips Petr.Co.; US2412595; (1942) View in Reaxys Pauschkin; Toptschijew; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 21; (1948); p.

1065,1070; ; (1949); p. 1732 View in Reaxys

OH

Cl

Cl

Al

H

zinc cyanide

Cl

Cl

O

OH

Rx-ID: 7048085 View in Reaxys 432/481 Yield

Conditions & References T= 0 °C , spaeter Erwaermen auf 50grad Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys

OH

Cl

Cl

Al

H

Cl

Cl

HO

Rx-ID: 7059452 View in Reaxys 433/481 Yield

Conditions & References T= 50 °C Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys

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Cl

Cl

Al

H

Cl

Cl

HO

HO

Rx-ID: 7444976 View in Reaxys 434/481 Yield

Conditions & References T= 50 °C Bell; Henry; Journal of the Chemical Society; (1928); p. 2226 View in Reaxys

NH

N

NH

N

N

NH

/PPKVB203-1550/

1-Methyl-3-phenyldihydroisoquinolines

Rx-ID: 7457401 View in Reaxys 435/481 Yield

Conditions & References

1.7 % Spectr., 2.0 % Spectr., 0.8 % Spectr., 0.5 % Spectr., 4.4 % Spectr., / PPKVB203 -1550/\3.0 % Spectr.

T= 320 - 350 °C , Sealed glass ampul, Product distribution, Mechanism Shurukhin, Yu. V.; Klyuev, N. A.; Grandberg, I. I.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 22; nb. 7; (1986); p. 723 - 732; Khimiya Geterotsiklicheskikh Soedinenii; vol. 22; nb. 7; (1986); p. 908 917 View in Reaxys

Cl (v2)

Zn

Cl

Rx-ID: 65397 View in Reaxys 436/481 Yield

Conditions & References Liebmann; Chemische Berichte; vol. 13; (1880); p. 46 View in Reaxys Liebmann; Chemische Berichte; vol. 13; (1880); p. 46 View in Reaxys 2

5 H –O

Ca 2+

H O O

2 O O–

Rx-ID: 545971 View in Reaxys 437/481

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Yield

Conditions & References Doebner; Chemische Berichte; vol. 24; (1891); p. 1755 View in Reaxys

O

N O

SH

S

S

S O

O

N

O

N

O

Rx-ID: 3041878 View in Reaxys 438/481 Yield

Conditions & References

32 % Chromat., 22 % Chromat., 33 % Chromat., 7 % Chromat., 5 % Chromat.

T= 200 °C , Product distribution Koikov, L. N.; Terent'ev, P. B.; Kulikov, N. S.; Journal of Organic Chemistry USSR (English Translation); vol. 17; (1981); p. 960 - 964; Zhurnal Organicheskoi Khimii; vol. 17; nb. 5; (1981); p. 1087 - 1093 View in Reaxys

Rx-ID: 3917171 View in Reaxys 439/481 Yield

Conditions & References With superhigh-silica zeolites H form, study of catalytic properties of catalysts containing 20 percent H-SHSZ and 80 percent γ-alumina; effect of components used at catalyst synthesis on the catalytic activity; various reaction conditions, Rate constant, Product distribution, Mechanism Baiburskii; Anokhina; Aleksandrova; Khadzhiev; Journal of applied chemistry of the USSR; vol. 59; nb. 5 pt 2; (1986); p. 1008 - 1012 View in Reaxys O O

soda lime O

Rx-ID: 5425482 View in Reaxys 440/481 Yield

Conditions & References Gabriel; Chemische Berichte; vol. 20; (1887); p. 1204 View in Reaxys

fewer effective nickel

hydrogen Rx-ID: 6416611 View in Reaxys 441/481

Yield

Conditions & References Tiffeneau; Annales de Chimie (Cachan, France); vol. <8>10; (1907); p. 190; Annales de Chimie (Cachan, France); vol. <8>11; (1907); p. 144 View in Reaxys

OH

sodium Rx-ID: 6416613 View in Reaxys 442/481

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Yield

Conditions & References Klages; Chemische Berichte; vol. 35; (1902); p. 2640,3506 View in Reaxys Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 134; (1902); p. 846; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 166 View in Reaxys O

P2O5 Rx-ID: 6674698 View in Reaxys 443/481 Yield

Conditions & References bei der Destillation Kerp; Justus Liebigs Annalen der Chemie; vol. 290; (1896); p. 148 View in Reaxys Fittig; Justus Liebigs Annalen der Chemie; vol. 112; (1859); p. 314 View in Reaxys

O

biphenyl, dibenzyl Rx-ID: 6726407 View in Reaxys 444/481 Yield

Conditions & References T= 446.4 - 493.7 °C , thermal elimination, Kinetics, Product distribution Taylor, Roger; Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999); (1988); p. 183 - 190 View in Reaxys

FeCl2-Al2O3 Rx-ID: 6801011 View in Reaxys 445/481 Yield

Conditions & References bei hoeheren Temperaturen und Drucken und auch auf verschiedenen Traegern Patent; Universal Oil Prod.Co.; US2329858; (1941) View in Reaxys Patent; Universal Oil Prod.Co.; US2402847; (1941) View in Reaxys

MgCl2-Al2O3 Rx-ID: 6801013 View in Reaxys 446/481 Yield

Conditions & References bei hoeheren Temperaturen und Drucken und auch auf verschiedenen Traegern Patent; Universal Oil Prod.Co.; US2329858; (1941) View in Reaxys Patent; Universal Oil Prod.Co.; US2402847; (1941) View in Reaxys

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tetramethyl-diphenyl-ethane (or 1.2-dimethyl-1.2-diphenyl-cyclobutane)

zinc dust I

Rx-ID: 7458352 View in Reaxys 447/481 Yield

Conditions & References Klages; Chemische Berichte; vol. 35; (1902); p. 2649; Chemische Berichte; vol. 39; (1906); p. 2591 View in Reaxys HO

HO

F

O

B

O

F

OH

F

O

OH

O

HO

Rx-ID: 7919964 View in Reaxys 448/481 Yield

Conditions & References Croxall; Sowa; Nieuwland; Journal of Organic Chemistry; vol. 2; (1937); p. 253,256 View in Reaxys O SiH SiH

SiH

Si SiH

Si O

Si

O

O

SiH

O

O

Si

SiH

Si O

Si O

Si

O

O

Si

Si O O

Si

SiH

Si

Si O

Si

SiH O

Si

O

Si

SiH O

Rx-ID: 28772762 View in Reaxys 449/481 Yield

Conditions & References De Vekki; Skvortsov; Russian Journal of General Chemistry; vol. 79; nb. 4; (2009); p. 762 - 777 View in Reaxys

Rx-ID: 1894987 View in Reaxys 450/481 Yield

Conditions & References ΔH (enthalpy of the reaction), Thermodynamic data Fuchs, Richard; Hallman, John H.; Perlman, Michael O.; Canadian Journal of Chemistry; vol. 60; (1982); p. 1832 - 1835 View in Reaxys

Br

Br Al

Br

Br

Rx-ID: 6416605 View in Reaxys 451/481 Yield

Conditions & References Gustavson; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 10; (1878); p. 272; Chemische Berichte; vol. 11; (1878); p. 1253 View in Reaxys Konowalow; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 27; (1895); p. 457; Bulletin de la Societe Chimique de France; vol. <3> 16; (1896); p. 864 View in Reaxys

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Cl Al

Cl

Cl

α.β-diphenylpropane

Cl

Rx-ID: 6416615 View in Reaxys 452/481 Yield

Conditions & References Konowalow; Dobrowolski; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 37; (1905); p. 548; Chem.

Zentralbl.; vol. 76; nb. II; (1905); p. 826 View in Reaxys Silva; Jahresbericht ueber die Fortschritte der Chemie und Verwandter Theile Anderer Wissenschaften; (1879); p.

380; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 318 View in Reaxys

Cl

β.β-diphenyl-propane

Cl

Rx-ID: 6416617 View in Reaxys 453/481 Yield

Conditions & References Silva; Bulletin de la Societe Chimique de France; vol. <2> 34; (1880); p. 674; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 318 View in Reaxys

boron fluoride alcoholate Rx-ID: 6801010 View in Reaxys 454/481 Yield

Conditions & References auch in fluessiger Phase bei Raumtemperatur oder wenig erhoehter Temperatur McAllister; Anderson; Bullard; ; vol. 43; (1947); p. 189 View in Reaxys

phosphoric acid kieselguhr Rx-ID: 6801014 View in Reaxys 455/481 Yield

Conditions & References Ausbeuten und Einfluss von Thiophen auf den Reaktionsverlauf McAllister; Anderson; Bullard; ; vol. 43; (1947); p. 189 View in Reaxys

O O

OH

S HO

HO

S OO

Rx-ID: 7242386 View in Reaxys 456/481 Yield

Conditions & References beim Erhitzen zerfaellt ohne zu schmelzen Jacobsen; Justus Liebigs Annalen der Chemie; vol. 146; (1868); p. 86 View in Reaxys

O

O

O S

O

O

Br–+Mg

Rx-ID: 170900 View in Reaxys 457/481

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Yield

Conditions & References Bushong; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 176; (1923); p. 841 View in Reaxys O Mg+ Br–

Rx-ID: 846852 View in Reaxys 458/481 Yield

Conditions & References Petrow; Kaplan; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1947); p. 295,303; ; (1949); p. 1718 View in Reaxys H

OH

N

H

sodium

H

OH

Rx-ID: 5801870 View in Reaxys 459/481 Yield

Conditions & References van der Zanden; ter Borg; Recueil des Travaux Chimiques des Pays-Bas; vol. 78; (1956); p. 1115,1118 View in Reaxys

Br Al

Br

Br

Br

Rx-ID: 6416604 View in Reaxys 460/481 Yield

Conditions & References Gustavson; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 10; (1878); p. 272; Chemische Berichte; vol. 11; (1878); p. 1253 View in Reaxys

Cl

Cl Al

β.β-diphenyl-propane

Cl

Cl

Rx-ID: 6416616 View in Reaxys 461/481 Yield

Conditions & References Silva; Bulletin de la Societe Chimique de France; vol. <2> 34; (1880); p. 674; Bulletin de la Societe Chimique de France; vol. <2> 43; (1885); p. 318 View in Reaxys

Cl Al

Cl

Br

n-propylbenzene

Br

Cl

Rx-ID: 6730114 View in Reaxys 462/481 Yield

Conditions & References Bodroux; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 155 View in Reaxys

Cl Al Cl

Cl

Br

n-propylbenzene

Br

Rx-ID: 6730115 View in Reaxys 463/481 Yield

Conditions & References Bodroux; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 155 View in Reaxys

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OH S OO

HO

Rx-ID: 6801007 View in Reaxys 464/481 Yield

Conditions & References Ausbeuten und Einfluss von Thiophen auf den Reaktionsverlauf McAllister; Anderson; Bullard; ; vol. 43; (1947); p. 189 View in Reaxys

H

OH

N

H

H

HO

sodium Rx-ID: 7154744 View in Reaxys 465/481

Yield

Conditions & References Birch; Journal of the Chemical Society; (1945); p. 809,812; Journal and Proceedings of the Royal Society of New South Wales; vol. 83; (1949); p. 245,249 View in Reaxys

Cl Al

Cl

Cl

Rx-ID: 7156981 View in Reaxys 466/481 Yield

Conditions & References beim Destillieren Bodroux; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 155 View in Reaxys

O

E

I

H

O

phosphorus

HO

HO

Rx-ID: 7248653 View in Reaxys 467/481 Yield

Conditions & References Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 138; (1904); p. 987; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 173 View in Reaxys

Z

Rx-ID: 1616780 View in Reaxys 468/481 Yield

Conditions & References Plasmolysis; var. power and flow rate, Product distribution Tokuda, Masao; Suginome, Hiroshi; Miller, L.L.; Tetrahedron Letters; vol. 23; nb. 44; (1982); p. 4573 - 4576 View in Reaxys

Cl Al Cl

C O

Cl

Cl

O

Rx-ID: 6727560 View in Reaxys 469/481

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Yield

Conditions & References Rothstein; Saville; Journal of the Chemical Society; (1949); p. 1946,1949 View in Reaxys

Cl Al

Cl

Cl

Rx-ID: 7047111 View in Reaxys 470/481 Yield

Conditions & References Patent; Dow Chem.Co.; US2403785; (1943) View in Reaxys

O Cl Al

B

O

O

Cl

Cl

Rx-ID: 7047177 View in Reaxys 471/481 Yield

Conditions & References Kuskow; Sheiman; Doklady Akademii Nauk SSSR; vol. 106; (1956); p. 479; Doklady Chemistry; 106-111<1956>83 View in Reaxys

Cl Al

Cl

Cl

Rx-ID: 7062814 View in Reaxys 472/481 Yield

Conditions & References Boedtker; Halse; Bulletin de la Societe Chimique de France; vol. <4> 19; (1916); p. 447 View in Reaxys

S

O

O

N O

Cl

H

O

O

S

S

N

O

O

O

S

N

O

Rx-ID: 3004978 View in Reaxys 473/481 Yield 4 % Chromat., 20 % Chromat., 30 % Chromat., 33 % Chromat.

Conditions & References Heating, Product distribution Koikov, L. N.; Terent'ev, P. B.; Kulikov, N. S.; Journal of Organic Chemistry USSR (English Translation); vol. 17; (1981); p. 960 - 964; Zhurnal Organicheskoi Khimii; vol. 17; nb. 5; (1981); p. 1087 - 1093 View in Reaxys

HO HO

OH

F

P OH O

F

B

F

polyisopropyl-benzene Rx-ID: 6730813 View in Reaxys 474/481 Yield

Conditions & References Toptschijew; Jegorowa; Wassilewa; Doklady Akademii Nauk SSSR; vol. 67; (1949); p. 475; ; (1949); p. 7915 View in Reaxys

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Cl Al

Cl

O

O

Cl

O

Rx-ID: 7043288 View in Reaxys 475/481 Yield

Conditions & References Kurssanow; Selwin; Zhurnal Obshchei Khimii; vol. 9; (1939); p. 2173,2176; Chem. Zentralbl.; vol. 111; nb. I; (1940); p. 3242 View in Reaxys

Cl Al

Cl

Cl

O

N O

Rx-ID: 7047112 View in Reaxys 476/481 Yield

Conditions & References Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys

Cl

O Al

Cl

N

O

Cl

Rx-ID: 7047113 View in Reaxys 477/481 Yield

Conditions & References Schmerling; Industrial and Engineering Chemistry; vol. 40; (1948); p. 2072,2074 View in Reaxys

Cl Al

Cl

Cl

Cl

Rx-ID: 7047114 View in Reaxys 478/481 Yield

Conditions & References Patent; Dow Chem.Co.; US2403785; (1943) View in Reaxys O HO OH

Rx-ID: 24982351 View in Reaxys 479/481 Yield

Conditions & References 2 : EXAMPLE 2 After completion of the reaction, the reaction mixture was poured into 500 ml of benzene, followed by stirring at 20° C. for 1 hour.

The precipitate so formed was collected by filtration and then dried to obtain 103.7 g of white crystals.

Liquid-chromatographic analysis revealed that this product comprised 82.2percent of 4,4-bis(4-hydroxyphenyl)cyclohexanecarboxylic acid methyl ester and 17.7percent of 4,4-bis(4-hydroxyphenyl)cyclohexanecarboxylic acid.

Next, 20.0 g of the aforesaid white crystals, 2.7 g of sodium hydroxide, 21.9 g of α-methylstyrene, 100 g of water, and 0.4 g of 5percent palladium-carbon catalyst were charged into a 300-ml stainless steel autoclave.

After the air within the autoclave was displaced with nitrogen gas, the reaction mixture was heated at 250° C. for 4 hours.

After completion of the reaction, the reaction mixture was cooled.

Since some crystals separated out, 30.0 g of a 20percent aqueous solution of sodium hydroxide was added to the reaction mixture so as to dissolve the crystals.

Thereafter, the reaction mixture was filtered to remove the catalyst therefrom.

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After the filtrate was extracted with 100 ml of benzene to recover α-methylstyrene and cumene, diluted hydroxhloric acid was added thereto so as to precipitate 4'-hydroxy-biphenyl-4-carboxylic acid.

The crystals so formed were collected by filtration, washed with water, and then dried to obtain 13.0 g of 4'-hydroxybiphenyl-4-carboxylic acid having a melting point of 297° C. Liquid-chromatographic analysis revealed that this product had a purity of 99percent, and its total yield based on the amount of cyclohexanone-4-carboxylic acid methyl ester used was 78percent.

Patent; Mitsui Toatsu Chemicals, Incorporated; US4755617; (1988); (A1) English View in Reaxys

Rx-ID: 25059827 View in Reaxys 480/481 Yield

Conditions & References 5 : EXAMPLE 5 EXAMPLE 5 A commercial mixture of 16 g (0.1 mol) diisopropylbenzene containing about 60percent of the para and 40percent of the ortho isomer, is dissolved in 150 ml of anhydrous hydrogen fluoride.

The reaction mixture is cooled to -20° to 0° and saturated, while stirred, with boron trifluoride.

After stirring at this temperature for 30 min. the temperature is raised and HF and BF3 is distilled off, (which can be reused).

After washing, neutralization and drying, the organic layer is separated, distilled and analyzed by gas liquid chromatography.

The diisopropylbenzene fraction consists of 99percent meta-diisopropylbenzene and 1percent para-diisopropylbenzene.

Cumene and 1,3,5-triisopropylbenzene are also formed, as products of disproportionation, amounting to about 20percent.

Patent; PCUK Produits Chimiques Ugine Kuhlmann; US4339613; (1982); (A1) English View in Reaxys

HO

OH

Rx-ID: 25136420 View in Reaxys 481/481 Yield

Conditions & References 1 : EXAMPLE 1 In the next step, a stainless steel autoclave was charged with the total amount of the above wet cake, 0.35 g of 5percent palladium-carbon, 5.9 g of α-methylstyrene and 100 ml of 2-ethylhexanol and the internal atmosphere was replaced with nitrogen gas.

The mixture was reacted at 180° C. for 3 hours, then cooled to 150° C. and filtered to recover the insoluble catalyst.

2-Ethylhexanol, α-methylstyrene and cumene formed by the reaction were distilled off from the filtrate under reduced pressure to obtain 33.6 g of 4,4'-biphenol as white crystals.

Patent; Mitsui Toatsu Chemicals, Incorporated; US4873374; (1989); (A1) English View in Reaxys

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