4-Methylbenzoic acid (p-Toluic acid)

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Reactions (774)

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Substances (1)

Citations (976)

Conditions

References

1

Synthesize Find similar 100%

With oxygen; potassium hydoxide in methanol; water

T=50°C; P=760.051 Torr; 4 h;

Synthesize Find similar

Rx-ID: 267471 Find similar reactions

WISCONSIN ALUMNI RESEARCH FOUNDATION; Stahl, Shannon S.; Powell, Adam B.; Root, Thatcher W.; Mannel, David S.; Ahmed, Maaz S.

Patent: US9593064 B2, 2017 ; Location in patent: Sheet 7; 20 ; Title/Abstract

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99%

With oxygen; potassium hydoxide in toluene

T=100°C; P=760.051 Torr; 12 h;

Yang, Huimin; Cui, Xinjiang; Deng, Youquan; Shi, Feng

RSC Advances, 2014 , vol. 4, # 104 p. 59754 - 59758 Title/Abstract

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98%

With periodic acid; pyridinium chlorochromate in acetonitrile

Hunsen, Mo

Synthesis, 2005 , # 15 art. no. M00905SS, p. 2487 - 2490 Title/Abstract

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98%

With periodic acid; PFC in acetonitrile

Hunsen, Mo

T=0°C; 3 h;

Journal of Fluorine Chemistry, 2005 , vol. 126, # 9-10 p. 1356 - 1360 Title/Abstract

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96%

With sodium periodate; MnTEPyP in water

T=60°C; 4 h;

Ren, Qing-Gang; Chen, Shao-Yun; Zhou, Xian-Tai; Ji, Hong-Bing

Bioorganic and Medicinal Chemistry, 2010 , vol. 18, # 23 p. 8144 - 8149 Title/Abstract

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96%

With dihydrogen peroxide in water; toluene

T=20 - 85°C; 4 h;

Hu, Yu Lin; Ma, Xiao Yun; Ge, Qiang; Lu, Ming

Acta Chimica Slovenica, 2010 , vol. 57, # 4 p. 927 - 930 Title/Abstract

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95.6%

With silica-supported Jones reagent in dichloromethane

0.035 h;

Wiles, Charlotte; Watts, Paul; Haswell, Stephen J.

Tetrahedron Letters, 2006 , vol. 47, # 30 p. 5261 - 5264 Title/Abstract

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95%

With lithium hydroxide monohydrate; oxygen in water

T=25°C; 12 h;

Tang, Lin; Guo, Xuefeng; Li, Yunfeng; Zhang, Shuai; Zha, Zhenggen; Wang, Zhiyong

Chemical Communications, 2013 , vol. 49, # 45 p. 5213 - 5215 Title/Abstract

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94%

Stage #1: With Oxonereg;; sodium 2-iodobenzenesulfonate in acetonitrile

T=70°C; 1 h; Stage #2: With water in acetonitrile

3 h;

Uyanik, Muhammet; Akakura, Matsujiro; Ishihara, Kazuaki

Journal of the American Chemical Society, 2009 , vol. 131, p. 251 - 262 Title/Abstract

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94%

With [MnIV,IV2(μ-O)3(N,N',N''-trimethyl-1,4,7-triazacyclononane)2] (PF6)2*H2O; dihydrogen peroxide; salicylic acid in water; acetonitrile

T=20°C;

Saisaha, Pattama; Buettner, Lea; Van Der Meer, Margarethe; Hage, Ronald; Feringa, Ben L.; Browne, Wesley R.; De Boer, Johannes W.

Advanced Synthesis and Catalysis, 2013 , vol. 355, # 13 p. 2591 - 2603 Title/Abstract

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94%

With Oxonereg;; pre-IBS; water in acetonitrile

T=70°C; 4 h; chemoselective reaction;

Uyanik, Muhammet; Kazuaki, Kazuaki

Organic Syntheses, 2012 , vol. 89, p. 105 - 114 Title/Abstract

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93%

With potassium pyrosulfate; potassium aquapentachlororuthenate(III); potassium hydoxide

T=20°C; 0.5 h; Sonication; Catalytic behavior; Hide Experimental Procedure

Shoair, Abdel Ghany F.

Journal of Molecular Liquids, 2015 , vol. 206, p. 68 - 74 Title/Abstract

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2.2.3. Ultrasonic-assisted catalytic dehydrogenation of primary amines to nitriles by trans-[RuO3(OH)2]2−/S2O8 2− To 50 cm3 of trans-[RuO3(OH)2]2-/S2O8 2- reagent, primary amine (2mmol) was added, the reaction mixture turned dark green. The reaction mixture was further irradiated for half an hour, after which time, the reaction is completed since the original orange color of ruthenate reappears. The mixture was then extracted with diethyl ether(3 × 25 cm3). The ether extracts were dried over anhydrous MgSO4then filtered and evaporated to give the product. Similarly, nitriles were hydrated to their respective amides at 100 °C. Also, primary alcohols were oxidized to their respective carboxylicacids. The alkaline aqueous layer was acidified with 2 M H2SO4 to pH 2 and extracted with diethyl ether. The extract was dried over anhydrous MgSO4 then filtered and evaporated to give the product.

93%

With oxygen; Azobenzene; sodium hydroxide in 1,4-dioxane

T=80°C; 24 h;

Liu, Chengkou; Fang, Zheng; Yang, Zhao; Li, Qingwen; Guo, Shiyu; Guo, Kai

RSC Advances, 2015 , vol. 5, # 97 p. 79699 - 79702 Title/Abstract

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92%

With sodium bromate; CeEPS10 in acetonitrile

24 h; Heating;

Al-Haq, Nazli; Sullivan, Alice C.; Wilson, John R. H.

Tetrahedron Letters, 2003 , vol. 44, # 4 p. 769 - 771 Title/Abstract

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92%

With oxygen; sodium t-butanolate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride in dichloromethane

T=20°C; 30 h; Molecular sieve; Reagent/catalyst; Hide Experimental Procedure

Yu, Dong-Fang; Xing, Ping; Jiang, Biao

Tetrahedron, 2015 , vol. 71, # 25 p. 4269 - 4273 Title/Abstract

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4.1. General procedure for the oxidation of aryl alcohol 1a-1o, or 6a-6h

General procedure: Under Oxygen atmosphere, aryl alcohol (2.00 mmol), precatalyst(SIMesHCl or SIPrHCl, 0.06 mmol), NaOtBu (960.5 mg,10.00 mmol), and 1 g 3 A molecular sieve were added todichloromethane (20 mL). This solutionwas allowed to stir for 30 h.After filtrating through a pad of Celite, the cake was added tohydrochloric acid (2N, 50 mL) and extracted with ethyl acetate(50 mL3). The organic layer was dried over Na2SO4 and concentratedunder reduced pressure. The products did not need furtherpurification.

91%

With potassium hydroxide; air in water

T=26.84°C; 4 h;

Tsunoyama, Hironori; Tsukuda, Tatsuya; Sakurai, Hidehiro

Chemistry Letters, 2007 , vol. 36, # 2 p. 212 - 213 Title/Abstract

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91%

With sodium tetrahydroborate; 1 Pd/C; water; potassium hydoxide in methanol

T=20°C; 12 h; In air;

An, Gwangil; Ahn, Hyunseok; De Castro, Kathlia A.; Rhee, Hakjune

Synthesis, 2010 , # 3 art. no. F19009SS, p. 477 - 485 Title/Abstract

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90%

With methyl 3,5-bis((1H-1,2,4-triazol-1-yl)methyl)benzoate; oxygen; sodium acetate; nickel dibromide

T=120°C; P=760.051 Torr; 72 h;

Urgoitia; Sanmartin; Herrero; Domínguez

Chemical Communications, 2015 , vol. 51, # 23 p. 4799 - 4802 Title/Abstract

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90%

With tert.-butylhydroperoxide in water

T=60°C; 4 h; Inert atmosphereGreen chemistry;

Azizi, Kobra; Esfandiary, Naghmeh; Karimi, Meghdad; Yazdani, Elahe; Heydari, Akbar

RSC Advances, 2016 , vol. 6, # 92 p. 89313 - 89321 Title/Abstract

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88%

Stage #1: With [RuCl2(p-cymene)(iPr2-imy)]; tricyclohexylphosphine tetrafluoroborate; potassium hydoxide in toluene

6 h; Schlenk techniqueInert atmosphereReflux; Stage #2: With hydrogenchloride in water

pH=1;

Santilli, Carola; Makarov, Ilya S.; Fristrup, Peter; Madsen, Robert

Journal of Organic Chemistry, 2016 , vol. 81, # 20 p. 9931 - 9938 Title/Abstract

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87%

With 1,4-diaza-bicyclo[2.2.2]octane; oxygen; copper(II) 2-ethylhexanoate; vanadyl acetylacetonate

T=95°C; P=760.051 Torr; 24 h;

Jiang, Nan; Ragauskas, Arthur J.

Journal of Organic Chemistry, 2007 , vol. 72, # 18 p. 7030 - 7033 Title/Abstract

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87%

With O40PW12(3-)*3C17H38NO3S(1+); dihydrogen peroxide T=70°C; 4 h; Green chemistry; Hide Experimental Procedure

Li, Xinzhong; Cao, Rong; Lin, Qi

Catalysis Communications, 2015 , vol. 69, p. 5 - 10 Title/Abstract

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2.3. General procedure for oxidation of alcohols

General procedure: A mixture of S4SiIL or S3PIL (0.05mmol) and alcohol (30mmol) in a 25 mL flask fitted with a reflux condenser was heated to the reactiontemperature, then the required amount of aqueous H2O2 was addeddropwise under stirring. The progress of the reaction was monitored by TLC (GF254 silica gel coloration in phosphomolybdic acid/ethanol for aromatic alcohol, in KMnO4 solution for aliphatic alcohol). After the completion, the reaction mixture was extracted with diethyl ether(3 × 20 mL), solvent was evaporated in a vacuum. The residual was analyzedby gas chromatography (HP 6890) equippedwith a flame ionizationdetector and an SE-54 column. The aqueous phase was subjected torotary evaporation, and then was dried at 85 °C under a vacuum for 8 hto give regenerated ionic liquids. Pure oxidation products were obtainedby column chromatography (petroleum ether-ethyl acetate 9:1 (V/V))and identified by the comparison of their IR and 1H NMR spectra withthose of authentic samples.

87%

With C32H25Cl2N6O2Rh2(1+)*Cl(1-); sodium hydroxide in water T=100°C; 12 h; Sealed tubeGreen chemistry;

Wang, Xuewei; Wang, Chao; Liu, Yuxuan; Xiao, Jianliang

Green Chemistry, 2016 , vol. 18, # 17 p. 4605 - 4610 Title/Abstract

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86%

With Styrene oxide; [(C6H5)3P]3Ru(CO)(Cl)H in toluene

T=90°C; 12 h; Inert atmosphere;

Barati, Behjat; Moghadam, Majid; Rahmati, Abbas; Tangestaninejad, Shahram; Mirkhani, Valiollah; Mohammadpoor-Baltork, Iraj

Synlett, 2013 , vol. 24, # 1 p. 90 - 96 Title/Abstract

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85%

With sodium hydroxide; osmium(VIII) oxide; sulfuric acid; potassium hexacyanoferrate(III) in water

3 h; Ambient temperature;

Bailey, Alan J.; Bhowon, Minu G.; Griffith, William P.; Shoair, Abdel G. F.; White, Andrew J. P.; Williams, David J.

Journal of the Chemical Society - Dalton Transactions, 1997 , # 18 p. 3245 - 3250 Title/Abstract

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83%

With C14H14N6O2; oxygen; sodium acetate; palladium diacetate

T=120°C; P=760.051 Torr; 72 h;

Urgoitia, Garazi; Maiztegi, Ainhoa; Sanmartin, Raul; Herrero, María Teresa; Domínguez, Esther

RSC Advances, 2015 , vol. 5, # 125 p. 103210 - 103217 Title/Abstract

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81%

With oxygen; sodium carbonate in water

T=100°C; P=52505.3 Torr; 0.533333 h; Flow reactorGreen chemistry;

Osako, Takao; Torii, Kaoru; Uozumi, Yasuhiro

RSC Advances, 2015 , vol. 5, # 4 p. 2647 - 2654 Title/Abstract

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80%

With sodium tungstate; dihydrogen peroxide; [Me(n-C8H17)3N]HSO4

T=90°C; 12 h;

Sato, Kazuhiko; Takagi, Junko; Aoki, Masao; Noyori, Ryoji

Tetrahedron Letters, 1998 , vol. 39, # 41 p. 7549 - 7552 Title/Abstract

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80%

With dihydrogen peroxide; [Me(n-C8H17)3N]HSO4; sodium tungstate in water

T=90°C; Oxidation; 12 h;

Sato, Kazuhiko; Aoki, Masao; Takagi, Junko; Zimmermann, Klaus; Noyori, Ryoji

Bulletin of the Chemical Society of Japan, 1999 , vol. 72, # 10 p. 2287 - 2306 Title/Abstract

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78.3%

With tert.-butylhydroperoxide

T=60°C; 15 h;

Zhang, Yuecheng; Chu, Ruosi; Zhang, Hongyu; Zhao, Jiquan

Transition Metal Chemistry, 2017 , vol. 42, # 2 p. 105 - 116

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Title/Abstract

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Catalytic oxidation of alcohols

General procedure: In a typical process, into a 5-ml two-necked round-bottomflask equipped with a magnetic stirrer were addedRu(pbbp)(pydic) (0.002 mmol) and alcohol (2 mmol)successively at room temperature. The mixture washeated to 60 C under stirring, and then TBHP (70percentaqueous solution) was slowly dropped in 0.5 h. Thereaction was monitored by GC equipped with a SE 54column (30 m 9 0.5 lm). After reaction, the product waspurified by column chromatography over silica gel (eluent:n-hexane/ethyl acetate) and characterized by 1HNMR. 74%

With tert.-butylhydroperoxide; vanadia in water

T=100°C; 9 h; Hide Experimental Procedure

Alagiri, Kaliyamoorthy; Prabhu, Kandikere Ramaiah

Tetrahedron, 2011 , vol. 67, # 44 p. 8544 - 8551 Title/Abstract

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4.3. Typical experimental procedure for oxidation of alcohols

General procedure: To a well-stirred suspension of alcohol (1 mmol) and V2O5 (0.05 mmol) in water (1 mL) was added aq TBHP (70percent, 4 mmol). The reaction mixture was heated at reflux until the completion of the reaction (monitored by TLC). The reaction mixture was extracted with ethyl acetate (3.x.15 mL). The combined organic layer was dried over Na2SO4 and evaporated under vacuum to furnish the crude product, which was purified on a silica gel column using EtOAc and hexane as the solvent mixture. In case of problem in isolating the acid, the solvent was evaporated under vacuum and the crude residue was purified by column chromatography on silica gel (EtOAc/hexane).

69%

With dihydrogen peroxide; benzenesulfonic acid; potassium bromide in dichloromethane; water

T=20°C; 24 h; Irradiation; Reagent/catalystSolvent;

Moriyama, Katsuhiko; Takemura, Misato; Togo, Hideo

Journal of Organic Chemistry, 2014 , vol. 79, # 13 p. 6094 - 6104 Title/Abstract

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60%

With carbon tetrabromide; oxygen; triphenylphosphine

fluorescent irradiation;

Sugai, Taichi; Itoh, Akichika

Tetrahedron Letters, 2007 , vol. 48, # 52 p. 9096 - 9099 Title/Abstract

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With sulfur

T=190 - 200°C;

Szperl

Roczniki Chemii, vol. 6, p. 736 Chem. Zentralbl., 1927 , vol. 98, # I p. 2985 Full Text View citing articles Show Details

With N-methylpyrrolidine-2-one hydrotribromide; dihydrogen peroxide in acetonitrile

Heating;

Joseph, Jomy K.; Jain, Suman L.; Sain, Bir

European Journal of Organic Chemistry, 2006 , # 3 p. 590 - 594 Title/Abstract

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100 %Chromat.

With oxygen; sodium hydroxide in tetrahydrofuran; water

T=25°C; 12 h;

Soule, Jean-Francois; Miyamura, Hiroyuki; Kobayashi, Shu

Journal of the American Chemical Society, 2011 , vol. 133, # 46 p. 18550 - 18553 Title/Abstract

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92 %Spectr.

With oxygen; sodium carbonate in water

T=100°C; P=760.051 Torr; 24 h; Green chemistry;

Osako, Takao; Uozumi, Yasuhiro

Chemistry Letters, 2009 , vol. 38, # 9 p. 902 - 903 Title/Abstract

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89 %Chromat.

With [(C6H5)3P]3Ru(CO)(Cl)H; diphenyl sulphoxide in tetrahydrofuran

T=70°C; 2.5 h; Inert atmosphereSealed tubeGreen chemistry; Hide Experimental Procedure

Barati, Behjat; Moghadam, Majid; Rahmati, Abbas; Mirkhani, Valiollah; Tangestaninejad, Shahram; Mohammadpoor-Baltork, Iraj

Inorganic Chemistry Communications, 2013 , vol. 29, p. 114 - 117 Title/Abstract

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Typical procedure for the ruthenium hydride-catalyzed direct oxidation of alcohols to carboxylic acids with diphenyl sulfoxide

General procedure: Benzyl alcohol 1a (108.1 mg, 1 mmol), diphenyl sulfoxide 2 (202.3 mg, 1 mmol), [RuHCl(CO)(PPh3)3] (39.1 mg, 0.04 mmol) and THF (2 mL) were placed in a screw capped test tube. The test tube was purged with argon and sealed. The mixture was stirred at 70 °C for 2.5 h. After the reaction was completed, the solvent was removed under reduce pressure. The residue was purified by silica gel chromatography (petroleum ether/ethyl acetate = 6/1) and recrystallized from H2O–methanol to give the compound 3a as a white crystal. #10;#10;

With E. coli xanthine dehydrogenase; F. graminearum galactose oxidase variant M35; oxygen; catalase in aq. phosphate buffer; acetonitrile

T=37°C; pH=7.6; Enzymatic reaction;

Bechi, Beatrice; Herter, Susanne; McKenna, Shane; Riley, Christopher; Leimkühler, Silke; Turner, Nicholas J.; Carnell, Andrew J.

Green Chemistry, 2014 , vol. 16, # 10 p. 4524 - 4529 Title/Abstract

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> 99 %Chromat.

With oxygen; potassium carbonate in water

T=80°C; P=759.826 Torr; 22 h; Green chemistry;

Karimi, Babak; Naderi, Zahra; Khorasani, Mojtaba; Mirzaei, Hamid M.; Vali, Hojatollah

ChemCatChem, 2016 , vol. 8, # 5 p. 906 - 910 Title/Abstract

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78 %Chromat.

With [2,2]bipyridinyl; Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1piperidinyloxy free radical; oxygen; acetic acid

T=80°C; P=760.051 Torr; 3 h;

Lagerblom, Kalle; Wrigstedt, Pauli; Keskiväli, Juha; Parviainen, Arno; Repo, Timo

ChemPlusChem, 2016 , vol. 81, # 11 p. 1160 - 1165 Title/Abstract

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98 %Chromat.

With water; potassium carbonate

T=80°C; Catalytic behavior;

Vessally, Esmail; Ghasemisarabbadeih, Mostafa; Ekhteyari, Zeynab; Hosseinzadeh-Khanmiri, Rahim; Ghorbani-Kalhor, Ebrahim; Ejlali, Ladan

RSC Advances, 2016 , vol. 6, # 108 p. 106769 - 106777 Title/Abstract

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67 %Chromat.

With C56H44Cl3CuN2OP2S; dihydrogen peroxide; 3-butyl-1-methyl-1H-imidazol-3ium hexafluorophosphate

T=70°C; 48 h; Hide Experimental Procedure

2.5 Procedure for catalytic oxidation

General procedure: To a mixture of alcohol (5mmol) and complex 1 (7mg, 0.007mmol) in [bmim][PF6] (0.1mL), hydrogen peroxide (6mmol, 0.678mL) was added. The reaction mixture was stirred for 48h at 70°C. After the appropriate time, the resulting mixture was extracted with n-hexane and then the extract was analyzed by GC. To identify the reaction products and determine their percentage yields, the retention times and corresponding peak areas were compared with authentic commercial samples under identical experimental conditions. To calculate the percentage yields of the formed products the area normalization method was used. To determine the isolated yields of acetophenone and benzoic acid, their crude mixture was purified by columnchromatography. To investigate the recyclability of the IL and the catalyst, [bmim][PF6] with complex 1 was recovered by overnight drying in vacuo. For the five consecutive cycles, the recovered complex 1 in [bmim][PF6] was used by adding fresh 1-phenylethanol (5mmol) and hydrogen peroxide (6mmol) under the same experimental conditions.

2

Rx-ID: 277164 Find similar reactions

A

B

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Gunasekaran; Bhuvanesh; Karvembu

Polyhedron, 2017 , vol. 122, p. 39 - 45 Title/Abstract

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A: 2% B: 85%

With N -hydroxyphthalimide; oxygen; cobalt(II) acetate in acetic acid

T=25°C; P=760 Torr; 20 h;

Yoshino, Yasushi; Hayashi, Yoshiaki; Iwahama, Takahiro; Sakaguchi, Satoshi; Ishii, Yasutaka

Journal of Organic Chemistry, 1997 , vol. 62, # 20 p. 6810 - 6813 Title/Abstract

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A: 5.4% B: 73.3%

With N -hydroxyphthalimide; oxygen in acetic acid

T=90°C; 2.5 h; Hide Experimental Procedure

Zhou, Yulu; Lin, Shasha; Bian, Yinghui; Xia, Daohong; Xiang, Yuzhi

Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2016 , vol. 55B, # 5 p. 624 - 628 Title/Abstract

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Experimental Section

General procedure: In a general procedure, into a three-neck flask, 3 mmol of aromatics, 5 mL of acetic acid, 5 mol percent of NHPI, and 0.83 mol percent of CoSPc were added. Thereafter, 02 was bubbled at 2.5 mL/s into the flask. The oxidation was carried out at 90°C under stirring. Oxidation process was monitored by TLC. After the original substrate was exhausted, the reaction solution was concentrated under reduced pressure and the reside was separated on silica gel. The products were confirmed by 'H NMR, and the assignments and yields determination of the volatile products, such as benzyl aldehyde, were estimated according to the retention times and peak areas by GC.

A: 70% B: 21%

With Marshall's acid; copper(II) sulfate in water; acetonitrile

T=75 - 80°C; 1 h;

Perumal, P. Thirumalai; Bhatt, M. Vivekananda

Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1981 , vol. 20, # 2 p. 153 - 155 Title/Abstract

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A: 70% B: 20%

With potassium bromate; ammonium cerium(IV) nitrate in 1,4dioxane; water; toluene

T=95°C; 24 h;

Ganin; Amer

Synthetic Communications, 1995 , vol. 25, # 20 p. 3149 - 3154 Title/Abstract

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A: 70% B: 20%

With potassium bromate; ammonium cerium(IV) nitrate in 1,4dioxane; water; toluene

T=95°C; 24 h;

Ganin; Amer

Synthetic Communications, 1995 , vol. 25, # 20 p. 3149 - 3154 Title/Abstract

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A: 21.7% B: 5.2%

With [FeCl2{κ3-HC(pyrazol-1-yl)3}]; dihydrogen peroxide; nitric acid in water; acetonitrile

T=35°C; 12 h; Green chemistry; Catalytic behavior; Overall yield = 31.7 percent; Hide Experimental Procedure

Mendes, Marta; Ribeiro, Ana Paula C.; Alegria, Elisabete C.B.A.; Martins, Luísa M.D.R.S.; Pombeiro, Armando J.L.

Polyhedron, 2017 , vol. 125, p. 151 - 155 Title/Abstract

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General procedure: The xylenes oxidations were carried out in air in round bottomflasks with vigorous stirring and using CH3CN as solvent (up to3 mL total volume). Typically, [FeCl2{j3-HC(pz)3}] (10 lmol) wasadded to the solvent as a solid or in the form of a stock solution.After the addition of xylene (o-, m- or p-; 5 mmol) the reactionstarted when hydrogen peroxide (50percent aq. sol., 10 mmol) was addedin one portion. In the experiments with HNO3 (65percent, 0.1–0.5 mmol)this acid was added immediately before the addition of the substrate.The reactions were stopped by cooling the reactional solution.Extraction was performed with 10 mL of diethyl ether and90 μL of cyclopentanone were inserted in the extracted mixture.All products formed were identified by GC.

With benzeneseleninic anhydride

T=120°C; 119 h; Yield given. Yields of byproduct given;

Barton, Derek H. R.; Hui, Raymond A. H. F.; Ley, Steven V.

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1982 , # 9 p. 2179 - 2186 Title/Abstract

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With iron(III) oxide; water; oxygen

T=235°C; P=44130.5 Torr;

I.G. Farbenind.

Patent: US1815985 , 1929 ;

B: 6 mg

With benzeneseleninic anhydride

T=120°C; 119 h; Yields of byproduct given;

Barton, Derek H. R.; Hui, Raymond A. H. F.; Ley, Steven V.

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1982 , # 9 p. 2179 - 2186 Title/Abstract

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With potassium bromate; ammonium cerium(IV) nitrate in 1,4-dioxane; toluene

T=95°C; 24 h; other alkyl benzenes; Product distributionMechanism;

Ganin; Amer

Synthetic Communications, 1995 , vol. 25, # 20 p. 3149 - 3154 Title/Abstract

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With Coprinus sp. peroxidase; tartaric acid buffer; dihydrogen peroxide in water; acetone

T=20°C; pH=5;

Russ, Rainer; Zelinski, Thomas; Anke, Timm

Tetrahedron Letters, 2002 , vol. 43, # 5 p. 791 - 793 Title/Abstract

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With N -hydroxyphthalimide; xanthone; oxygen; tetramethlyammonium chloride in acetonitrile

T=60°C; P=3750.38 Torr; 3 h; Autoclave;

Du, Zhongtian; Sun, Zhiqiang; Zhang, Wei; Miao, Hong; Ma, Hong; Xu, Jie

Tetrahedron Letters, 2009 , vol. 50, # 15 p. 1677 - 1680 Title/Abstract

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With ([MnIII(5,10,15,20-tetra(4-chlorophenyl)porphyrin)]chloride); cobalt(II) diacetate tetrahydrate

T=170°C; P=9000.9 Torr; 5 h; Neat (no solvent)Autoclave;

Xiao, Yang; Zhang, Xiaoyan; Wang, Qin Bo; Tan, Ze; Guo, Can Cheng; Deng, Wei; Liu, Zhi Gang; Zhang, He Fei

Chinese Chemical Letters, 2011 , vol. 22, # 2 p. 135 - 138 Title/Abstract

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With dmap; oxygen; benzyl bromide in acetonitrile

T=140°C; P=7500.75 Torr; 3 h; Autoclave;

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968 Title/Abstract

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With C36H36ClMnN6O8

T=120°C; P=760.051 Torr; 9.5 h;

Li, Jian-Zhang; He, Xi-Yang; Zeng, Jun; Xiao, Zheng-Hua; Qin, Sheng-Ying

Transition Metal Chemistry, 2012 , vol. 37, # 1 p. 31 - 35 Title/Abstract

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With N -hydroxyphthalimide; oxygen; cobalt(II) acetate

T=80°C; P=760.051 Torr; Ionic liquid;

Lu, Tingting; Lu, Ming; Yu, Wang; Liu, Zhongjie

Croatica Chemica Acta, 2012 , vol. 85, # 3 p. 277 - 282 Title/Abstract

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With dihydrogen peroxide; acetic acid

T=30°C; 20 h; Reagent/catalystTemperatureTimeConcentration; Hide Experimental Procedure

Rohitha; Kulkarni; Narender

Synthetic Communications, 2013 , vol. 43, # 21 p. 2853 - 2866 Title/Abstract

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General Procedure for Oxidation of p-Xylene

The liquid-phase oxidation of p-xylene was carried out over metallomacrocycle encapsulated in MCM-41. In a typical reaction, 0.1 g of dried catalyst was added to the stirred solution of p-xylene (2 mmol) in acetic acid (6 ml), followed by 8 mmol of 30percent H2O2 (dropwise). Then reaction mixture was allowed to stir in the temperaturerange of 30-100°C. The reaction was monitored by thin-layer chromatography (TLC). After completion of the reaction, the catalyst was filtered and washed with ethyl acetate. The combined filtrates were washed with saturated sodium bicarbonate solution. The organic extract was dried over anhydrous sodium sulfate and solvent was evaporated under reduced pressure. The products were quantified by gas chromatography, verified by GC-MS and purified by column chromatography over silica gel (finer than 200 mesh). All the products are characterized by 1HNMR, 13C NMR,and mass spectroscopy.

With oxygen in acetonitrile

T=24.84°C; P=760.051 Torr; IrradiationGreen chemistry; Reagent/catalyst;

Tsukamoto, Daijiro; Shiraishi, Yasuhiro; Hirai, Takayuki

Catalysis Science and Technology, 2013 , vol. 3, # 9 p. 2270 - 2277 Title/Abstract

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With N -hydroxyphthalimide; oxygen; cobalt(II) diacetate tetrahydrate; acetic acid

T=20°C; 3 h; Kinetics;

Gaster, Eden; Kozuch, Sebastian; Pappo, Doron

Angewandte Chemie - International Edition, 2017 , vol. 56, # 21 p. 5912 - 5915 Angew. Chem., 2017 , vol. 129, p. 6006 - 6009,4 Title/Abstract

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3

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100%

With phosphate-buffered silica gel supported KMnO4 in cyclohexane

T=65°C;

Takemoto; Yasuda; Ley

Synlett, 2001 , # 10 p. 1555 - 1556 Title/Abstract

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100%

With periodic acid; PFC in acetonitrile

T=0°C; 1.5 h;

Hunsen, Mo

Journal of Fluorine Chemistry, 2005 , vol. 126, # 9-10 p. 1356 - 1360 Title/Abstract

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100%

With [Cu2C6H4(CHNCH2CH2N(CH2C5H4N)2)2](2+)*2ClO4(1)=C H Cu N (ClO )2; oxygen in acetone

36 38 2 8 4

Garcia-Bosch, Isaac; Company, Anna; Cardellach, Mar; Costas, Miquel; Frisch, Jonathan R.; Que Jr., Lawrence; Torrent-Sucarrat, Miquel; Gamba, Ilaria; Casella, Luigi; Gueell, Mireia; Luis, Josep M.

Angewandte Chemie, International Edition, 2010 , vol. 49, # 13 p. 2406 - 2409 Angewandte Chemie, 2010 , vol. 122, # 13 p. 2456 - 2459 Title/Abstract

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T=-90.16°C;

Hide Details

99%

With periodic acid; pyridinium chlorochromate in acetonitrile

1.5 h;

Hunsen, Mo

Synthesis, 2005 , # 15 art. no. M00905SS, p. 2487 - 2490 Title/Abstract

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99%

With tert.-butylhydroperoxide; di-tert-butyl peroxide; silica-supported selenamide in water; tert-butyl alcohol

T=75°C; 7 h;

Giurg; Brzaszcz; Mlochowski

Polish Journal of Chemistry, 2006 , vol. 80, # 3 p. 417 - 428 Title/Abstract Full Text View citing articles Show Details

99%

With 2-mesityl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate; 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine in acetonitrile

T=20°C;

Zhao, Junfeng; Mueck-Lichtenfeld, Christian; Studer, Armido

Advanced Synthesis and Catalysis, 2013 , vol. 355, # 6 p. 1098 - 1106 Title/Abstract

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99%

With tert.-butylhydroperoxide; iron oxide; ethyl acetoacetate in decane

T=75 - 80°C; 24 h; Green chemistry; Reagent/catalyst; Hide Experimental Procedure

Villano, Rosaria; Acocella, Maria Rosaria; Scettri, Arrigo

Tetrahedron Letters, 2014 , vol. 55, # 15 p. 2442 - 2445 Title/Abstract

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Typical procedure for the oxidation of aldehydes to carboxylic acids

General procedure: To a vial with the catalyst (20 mol percent) under air, aldehyde (0.0625 mmol) and ethyl acetoacetate (1 equiv) were added. The mixture was heated at 75–80 °C for 24 h. After cooling at rt, ethyl acetate (1.0 ml) was added and the catalyst was separated by simple magnetic decantation. Then, the combined solvent was removed in vacuo and the mixture was purified via trituration or flash column. Spectroscopic data of products 2 were consistent with those reported in the literature (2a,14 2b,15 2c,16 2d,14 2e,17 2f,14 2h,18 2i,19 2j20 and 2k21). 4-Methylbenzoic acid (2d): 6.0 mg, 71percent yield. 1H NMR (400 MHz, CDCl3) δ 7.99 (d, 2H, J = 8.0 Hz), 7.27 (d, 2H, J = 8.0 Hz), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 172.3, 144.7, 130.3, 129.2, 126.5, 21.8.

99%

With C4H11FeMo6NO24(3-)*3C16H36N(1+); water; oxygen; sodium carbonate

T=50°C; P=760.051 Torr; 8 h; Green chemistry;

Yu, Han; Ru, Shi; Dai, Guoyong; Zhai, Yongyan; Lin, Hualin; Han, Sheng; Wei, Yongge

Angewandte Chemie - International Edition, 2017 , vol. 56, # 14 p. 3867 - 3871 Angew. Chem., 2017 , vol. 129, # 14 p. 3925 - 3929,5 Title/Abstract

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97%

With Oxonereg; in N,N-dimethyl-formamide

T=20°C; 3 h;

Travis, Benjamin R.; Sivakumar, Meenakshi; Hollist, G. Olatunji; Borhan, Babak

Organic Letters, 2003 , vol. 5, # 7 p. 1031 - 1034 Title/Abstract

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97%

With sodium hydroxide in water

T=20 - 75°C; 18 h; Catalytic behavior; Hide Experimental Procedure

Saadati, Fariba; Khani, Neda; Rahmani, Mohammad; Piri, Farideh

Catalysis Communications, 2016 , vol. 79, p. 26 - 30 Title/Abstract

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2.4. Oxidation of aldehydes catalyzed by CuO(at)HPS

General procedure: In a two-necked round bottom flask equipped with a condenser, the aldehyde (1 mmol), was dropped into the mixture of catalyst (4 molpercent) and NaOH (1.5 mmol) in deionized water (3 mL). The resulting mixture was stirred at room temperature under air atmosphere for 15 min and then the temperature reached 75 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was filtered off and the catalyst rinsed with deionized water and ethanol. The filtrate was treated with H2SO4 (30 wt.percent). The precipitated carboxylic acid was filtered, washed with water and dried in vacuum. (For liquid products after addition of H2SO4, the product was extracted using diethyl ether (4 × 5 mL).

96%

With aluminum oxide; oxone; water

0.15 h; microwave irradiation;

Alavi Nikje, Mir M.; Bigdeli, Mohammad A.

Phosphorus, Sulfur and Silicon and the Related Elements, 2004 , vol. 179, # 7 p. 1445 - 1448 Title/Abstract

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95%

With tert.-butylhydroperoxide; potassium tert-butylate in water

T=60°C; 5 h; Hide Experimental Procedure

Shaikh, Tanveer Mahammadali; Hong, Fung-E

Tetrahedron, 2013 , vol. 69, # 42 p. 8929 - 8935 Title/Abstract

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4.1.1 Typical experimental procedure for oxidation of aldehydes to carboxylic acids (2a–q)

General procedure: In a 25mL round-bottom flask, t-BuOK (0.5mmol) was dissolved in water (1mL), and an aldehyde (0.5mmol) was added. Subsequently, aq 70percent TBHP (1mmol) was slowly added to this flask. The resulting slurry was stirred at 60°C or (optional) 25°C for 5h or 40h. After completion of reaction this slurry was cooled to room temperature. The slurry was then acidified with 2M hydrochloric acid until the aqueous layer was strongly acidic by pH paper. This on simple filtration resulted in pure carboxylic acids.

92%

With sodium perborate in acetic acid

T=45 - 50°C;

McKillop, Alexander; Kemp, Duncan

Tetrahedron, 1989 , vol. 45, # 11 p. 3299 - 3306 Title/Abstract

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92%

With potassium permanganate in ethanol; water

T=80°C; 4 h;

Shojaei, Abdollah Fallah; Rezvani, Mohamad Ali; Heravi, Majid

Journal of the Serbian Chemical Society, 2011 , vol. 76, # 11 p. 1513 - 1522 Title/Abstract

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91%

With potassium hydroxide; sodium tetrahydroborate; air; palladium on activated charcoal in methanol

T=20°C; 1.5 h;

Lim, Minkyung; Yoon, Cheol Min; An, Gwangil; Rhee, Hakjune

Tetrahedron Letters, 2007 , vol. 48, # 22 p. 3835 - 3839 Title/Abstract

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91%

Stage #1: With tin(II) oxide; dihydrogen peroxide in water; acetonitrile

T=60°C; 0.833333 h; Stage #2: With hydrogenchloride in water

pH=2.0;

Dehbashi, Mohsen; Aliahmad, Mousa; Shafiee, Mohammad Reza Mohammad; Ghashang, Majid

Phosphorus, Sulfur and Silicon and the Related Elements, 2013 , vol. 188, # 7 p. 864 - 872 Title/Abstract

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90%

With (bipyH2)-CrOCl5 in dichloromethane

T=28 - 30°C; 3 h; oxidation with further chromium reagents;

Chakraborty, T.K.; Chandrasekaran, S.

Synthetic Communications, 1980 , vol. 10, # 12 p. 951 - 956 Title/Abstract

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90%

With dihydrogen peroxide; benzeneseleninic acid in tetrahydrofuran

20 h; Heating;

Choi, Joong-Kwon; Chang, Young-Kil; Hong, Sung Yeap

Tetrahedron Letters, 1988 , vol. 29, # 16 p. 1967 - 1970 Title/Abstract

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89%

With polysterene-bound phenylseleninic acid; dihydrogen peroxide in tetrahydrofuran

24 h; Heating;

Qian, Hao; Shao, Li-Xiong; Huang, Xian

Journal of Chemical Research - Part S, 2002 , # 10 p. 514 - 515 Title/Abstract

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88%

With aluminium trichloride; silver bromate in acetonitrile

0.5 h; Heating;

Firouzabadi, Habib; Mohammadpoor-Baltork, Iraj

Bulletin of the Chemical Society of Japan, 1995 , vol. 68, # 8 p. 2319 - 2326 Title/Abstract

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88%

With selenium(IV) oxide; dihydrogen peroxide in tetrahydrofuran

7 h; Heating;

Brzaszcz; Kloc; Maposah; Mlochowski

Synthetic Communications, 2000 , vol. 30, # 24 p. 4425 - 4434 Title/Abstract

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88%

With tert.-butylhydroperoxide in water

T=97°C; 2 h;

Choudhary, Vasant R.; Dumbre, Deepa K.; Narkhede, Vijay S.

Journal of Chemical Sciences, 2012 , vol. 124, # 4 p. 835 - 839 Title/Abstract

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86%

With [Ni(cdacacen)]; dihydrogen peroxide in water; acetonitrile

T=60°C; 2 h;

Esfandiari, Hadi; Jameh-Bozorghi, Saeed; Esmaielzadeh, Sheida; Shafiee, Mohammad Reza Mohammad; Ghashang, Majid

Research on Chemical Intermediates, 2013 , vol. 39, # 7 p. 3319 - 3325 Title/Abstract

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85%

With urea-hydrogen peroxide in formic acid

T=20°C; 2.5 h;

Balicki

Synthetic Communications, 2001 , vol. 31, # 14 p. 2195 - 2198 Title/Abstract

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85%

With dihydrogen peroxide; toluene-4-sulfonic acid; captisol® in water

T=50°C; 15 h; Hide Experimental Procedure

Jeong, Se Young; Kim, Nagyeong; Lee, Jong Chan

Bulletin of the Korean Chemical Society, 2014 , vol. 35, # 11 p. 3366 - 3368 Title/Abstract

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General Procedure.

General procedure: To a solution of 30percent hydrogen peroxide(5.0 mmol) was added aldehyde (1.0 mmol), PTSA(1.0 mmol) and β-cyclodextrin (0.1 mmol). The reactionmixture was stirred for 15 h at 50 oC. After cooling to roomtemperature, the reaction mixture was dissolved in the solutionof 10percent aqueous sodium bicarbonate, extracted intodiethyl ether (2 × 25 mL), and washed with water. The aqueouslayer was acidified to pH 3 with 2 M hydrochloric acid.The product was extracted with dichloromethane (2 × 25mL) and dried over magnesium sulfate. Evaporation of organiclayer under reduced pressure gave the desired carboxylicacid.

85%

With diphenyl diselenide; dihydrogen peroxide in water

T=20°C; 6 h; Green chemistry; Hide Experimental Procedure

Sancineto, Luca; Tidei, Caterina; Bagnoli, Luana; Marini, Francesca; Lenardo, Eder J.; Santi, Claudio

Molecules, 2015 , vol. 20, # 6 p. 10496 - 10510 Title/Abstract

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3.2. General Procedure for the Synthesis of Carboxylic Acids 2

General procedure: Diphenyl diselenide (3, 0.006 g; 0.02 mmol) was treated with H2O2 (30percent·w/w, 0.1 mL, 1 mmol) andwater (0.2 mL) and stirred at room temperature at 800 rpm until the discoloration of the reaction mixture;then, the aldehyde 1 (1 mmol) was added. After 6 h, the aqueous mixture was extracted three times withEtOAc (3 × 20 mL). The collected organic layers were dried over Na2SO4 and the solvent evaporatedunder reduced pressure.

82%

With sodium chlorite in dichloromethane; acetic acid

Bayle, J. P.; Perez, F.; Courtieu, J.

Bulletin de la Societe Chimique de France, 1990 , # 4 p. 565 - 567 Title/Abstract

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82%

With oxygen; sodium hydride; 1-butyl-3-methylimidazolium chloride in tetrahydrofuran; mineral oil

T=20°C; P=760.051 Torr; 8 h;

Kim, Sun Min; Kim, Young Sug; Yang, Jung Woon

Bulletin of the Korean Chemical Society, 2011 , vol. 32, # 8 p. 2529 - 2530 Title/Abstract

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82%

With oxygen

T=120°C; 5 h; Neat (no solvent);

Choudhary, Vasant R.; Dumbre, Deepa K.

Catalysis Communications, 2011 , vol. 13, # 1 p. 82 - 86 Title/Abstract

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80%

With sodium bromate; sodium hydrogen sulfate in acetonitrile

15 h; Heating;

Shirini, Farhad; Ali Zolfigol, Mohammad; Torabi, Shayesteh

Synthetic Communications, 2006 , vol. 36, # 19 p. 2833 - 2840 Title/Abstract

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80%

With 1,4-diaza-bicyclo[2.2.2]octane; oxygen; copper(II) 2-ethylhexanoate; vanadyl acetylacetonate

T=95°C; P=760.051 Torr; 12 h;

Jiang, Nan; Ragauskas, Arthur J.

Journal of Organic Chemistry, 2007 , vol. 72, # 18 p. 7030 - 7033 Title/Abstract

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77%

With dihydrogen peroxide; 7-(trifluoromethyl)-1,10-ethyleneisoalloxazinium chloride in water; acetonitrile

T=85°C; 18 h;

Murray, Alexander T.; Matton, Pascal; Fairhurst, Nathan W. G.; John, Matthew P.; Carbery, David R.

Organic Letters, 2012 , vol. 14, # 14 p. 3656 - 3659 Title/Abstract

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76%

With tetraethylammonium bromide in N,N-dimethyl-formamide

T=20°C; Oxidation;

Singh, Sundaram; Singh, Krishna Nand

Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1997 , vol. 36, # 9 p. 805 - 807 Title/Abstract

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75%

With oxygen; acetic anhydride; butyraldehyde; cobalt(II) chloride in acetonitrile

Ambient temperature;

Punniyamurthy; Kalra, Swinder Jeet Singh; Iqbal, Javed

Tetrahedron Letters, 1994 , vol. 35, # 18 p. 2959 - 2960 Title/Abstract

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75%

With N-hydroxy-o-benzenedisulphonimide in acetic acid; acetonitrile

T=60°C; 4.5 h;

Barbero, Margherita; Degani, Lacopo; Fochi, Rita; Perracino, Paolo

Journal of Organic Chemistry, 1996 , vol. 61, # 25 p. 8762 - 8764 Title/Abstract

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74%

With oxygen

Oxidation; 0.133333 h; microwave irradiation;

Sahadeva Reddy; Pratap Reddy; Reddy

Synthetic Communications, 1999 , vol. 29, # 17 p. 2949 - 2951 Title/Abstract

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74%

With air; octadecafluorodecahydronaphthalene

Liu, Chao; Shen, Dong-Mei; Chen, Qing-Yun

(cis+trans); isobutyraldehyde; [Co{TPP(C8F17)4}] in acetonitrile

P=760 Torr; 10 h;

European Journal of Organic Chemistry, 2006 , # 12 p. 2703 - 2706 Title/Abstract

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68%

With dihydrogen peroxide in acetonitrile

T=20 - 90°C; 10 h; Green chemistry; Reagent/catalystSolvent;

Kashyap, Rajarshi; Talukdar, Dhruba Joyti; Pratihar, Sanjay

New Journal of Chemistry, 2015 , vol. 39, # 2 p. 1430 - 1437 Title/Abstract

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63%

With oxygen; nickel(II) acetylacetonate in various solvent(s) T=60°C; Oxidation; 12 h;

Howarth

Tetrahedron Letters, 2000 , vol. 41, # 34 p. 6627 - 6629 Title/Abstract

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62%

With oxygen; acetic anhydride; CoCl2 in 1,2-dichloro-ethane

T=25°C;

Bhatia, Beena; Iqbal, Javed

Tetrahedron Letters, 1992 , vol. 33, # 51 p. 7961 - 7964 Title/Abstract

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62%

With oxygen; acetic anhydride; cobalt(II) chloride in 1,2-dichloro-ethane

T=25°C; 20 h;

Bhatia, Beena; Punniyamurthy, T.; Iqbal, Javed

Journal of Organic Chemistry, 1993 , vol. 58, # 20 p. 5518 - 5523 Title/Abstract

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62%

With carbon dioxide; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,3-bis(2,4,6trimethylphenyl)-4,5-dihydroimidazolium chloride in tetrahydrofuran

T=20°C; 0.25 h;

Nair, Vijay; Varghese, Vimal; Paul, Rony Rajan; Jose, Anu; Sinu; Menon, Rajeev S.

Organic Letters, 2010 , vol. 12, # 11 p. 2653 - 2655 Title/Abstract

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58%

With dihydrogen peroxide in acetic acid

T=90°C; 7 h;

Yang, Xiaomei; Tang, Si; Lu, Tianliang; Chen, Chen; Zhou, Lipeng; Su, Yunlai; Xu, Jie

Synthetic Communications, 2013 , vol. 43, # 7 p. 979 - 985 Title/Abstract

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57%

With dihydrogen peroxide; methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate

T=90°C; 1.5 h;

Venturello, Carlo; Gambaro, Mario

Journal of Organic Chemistry, 1991 , vol. 56, # 20 p. 5924 - 5931 Title/Abstract

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43%

With barium manganate in dichloromethane

13 h; Ambient temperature;

Srivastava, R.G.; Venkataramani, P.S.

Synthetic Communications, 1988 , vol. 18, # l6-17 p. 2193 - 2200 Title/Abstract

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41%

With dihydrogen peroxide; [Me(n-C8H17)3N]HSO4 in water

T=90°C; Oxidation; 3 h;

Sato, Kazuhiko; Hyodo, Mamoru; Takagi, Junko; Aoki, Masao; Noyori, Ryoji

Tetrahedron Letters, 2000 , vol. 41, # 9 p. 1439 - 1442 Title/Abstract

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41.3%

With 1,3-dinitrobenzene; sodium hydroxide in water

T=100°C; 2.5 h; Sealed tube;

Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco

Organic Process Research and Development, 2001 , vol. 5, # 2 p. 136 - 140 Title/Abstract

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39 % Turnov.

With ammonium cerium(IV) nitrate; sodium dodecyl-sulfate in cyclohexane; water

Skrzewski; Cichacz

Bulletin of the Chemical Society of Japan, 1984 , vol. 57, # 1 p. 271 - 274 Title/Abstract

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T=25°C; 1 h; var. catalyst conc.; Product distribution;

With perchloric acid; pyridinium chlorochromate in acetic acid

T=29.9 - 59.9°C; E(a), ΔH(excit.), ΔS(excit.), ΔG(excit.); Thermodynamic data;

Pillay, M Krishna; Jameel, A Abdul

Indian Journal of Chemistry, Section A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical Chemistry, 1992 , vol. 31, # 1.2 p. 46 - 48 Title/Abstract

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With perchloric acid; N-bromobenzamide; water in acetic acid

T=19.9°C; ΔH*, ΔS*, other temp.; Thermodynamic dataKineticsRate constant;

Banerji, Kalyan K.

Journal of Organic Chemistry, 1986 , vol. 51, # 25 p. 4764 - 4767 Title/Abstract

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With potassium sulfate; potassium hydrogensulfate; disodium hydrogenphosphate; sodium dihydrogenphosphate; oxone in water; acetonitrile

T=29.9°C; pH = 6; Rate constantMechanism;

Naseeruddin, Ahmad; Swamy, A. S. R.; Jagannadham, V.

Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1987 , vol. 26, # 5 p. 427 - 429 Title/Abstract

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With perchloric acid; mercury(II) diacetate; N-bromoacetamide in acetic acid

Gupta, Anita; Mathur, Sandhya; Banerji, Kalyan K.

T=24.9°C; other temperatures, ΔG(excit.), ΔH(excit.), ΔS(excit.); KineticsMechanismThermodynamic data;

Journal of Chemical Research, Miniprint, 1988 , # 1 p. 201 - 223 Title/Abstract

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With perchloric acid; PFC in water; acetic acid

T=34.9°C; Rate constant;

Ramakrishnan, P. S.; Chockalingam, P.

Journal of the Indian Chemical Society, 1993 , vol. 70, # 6 p. 581 - 582 Title/Abstract

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With potassium hydroxide; potassium metaperiodate; diperiodato cuprate(III) in water; tert-butyl alcohol

T=26.9°C; E(excit.), ΔG(excit.), ΔS(excit.), other temperatures; KineticsMechanismThermodynamic data;

Bal Reddy, K.; Sethuram, B.; Navaneeth Rao, T.

Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1984 , vol. 23, # 7 p. 593 - 595 Title/Abstract

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With potassium bromate; perchloric acid; ruthenium(III) in water

T=50°C; ΔEa, ΔH(excit.), ΔS(excit.); further solvent: AcOH:H2O (10-30percent); further temperatures: 60, 70 deg C; Thermodynamic dataKineticsMechanism;

Radhakrishnamurti, P. S.; Sarangi, L. D.

Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1980 , vol. 19, # 11 p. 1124 - 1126 Title/Abstract

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With perchloric acid; trichloroisocyanuric acid in acetic acid

T=35°C; Rate constant;

Pati, Subas C.; Sahu, Ashok Kumar; Sriramulu, Y.

Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1987 , vol. 26, # 8 p. 693 - 695 Title/Abstract

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in water

T=25°C; xanthine oxidase; also in aerosol OT/isooctane and cationic and nonionic micellar systems; Rate constant;

Bommarius, Andreas S.; Hatten, T. Alan; Wang, Daniel I. C.

Journal of the American Chemical Society, 1995 , vol. 117, # 16 p. 4515 - 4523 Title/Abstract

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With perchloric acid; bis(2,2'-bipyridyl) copper(II) permanganate in water; acetic acid

T=14.9°C; other temperatures; ΔH, ΔS, ΔG; kinetics and mechanism of the oxidation of monosubstituted benzaldehydes by bis(2,2'-bipyridyl)copper(II) permanganate (BBCP); formation and decomposition of benzaldehyde-BBCP complexes; Rate constantKineticsThermodynamic data;

Mohnot, Kavita; Sharma, Pradeep K.; Banerji, Kalyan K.

Journal of Organic Chemistry, 1996 , vol. 61, # 4 p. 1310 - 1314 Title/Abstract

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With tert-butylhypochlorite; acetic acid

Ginsburg

Journal of the American Chemical Society, 1951 , vol. 73, p. 702 Full Text View citing articles Show Details

With iodine

Irradiation;

Mascarelli; Russi

Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1910 , vol. <5> 19 II, p. 241 Gazzetta Chimica Italiana, 1912 , vol. 42 I, p. 94 Full Text View citing articles Show Details

With potassium permanganate; Aliquatreg; 336 in water; benzene

0.25 h; Ambient temperature;

Hanumantha Rao; Bhagawanth Rao

Journal of the Indian Chemical Society, 1991 , vol. 68, # 3 p. 132 - 134 Title/Abstract

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With rat hepatic microsomal aldehyde dehydrogenase; NAD in phosphate buffer; N,N-dimethyl-formamide

T=37°C; Dehydrogenation; pH=7.4; Enzyme kinetics;

Martini, Robert; Murray, Michael

Chemical Research in Toxicology, 1996 , vol. 9, # 1 p. 268 - 276 Title/Abstract

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With ((2,2'-(ethane-1,2diylbis[(nitrilo-.kappa.N)methylidyne])bis(phenolato-.kappa.O))(2))oxomanganese(1+) hexafluorophosphate in acetonitrile

T=14.85°C; Oxidation; Kinetics; Further Variations:CatalystsTemperatures;

Bansal, Varsha; Sharma, Pradeep K.; Banerji, Kalyan K.

Journal of Chemical Research, Miniprint, 1999 , # 8 p. 2052 - 2074 Title/Abstract

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With acetic acid; QCC in water

T=29.85°C; Oxidation; Kinetics; Further Variations:Temperatures;

Jameel, A. Abdul

Journal of the Indian Chemical Society, 1998 , vol. 75, # 8 p. 439 - 442 Title/Abstract

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With HABR in water; acetic acid

T=14.85 - 44.85°C; Oxidation; pH=2.04; Kinetics;

Gangwani; Sharma; Banerji

International Journal of Chemical Kinetics, 2000 , vol. 32, # 10 p. 615 - 622 Title/Abstract

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With pyridinium hydrobromide perbromide in water; acetic acid

T=44.85°C; Activation energyKineticsThermodynamic data; Further Variations:Temperatures;

Aneja, Meenakshi; Kothari, Seema; Banerji, Kalyan K.

Journal of Physical Organic Chemistry, 2001 , vol. 14, # 9 p. 650 - 656 Title/Abstract

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With benzyltrimethylammonium tribromide; potassium bromide in water; acetic acid

T=44.85°C; 10 h; Kinetics; Further Variations:Temperatures;

Mehla, Satish K.; Kothari, Seema; Banerji, Kalyan K.

Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2002 , vol. 41, # 4 p. 832 - 838 Title/Abstract

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With perchloric acid; nicotinium dichromate in water; acetic acid

T=26.85°C; 24 h; Kinetics; Further Variations:Temperatures;

Sekar

Journal of Chemical Research - Part S, 2002 , # 12 p. 626 - 627 Title/Abstract

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With sodium chlorite; 2-methyl-but-2-ene; acetic acid in DME; water

T=20°C; 16 h;

Deady, Leslie W.; Devine, Shane M.; Rogers, Michael L.

Organic Preparations and Procedures International, 2003 , vol. 35, # 6 p. 627 - 630 Title/Abstract

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With sulfuric acid; quinolinium dichromate(VI) in acetic acid

T=29.85°C; KineticsThermodynamic data; Further Variations:Temperatures;

Medien, Hesham A. A.

Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2003 , vol. 58, # 12 p. 1201 - 1205 Title/Abstract

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With NaBO3; acetic acid in water

T=49.85°C; Kinetics; Further Variations:Temperatures;

Medien

Polish Journal of Chemistry, 2004 , vol. 78, # 3 p. 437 - 445 Title/Abstract

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With N-chloro-succinimide; perchloric acid; acetic acid; sodium chloride

T=34.85°C; 36 h; Kinetics; Further Variations:Temperatures;

Mathiyalagan; Sridharan

Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, 2005 , vol. 44, # 10 p. 2044 - 2047 Title/Abstract

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With potassium hydroxide; dihydrogen peroxide in methanol; water

Heating;

Cong, Zhi-Qi; Wang, Chun-Ian; Chen, Tie; Yin, Bing-Zhu

Synthetic Communications, 2006 , vol. 36, # 5 p. 679 - 683 Title/Abstract

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With benzyltrimethylammonium chlorobromate in water; acetic acid

T=24.84°C; Oxidation; pH=2.04; KineticsThermodynamic data; Further Variations:Temperatures;

Raju, V. Sitarama; Sharma, Pradeep K.; Banerji, Kalyan K.

Journal of Organic Chemistry, 2000 , vol. 65, # 11 p. 3322 - 3325 Title/Abstract

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42 %Chromat.

With dihydrogen peroxide; Nafion NR50 in water

T=90°C; 2 h; Hide Experimental Procedure

Sato, Kazuhiko; Usui, Yoko

Patent: US2006/167311 A1, 2006 ; Location in patent: Page/Page column 4 ; Title/Abstract

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8:

Example 8; Nafion NR50 (500 mg), 30percent aqueous hydrogen peroxide solution (1.3 mL, 11 mmol), and p-tolualdehyde (1.6 mL, 10 mmol) were mixed and stirred at 90° C. for 2 hours. After the reaction solution was cooled to room temperature, the yield of p-toluic acid by measurement of GLC was 42percent.

100 % Turnov.

With tert.-butylhydroperoxide in tert-butyl alcohol

T=80°C; 72 h;

Wojtowicz, Halina; Soroko, Grazyna; Mlochowski, Jacek

Synthetic Communications, 2008 , vol. 38, # 12 p. 2000 - 2010 Title/Abstract

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With tetra-N-butylammonium tribromide; acetic acid

T=14.84°C; Kinetics; Further Variations:Temperatures;

Chouhan; Sharma, Monica; Sharma, Vinita

Journal of the Indian Chemical Society, 2007 , vol. 84, # 6 p. 582 - 587 Title/Abstract

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With BPCC in dimethyl sulfoxide

T=24.84°C; Kinetics; Temperature;

Sharma, Pradeep K.

Journal of the Indian Chemical Society, 2008 , vol. 85, # 12 p. 1281 - 1288 Title/Abstract

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With MCC in dimethyl sulfoxide

T=44.84°C; Kinetics; Temperature;

Choudhary, Anurag; Malani; Agarwal; Sharma; Sharma, Vinita

Journal of the Indian Chemical Society, 2009 , vol. 86, # 9 p. 927 - 935 Title/Abstract

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With O2CrClO(1-)*NEt4(1+) in dimethyl sulfoxide

T=24.84°C; Kinetics; Temperature;

Gehlot; Prasadrao; Sharma

Asian Journal of Chemistry, 2011 , vol. 23, # 3 p. 1173 - 1178 Title/Abstract

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With methanol; dihydrogen peroxide in water

T=20°C;

Shokrolahi, Arash; Zali, Abbas; Keshavarz, Mohammad Hossein

Chinese Journal of Catalysis, 2010 , vol. 31, # 11-12 p. 1427 - 1432 Title/Abstract

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With bis(tetrabutylammonium) hexatungstate; dihydrogen peroxide in neat (no solvent) 0.0666667 - 0.0833333 h; Microwave irradiationGreen chemistry;

Bamoharram, Fatemeh F.; Heravi, Majid M.; Omidinia, Raheleh; Tavakoli-Hoseini, Niloofar

Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2013 , vol. 43, # 2 p. 125 - 130 Title/Abstract

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With bis(tetrabutylammonium) hexatungstate; dihydrogen peroxide in water; acetonitrile

6 h; RefluxGreen chemistry; TemperatureTimeConcentration;

Bamoharram, Fatemeh F.; Heravi, Majid M.; Omidinia, Raheleh; Tavakoli-Hoseini, Niloofar

Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2013 , vol. 43, # 2 p. 125 - 130 Title/Abstract

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Multi-step reaction with 2 steps 1.1: aluminium; potassium hydoxide / methanol / 1 h / 0 °C / |Inert atmosphere 2.1: sodium t-butanolate; oxygen / tetrahydrofuran / 5 h / 20 °C / 760.05 Torr 2.2: pH 1 View Scheme

Kim, Sun Min; Kim, Dong Wan; Yang, Jung Woon

Organic Letters, 2014 , vol. 16, # 11 p. 2876 - 2879 Title/Abstract

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With potassium permanganate in water; acetonitrile

Pratihar, Sanjay

Organic and Biomolecular Chemistry, 2014 , vol. 12, # 30 p. 5781 - 5788 Title/Abstract

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4

Stage #1: With [Ag(py)2MnO4]; acetic acid in water

T=24.84°C; 10 h; Darkness; Stage #2: With hydrogenchloride

Kinetics; Temperature;

Purohit, Trupti; Banerji, Jayshree; Kotai, Laszlo; Sajo; Banerji; Sharma, Pradeep K.

Journal of the Indian Chemical Society, 2012 , vol. 89, # 8 p. 1045 - 1052 Title/Abstract

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95 %Chromat.

With water; copper dichloride

T=250°C; P=30003 Torr; 6 h; Sealed tubeGreen chemistry;

Yang, Ziming; Hartnett, Hilairy E.; Shock, Everett L.; Gould, Ian R.

Journal of Organic Chemistry, 2015 , vol. 80, # 24 p. 12159 - 12165 Title/Abstract

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With oxygen

T=100°C; P=26252.6 Torr; 6 h; Autoclave;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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70 %Spectr.

With C59H45BFeN6O3; oxygen in benzene

T=20°C; 0.333333 h;

Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K.

Chemistry - A European Journal, 2017 , vol. 23, # 16 p. 3815 - 3818 Title/Abstract

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97%

With copper(II) nitrate trihydrate; oxygen in acetonitrile

T=120°C; P=4500.45 Torr; 10 h; Autoclave; Hide Experimental Procedure

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Rx-ID: 719041 Find similar reactions

Liu, Huifang; Wang, Min; Li, Hongji; Luo, Nengchao; Xu, Shutao; Wang, Feng

Journal of Catalysis, 2017 , vol. 346, p. 170 - 179 Title/Abstract

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2.2.1. The oxidation of acetophenone and substituted aryl ketones

General procedure: The catalytic reactions were performed in a 15-mL autoclavereactor with an internal Teflon insert. Typically, 0.5 mmol ofketone, 0.1 mmol of copper salt and 2 mL of solvent were addedinto the reactor. Then, the reactor was charged with 0.6 MPa O2and heated to 120 °C under magnetic stirring. After cooling to theroom temperature, the reaction mixture was diluted with 4 mLmethanol before analysis. The products were identified and quantifiedusing gas chromatography-mass spectrometry (GC–MS) andan Agilent 7890A/5975C instrument equipped with an HP-5 MScolumn (30 m in length, 0.25 mm in diameter). p-Xylene was usedas the internal standard.

96%

With sodium hydroxide; sodium bromite; sodium bromide in water

6 h; Ambient temperature;

Kajigaeshi, Shoji; Nakagawa, Takashi; Nagasaki, Noritaka; Fujisaki, Shizuo

Synthesis, 1985 , # 6/7 p. 674 - 675 Title/Abstract

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93%

With copper(l) iodide; hydroxylamine hydrochloride; oxygen in dimethyl sulfoxide

T=100°C; 8 h;

Sathyanarayana, Pochampalli; Ravi, Owk; Muktapuram, Prathap Reddy; Bathula, Surendar Reddy

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 37 p. 9681 - 9685 Title/Abstract

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93%

With phen; oxygen; copper diacetate; potassium hydoxide in dimethyl sulfoxide

T=130°C; P=3000.3 Torr; 12 h; Autoclave; Hide Experimental Procedure

Wang, Min; Lu, Jianmin; Li, Lihua; Li, Hongji; Liu, Huifang; Wang, Feng

Journal of Catalysis, 2017 , vol. 348, p. 160 - 167 Title/Abstract

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2.2. Catalytic tests

General procedure: The catalytic reactions were performed in a 10-mL autoclave reactor with an internal Teflon insert. Typically, 0.5 mmol of secondary alcohols, 0.04 mmol of Cu(OAc)2 and 0.04 mmol of ligand, 1 mmol of base, and 2 mL of solvent were added to the reactor.Then, the reactor was charged with 0.4 MPa O2 and heated to the desired temperature under magnetic stirring. When the reaction reached completion, the reaction mixture was diluted with 4 mL of methanol, and the catalyst was separated via centrifugation.The acid product was esterified with addition of 40 μl of BF3OEt2 at 100 °C for 6 h in Ar atmosphere. In reaction condition optimization experiment, the products were identified and quantified using gas chromatography-mass spectrometry (GC–MS) and an Agilent7890A/5975C instrument equipped with an HP-5 MS column (30 m in length, 0.25 mm in diameter). p-Xylene was used as the internal standard. In the substrate scope experiment, the product was isolated and identified by NMR. The procedure for the isolation of the product is as follows: after the reaction completed, the reactor was cooled to room temperature in water and vented the gas.The reaction mixture was acidified with HCl 1.0 M (pH 1–2,15 mL) and then extracted with Et2O (3 x 20 mL). Next, the combined organic layers were washed with HCl 1.0 M (pH 1–2,3 10 mL), dried over anhydrous Na2SO4, and filtered and the Et2O was rotary evaporated. Solid products obtained were vacuum dried for 10 h at 60 °C. 83%

Stage #1: With tert.-butylhydroperoxide; sodium hydroxide; tungsten(VI) oxide in water

T=80°C; 8 h; Stage #2: With hydrogenchloride in water

Shaikh, Tanveer Mahammad Ali; Sudalai, Arumugam

European Journal of Organic Chemistry, 2008 , # 29 p. 4877 - 4880 Title/Abstract

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82%

With oxygen; manganese (II) acetate tetrahydrate in acetic acid

T=100°C; P=760.051 Torr; 15 h;

Nakamura, Ryota; Obora, Yasushi; Ishii, Yasutaka

Advanced Synthesis and Catalysis, 2009 , vol. 351, # 10 p. 1677 - 1684 Title/Abstract

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61%

With potassium hydroxide in N,N-dimethyl-formamide

T=65 - 68°C; alkaline cleavage; 12 h;

Zabjek, Alenka; Petric, Andrej

Tetrahedron Letters, 1999 , vol. 40, # 33 p. 6077 - 6078 Title/Abstract

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60%

With tert.-butylhydroperoxide; rhenium(VII) oxide; acetic acid

T=100°C; 4 h;

Gurunath; Sudalai

Synlett, 1999 , # 5 p. 559 - 560 Title/Abstract

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55%

With hydroxylamine hydrochloride; iodine in dimethyl sulfoxide

T=100°C; 10 h;

Sathyanarayana, Pochampalli; Upare, Atul; Ravi, Owk; Muktapuram, Prathap Reddy; Bathula, Surendar Reddy

RSC Advances, 2016 , vol. 6, # 27 p. 22749 - 22753 Title/Abstract

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15%

With Ambelyst 15 in toluene

30 h; Reflux;

Kumar, Amit; Dixit, Manish; Singh, Salil P.; Raghunandan, Resmi; Maulik, Prakas R.; Goel, Atul

Tetrahedron Letters, 2009 , vol. 50, # 30 p. 4335 - 4339 Title/Abstract

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With sodium hydroxide; chlorine

Van Arendonk; Cupery

Journal of the American Chemical Society, 1931 , vol. 53, p. 3184 Full Text View citing articles Show Details

With sodium hypobromide

With sodium hypobromide

Coulson

Journal of the Chemical Society, 1934 , p. 1406,1410 Full Text View citing articles Show Details

Buu-Hoi et al.

Journal of Organic Chemistry, 1952 , vol. 17, p. 1463 Full Text View citing articles Show Details

With alkaline potassium ferricyanide

Buchka; Irish

Chemische Berichte, 1887 , vol. 20, p. 1763 Full Text View citing articles Show Details

5

With air

T=150 - 200°C; unter Lichtausschluss;

Maruyama; Goto

Wood Res. KyotoChem.Abstr., 1956 , # 16 p. 16,20; engl. Ref. S. 24 Wood Res. KyotoChem.Abstr., 1957 , p. 4313 Full Text Show Details

With 18-crown-6 ether; acetophenone in benzene

T=25°C; 24 h; relative reactivity; further oxidative agents; Mechanism;

Lissel, Manfred

Zeitschrift fuer Naturforschung, B: Chemical Sciences, 1987 , vol. 42, # 1 p. 12 - 14 Title/Abstract

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With manganese(II) nitrate; oxygen; cobalt(II) nitrate in acetic acid

T=100°C; 6 h;

Minisci, Francesco; Recupero, Francesco; Fontana, Francesca; Bjorsvik, Hans-Rene; Liguori, Lucia

Synlett, 2002 , # 4 p. 610 - 612 Title/Abstract

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85 % Chromat.

With dihydrogen peroxide; oxygen; Ce(NTf2)x in acetic acid

Baeyer-Villiger oxidation; 6 h; Heating;

Baudry, Denise Barbier; Dormond, Alain; Duris, Fanny; Bernard, Jean Marie; Desmurs, Jean Roger

Journal of Fluorine Chemistry, 2003 , vol. 121, # 2 p. 233 - 238 Title/Abstract

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With dihydrogen peroxide in water

T=22 - 25°C; 11688 h;

Terent'ev, Alexander O.; Pastukhova, Zhanna Yu.; Yaremenko, Ivan A.; Bruk, Lev G.; Nikishin, Gennady I.

Mendeleev Communications, 2016 , vol. 26, # 4 p. 329 - 331 Title/Abstract

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With oxygen

T=140°C; P=15001.5 Torr; 6 h; Autoclave;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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B

C

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A

A: 7% B: 21.1% C: 5.8%

With [FeCl2{κ3-HC(pyrazol-1-yl)3}]; dihydrogen peroxide; nitric acid in water; acetonitrile

T=35°C; 9 h; Green chemistry; Catalytic behavior; Time; Overall yield = 33.9 percent; Hide Experimental Procedure

Mendes, Marta; Ribeiro, Ana Paula C.; Alegria, Elisabete C.B.A.; Martins, Luísa M.D.R.S.; Pombeiro, Armando J.L.

Polyhedron, 2017 , vol. 125, p. 151 - 155 Title/Abstract

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General procedure: The xylenes oxidations were carried out in air in round bottomflasks with vigorous stirring and using CH3CN as solvent (up to3 mL total volume). Typically, [FeCl2{j3-HC(pz)3}] (10 lmol) wasadded to the solvent as a solid or in the form of a stock solution.After the addition of xylene (o-, m- or p-; 5 mmol) the reactionstarted when hydrogen peroxide (50percent aq. sol., 10 mmol) was addedin one portion. In the experiments with HNO3 (65percent, 0.1–0.5 mmol)this acid was added immediately before the addition of the substrate.The reactions were stopped by cooling the reactional solution.Extraction was performed with 10 mL of diethyl ether and90 μL of cyclopentanone were inserted in the extracted mixture.All products formed were identified by GC.

A: 19 % Chromat.

B: 11 % Chromat.

C: 27 % Chromat.

With (NH4)6H2lt;Ce(IV)Mo12O42*10H2O; tetrabutylammonium acetate in water; acetic acid

T=50°C; 2 h; without protection from air; Product distribution;

Eberson, Lennart; Joensson, Lennart

Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry, 1986 , vol. 40, # 2 p. 79 - 91 Title/Abstract

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A: 10 % Chromat.

B: 60 % Chromat.

C: 10 % Chromat.

With air; Ptlt;NPhNC(S)SCH3gt;2 in acetonitrile

Ambient temperatureIrradiationrelative rate; Product distribution;

Monaci, Anna

Gazzetta Chimica Italiana, 1986 , vol. 116, # 6 p. 339 - 340 Title/Abstract

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A: 2.7 % Turnov.

B: 67.4 % Turnov.

C: 29.9 % Turnov.

With N -hydroxyphthalimide; tetrabutyl-ammonium chloride; oxygen in acetonitrile T=75°C; 20 h; atmospheric pressure;

Figiel; Sobczak

Polish Journal of Chemistry, 2001 , vol. 75, # 6 p. 869 - 873 Title/Abstract

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With oxygen; pyridine; manganese acetate (II); hydrogen bromide; cobalt(II) acetate

T=170°C; P=10501.1 Torr; 5 h; Product distribution / selectivity;

Toray Industries, Inc.

Patent: JP2005/213181 A, 2005 ; Location in patent: Page/Page column 7; 9 ;

With oxygen; pyridine; manganese acetate (II); hydrogen bromide; cobalt(II) acetate; copper (I) acetate

T=170°C; P=10501.1 Torr; 5 h; Product distribution / selectivity;

Toray Industries, Inc.

Patent: JP2005/213181 A, 2005 ; Location in patent: Page/Page column 7-9 ;

With oxygen; pyridine; manganese acetate (II); hydrogen bromide; cobalt(II) acetate; cerium(III) acetate

T=170°C; P=10501.1 Torr; 5 h; Product distribution / selectivity;

Toray Industries, Inc.

Patent: JP2005/213181 A, 2005 ; Location in patent: Page/Page column 8-9 ;

With oxygen; pyridine; hydrogen bromide; cobalt(II) acetate; copper (I) acetate

T=170°C; P=10501.1 Torr; 5 h; Product distribution / selectivity;

Toray Industries, Inc.

Patent: JP2005/213181 A, 2005 ; Location in patent: Page/Page column 7; 9 ;

Title/Abstract

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Title/Abstract

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Title/Abstract

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Title/Abstract

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With oxygen; pyridine; hydrogen bromide; cobalt(II) acetate

T=170°C; P=10501.1 Torr; 5 h; Product distribution / selectivity;

Toray Industries, Inc.

Patent: JP2005/213181 A, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract

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With oxygen

T=100°C; P=760.051 Torr; 24 h;

Hu, Lei; Shi, Linyan; Hong, Haiyan; Li, Min; Bao, Qinye; Tang, Jianxin; Ge, Jianfeng; Lu, Jianmei; Cao, Xueqin; Gu, Hongwei

Chemical Communications, 2010 , vol. 46, # 45 p. 8591 - 8593 Title/Abstract

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With oxygen in acetonitrile

T=150°C; P=7500.75 Torr; 22 h; Autoclave; chemoselective reaction;

Li, Xin-Hao; Chen, Jie-Sheng; Wang, Xinchen; Sun, Jianhua; Antonietti, Markus

Journal of the American Chemical Society, 2011 , vol. 133, # 21 p. 8074 - 8077 Title/Abstract

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With ([MnIII(5,10,15,20-tetra(4-chlorophenyl)porphyrin)]chloride)

T=190°C; P=9000.9 Torr; 5 h; Neat (no solvent)Autoclave;

Xiao, Yang; Zhang, Xiaoyan; Wang, Qin Bo; Tan, Ze; Guo, Can Cheng; Deng, Wei; Liu, Zhi Gang; Zhang, He Fei

Chinese Chemical Letters, 2011 , vol. 22, # 2 p. 135 - 138 Title/Abstract

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B: 221 μmol

With oxygen

T=20°C; P=750.075 Torr; 4 h; Irradiation; Kinetics; Reagent/catalystTimeSolvent;

Yuan, Rusheng; Fan, Shaolong; Zhou, Huaxi; Ding, Zhengxin; Lin, Sen; Li, Zhaohui; Zhang, Zizhong; Xu, Chao; Wu, Ling; Wang, Xuxu; Fu, Xianzhi

Angewandte Chemie - International Edition, 2013 , vol. 52, # 3 p. 1035 - 1039 Angew. Chem., 2013 , vol. 125, # 3 p. 1069 - 1073 Title/Abstract

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With cobalt naphthenate; 5,10,15,20-tetrakis(4methylphenyl)porphyrinatocopper(II); C40H32MnN8

T=130°C; P=3750.38 - 7500.75 Torr; 5 h; Reagent/catalystPressureTemperature;

Quzhou Qunying Chemical Technology Co. Ltd; Wang, Qinbo; Xiong, Zhenhua; Chen, Chuxiong

Patent: CN105237343 A, 2016 ; Location in patent: Paragraph 0060; 0061 ;

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Title/Abstract

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3:

550 g of p-xylene was added to a 1 L batch-type oxidation reactor, and 800 ppm (concentration in p-xylene) of cobalt naphthenate, metal phthalocyanine of the general formula (IV) (R1= CH3CH2, R2= H, M = Mn), metalloporphyrins having the structure of general formula (I)1= R2= H, R3= CH3, M = Cu) as a catalyst, and 99.0 g of a mixture of p-carboxybenzyl alcohol, p-methylbenzaldehyde and p-methylbenzyl alcohol as a co-oxidizing agent, 1.0 MPa of air was continuously introduced, The reactor was kept at a pressure of 0.5 MPa while the temperature of the reactor was kept at 130 . After 5 hours, the reaction was stopped and the reaction mixture was rapidly cooled and sampled and analyzed.The analytical results of the liquid chromatography showed that the conversion of p-xylene was 11.9percent, the total selectivity of the alcoholic acid in the final oxidation product was 98.0percent, and the total selectivity of the aldol was 83.9percent. The selectivity to pmethylbenzyl alcohol was 37.7percent The selectivity to p-methylbenzaldehyde was 46.2percent The selectivity to p-toluic acid was 14. 1percent.

With hafnium(IV) oxide; N-hydroxy-o-sulphonyl benzamide; C44H28N4O8Ru; C32H12F4FeN8; oxygen in water

T=168 - 179°C; P=4500.45 - 5250.53 Torr; 2.9 h; Flow reactor; PressureReagent/catalystTemperature; Hide Experimental Procedure

Quzhou Qunying Chemical Technology Co. Ltd.,; Wang, Qinbo; Xiong, Zhenhua; Chen, Chuxiong

Patent: CN105237344 A, 2016 ; Location in patent: Paragraph 0065-0066 ; Title/Abstract

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1:

The catalyst dissolved in the fresh paraxylene of the system is Hf02, N-hydroxy-o-sulphonylbenzamide, metal phthalocyanine with structure of formula (IV) = H, R2 = F, M = Fe) And metalloporphyrins d having the general formula (1) = R3 = 0H, R2 = H, and M = Ru) in a total concentration of 600 ppm. The steady-state operation of the apparatus, the fresh paraxylene in the primary oxidation reactor was fed at a flow rate of 15. 7 mL / h and the recycle of the octa-rich oxygen-containing compound and para-xylene The flow rate is 125. OmL / h, and the total flow rate is 140.7mL / h in the primary oxidation reactor. The average residence time of the primary oxidation reactor in the liquid phase was 1.6 h, and the pressurized pure oxygen was continuously fed into the primary oxidation reactor. The reaction temperature was 179 ° C and the reaction pressure was 0.6 MPa . The volume of water added into the secondary oxidation reactor was 46.3 mL / h, and the volume of water added into the secondary oxidation reactor was 0.33: 1, and the pressurized pure oxygen was continuously fed into the reactor. The reaction temperature in the secondary oxidation reactor was maintained at 175 ° C and the reaction pressure was 0.7 MPa. The residence time of the liquid phase in the secondary oxidation reactor was 1.3 h.The outlet of the secondary oxidation reactor was continuously introduced into the liquid-liquid delaminator. The temperature of the delaminator was 168 ° C, The pressure was 0.6 MPa. The oil phase rich in octa-carbon oxygen-containing compounds and paraxylene at the upper portion of the liquid-liquid delaminator is recirculated back to primary oxygen The lower layer contains p-methylbenzoic acid, p-methylbenzyl alcohol / aldehyde and a small amount of impurities in the aqueous phase of terephthalic acid into the subsequent units. The conversion of p-xylene in the system was 99.5percent, and the conversion of pmethylbenzene The total selectivity of formic acid and p-methylbenzyl alcohol / aldehyde was 98.74percent. The selectivity of p-methylbenzoic acid was 93. 9percent.

6

With dihydrogen peroxide in 1,4-dioxane

T=55°C; 4 h;

Domínguez, María Isabel; Cojocaru, Bogdan; Tudorache, Madalina; Odriozola, José Antonio; Centeno, Miguel Angel; Parvulescu, Vasile I.

Comptes Rendus Chimie, 2016 , vol. 19, # 10 p. 1156 - 1165 Title/Abstract

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90%

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With phen; oxygen; copper diacetate; potassium hydoxide in dimethyl sulfoxide

T=130°C; P=3000.3 Torr; 12 h; Autoclave; Hide Experimental Procedure

Rx-ID: 40158574 Find similar reactions

Wang, Min; Lu, Jianmin; Li, Lihua; Li, Hongji; Liu, Huifang; Wang, Feng

Journal of Catalysis, 2017 , vol. 348, p. 160 - 167 Title/Abstract

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2.2. Catalytic tests

General procedure: The catalytic reactions were performed in a 10-mL autoclave reactor with an internal Teflon insert. Typically, 0.5 mmol of secondary alcohols, 0.04 mmol of Cu(OAc)2 and 0.04 mmol of ligand, 1 mmol of base, and 2 mL of solvent were added to the reactor.Then, the reactor was charged with 0.4 MPa O2 and heated to the desired temperature under magnetic stirring. When the reaction reached completion, the reaction mixture was diluted with 4 mL of methanol, and the catalyst was separated via centrifugation.The acid product was esterified with addition of 40 μl of BF3OEt2 at 100 °C for 6 h in Ar atmosphere. In reaction condition optimization experiment, the products were identified and quantified using gas chromatography-mass spectrometry (GC–MS) and an Agilent7890A/5975C instrument equipped with an HP-5 MS column (30 m in length, 0.25 mm in diameter). p-Xylene was used as the internal standard. In the substrate scope experiment, the product was isolated and identified by NMR. The procedure for the isolation of the product is as follows: after the reaction completed, the reactor was cooled to room temperature in water and vented the gas.The reaction mixture was acidified with HCl 1.0 M (pH 1–2,15 mL) and then extracted with Et2O (3 x 20 mL). Next, the combined organic layers were washed with HCl 1.0 M (pH 1–2,3 10 mL), dried over anhydrous Na2SO4, and filtered and the Et2O was rotary evaporated. Solid products obtained were vacuum dried for 10 h at 60 °C.

88%

With oxygen; 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride; sodium t-butanolate in dichloromethane

T=20°C; 30 h; Molecular sieve; Reagent/catalyst; Hide Experimental Procedure

Yu, Dong-Fang; Xing, Ping; Jiang, Biao

Tetrahedron, 2015 , vol. 71, # 25 p. 4269 - 4273 Title/Abstract

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4.1. General procedure for the oxidation of aryl alcohol 1a-1o, or 6a-6h

General procedure: Under Oxygen atmosphere, aryl alcohol (2.00 mmol), precatalyst(SIMesHCl or SIPrHCl, 0.06 mmol), NaOtBu (960.5 mg,10.00 mmol), and 1 g 3 A molecular sieve were added todichloromethane (20 mL). This solutionwas allowed to stir for 30 h.After filtrating through a pad of Celite, the cake was added tohydrochloric acid (2N, 50 mL) and extracted with ethyl acetate(50 mL3). The organic layer was dried over Na2SO4 and concentratedunder reduced pressure. The products did not need furtherpurification.

7

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85%

8

With tert.-butylhydroperoxide; copper diacetate in neat (no solvent) T=80°C; 5 h; Green chemistry;

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With water in acetonitrile

1.5 h; Photolysis; Quantum yield; Wavelength;

Hashemi; Saberi; Poorsadeghi; Niknam

RSC Advances, 2017 , vol. 7, # 13 p. 7619 - 7622 Title/Abstract

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Rx-ID: 45035013 Find similar reactions

Chaudhuri, Amrita; Venkatesh, Yarra; Behara, Krishna Kalyani; Singh, N. D. Pradeep

Organic Letters, 2017 , vol. 19, # 7 p. 1598 - 1601 Title/Abstract

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Rx-ID: 44747965 Find similar reactions

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9

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84%

With iodine; dimethyl sulfoxide

T=120°C; 28 h; Sealed tubeGreen chemistry;

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Rx-ID: 45050952 Find similar reactions

Kalmode, Hanuman P.; Vadagaonkar, Kamlesh S.; Shinde, Suresh L.; Chaskar, Atul C.

Journal of Organic Chemistry, 2017 , vol. 82, # 7 p. 3781 - 3786 Title/Abstract

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10

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Rx-ID: 277170 Find similar reactions

88%

With MoO(O2)(8-quinolinolate)2; dihydrogen peroxide in acetonitrile

Oxidation; 6 h; Heating;

Bandyopadhyay, Ratna; Biswas, Sudeb; Guha, Subhadra; Mukherjee, Alok K.; Bhattacharyya, Ramgopal

Chemical Communications, 1999 , # 17 p. 1627 - 1628 Title/Abstract

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86%

T=165°C; P=2432.16 Torr; Hide Experimental Procedure

Yuanjiang Hualong Catalyst Technology Co., Ltd.; Guo, Cancheng; Guo, Xin

Patent: CN105218344 A, 2016 ; Location in patent: Paragraph 0049; 0050 ; Title/Abstract

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2:Example 2

The p-methylbenzoic acid product was prepared by air oxidation of p-xylene using the reaction separation synchronous reactor shown in Fig. 1;ContainingP-xylene raw materialsCopper tetraphenylporphyrin (concentration: 30 ppm)And cobalt oxide (concentration up to 120 ppm)As the composite catalyst,The mixed solution is fed from the reaction material inlet in the top of the constant temperature settling tower into the thermostatic settling tower and the bubbling gravity reaction tower connected with the thermostatic settling tower until it is filled with the reaction zone of the constant temperature settling tower and the bubble gravity reaction tower, Of the gas feed inlet into the air, the bubble gravity reactor temperature is adjusted to 165 , the pressure inside the tower to maintain 3.2atm oxidation reaction, open the loop of the valve, open the circulating pump, the reaction of p-methyl benzoic acid products along The rapid settlement of the gravity settling plate, into the thermostat settling tower, p-methylbenzoic acid product retained in the porous plate. When the p-methylphenyl formic acid is required to be withdrawn, the circulation pump is stopped, the reaction liquid is recovered from the bottom of the thermostat settling column, the thermostat settling column is taken out and the p-methylphenyl formic acid in the constant temperature settling column is collected. After simple drying of the collected p-methylbenzoic acid product, the product was detected, the p-xylene conversion was 92.0percentThe yield of p-toluic acid was 86.0percent.The reaction continued and no pipe plugging occurred.

83%

With 2-chloroanthracene-9,10-dione; water; oxygen; trifluoroacetic acid in ethyl acetate

24 h; Irradiation;

Tada, Norihiro; Hattori, Kasumi; Nobuta, Tomoya; Miura, Tsuyoshi; Itoh, Akichika

Green Chemistry, 2011 , vol. 13, # 7 p. 1669 - 1671 Title/Abstract

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80.2%

With 2H(1+)*Co(2+)*C16H24N4O10(4-)

T=110°C; 5 h; Catalytic behavior; Reagent/catalyst; Hide Experimental Procedure

Wei, Xing-Yue; Wang, Xing-Min; Li, Ning; Qin, Sheng-Ying

Chinese Chemical Letters, 2015 , vol. 26, # 1 p. 100 - 102 Title/Abstract

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2 Experimental

The oxidation of p-xylene to p-toluic acid (PTA) catalyzed by CoL1–CoL4 were conducted in a normal gas–liquid apparatus. Air was bubbled into the mixture of p-xylene (40 mL) and CoL (1×10−3molL−1) with a 2.0 Lmin−1 flow rate at 110°C. The reaction mixture (0.1 mL) was sampled by pipette periodically before the precipitates appeared (in 5 h), and diluted to 15 mL with ethanol. The accumulative concentration of PTA was determined by the standard acid–base titration. The selective oxidation for PTA was determined by HPLC. The catalytic oxidation performances of CoL1–CoL4 were shown in Table 2.

78%

Stage #1: With tert.-butylhydroperoxide; sodium hydroxide; tungsten(VI) oxide in water

T=80°C; 10 h; Stage #2: With hydrogenchloride in water

Shaikh, Tanveer Mahammad Ali; Sudalai, Arumugam

European Journal of Organic Chemistry, 2008 , # 29 p. 4877 - 4880 Title/Abstract

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77%

With zinc(II) oxide in N,N-dimethyl-formamide

0.1 h; microwave irradiation;

Gupta, Monika; Paul, Satya; Gupta, Rajive; Loupy, Andre

Tetrahedron Letters, 2005 , vol. 46, # 30 p. 4957 - 4960 Title/Abstract

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72%

With sodium bromate; 1-n-butyl-3-methylimidazolim bromide

T=70°C; 12 h;

Shaabani, Ahmad; Farhangi, Elham; Rahmati, Abbas

Monatshefte fur Chemie, 2008 , vol. 139, # 8 p. 905 - 908 Title/Abstract

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70%

With sodium periodate; sulfuric acid; lithium bromide in water

T=95°C; 18 h;

Shaikh, Tanveer Mahammad Ali; Emmanuvel, Lourdusamy; Sudalai, Arumugam

Journal of Organic Chemistry, 2006 , vol. 71, # 13 p. 5043 - 5046 Title/Abstract

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51%

With 2,2'-azobis(isobutyronitrile); oxygen; sodium bromide; cobalt(II)

Yang, Fan; Sun, Jing; Zheng, Rui; Qiu, Wenwei; Tang, Jie; He, Mingyuan

acetate; acetic acid in various solvent(s) T=110°C; P=760.051 Torr; 2 h;

Tetrahedron, 2004 , vol. 60, # 5 p. 1225 - 1228 Title/Abstract

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35%

With (CH3)3NO SbCl5; oxygen

Yamamoto, Jiro; Murakami, Mitushige; Kameoka, Noriaki; Otani, Norio; Umezu, Masahiro; Matsuura, Teruo

Bulletin of the Chemical Society of Japan, 1982 , vol. 55, # 1 p. 345 - 346 Title/Abstract

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30%

With chromium(VI) oxide; acetic acid

T=7°C; 2 h; Irradiation;

Shul'pin, G. B.; Macova, E.; Lederer, P.

J. Gen. Chem. USSR (Engl. Transl.), 1989 , vol. 59, # 11 p. 2604 - 2611,2329 - 2334 Title/Abstract

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30%

With water; ozone in acetonitrile

15 h; Hide Experimental Procedure

NATIONAL TSING HUA UNIVERSITY; HWANG, Kuo-Chu

Patent: US2016/102038 A1, 2016 ; Location in patent: Paragraph 0049 ; Title/Abstract

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On the other hand, the present invention may also only use ozone and substrates to carry out the reaction without additional irradiation, but yield thereof is lower (as compared to the photo-irradiated reaction). The mechanism of the dark reaction is also not the same as that of the photo-irradiated reaction. The mechanism of the dark reaction mainly involves that ozone abstracts a hydrogen atom directly from substrates to produce HOOO. and alkyl (R.) free radicals. The alkyl free radical can further react with molecular oxygen to proceed through a peroxidation chain reaction to generate alkyl hydroperoxide (ROOH). Consequently, the Embodiments 19 to 35 in accordance with the present invention are akin to the Embodiments 2 to 18 which are to use the same reactants, co-solvent; and the reaction time is the same, as well. The difference thereof only lies in that the former is the reaction carried out in the presence of ozone in the dark, and the related reaction conditions and yields of the Embodiments 19 to 35 in accordance with the present invention are summarized in the following Tables 4, 5 and 6.

25%

With Co4O4(O2CMe)4(py)4; oxygen

T=130°C; 7 h; neat (no solvent);

Das, Birinchi Kumar; Chakrabarty, Rajesh

Journal of Chemical Sciences, 2011 , vol. 123, # 2 p. 163 - 173 Title/Abstract

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With air; magnesium naphthenate

T=130°C;

Farbenfabr. Bayer

Patent: DE767366 , 1940 ; DRP/DRBP Org.Chem.

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With cobalt(II) 4-methylbenzoate; oxygen

Hercules Powder Co.

Patent: US2727921 , 1954 ;

With oxygen; thallium(I) acetate

With nitric acid

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Union Oil Co. of California

Patent: US2887511 , 1953 ; Full Text Show Details

Brueckner

Justus Liebigs Annalen der Chemie, 1880 , vol. 205, p. 118 Full Text View citing articles Show Details

Fittig; Ahrens; Mattheides

Justus Liebigs Annalen der Chemie, 1868 , vol. 147, p. 29 Full Text View citing articles Show Details

Dittmar; Kekule

Justus Liebigs Annalen der Chemie, 1872 , vol. 162, p. 339 Full Text View citing articles Show Details

Yssel de Schepper; Beilstein

Justus Liebigs Annalen der Chemie, 1866 , vol. 137, p. 302 Full Text Show Details

With 9,10-phenanthrenequinone

Irradiation;

Eckert

Patent: DE383030 ; Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 14, p. 442 Full Text Show Details

With air; sodium carbonate

T=250°C; P=45600 Torr;

Fischer,F.

Patent: DE364442 ; Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 14, p. 439 Full Text Show Details

With water; oxygen

im Sonnenlicht;

Ciamician; Silber

Chemische Berichte, 1912 , vol. 45, p. 41

Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1911 , vol. <5> 20 II, p. 675 Full Text View citing articles Show Details

With manganese(IV) oxide; sulfuric acid

T=20 - 25°C;

Wegscheider; Suida

Monatshefte fuer Chemie, 1912 , vol. 33, p. 1010 Full Text View citing articles Show Details

With chloropicrin

Irradiation;

Piutti; Badolato

Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1924 , vol. <5> 33 I, p. 478 Full Text View citing articles Show Details

With oxygen; cobalt(II) acetate

Manukowskaja et al.

Zhurnal Obshchei Khimii, 1959 , vol. 29, p. 158; engl. Ausg. S. 162 Full Text View citing articles Show Details

85 % Chromat.

With N -hydroxyphthalimide; oxygen; cobalt(II) acetate in acetic acid

T=25°C; P=760.051 Torr; 20 h;

Tashiro, Yasutaka; Iwahama, Takahiro; Sakaguchi, Satoshi; Ishii, Yasutaka

Advanced Synthesis and Catalysis, 2001 , vol. 343, # 2 p. 220 - 225 Title/Abstract

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With oxygen; acetic acid; palladium diacetate; V(acac)3; C8H12HfO8; antimony(III) acetate in water

T=167°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ; Title/Abstract

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43-17:

EXAMPLE 43; Following the procedure of Examples 1-4, a series of para-xylene oxidation trials in aqueous acetic acid solvent was conducted using compositions prepared from various combinations of one or more acetic acid soluble salts of palladium, platinum, vanadium, titanium, molybdenum, chromium, tin, antimony and, in some cases, acetic acid-soluble salts of one or more of additional metal or metalloid or standardized solutions thereof in aqueous acetic acid in amounts providing the metals or metalloids in about equal parts by weight corresponding to about 500 ppmw based on weight of acetic acid solvent used in the oxidations. Metal and metalloid combinations, temperatures and oxidation results are reported in TABLE 14; results of Examples 1-4 are also included for reference.

28 %Chromat.

With PEG-1000; carbon dioxide; oxygen; cobalt(II) acetate

T=100°C; P=75007.5 Torr; 12 h; AutoclaveNeat (no solvent);

Wang, Jin-Quan; He, Liang-Nian

New Journal of Chemistry, 2009 , vol. 33, # 8 p. 1637 - 1640 Title/Abstract

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7.8 %Chromat.

With oxygen

T=140°C; 3 h; Neat (no solvent);

Beier, Matthias J.; Schimmoeller, Bjoern; Hansen, Thomas W.; Andersen, Jens E.T.; Pratsinis, Sotiris E.; Grunwaldt, Jan-Dierk

Journal of Molecular Catalysis A: Chemical, 2010 , vol. 331, # 1-2 p. 40 - 49 Title/Abstract

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With sodium nitrate; C35H34Cl2MnN3O6

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With sodium nitrate; C36H37ClMnN3O6

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With sodium nitrate; C25H22Cl2MnN3O3

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With sodium nitrate; C25H22BrClMnN3O3(2+)

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With sodium nitrate; C20H13Cl2MnN2O2

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With C20H13BrClMnN2O2; potassium nitrate

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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With sodium nitrate; C35H34BrClMnN3O6

T=120°C; P=760.051 Torr; 12 h;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Qin, Sheng-Ying

Journal of Chemical Research, 2010 , # 10 p. 581 - 584 Title/Abstract

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15.5 %Chromat.

With oxygen; acetic acid

T=80°C; P=104260 Torr; 22 h; Supercritical conditions;

Zuo, Xiaobin; Niu, Fenghui; Snavely, Kirk; Subramaniam, Bala; Busch, Daryle H.

Green Chemistry, 2010 , vol. 12, # 2 p. 260 - 267 Title/Abstract

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29.7 %Chromat.

With oxygen; cobalt(II) acetate; manganese(II) acetate; 1,3,5trihydroxyhexahydro-1,3,5-triazine-2,4,6-trione in water

T=150°C; P=3750.38 Torr; 5 h; Product distribution / selectivity; Hide Experimental Procedure

Shibamoto, Akihiro

Patent: US2011/71313 A1, 2011 ; Location in patent: Page/Page column 11-12 ; Title/Abstract

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2:

Example 2; The reaction was conducted in the same manner as in Example 1 except that 0.025 g (0.141 mmol) of trihydroxyisocyanuric acid was used instead of N-hydroxysuccinimide. The conversion of the substrate and the amount and yield of the product were determined. As the results, the conversion of p-xylene was 36.4percent, and 113 g of p-toluic acid (yield 29.7percent), 21 g of terephthalic acid (yield 4.52percent), and 0.30 g of benzoic acid as a by-product (yield 0.0878percent) were obtained.

With C56H60Cl3MnN4O10

T=120°C; P=760.051 Torr; 9.5 h;

Li, Jian-Zhang; He, Xi-Yang; Zeng, Jun; Xiao, Zheng-Hua; Qin, Sheng-Ying

Transition Metal Chemistry, 2012 , vol. 37, # 1 p. 31 - 35 Title/Abstract

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With 2-pyridinecarboxylic acid; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; iodobenzene; oxygen

T=120°C; 12 h;

Yan, Yunyun; Chen, Yanyan; Yan, Ming; Li, Xingshu; Zeng, Wei

Catalysis Communications, 2013 , vol. 35, p. 64 - 67 Title/Abstract

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With acetic acid

T=64.84°C; P=760.051 Torr; 3 h; KineticsCatalytic behavior; Concentration;

Plekhov; Kushch; Opeida; Kompanets

Russian Journal of Applied Chemistry, 2014 , vol. 87, # 7 p. 982 - 985 Zh. Prikl. Khim. (S.-Peterburg, Russ. Fed.), 2014 , vol. 87, # 7 p. 986 - 989,4 Title/Abstract

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With C16H26CoN4O10

T=110°C; 5 h; Reagent/catalyst;

Long, Liang-Jun; Wei, Xing-Yue; Wang, Xing-Min; Li, Ning

Journal of the Chemical Society of Pakistan, 2015 , vol. 37, # 6 p. 1099 - 1102 Title/Abstract

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11

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With manganese(IV) oxide; oxygen

T=140 - 170°C;

Sensemann; Stubbs

Industrial and Engineering Chemistry, 1932 , vol. 24, p. 1184 Full Text View citing articles Show Details

With manganese p-toluate; oxygen

T=140 - 170°C;

Sensemann; Stubbs

Industrial and Engineering Chemistry, 1932 , vol. 24, p. 1184 Full Text View citing articles Show Details

With air; vanadia

T=375°C;

Sensemann; Stubbs

Industrial and Engineering Chemistry, 1931 , vol. 23, p. 1129 Full Text View citing articles Show Details

Hide Details

With air; sodium carbonate

T=210°C; unter Druck;

Schrader

Abh. Kenntnis Kohle, vol. 4, p. 329 Chem. Zentralbl., 1921 , vol. 92, # I p. 537 Full Text Show Details

With chromium(III) oxide; sulfuric acid

T=100°C;

Meyer,H.; Bernhauer

Monatshefte fuer Chemie, 1929 , vol. 53/54, p. 728 Full Text View citing articles Show Details

With nitric acid

Tuley; Marvel

Organic Syntheses, 1947 , vol. 27, p. 86 Full Text Show Details

With sulfuric acid; nitric acid

Halse; Dedichen; Aschan; zit. bei Alfthan

Chemische Berichte, 1920 , vol. 53, p. 83,84 Full Text Show Details

Multi-step reaction with 2 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 2 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 2 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 2 steps 1: oxygen / 6 h / 80 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 2 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Multi-step reaction with 3 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 24 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 24 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 80 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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View Scheme

Multi-step reaction with 3 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr 2: oxygen / 6 h / 100 °C / 26252.6 Torr 3: oxygen / 6 h / 100 °C / 26252.6 Torr 4: oxygen / 6 h / 100 °C / 26252.6 Torr View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr 2: oxygen / 6 h / 100 °C / 26252.6 Torr 3: oxygen / 6 h / 100 °C / 26252.6 Torr 4: oxygen / 6 h / 140 °C / 15001.5 Torr View Scheme

Multi-step reaction with 4 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr 2: oxygen / 6 h / 100 °C / 26252.6 Torr 3: oxygen / 6 h / 100 °C / 26252.6 Torr 4: oxygen / 6 h / 140 °C / 15001.5 Torr View Scheme

Multi-step reaction with 4 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 24 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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/ / / /

|Autoclave |Autoclave |Autoclave |Autoclave

/ / / /

|Autoclave |Autoclave |Autoclave |Autoclave

/ / / /

|Autoclave |Autoclave |Autoclave |Autoclave

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 24 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 6 h / 80 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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12

Multi-step reaction with 4 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen / 1 h / 100 °C / 26252.6 Torr 2: oxygen / 6 h / 100 °C / 26252.6 Torr 3: oxygen / 6 h / 100 °C / 26252.6 Torr 4: oxygen / 6 h / 100 °C / 26252.6 Torr 5: oxygen / 6 h / 140 °C / 15001.5 Torr View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen / 24 h / 100 °C / 15001.5 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 5: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen / 24 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 5: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen / 6 h / 100 °C / 6000.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 5: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen; iron(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 5: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 5 steps 1: oxygen; manganese(III) oxide / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 4: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 5: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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/ / / / /

|Autoclave |Autoclave |Autoclave |Autoclave |Autoclave

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97%

With iron(III) sulfate; water in toluene

T=110°C; 1.5 h; Ionic liquid;

Hu, Yu Lin; Jiang, Hui; Zhu, Jie; Lu, Ming

New Journal of Chemistry, 2011 , vol. 35, # 2 p. 292 - 298 Title/Abstract

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90%

With potassium hydroxide in methanol

T=35°C; 0.5 h;

Khurana, Jitender M.; Chauhan, Sushma; Bansal, Geeti

Monatshefte fur Chemie, 2004 , vol. 135, # 1 p. 83 - 87 Title/Abstract

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90%

With high-silica Hβ-75 zeolite in water

T=130°C; 24 h; Reagent/catalyst; Hide Experimental Procedure

Siddiki; Toyao, Takashi; Kon, Kenichi; Touchy, Abeda S.; Shimizu, Ken-ichi

Journal of Catalysis, 2016 , vol. 344, p. 741 - 748 Title/Abstract

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2.4. Catalytic tests

General procedure: The heterogeneous catalysts, stored under ambient conditions,were used for catalytic reactions without any pretreatment. Typically,ester (1 mmol), 1 mL H2O and 10 mg of catalysts and a magneticstarter bar were added to a reaction vessel (Pyrex pressuretube, 13 mL), and the mixture was heated at 130 °C under air withstirring at 300 rpm. For the catalytic tests in Table 1 and kineticstudy, conversions and yields were determined by GC-FID usingn-dodecane as an internal standard as follows. After completionof the reaction, acetone (7 mL) was added to the mixture, andthe catalyst was separated by centrifugation. Then, n-dodecane(0.2 mmol) was added to the reaction mixture, and the mixturewas analyzed by GC-FID and GC-MS. The GC-FID sensitivities ofthe products were determined using commercial carboxylic acidsor the isolated products after the reaction. For some of the productsin Tables 2 and 3, we determined isolated yields of the carboxylicacids as follows. After the filtration of the catalyst, followed bywashing the catalyst with acetone (6 mL), and by evaporation,the product was isolated by column chromatography using silicagel 60 (spherical, 63-210 μm, Kanto Chemical Co. Ltd.) with hexane/ethyl acetate (60/40-80/20) as the eluting solvent, followedby analyses by 1H NMR, 13C NMR and GC-MS equipped with thesame column as GC-FID. Hide Details

With tetraethylammonium hydroxide in water; dimethyl sulfoxide

T=25°C; ΔH; Thermodynamic data;

Guthrie, J. Peter; Pike, David C.; Lee, Yiu-Chung

Canadian Journal of Chemistry, 1992 , vol. 70, # 6 p. 1671 - 1683 Title/Abstract

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With hydrogenchloride in methanol; water

T=25°C; Equilibrium constant;

Guthrie, J. Peter; Pike, David C.; Lee, Yiu-Chung

Canadian Journal of Chemistry, 1992 , vol. 70, # 6 p. 1671 - 1683 Title/Abstract

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Multi-step reaction with 2 steps 1: 90 percent Chromat. / methyl iodide / toluene / 79 h / 100 - 110 °C 2: H2O / 0.5 h View Scheme

Yamamoto, Yasushi; Shimizu, Hideaki; Hamada, Yoshitaka

Journal of Organometallic Chemistry, 1996 , vol. 509, # 2 p. 119 - 122 Title/Abstract

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Multi-step reaction with 2 steps 1: 95 percent Chromat. / methyl iodide / toluene / 53 h / 90 - 115 °C 2: H2O / 0.5 h View Scheme

Yamamoto, Yasushi; Shimizu, Hideaki; Hamada, Yoshitaka

Journal of Organometallic Chemistry, 1996 , vol. 509, # 2 p. 119 - 122 Title/Abstract

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With potassium hydoxide in methanol

T=63°C; 2 h;

Khaibulova, T. Sh.; Boyarskaya; Boyarskii

Russian Journal of Organic Chemistry, 2013 , vol. 49, # 3 p. 360 - 365 Zh. Org. Khim., 2013 , vol. 49, # 3 p. 373 - 378 Title/Abstract

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Stage #1: With sodium hydroxide in methanol; diethyl ether

T=20°C; 20 h; Stage #2: With hydrogenchloride in water

pH=2 - 3; Hide Experimental Procedure

Far Eastern New Century Corporation; Chen, Guei-San; Chi, Fa-Chen; Chou, Cheng-Han; Lu, Xin-An

Patent: US9061989 B1, 2015 ; Location in patent: Page/Page column 3; 4 ; Title/Abstract

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E1.C; 1.C:Hydrolysis Reaction

C. Hydrolysis Reaction The dehydrogenated product (3 g) obtained in step B was dissolved in ethyl ether (50 mL). A methanol solution of sodium hydroxide (20 mL, 2 M) was then added at room temperature, followed by stirring for 20 hours. To the mixture was added water (100 mL) so as to partition the mixture and to separate a water layer from the mixture. The water layer thus obtained was then acidified with hydrochloric acid (6 M) to a pH value ranging from 2 to 3. Ethyl ether (100 mL) was then added to extract the organic product. The extracted organic product was dried with magnesium sulfate (to remove water), then concentrated in vacuo to give the hydrolysis product.

A

B

13

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A: 96% B: 3%

With N -hydroxyphthalimide; oxygen; nitric acid

T=110°C; P=760.051 Torr; 6 h; Ionic liquid;

Yavari, Issa; Karimi, Elham

Synthetic Communications, 2009 , vol. 39, # 19 p. 3420 - 3427 Title/Abstract

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A: 90% B: 9.7%

Stage #1: With N -hydroxyphthalimide; cobalt(II) phthalocyanine; .mu.oxo[manganese(III) tetraphenylporphine]2; oxygen

T=120°C; P=3750.38 Torr; Stage #2: With N -hydroxyphthalimide; cobalt(II) phthalocyanine; .mu.oxo[manganese(III) tetraphenylporphine]2; oxygen; acetic acid

T=232°C; P=16501.7 Torr; 1.5 h; TemperaturePressureReagent/catalyst; Hide Experimental Procedure

Quzhou Qunying Chemical Technology Co., Ltd.; Wang, Qinbo; Xiong, Zhenhua; Chen, Chuxiong

Patent: CN105348067 A, 2016 ; Location in patent: Paragraph 0068; 0069; 0114; 0117; 0119 ; Title/Abstract

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1:Example 1

Example 1 Fresh catalyst dissolved in p-xylene added to the first oxidation reactor is a mixture of N-hydroxyphthalimide, Metal phthalocyanine (R1=H, R2=H, M=Co) having a structure of general fomula IV, Cobalt acetylacetonate and Metal porphyrin (R1= R2= =R3=H, M1=M2= Mn) having a structure of general fomula III, total concentration is 800ppm. When set up is in a steady state operation, enter fresh p-xylene into the first oxidation reactor with a rate of 73.2L/h and recycled rich 8-carbon oxygenated intermediate compounds from the first filtrate with a rate of 7.3L/h, a total flow rate of 80.5L/h. At this time, the average residence of the liquid substance of the first oxidation reactor is 1.5h, continuously introduce pressurized air with 21percent percentage concentration of oxygen mass to the first oxidation reactor, maintain the temperature of the reaction system at 120°C, reaction pressure is 0.5MPa. Continuously introduce first oxidation reaction solution to the first separator system obtaining 7.8kg/h of the product p-toulic acid with a purity of 99.9percent, at the same time, also obtaining the rich 8-carbon oxygenated intermediate compounds of the first filtrate. 10percent of this rich 8-carbon oxygenated intermediate compounds is to be recycled to the first oxidation reactor, the remaining first filtrate is continuously fed into the second oxidation reactor. Add HAc to the second oxidation reactor with a flow of 325.0L/h, the amoumt Co/Mn/Bt catalyst used has an acetic acid amount of 220ppm. At this time, the volumetric flow ratio of the added amount of acetic acid and the rich 8-carbon oxygenated intermediate compounds of the first filtrate entering the second oxidation reactor is 4.9:1, continuously bubble pressurized air with 21percent percentage concentration of oxygen mass, maintain reaction temperature of secondary oxidation reactor at 232°C, reaction pressure is 2.2MPa, at this time, the residence time of the liquid in the secondary oxidation ractor is 1.5h. Secondary oxidation reactor's leaving liquid is continuously fed into the second separation system, obtaining the filter cake of second filtrate and terephthalic acid with a flow of 88.7kg/h. Through computation, conversion of p-xylene is 99.6percent, overall yield product is 99.6percent. Where: yield of p-methylbenzoic acid is 9.7percent, 9.7percent selectivity; yield of p-benzenedicarboxylic acid is 90.0percent, 90.3percent selectivity.

A: 6% B: 86%

With chromium(VI) oxide; periodic acid in acetonitrile

T=20°C; 1 h;

Yamazaki, Shigekazu

Organic Letters, 1999 , vol. 1, # 13 p. 2129 - 2132 Title/Abstract

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A: 26% B: 71%

With oxygen; N -hydroxyphthalimide; cobalt(II) acetate in acetic acid

T=100°C; P=44475.9 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 5-6 ; Title/Abstract

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10:

Example 10; Oxidation of p-Xylene Using CAT and NHPI; In this example, a solution of 0.1648 g (1.01 mmol) of N-hydroxyphthalimide ("NHPI"), 0.5200 g (4.9 mmol) of p-xylene and 0.1273 g (0.511 mmol) cobalt acetate tetrahydrate in 40 ml of acetic acid was heated to 100° C. in a Parr Hastelloy reactor fitted with temperature and pressure controllers. After the temperature reached 100° C., 860 psi of air was slowly introduced into the reactor. The mixture was stirred under pressure for one hour at 100° C., the pressure was released, and the mixture cooled to room temperature. Within roughly 15 minutes following O2 introduction, a rapid temperature rise occurred (due to heat generated by the exothermic oxidation) accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicating rapid reaction. These profiles are steep and level off within minutes after induction. The white solid of terephthalic acid (TPA) was filtered, and the filtrate analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with additional acetic acid (20 ml) and dried in an oven at 120° C. for six hours to obtain, 26percent TPA and 71percent PTA. A: 70% B: 7.5%

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=200°C; P=33718.9 - 49647.5 Torr; 0.0833333 h; Inert atmosphere; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF KANSAS; SUBRAMANIAM, Bala; BUSCH, Daryle, H.; NIU, Fenghui

Patent: WO2010/111288 A2, 2010 ; Location in patent: Page/Page column 18-20 ; Title/Abstract

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EXPERIMENTALA reaction system substantially as shown in Figure 1 was utilized for an oxidation reaction. The maximum operating pressure for the spray reactor unit is 2500 psi at a temperature of 300 0C. However, the spray reactor can be configured to operate at any pressure or temperature. The reactor unit is a titanium reactor equipped with silica capillary nozzles or commercial spray nozzles. Two reactors, 40 mL (1.16" ID x 1.6" height) and 700 mL (3" ID x 6" height), have been successfully used, and as such, volumes at 1 L, 10, L, 10OL, or larger are likely to also be effective. The larger reactors can provide a longer residence time for the droplets/particles to descend before reaching the acetic acid dominated liquid phase at the bottom of the vessel, which can be beneficial for increasing yield and conversion. The inner diameter of the tested silica capillary nozzles ranged from 50 to 180 microns. N2 or other inert gas can be used for leakage testing and as the energizing gas or diluents gas. Also, CO2 was used as an inert gas inside the reactor to reduce vapor phase flammability; however, other inert gases can be used, such as noble gases. A mass flow controller can be used to feed the energizing gas through the capillary nozzle. An HPLC pump or a syringe pump (e.g., used mostly to avoid pulsating spray) are available to feed the solution through the nozzle. The spray solution can be preheated to the reaction temperature by a tubular heater.For a typical spray oxidation experiment, the spray solution can be prepared as described herein. The catalytic components (2.5 mM Co as cobalt acetate, 2.5 mM Mn as Mn acetate and 6.5 mM Br as HBr) can be dissolved in a liquid phase containing 2.7 wtpercent /-xylene, 6.9percent water and 90.43percent acetic acid. A known amount of acetic acid (4 mL) can be pre-loaded in the reactor and preheated to the reaction temperature. In this manner, the spray can enter a vapor phase saturated with acetic acid at the reaction temperature and pressure, thereby avoiding acetic acid evaporation from the spray droplets that would lead to unwanted catalyst precipitation. The whole system can be leak-tested using N2. Following leak testing, the reactor can be pressurized with CO2 to 103 psi. The vessel can be heated by a heating tape/band or the like to the chosen operating temperature. When the temperature is obtained, O2 can be added to the final pressure at equal partial pressures.A Lab View program or other like software can be used to monitor, control, and record process temperatures (e.g., pre-heater, reactor) and pressure, or other reaction conditions. When the reactor is stabilized at the set-point temperature, N2 gas can be introduced into the reactor via a mass flow controller, a pre-heater (an oil bath), and a mixing tee. The spray solution can be pumped at a predetermined flow rate through the mixing tee and the capillary nozzle. The flowing N2 serves to break up the solution stream, causing it to be sprayed as a fine mist into the reactor where it meets the preheated O2/N2/CO2 mixture. The />;-xylene (or other reactant) in the small droplets reacts with O2 in the reactor to form TPA (or other corresponding product). After a predetermined amount of solution is fed into the reactor, the solution pump can be stopped. The solution in the feed line between the 3-way valve and the tee can be purged out through the 3-way valve.

The N2 flow can be stopped and the reactor can be allowed to cool by turning off the heaters. When the reactor has cooled to room temperature, the solid TPA (or other product) and the solution can be removed from the reactor. The solids can be filtered from the solution, dried in an oven and weighed. The solid residue in the reactor can be recovered by washing with DMSO. The purity of TPA can be analyzed by HPLC and/or UV spectrophotometer. The wash liquid was also analyzed by HPLC.Alternatively, the reactor can be fitted with mesh or sieve membranes at various sizes that catch the precipitated product and allow the solution to fall through. /7-Xylene oxidation to TPA using spray methodExperimental conditions: 40 mL bomb reactor, 100 μm silica capillary nozzle, 0.6 mL/min of solution, 54 scc/min of N2. The reaction temperatures and pressures are shown in the following table. Before the spray was introduced, the vessel was loaded with 4 mL of acetic acid, and gas composed of 50percent CO2 and 50percent O2.Experimental results'. The experimental results using the small reactor and HPLC pump are shown in Table 1, where X p-x is the conversion of p-xylene, YTPA is the yield of terephthalic acid, Y4-CBA is the yield of the 4-carboxybenzaldehyde byproduct, YPTA S the yield of p-toluic acid, Yp-Ta is the yield observed of p-tolualdehyde and OD340 is the optical density of the desired TPA product determined by UV-Vis.*purity (wt.percent) of the recovered solid product The solid TPA products from all experiments listed in Table 1 have 99+percent purity. The use of higher temperature (225 0C) slightly reduces the intermediate product yields. At 225 0C, allowing a further four hours of reaction time post-spraying further reduces the intermediate products and increases TPA purity suggesting continued oxidation of the intermediate products in the liquid phase. The TPA product is a white crystalline solid. The optical density (OD340) values confirm the high purity of the solid TPA product

A: 32% B: 65%

With oxygen; N-hydroxymaleimide; cobalt(II) acetate in acetic acid

T=60°C; P=44475.9 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 6 ; Title/Abstract

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11:

Example 11; Oxidation of p-Xylene Using CAT and NHMI; In this example, a solution of 0.1140 g (1.01 mmol) of N-hydroxymaleimide ("NHMI"), 0.5201 g (4.9 mmol) of p-xylene and 0.1273 g (0.511 mmol) cobalt acetate tetrahydrate in 40 ml of acetic acid was heated to 60° C. in a Parr Hastelloy reactor fitted with temperature and pressure controllers. After the temperature reached 60° C., 860 psi of air was slowly introduced into the reactor. The mixture was stirred under pressure for one hour at 60° C., the pressure was released, and the mixture cooled to room temperature. Within roughly 15 minutes following O2 introduction, a rapid temperature rise occurred (due to heat generated by the exothermic oxidation) accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicating rapid reaction. These profiles are steep and level off within minutes after induction. The white solid of terephthalic acid (TPA) was filtered, and the filtrate analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with additional acetic acid (20 ml) and dried in an oven at 120° C. for six hours. Product analysis: 32percent TPA, and 65percent p-toluic acid ("PTA").

A: 65% B: 32%

With sodium 2-iodobenzenesulfonate; Oxone; tetra(n-butyl)ammonium hydrogensulfate in acetonitrile

T=60°C; 24 h;

Cui, Li-Qian; Liu, Kai; Zhang, Chi

Organic and Biomolecular Chemistry, 2011 , vol. 9, # 7 p. 2258 - 2265 Title/Abstract

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A: 65% B: 32%

With water; ozone in acetonitrile

20 h; Irradiation; Reagent/catalyst; Hide Experimental Procedure

NATIONAL TSING HUA UNIVERSITY; HWANG, Kuo-Chu

Patent: US2016/102038 A1, 2016 ; Location in patent: Paragraph 0040-0043; 0046 ; Title/Abstract

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In accordance with the Embodiment 9 of the present invention, firstly, neat p-xylene is filled in a glass tube, and ozone gas flow is introduced to the glass tube for about 10 minutes. The reaction solution was exposed to 100 W Hg lamp light irradiation for about 15 hours. White precipitate is produced gradually. After light irradiation, solvents are added therein to wash away unreacted substrate from the solid precipitate; and the white solid precipitate was collected by either centrifugation or filtration. The white solid is composed of terephthalic acid and p-toluic acid; and the conversion was determined to be 80 mol percent.-Embodiment 9 in accordance with the present invention is shown in the Reaction 5. (0041) Please refer to the Reaction 5, the condition of the Embodiment 9 leads to formation of 20 mol percent terephthalic acid and 60 mol percent p-toluic acid. Because p-toluic acid does not dissolve in p-xylene and exists in the form of a solid, the poor contact of solid ptoluic acid forbids further oxidative conversion of p-toluic acid to terephthalic acid. Consequently, if increase in the yield of terephthalic acid is expected when a “better” solvent is used to help dissolution of p-toluic acid, which allows p-tuluic acid to be easily accessed by oxidants in the solution. As a result, Embodiments 10 in accordance with the present invention is akin to the Embodiment 9; and the difference thereof only lies in the process of reaction. 45 mol percent of terephthalic acid and 45 mol percent of p-Toluic acid are, respectively, produced after 10 hours of reaction. Hence, the yield of terephthalic acid is effectively enhanced. (0042) Embodiment 11 in accordance with the present invention is akin to the Embodiment 9; and the difference thereof only lies in the fact that a co-solvent of xylene, acetonitrile and water (in 5:3:2 volume ratio) is used in the reaction, and the pH value is controlled to be 4.5. The co-solvent is a so-called “green solvent” which is composed of a mixture of several environmentally-friendly solvents; and the purpose of using the co-solvent is to dissolve the otherwise insoluble, reaction intermediate, such as, p-toluic acid, so that further oxidation of p-toluic acid can be proceeded and the yield of the desirable ultimate product, i.e., terephthalic acid, is increased. Hence, in the Embodiment 11 in accordance with the present invention, the p-toluic acid is re-dissolved by the co-solvent to allow further oxidation and the yield of terephthalic acid is effectively promoted up to 65percent. (0043) In the Embodiment 11 in accordance with the present invention, even though re-dissolving in the co-solvent of xylene, acetonitrile and water (in 5:3:2 volume ratio), the yield of p-toluic acid is 32percent. In addition, another reaction intermediate, i.e., 4-carboxybenzaldehyde (4-CBA), may be detected by NMR spectrum. Hence, Embodiment 12 in accordance with the present invention is to treat 1 M p-toluic acid in an acetonitrile-water co-solvent (in a 2:1 volume ratio) with ozone-uv irradiation for 8 hours, and terephthalic acid is produced with a yield up to 95percent. Embodiment 13 in accordance with the present invention is to treat 1 M 4-carboxybenzaldehyde in a acetonitrile-water (in a 2:1 volume ratio) co-solvent with ozone-uv irradiation for 5 hours; and terephthalic acid is produced with a yield up to 98percent. As a result, in Embodiment 11, ozone-uv irradiation of a p-xylene-acetonitrile-water (in 5:3:2 volume ratio) solution leads to formation of terephthalic acid with a higher yield of 65percent.

A: 34.3% B: 65.6%

Stage #1: With 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II); oxygen

T=200°C; P=19502 Torr; 0.5 h; Stage #2: With 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II); oxygen; acetic acid

T=186°C; P=18001.8 Torr; 1.4 h; TemperaturePressureReagent/catalyst; Hide Experimental Procedure

Quzhou Qunying Chemical Technology Co., Ltd.; Wang, Qinbo; Xiong, Zhenhua; Chen, Chuxiong

Patent: CN105348067 A, 2016 ; Location in patent: Paragraph 0078; 0079; 0114; 0117; 0119 ; Title/Abstract

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6:Example 6

Example 6 Fresh catalyst dissolved in p-xylene added to the first oxidation reactor is a metal porphyrin (R1= R2= =R3=H, M= Co) having a structure of general fomula I, total concentration is 10ppm. When set up is in a steady state operation, Example 1 operations were followed. The first oxidation reactor operating conditions are shown in Table 1. The secondary oxidation reactor operating conditions as shown in Table 2. The quality of each product, purity, yield, yield and paraxylene conversion rate listed in Table 3.

A: 8% B: 61%

With nitric acid; 1-n-butyl-3-methylimidazolium methanesulfonate in water

144 h; Heating / reflux;

THE QUEEN'S UNIVERSITY OF BELFAST

Patent: JP2004/523477 A, 2004 ; Location in patent: Page/Page column 7 ; Title/Abstract

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A: 52.9% B: 38.2%

With air; cobalt(II) bromide in various solvent(s) T=150°C; P=15001.2 Torr; 4 h; other catalyst, time, temperature, solvent.; Product distribution;

Hronec, Milan; Masarovic, Frantisek; Cvengrosova, Zuzana; Ilavsky, Jan

Collection of Czechoslovak Chemical Communications, 1987 , vol. 52, # 9 p. 2241 - 2247 Title/Abstract

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A: 44% B: 29%

With anthracene; oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=170°C; P=21446.5 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

Schammel, Wayne P.; Adamian, Victor A.; Viswanath, Yenamandra; Zakharov, Igor V.

Patent: US2005/137420 A1, 2005 ; Location in patent: Page/Page column 9 ; Title/Abstract

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7:

EXAMPLES 6 AND 7; Oxidation of Para-Xylene to Terephthalic Acid; Experiments are conducted in a 300 mL titanium Parr mini-reactor. Initial reactor charge contained catalyst and 10 g of 95percent HOAc. Reactor was pressurized to 400 psig under N2 and heated to 170° C. After desired temperature has been reached, nitrogen atmosphere is switched to a continuous flow of 8 vol percent O2 in N2. After reactor is saturated with 8percent O2 (as determined by level of O2 in vent gas), feedstock (paraxylene) is pumped in at a rate of 0.5 mL/min for 60 min. After 60 min, 8percent O2 is switched to nitrogen, and the reactor is cooled down to room temperature, total reactor effluent (TRE) is removed and submitted for HPLC analysis. Vent gas is continuously analyzed for O2, CO2, CO. Vent gas is also sampled two or three times during each experiment and analyzed for volatile organic compounds using in-lab gas chromatography (GC).). In examples 6, and 7, catalyst in the initial charge consisted of: Co(OAc)2.4H2O=0.400 g; Mn(OAc)2.4H2O=0.115 g; 48percent HBr=0.127 g. In Example 7, AC (0.300 g) was added to the initial reactor charge.

A: 38% B: 16.2%

With dihydrogen peroxide; hydrogen bromide; copper(ll) bromide in water

T=380°C; P=187519 Torr; Condensed phase; Product distribution / selectivity; Hide Experimental Procedure

INVISTA TECHNOLOGIES S.A.R.L.

Patent: WO2009/134872 A2, 2009 ; Location in patent: Page/Page column 29-30; 35 ; Title/Abstract

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24:

Experimental conditions were the same as in Examples 1-22 except that: Flow rate of p-xylene = 0.28 mL/min Pressure = approx. 250 baraFlow rate oxidant (H2O2 in H2O) = 8.1 mL/min. (providing an amount of [O2] as aqueous H2O2 of 1.26 mol.L"1 (1.5 molar equivalents of the stoichiometry required for complete oxidation of the organic precursor to the aromatic acid, the molar ratio for which in the case of p-xylene is 3O2 / organic)).The data in Table 5 demonstrate that increase in catalyst concentration increases yield of terephthalic acid and reduces burn to carbon dioxide. It also further demonstrates the increased activity and reduced burn achieved with a copper-cobalt catalyst.

A: 5% B: 35%

With tert.-butylhydroperoxide; mesoporous chromosilicate (Cr-MCM-41) in methanol

20 h; Heating;

Das; Chaudhari; Nandanan; Chandwadkar; Sudalai; Ravindranathan; Sivasanker

Tetrahedron Letters, 1997 , vol. 38, # 20 p. 3631 - 3634 Title/Abstract

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A: 5% B: 35%

With tert.-butylhydroperoxide; mesoporous chromosilicate (Cr-MCM-41) in methanol

20 h; Heating;

Das; Chaudhari; Nandanan; Chandwadkar; Sudalai; Ravindranathan; Sivasanker

Tetrahedron Letters, 1997 , vol. 38, # 20 p. 3631 - 3634 Title/Abstract

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A: 5% B: 29%

With air; silica supported 3lt;(2-hydroxybenzylidene)aminopropylgt;(triethoxy)silane Cr(III)

T=130°C; 24 h;

Chisem, Ian C.; Rafelt, John; Shieh, M. Tantoh; Chisem, Janet; Clark, James H.; Jachuck, Roshan; Macquarrie, Duncan; Ramshaw, Colin; Scott, Keith

Chemical Communications, 1998 , # 18 p. 1949 - 1950 Title/Abstract

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A: 5% B: 29%

With air; silica supported 3lt;(2-hydroxybenzylidene)aminopropylgt;(triethoxy)silane Cr(III)

T=130°C; 24 h;

Chisem, Ian C.; Rafelt, John; Shieh, M. Tantoh; Chisem, Janet; Clark, James H.; Jachuck, Roshan; Macquarrie, Duncan; Ramshaw, Colin; Scott, Keith

Chemical Communications, 1998 , # 18 p. 1949 - 1950 Title/Abstract

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A: 20.8% B: 26.1%

With dihydrogen peroxide; hydrogen bromide; copper(ll) bromide in water

T=380°C; P=187519 Torr; Condensed phase; Product distribution / selectivity; Hide Experimental Procedure

INVISTA TECHNOLOGIES S.A.R.L.

Patent: WO2009/134872 A2, 2009 ; Location in patent: Page/Page column 29-30; 35 ; Title/Abstract

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23:

Experimental conditions were the same as in Examples 1-22 except that: Flow rate of p-xylene = 0.28 mL/min Pressure = approx. 250 baraFlow rate oxidant (H2O2 in H2O) = 8.1 mL/min. (providing an amount of [O2] as aqueous H2O2 of 1.26 mol.L"1 (1.5 molar equivalents of the stoichiometry required for complete oxidation of the organic precursor to the aromatic acid, the molar ratio for which in the case of p-xylene is 3O2 / organic)).The data in Table 5 demonstrate that increase in catalyst concentration increases yield of terephthalic acid and reduces burn to carbon dioxide. It also further demonstrates the increased activity and reduced burn achieved with a copper-cobalt catalyst.

A: 3% B: 24%

With nitric acid; 1-n-butyl-3-methylimidazolium methanesulfonate in water

24 - 120 h; Heating / reflux; Hide Experimental Procedure

Earle, Martyn John; Katdare, Suhas Prabhakar

Patent: US2004/15009 A1, 2004 ; Location in patent: Page 2 ; Title/Abstract

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5:5. Oxidation of p-xylene

In a 50 cm3 round bottomed flask, equipped with a magnetic stirrer and reflux condenser, was added p-xylene (1.07 g, 10 mmol) and [bmim] [OMs] (2.0 g). 67percent Nitric acid (0.90 g, 10 mmol) was cautiously added and the mixture heated under reflux. After 24 hours the mixture was analysed by gas chromatography (approximately 50percent conversion), cooled and water (50 cm3) was added. The resultant precipitate was collected by filtration and purified by vacuum sublimation on a Kugelrohr apparatus. This gave two crystalline solids, that were identified as 4-methylbenzoic acid (0.50 g, 37percent) and benzene-1,4-dioic acid (terephthalic acid) (0.08 g, 5percent). The remainder was unreacted p-xylene. [0033] The aqueous filtrate containing the ionic liquid was concentrated on a rotary evaporator (80° C. at 50 mmHg) and transferred to the 50 cm3 round bottomed flask, equipped with a magnetic stirrer and reflux condenser. p-Xylene (5.35 g, 50 mmol) and 67percent nitric acid (0.90 g, 10 mmol) was added. The mixture was heated under reflux for 5 days, then cooled to room temperature. During this time some of the p-xylene was lost through evaporation. Dilution with water, filtration and sublimation (as above) gave 4-methylbenzoic acid (1.63 g, 24percent) and benzene-1,4-dioic acid (terephthalic acid) (0.24 g, 3percent). The remainder was unreacted p-xylene.

A: 24% B: 22%

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=170°C; P=21446.5 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

Schammel, Wayne P.; Adamian, Victor A.; Viswanath, Yenamandra; Zakharov, Igor V.

Patent: US2005/137420 A1, 2005 ; Location in patent: Page/Page column 9 ; Title/Abstract

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6:

EXAMPLES 6 AND 7; Oxidation of Para-Xylene to Terephthalic Acid; Experiments are conducted in a 300 mL titanium Parr mini-reactor. Initial reactor charge contained catalyst and 10 g of 95percent HOAc. Reactor was pressurized to 400 psig under N2 and heated to 170° C. After desired temperature has been reached, nitrogen atmosphere is switched to a continuous flow of 8 vol percent O2 in N2. After reactor is saturated with 8percent O2 (as determined by level of O2 in vent gas), feedstock (paraxylene) is pumped in at a rate of 0.5 mL/min for 60 min. After 60 min, 8percent O2 is switched to nitrogen, and the reactor is cooled down to room temperature, total reactor effluent (TRE) is removed and submitted for HPLC analysis. Vent gas is continuously analyzed for O2, CO2, CO. Vent gas is also sampled two or three times during each experiment and analyzed for volatile organic compounds using in-lab gas chromatography (GC).). In examples 6, and 7, catalyst in the initial charge consisted of: Co(OAc)2.4H2O=0.400 g; Mn(OAc)2.4H2O=0.115 g; 48percent HBr=0.127 g. In Example 7, AC (0.300 g) was added to the initial reactor charge.

A: 27 % Spectr.

B: 27 % Spectr.

With potassium permanganate; 2,3,5-triphenyl-2H-tetrazolium chloride in water; nitrobenzene

T=95°C; 1.25 h;

Kulic, J.; Adamek, M.; Zhivich, A. B.; Koldobskii, G. I.; Myznikov, Yu. E.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 10 p. 2370 - 2374,2118 - 2122 Title/Abstract

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A: 15 %

With N -hydroxyphthalimide; oxygen; cobalt acetylacetonate in acetic acid

Ishii, Yasutaka; Iwahama, Takahiro; Sakaguchi, Satoshi; Nakayama, Kouichi; Nishiyama, Yutaka

Turnov.

B: 78 % Turnov.

T=100°C; 6 h;

Journal of Organic Chemistry, 1996 , vol. 61, # 14 p. 4520 - 4526 Title/Abstract

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A: 51 % Spectr.

B: 10 % Spectr.

With potassium permanganate; 2,3,5-triphenyl-2H-tetrazolium chloride in water; nitrobenzene

T=95°C; 1.25 h;

Kulic, J.; Adamek, M.; Zhivich, A. B.; Koldobskii, G. I.; Myznikov, Yu. E.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 10 p. 2370 - 2374,2118 - 2122 Title/Abstract

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A: 68 % Turnov.

B: 23 % Turnov.

With N -hydroxyphthalimide; oxygen; cobalt acetylacetonate in acetic acid

T=100°C; 12 h;

Ishii, Yasutaka; Iwahama, Takahiro; Sakaguchi, Satoshi; Nakayama, Kouichi; Nishiyama, Yutaka

Journal of Organic Chemistry, 1996 , vol. 61, # 14 p. 4520 - 4526 Title/Abstract

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With oxygen; acetic acid; 1,3,5-trihydroxyhexahydro-1,3,5-triazine-2,4,6trione; cobalt(II) acetate

T=100°C; P=760 Torr; Product distribution; Further Variations:Reagents;

Hirai, Naruhisa; Sawatari, Naoko; Nakamura, Norihiro; Sakaguchi, Satoshi; Ishii, Yasutaka

Journal of Organic Chemistry, 2003 , vol. 68, # 17 p. 6587 - 6590 Title/Abstract

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With oxygen; cobalt(II) acetate; cerium(III) acetate in water

T=130°C; 6 h; Product distribution / selectivity; Hide Experimental Procedure

Saxena, Mahendra Pratap; Gupta, Ashok Kumar; Sharma, Satish Kumar; Bangwal, Dinesh Prasad; Kumar, Krishan

Patent: US2006/247464 A1, 2006 ; Location in patent: Page/Page column 3 ; Title/Abstract

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4:

EXAMPLE-4; p-Xylene (30.01 g) was oxidized with oxygen at 150° C. in the presence of 4.4 g cobaltous acetate and 0.3 g cerium(III)acetate as catalyst in 150 g of water. The reaction was carried out and worked up as in example-1. In the absence of p-TA but in the presence of cerium with cobalt. 20.05percent Of p-xylene was converted into oxygenated compounds. White solid product was found consisting of p-TA 96.62percent terephthalic acid 0.42percent and others 2.96percent.

With oxygen; acetic acid; diacetoxyplatinum; tetrakis(acetato)dimolybdenum(II) in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ; Title/Abstract

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43-23:

EXAMPLE 43; Following the procedure of Examples 1-4, a series of para-xylene oxidation trials in aqueous acetic acid solvent was conducted using compositions prepared from various combinations of one or more acetic acid soluble salts of palladium, platinum, vanadium, titanium, molybdenum, chromium, tin, antimony and, in some cases, acetic acid-soluble salts of one or more of additional metal or metalloid or standardized solutions thereof in aqueous acetic acid in amounts providing the metals or metalloids in about equal parts by weight corresponding to about 500 ppmw based on weight of acetic acid solvent used in the oxidations. Metal and metalloid combinations, temperatures and oxidation results are reported in TABLE 14; results of Examples 1-4 are also included for reference.

With N-hydroxy-1,8-naphthalenedicarboximide; oxygen; cobalt(II) acetate; manganese(II) acetate; acetic acid

T=99.84°C; P=750.075 Torr; 24 h;

Falcon; Campos-Martin; Al-Zahrani; Fierro

Catalysis Communications, 2010 , vol. 12, # 1 p. 5 - 8 Title/Abstract

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With oxygen; acetic acid; cobalt(II) acetate; manganese(II) acetate in water

T=120 - 160°C; P=750.075 - 2250.23 Torr; Product distribution / selectivity; Hide Experimental Procedure

Zhou, Xiangjin

Patent: EP2281799 A1, 2011 ; Location in patent: Page/Page column 11-13 ; Title/Abstract

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3:

Example 3:; for the combination with two oxidation reactors instance: wherein the first oxidation reactor apply tower type reactor with the assistant material of compressed air; Apply a tower type reactor with the assistant material of oxygen at the second oxidation reactor. Apply a tower type oxidation reactor with the diameter of 4000mm, and with the height of 24000mm as the first oxidation reactor, apply paraxylene (PX) as material, acetic acid as start solvent, cobalt acetate, manganese acetate as catalyst, the ion content (the sum of ion mass) of cobalt and manganese of effective ingredients in catalyst is 700ppm, the proportion of cobalt to manganese is 1:1. The feed-in proportions (as mass) of start materials of PX, acetic acid, and water are respectively 30percent, 64percent, and 6percent. The prepared materials and catalysts are fed from the top of oxidation reactor, and the liquid phase materials go downwards. The feed-in flow rate of PX is 128t/h. Blow into compressed air from the bottom of reactor, the reaction heat is removed from the top of reactor by solvent flash vaporization, then recycle the heat by heat exchanger which can be a condensation tower, after removing a little of acetic acid, part of the water is sent back to the oxidation reactor. The water content inside reactor is 8-20percent, the typical water content is 12percent. Control the oxygen content in tail gas from reactor to be less than 1-3percent, so as to ensure the safety of oxidation reactor and increase the utilization rate of compressed air. The inlet pressure of compressed air is 0.5 MPaG. The pressure inside reactor is 0.1-0.3MPaG. The reaction temperature is 120-160°C, the typical temperature is 128-130°C. Because it is difficult to oxidize PT acid further, and without the assistant catalyst of hydrobromic acid inside system, in this condition, the PX is mainly oxidized into PT acid, and a little of PT acid can be further oxidized into TA and deposit in the form of crystal. There is no PX near the outlet area at the bottom of reactor. The materials come out from bottom, and are vaporized and concentrated to remove the acetic acid, water, and a little of PX to obtain the mixture consisted of 73percent PT acid, 15percentTA, 8percent acetic acid, and 4percent water. In the proportion of 1:2.5, mix and beat this mixture with deionized water into slurry, add the hydrobromic acid as assistant catalyst according to the PX content of 350ppm (ion mass concentration), and the cobalt and manganese catalysts added in the first stage still exist and are available. Send the slurry into the upside of liquid phase at the reactor with a high velocity pump. The second oxidation reactor applies a set of tower type oxidation reactor (or oxidation reactor with the structure of internal and external chambers, or oxidation reactor with the structure of internal, medium, and external chambers, or horizontal plug-flow oxidation reactor) with the diameter of 4500mm, and the height of 28000mm. Apply oxygen (or compressed air) as assistant material. The liquid phase temperature at the second oxidation reactor is 285-300°C, the typical temperature is 288°C. Temperature is the first control factor, pressure is the second. Apply solvent flash vaporization to remove heat that the vapor comes out of the reactor from the top of reactor, the solvent consisted of water and acetic acid is segregated by condensation tower on the top of oxidation reactor, then the water and acetic acid are respectively enter into tanks. Heat up the vapor by segregation tower to recycle the heat. Part of condensation water is sent back into oxidation reactor to make sure that the proportion of acetic acid and water of solvent phase inside reactor is 1:4 to 1:99, and the typical proportion is 3:17. Because the water content in liquid phase materials at the place of feeding oxygen is up to 61 percent, the sum of organic phase is about 39percent, the condition of acute oxidation reaction does not occur. Control the oxygen content in tail gas from reactor to be less than 1-2percent, so as to ensure the safety of oxidation reactor and increase the utilization rate of oxygen. Because of the exothermic reaction of liquid phase materials at the bottom of reactor, result in the local warming (or trend), and the water and acetic acid is gasified and ascended, then the water and acetic acid vapors arrive into the gas phase at the top of reactor, enter into segregation tower, so that the heat is removed. The ascending process of vapors has a disturbance effect on the plunger-flow travelling downwards of liquid phase materials, but it is unable to result in the top material containing PT acid quickly depositing into bottom. The TA crystal in the slurry added from the top of liquid phase at the reactor dissolves very quickly during the deposition process, and the 4-CBA contained in TA crystal is also oxidized into TA very quickly. The inlet pressure of oxygen is 8.1 MPaG. The pressure inside reactor is 7.3-7.5MPaG. The main ingredient of oxidized tail gas is a little of oxygen, carbon dioxide, carbon monoxide, and trace acetic acid and other organic ingredients. The pressure is 7.5MPaG. The outlet from oxidation reactor bottom is TA solution, wherein the TA is 27percent, acetic acid is 11percent, and water is 72percent. The TA solution is sent into the first crystallizer and flash vaporized and crystallized at 255°C, about 19.5percent of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Refine the acetic acid, then use it as solvent of preparing PX material, add the water which is used as deionized water for the second oxidation reactor into reactor to complement the assistant solvent water, decrease the concentration of acetic acid and reduce the consumption of acetic acid. The residual solution from the first crystallizer is sent into the second crystallizer, and flash vaporized and crystallized at 200°C, about 7percent of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Crude acetic acid and water are respectively sent into tanks. The residual solution from the second crystallizer is sent into the third crystallizer, and flash vaporized and crystallized at 150°C, about 0.8percent of TA is crystallized into crystal. The residual solution from the third crystallizer is filtered to remove the solid impurities, a part of it is sent into recycle system for mother liquor to recycle the catalyst and remove the soluble impurities, the other mother liquor are used for the beating of PT acid. Acetic acid wash(remove the catalyst and assistant catalyst of cobalt, manganese, and bromine, also this process can be omitted), separate, and dry the CTA crystal obtained from crystallization system, and then water wash, separate, and dry it, obtain the PPTA production wherein the contents of 4-CBA is less than 10ppm, and the PT acid is less than 5ppm. PPTA yield per hour is 200t. The consumption of PX per PPTA product is 652kg/t, the consumption of fuel and power is 99kg standard oil per ton. The consumption of acetic acid is 9kg/t.

With air; cobalt(II) acetate; manganese(II) acetate in water; acetic acid

T=128 - 130°C; Hide Experimental Procedure

Zhou, Xiangjin

Patent: US2011/40121 A1, 2011 ; Location in patent: Page/Page column 8-9 ; Title/Abstract

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3:

for the combination with two oxidation reactors instance: wherein the first oxidation reactor apply tower type reactor with the assistant material of compressed air; Apply a tower type reactor with the assistant material of oxygen at the second oxidation reactor.Apply a tower type oxidation reactor with the diameter of 4000 mm, and with the height of 24000 mm as the first oxidation reactor, apply paraxylene (PX) as material, acetic acid as start solvent, cobalt acetate, manganese acetate as catalyst, the ion content (the sum of ion mass) of cobalt and manganese of effective ingredients in catalyst is 700 ppm, the proportion of cobalt to manganese is 1:1. The feed-in proportions (as mass) of start materials of PX, acetic acid, and water are respectively 30percent, 64percent, and 6percent. The prepared materials and catalysts are fed from the top of oxidation reactor, and the liquid phase materials go downwards. The feed-in flow rate of PX is 128 t/h.Blow into compressed air from the bottom of reactor, the reaction heat is removed from the top of reactor by solvent flash vaporization, then recycle the heat by heat exchanger which can be a condensation tower, after removing a little of acetic acid, part of the water is sent back to the oxidation reactor. The water content inside reactor is 8-20percent, the typical water content is 12percent. Control the oxygen content in tail gas from reactor to be less than 1-3percent, so as to ensure the safety of oxidation reactor and increase the utilization rate of compressed air.The inlet pressure of compressed air is 0.5 MPaG The pressure inside reactor is 0.1-0.3 MPaG. The reaction temperature is 120-160° C., the typical temperature is 128-130° C. Because it is difficult to oxidize PT acid further, and without the assistant catalyst of hydrobromic acid inside system, in this condition, the PX is mainly oxidized into PT acid, and a little of PT acid can be further oxidized into TA and deposit in the form of crystal.There is no PX near the outlet area at the bottom of reactor. The materials come out from bottom, and are vaporized and concentrated to remove the acetic acid, water, and a little of PX to obtain the mixture consisted of 73percent PT acid, 15percent TA, 8percent acetic acid, and 4percent water. In the proportion of 1:2.5, mix and beat this mixture with deionized water into slurry, add the hydrobromic acid as assistant catalyst according to the PX content of 350 ppm (ion mass concentration), and the cobalt and manganese catalysts added in the first stage still exist and are available. Send the slurry into the upside of liquid phase at the reactor with a high velocity pump.The second oxidation reactor applies a set of tower type oxidation reactor (or oxidation reactor with the structure of internal and external chambers, or oxidation reactor with the structure of internal, medium, and external chambers, or horizontal plug-flow oxidation reactor) with the diameter of 4500 mm, and the height of 28000 mm. Apply oxygen (or compressed air) as assistant material.The liquid phase temperature at the second oxidation reactor is 285-300° C., the typical temperature is 288° C. Temperature is the first control factor, pressure is the second. Apply solvent flash vaporization to remove heat that the vapor comes out of the reactor from the top of reactor, the solvent consisted of water and acetic acid is segregated by condensation tower on the top of oxidation reactor, then the water and acetic acid are respectively enter into tanks. Heat up the vapor by segregation tower to recycle the heat. Part of condensation water is sent back into oxidation reactor to make sure that the proportion of acetic acid and water of solvent phase inside reactor is 1:4 to 1:99, and the typical proportion is 3:17.Because the water content in liquid phase materials at the place of feeding oxygen is up to 61percent, the sum of organic phase is about 39percent, the condition of acute oxidation reaction does not occur. Control the oxygen content in tail gas from reactor to be less than 1-2percent, so as to ensure the safety of oxidation reactor and increase the utilization rate of oxygen.Because of the exothermic reaction of liquid phase materials at the bottom of reactor, result in the local warming (or trend), and the water and acetic acid is gasified and ascended, then the water and acetic acid vapors arrive into the gas phase at the top of reactor, enter into segregation tower, so that the heat is removed. The ascending process of vapors has a disturbance effect on the plunger-flow travelling downwards of liquid phase materials, but it is unable to result in the top material containing PT acid quickly depositing into bottom. The TA crystal in the slurry added from the top of liquid phase at the reactor dissolves very quickly during the deposition process, and the 4-CBA contained in TA crystal is also oxidized into TA very quickly.The inlet pressure of oxygen is 8.1 MPaG. The pressure inside reactor is 7.3-7.5 MPaG.The main ingredient of oxidized tail gas is a little of oxygen, carbon dioxide, carbon monoxide, and trace acetic acid and other organic ingredients. The pressure is 7.5 MPaG.The outlet from oxidation reactor bottom is TA solution, wherein the TA is 27percent, acetic acid is 11percent, and water is 72percent. The TA solution is sent into the first crystallizer and flash vaporized and crystallized at 255° C., about 19.5percent of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Refine the acetic acid, then use it as solvent of preparing PX material, add the water which is used as deionized water for the second oxidation reactor into reactor to complement the assistant solvent water, decrease the concentration of acetic acid and reduce the consumption of acetic acid.The residual solution from the first crystallizer is sent into the second crystallizer, and flash vaporized and crystallized at 200° C., about 7percent of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Crude acetic acid and water are respectively sent into tanks.The residual solution from the second crystallizer is sent into the third crystallizer, and flash vaporized and crystallized at 150° C., about 0.8percent of TA is crystallized into crystal.The residual solution from the third crystallizer is filtered to remove the solid impurities, a part of it is sent into recycle system for mother liquor to recycle the catalyst and remove the soluble impurities, the other mother liquor are used for the beating of PT acid.Acetic acid wash (remove the catalyst and assistant catalyst of cobalt, manganese, and bromine, also this process can be omitted), separate, and dry the CTA crystal obtained from crystallization system, and then water wash, separate, and dry it, obtain the PPTA production wherein the contents of 4-CBA is less than 10 ppm, and the PT acid is less than 5 ppm.PPTA yield per hour is 200 t. The consumption of PX per PPTA product is 652 kg/t, the consumption of fuel and power is 99 kg standard oil per ton. The consumption of acetic acid is 9 kg/t.

With oxygen; 1-hydroxy-pyrrolidine-2,5-dione; cobalt(II) acetate; manganese(II) acetate in water

T=150°C; P=3750.38 Torr; 5 h; Product distribution / selectivity; Hide Experimental Procedure

Shibamoto, Akihiro

Patent: US2011/71313 A1, 2011 ; Location in patent: Page/Page column 12 ; Title/Abstract

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3:

Example 3; The reaction was conducted in the same manner as in Example 1 except that 10 g (73.5 mmol) of p-toluic acid was used in addition to 300 g (2.8 mol) of p-xylene and that the amount of manganese acetate (bivalent) was 0.10 g instead of 0.20 g and the amount of N-hydroxysuccinimide was 0.17 g instead of 0.25 g. The conversion of the substrate and the amount of the product were determined. As the results, the conversion of p-xylene was 48.9percent, and the amounts of the products were as follows: 150 g of p-toluic acid, 44 g of terephthalic acid, and 0.40 g of benzoic acid as a by-product.

With N -hydroxyphthalimide; oxygen; acetic acid

T=89.84°C; P=15001.5 Torr; 3 h; Autoclave;

Aguadero; Falcon; Campos-Martin; Al-Zahrani; Fierro; Alonso

Angewandte Chemie - International Edition, 2011 , vol. 50, # 29 p. 6557 - 6561 Title/Abstract

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With oxygen; 1,3,5-trihydroxyhexahydro-1,3,5-triazine-2,4,6-trione; acetone oxime

T=80°C; 13 h; Ionic liquid;

Lu, Tingting; Mao, Yang; Yao, Kai; Xu, Jian; Lu, Ming

Catalysis Communications, 2012 , vol. 27, p. 124 - 128 Title/Abstract

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With manganese(IV) oxide; oxygen; 1,3,5-trihydroxyhexahydro-1,3,5-triazine2,4,6-trione

T=80°C; 15 h; Ionic liquid;

Lu, Tingting; Zhang, Lijie; Ge, Zhongxue; Ji, Yueping; Lu, Ming

Applied Organometallic Chemistry, 2015 , vol. 29, # 5 p. 276 - 279 Title/Abstract

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A

B

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14

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A: 93% B: 93%

Stage #1: With potassium hydoxide in water

T=20°C; Cannizzaro reaction; Stage #2: With hydrogenchloride in water

Chandrasekhar, Sosale; Srimannarayana, Malempati

Synthetic Communications, 2009 , vol. 39, # 24 p. 4473 - 4478 Title/Abstract

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A: 91%

With TEA; magnesium bromide in dichloromethane

T=20°C; Cannizzaro reaction; 48 h;

Abaee, M. Saeed; Sharifi, Roholah; Mojtahedi, Mohammad M.

Organic Letters, 2005 , vol. 7, # 26 p. 5893 - 5895 Title/Abstract

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A: 18% B: 51%

With potassium hydroxide

T=80°C; solvent-free Cannizzaro reaction; 0.05 h;

Yoshizawa, Kazuhiro; Toyota, Shinji; Toda, Fumio

Tetrahedron Letters, 2001 , vol. 42, # 45 p. 7983 - 7985

Title/Abstract

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With C-200 Ba(OH)2*0.8H2O in ethanol

0.166667 h; bain a ultrasons; Yield given. Yields of byproduct given;

Fuentes, A.; Sinisterra, J. V.

Tetrahedron Letters, 1986 , vol. 27, # 26 p. 2967 - 2970 Title/Abstract

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A: 85 % Chromat.

B: 10 % Chromat.

With barium dihydroxide; formaldehyd

T=100 - 110°C; 0.616667 h;

Varma, Rajender S.; Naicker, Kannan P.; Liesen, Per J.

Tetrahedron Letters, 1998 , vol. 39, # 46 p. 8437 - 8440 Title/Abstract

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With aluminum oxide; sodium hydroxide; water

0.00416667 h; Irradiation; Yield givenYields of byproduct given;

Sharifi; Mojtahedi; Saidi

Tetrahedron Letters, 1999 , vol. 40, # 6 p. 1179 - 1180 Title/Abstract

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With sodium hydroxide in water

T=20°C; Cannizzaro Reaction; 2.5 h;

Daemi, Hamed; Rad, Reza Rezaieyeh; Barikani, Mehdi; Adib, Mehdi

Applied Catalysis A: General, 2013 , vol. 468, p. 10 - 17 Title/Abstract

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A: 66 %Spectr.

With 1-hydrosilatrane; sodium hydroxide in N,N-dimethyl-formamide

T=20°C; 0.5 h;

Skrypai, Vladislav; Hurley, Joseph J. M.; Adler, Marc J.

European Journal of Organic Chemistry, 2016 , vol. 2016, # 12 p. 2207 - 2211 Title/Abstract

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Stage #1: in neat (no solvent) 0.0333333 h; Green chemistry; Stage #2: With 1,4-diaza-bicyclo[2.2.2]octane in neat (no solvent) T=40°C; Cannizzaro Reaction; 0.0111111 h; Microwave irradiationGreen chemistry; Reagent/catalyst; Hide Experimental Procedure

Marvi, Omid; Talakoubi, Maryam

Oriental Journal of Chemistry, 2016 , vol. 32, # 1 p. 359 - 365 Title/Abstract

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General procedure: In a 50 mL beaker, aldehyde (1 mmol) was roughly mixed with 1 g montmorillonite. After 2 min of mechanical stirring, DABCO (10 mmol) was added and then mixture was submitted into a single mode focused microwave reactor with continuous rotation for the time described in Table 1 (optimized time) at 40 °C. After completing the reaction (TLC), water (30 mL) was added to the mixture ,the product was washed by CH2Cl2(2×10 mL), clay was filtered, and the solvent was evaporated to give the alcohol component. To obtain the acid component, the filtrate was acidified, extracted with CH2Cl2, and dried over magnesium sulphate. Then the solvent was evaporated to givethe acid component.The solid clay portion was washed with methanol and dried at 120 °C under a reduced pressure to be reused in the subsequent reactions which showed the gradual decrease in the activity (Table 1). The filtrate was dried over MgSO4, the organic solvent was evaporated, and aryl alcohol was obtained. Isolated products were characterized by melting points, 1HNMR and 13C NMR spectrometric data and were compared with the literature and/or with authentic samples.

15

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Rx-ID: 2723755 Find similar reactions

With water in methanol

T=25°C; ΔS, ΔH (excit.), variation of solvent system; Kinetics;

Bentley, T. William; Carter, Gillian E.; Harris, H. Carl

Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1985 , p. 983 - 990 Title/Abstract

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With water; β-CD in acetonitrile

T=25°C; Kinetics; Further Variations:Reagents;

Bascuas; Garcia-Rio; Leis

Organic and Biomolecular Chemistry, 2004 , vol. 2, # 8 p. 1186 - 1193 Title/Abstract

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Multi-step reaction with 2 steps 1: pyridine 2: octacarbonyldicobalt / benzene / 1.25 h / 65 - 70 °C View Scheme

Roberto, Dominique; Alper, Howard

Journal of the Chemical Society, Chemical Communications, 1987 , # 3 p. 212 - 213 Title/Abstract

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Hide Details

Multi-step reaction with 2 steps 1: 85.2 percent 2: 1.) AcOH, Ac2O, 96percent H2SO4, 40percent H2O2, 2.) base / 1.) r.t., 4 h View Scheme

Conte, L.; Napoli, M.; Gambaretto, J. P.; Guerrato, A.; Carlini, F. M.

Journal of Fluorine Chemistry, 1994 , vol. 67, # 1 p. 41 - 46 Title/Abstract

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With hydrogenchloride; water in acetonitrile

T=25°C; Solvolysis; Kinetics; Concentration;

Campos-Rey; Cabaleiro-Lago; Hervés

Journal of Physical Chemistry B, 2010 , vol. 114, # 44 p. 14004 - 14011 Title/Abstract

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Multi-step reaction with 3 steps 1: triethylamine / diethyl ether 2: hydrogenchloride / water; acetonitrile 3: water; dimethyl sulfoxide / 25 °C View Scheme

Um, Ik-Hwan; Kim, Eun-Hee; Kang, Ji-Sun

Organic and Biomolecular Chemistry, 2011 , vol. 9, # 23 p. 8062 - 8067 Title/Abstract

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Multi-step reaction with 2 steps 1.1: triethylamine / dichloromethane / 0 - 20 °C / |Inert atmosphere; |Schlenk technique 2.1: ozone / dichloromethane / -78 °C / |Inert atmosphere 2.2: 24 h / 20 °C / |Inert atmosphere View Scheme

Berger, Martin; Chauhan, Rajan; Rodrigues, Catarina A. B.; Maulide, Nuno

Chemistry - A European Journal, 2016 , vol. 22, # 47 p. 16805 - 16808 Title/Abstract

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16

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Rx-ID: 2945719 Find similar reactions

With sodium periodate; lt;Pt(OH)2lt;IO5(OH)gt;2gt;(6-); sulfuric acid

1) aq. KOH, rt, 4 h; Yield given. Multistep reaction;

Dengel, Andrew C.; El-Hendawy, Ahmed M.; Griffith, William P.; Mostafa, Sahar I.; Williams, David J.

Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999), 1992 , # 24 p. 3489 - 3496 Title/Abstract

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With tert.-butylhydroperoxide in water

T=80°C; 12 h; Green chemistry;

Singh, Ajay K.; Basavaraju; Sharma, Siddharth; Jang, Seungwook; Park, Chan Pil; Kim, Dong-Pyo

Green Chemistry, 2014 , vol. 16, # 6 p. 3024 - 3030 Title/Abstract

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Multi-step reaction with 2 steps 1: silver(I) nitrite / diethyl ether / 5 h / 0 °C / |Reflux 2: tetra-(n-butyl)ammonium iodide; zinc diacetate; water / 24 h / 80 °C View Scheme

Marcé, Patricia; Lynch, James; Blacker, A. John; Williams, Jonathan M. J.

Chemical Communications, 2016 , vol. 52, # 5 p. 1013 - 1016 Title/Abstract

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Multi-step reaction with 2 steps 1.1: sodium hydride / tetrahydrofuran / 0.08 h / |Inert atmosphere 1.2: 5 h / |Inert atmosphere; |Reflux 2.1: bis(acetylacetonate)oxovanadium; sodium acetate; methyl 3,5-bis((1H-1,2,4triazol-1-yl)methyl)benzoate; oxygen / 48 h / 120 °C View Scheme

Urgoitia, Garazi; SanMartin, Raul; Herrero, María Teresa; Domínguez, Esther

Advanced Synthesis and Catalysis, 2016 , vol. 358, # 20 p. 3307 - 3312 Title/Abstract

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17

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Rx-ID: 4511036 Find similar reactions

89%

Stage #1: With tert.-butylhydroperoxide; FeCl3*6H2O; sodium hydroxide in water

T=80°C; 10 h; Stage #2: With hydrogenchloride in water

T=20°C;

Shaikh, Tanveer Mahamadali; Hong, Fung-E

Advanced Synthesis and Catalysis, 2011 , vol. 353, # 9 p. 1491 - 1496 Title/Abstract

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86%

With methyl 3,5-bis((1H-1,2,4-triazol-1-yl)methyl)benzoate; oxygen; sodium acetate; nickel dibromide

T=120°C; P=760.051 - 912.061 Torr; 48 h; chemoselective reaction;

Urgoitia, Garazi; Sanmartin, Raul; Herrero, María Teresa; Domínguez, Esther

Advanced Synthesis and Catalysis, 2016 , vol. 358, # 7 p. 1150 - 1156 Title/Abstract

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82%

With Oxonereg;; 2-iodo-3,4,5,6-tetramethylbenzoic acid in water; acetonitrile

12 h;

Moorthy, Jarugu Narasimha; Parida, Keshaba Nanda

Journal of Organic Chemistry, 2015 , vol. 79, # 23 p. 11431 - 11439 Title/Abstract

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81%

With iodine; oxygen; silica gel in di-isopropyl ether

T=20°C; 48 h; Irradiation;

Itoh, Akichika; Kodama, Tomohiro; Masaki, Yukio; Inagaki, Shinji

Synlett, 2002 , # 3 p. 522 - 524 Title/Abstract

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43%

With Oxonereg; in water; acetonitrile

24 h; Reflux; Hide Experimental Procedure

Parida, Keshaba Nanda; Moorthy, Jarugu Narasimha

Tetrahedron, 2014 , vol. 70, # 13 p. 2280 - 2285 Title/Abstract

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1:5.2 General procedure for the oxidative cleavage of olefins

General procedure: To a solution of the olefin (0.5–1.2 mmol) in 16 mL of acetonitrile–water (1:1) mixture at reflux was introduced oxone incrementally over the entire duration of the reaction. Progress of the reaction in each case was monitored by TLC analysis. After completion of the reaction as judged by TLC analysis, the reaction mixture was cooled to rt, and the organic matter was extracted with ethyl acetate. The combined organic extract was dried over anhyd Na2SO4 and concentrated in vacuo. The residue was subjected to a short-pad silica gel column chromatography to isolate pure product/s. All the products were characterized by their 1H NMR spectral data.

40%

With sodium hypochlorite; ruthenium tetroxide in tetrachloromethane; water

activation energy; KineticsThermodynamic data;

Hansen, Keith C.; Lin, Qing; Aminabhavi, Tejraj M.

Journal of the Chemical Society - Faraday Transactions, 1996 , vol. 92, # 19 p. 3643 - 3646 Title/Abstract

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A

B

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18

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With hydroxide in water; dimethyl sulfoxide

T=25°C; for determination of Hammett plot; Rate constant;

Um, Ik-Hwan; Chung, Eun-Kyung; Kwon, Dong-Sook

Tetrahedron Letters, 1997 , vol. 38, # 27 p. 4787 - 4790 Title/Abstract

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With sodium hydroxide in water; dimethyl sulfoxide

T=25°C; Kinetics;

Shin, Young-Hee; Kang, Ji-Sun; Um, Ik-Hwan

Bulletin of the Korean Chemical Society, 2016 , vol. 37, # 12 p. 2062 - 2065 Title/Abstract

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19

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89%

Rx-ID: 5855658 Find similar reactions

FINORGA

Patent: WO2006/66975 A1, 2006 ; Location in patent: Page/Page column 10-11; 13-14 ; Title/Abstract

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81%

Hide Experimental Procedure

Halcon International, Inc.

Patent: US4021453 A1, 1977 ; Title/Abstract

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11:EXAMPLE 11

EXAMPLE 11 Again repeating Example 7, but replacing the 4-nitrobenzoic acid with an equal molar quantity of p-toluic acid produced an oxidate in which 29percent of the thallic ion had been reduced and ethylene oxide had been produced in a quantity corresponding to a yield of 81percent based on thallic carboxylate reacted, the selectivity to acetaldehyde being 14percent.

Yamazaki,M. et al.

Chemical and Pharmaceutical Bulletin, 1970 , vol. 18, p. 901 - 907 Full Text View citing articles Show Details

Achmatowicz,O.; Achmatowicz,O.

Roczniki Chemii, 1961 , vol. 35, p. 813 - 820 Full Text View citing articles Show Details

Nakagawa,K. et al.

Journal of Organic Chemistry, 1962 , vol. 27, p. 1597 - 1601 Full Text View citing articles Show Details

Skvarchenko,V.R. et al.

J. Gen. Chem. USSR (Engl. Transl.), 1960 , vol. 30, # 11 p. 3535 - 3541,3502 - 3507 Full Text View citing articles Show Details

Dombrovskii,A.V. et al.

J. Gen. Chem. USSR (Engl. Transl.), 1962 , vol. 32, # 2 p. 603 - 607,592 - 596 Full Text View citing articles Show Details

Goethals,E.; de Radzitzky,P.

Bulletin des Societes Chimiques Belges, 1964 , vol. 73, p. 579 - 584 Full Text Show Details

Yano et al.

Kogyo Kagaku Zasshi, 1968 , vol. 71, p. 217,218, 219 Full Text Show Details

Schrauzer

Chemische Berichte, 1961 , vol. 94, p. 1891,1898 Full Text Show Details

Nenz; Ribaldone

Chimica e l'Industria (Milan, Italy), 1966 , vol. 48, p. 142 Full Text Show Details

Ho et al.

Synthesis, 1972 , p. 562 Full Text Show Details

Toland

Journal of the American Chemical Society, 1960 , vol. 82, p. 1911,1916 Full Text Show Details

Ikwartschenko et al.

J. Gen. Chem. USSR (Engl. Transl.), 1960 , vol. 30, p. 3535,3502 Full Text Show Details

Toland

Journal of Organic Chemistry, 1961 , vol. 26, p. 2929,2930 Full Text Show Details

Ayres; Gopalan

Journal of the Chemical Society, Chemical Communications, 1976 , p. 890 Full Text View citing articles Show Details

Seyferth et al.

Journal of Organometallic Chemistry, 1974 , vol. 65, p. 99,114 Full Text Show Details

Sicedison

Patent: IT702061 , 1966 ; Chem.Abstr., 1967 , vol. 67, # 21461 Full Text Show Details

Abdel-Wahhab et al.

Journal of Chemistry of the United Arab Republic, 1968 , vol. 11, p. 293,298 Full Text Show Details

Sam; Simmons

Journal of the American Chemical Society, 1972 , vol. 94, p. 4024 Full Text View citing articles Show Details

Kunichika et al.

Bulletin of the Institute for Chemical Research, Kyoto University, 1965 , vol. 43, p. 250,256 Full Text Show Details

Fahmy; Essawy

Egyptian Journal of Chemistry, 1976 , vol. 19, p. 937,942 Full Text Show Details

Ferguson; Wims

Journal of Organic Chemistry, 1960 , vol. 25, p. 668,669 Full Text Show Details

Barnes; Hickinbottom

Journal of the Chemical Society, 1961 , p. 2619 Full Text Show Details

Olah; Olah

Journal of Organic Chemistry, 1965 , vol. 30, p. 2386,2387 Full Text Show Details

Grekov et al.

Zhurnal Organicheskoi Khimii, 1970 , vol. 6, p. 94,93 Full Text Show Details

Buechi et al.

Arzneimittel Forschung, 1974 , vol. 24, p. 485,486 Full Text Show Details

Susuki et al.

Bulletin of the Chemical Society of Japan, 1968 , vol. 41, p. 2663 Full Text Show Details

Ethyl Corp.

Patent: US3647715 , 1966 ; Chem.Abstr., 1972 , vol. 76, # 112911y Full Text Show Details

Golubew et al.

Neftekhimiya, 1975 , vol. 15, p. 593,150 Full Text Show Details

Kornblum; Scott

Journal of the American Chemical Society, 1974 , vol. 96, p. 590 Full Text View citing articles Show Details

Allied Chemical Corp.

Patent: NL6415195 , 1963 ; Chem.Abstr., 1966 , vol. 64, # 2020b Full Text Show Details

Lin et al.

Journal of Labelled Compounds and Radiopharmaceuticals, 1976 , vol. 12, p. 631,632,633 Full Text View citing articles Show Details

Mehrotra; Pandey

Chemistry Letters, 1979 , p. 195 Full Text Show Details

Shigeyasu; Inoue

Kogyo Kagaku Zasshi, 1967 , vol. 70, p. 1155,1156,1157,1159 Full Text Show Details

Shigeyasu

Kogyo Kagaku Zasshi, 1967 , vol. 70, p. 1150,1151 Full Text Show Details

Omori et al.

Agricultural and Biological Chemistry, 1967 , vol. 31, p. 1337 Full Text Show Details

Otto; Paluch

Roczniki Chemii, 1972 , vol. 46, p. 1551,1552 Full Text Show Details

Tschernikow et al.

Azerbaidzhanskii Khimicheskii Zhurnal, 1974 , vol. 2, p. 18,21 Chem.Abstr., 1975 , vol. 82, # 31094 Full Text Show Details

Tsutsumi; Koyama

Discussions of the Faraday Society, 1968 , vol. 45, p. 247,248 Full Text Show Details

Stefanova et al.

J. Appl. Chem. USSR (Engl. Transl.), 1972 , vol. 45, p. 338,333

Full Text Show Details

Mechtiew et al.

Azerbaidzhanskii Khimicheskii Zhurnal, 1963 , vol. 4, p. 33,36-37 Chem.Abstr., 1964 , vol. 61, # 2884a Full Text Show Details

Hanna; Sarac

Journal of Organic Chemistry, 1977 , vol. 42, p. 2069 Full Text View citing articles Show Details

Lebedev et al.

Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1972 , vol. 21, p. 929 Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1972 , vol. 21, p. 967 Full Text View citing articles Show Details

Digurow et al.

Neftekhimiya, 1970 , vol. 10, p. 549 Chem.Abstr., 1970 , vol. 73, # 109438 Full Text Show Details

Sawgorodnii; Kogutowa

Neftekhimiya, 1965 , vol. 5, p. 869,870 Chem.Abstr., 1966 , vol. 64, # 8071 Full Text Show Details

Golubev et al.

Patent: SU362004 , 1973 ; Ref. Zh., Khim., 1973 , vol. 22, # N136P Full Text Show Details

Gitis et al.

Zhurnal Organicheskoi Khimii, 1966 , vol. 2, p. 666,667 Full Text Show Details

Manukowskaja et al.

Neftekhimiya, 1962 , vol. 2, p. 531 p. 291 Full Text Show Details

Fumasoni; Collepardi

Annali di Chimica (Rome, Italy), 1964 , vol. 54, p. 1122,1123,1124 Full Text Show Details

Kretow et al.

J. Appl. Chem. USSR (Engl. Transl.), 1960 , vol. 33, p. 2329,2295 Chem.Abstr., 1961 , # 6432 Full Text Show Details

Strickland; Bell

Industrial and Engineering Chemistry, 1961 , vol. 53, p. 7,9 Full Text Show Details

Errede; English

Journal of Organic Chemistry, 1963 , vol. 28, p. 2646 Full Text View citing articles Show Details

Stevens; van Es

Recueil des Travaux Chimiques des Pays-Bas, 1964 , vol. 83, p. 1294,1298 Full Text Show Details

Omori; Yamada

Agricultural and Biological Chemistry, 1970 , vol. 34, p. 659,661 Full Text Show Details

Pritzkow; Hofmann

Journal fuer Praktische Chemie (Leipzig), 1960 , vol. 12, p. 11,13,15 Full Text Show Details

Farah et al.

Journal of Organic Chemistry, 1965 , vol. 30, p. 1006,1007 Full Text Show Details

Ogata et al.

Journal of Organic Chemistry, 1961 , vol. 26, p. 4803,4805 Full Text Show Details

Thomason; Kubler

Journal of Chemical Education, 1968 , vol. 45, p. 546,547 Chem.Abstr., 1969 , vol. 70, # 47025x Full Text Show Details

Anantakrishnan; Jayaraman

Indian Journal of Chemistry, 1964 , vol. 2, p. 91 Full Text Show Details

Effenberger; Gleiter

Chemische Berichte, 1964 , vol. 97, p. 480 Full Text Show Details

Feifer; Welstead

Journal of Organic Chemistry, 1961 , vol. 26, p. 2567 Full Text View citing articles Show Details

Zimmermann; Zweig

Journal of the American Chemical Society, 1961 , vol. 83, p. 1211,1212 Full Text Show Details

Frimer et al.

Tetrahedron Letters, 1977 , p. 4631,4632, 4634 Full Text View citing articles Show Details

Allied Chem. Corp.

Patent: US3354148 , 1965 ; Chem.Abstr., 1968 , vol. 68, # 12501f Full Text Show Details

Schik et al.

Azerbaidzhanskii Khimicheskii Zhurnal, 1975 , vol. 5, p. 14 Chem.Abstr., 1976 , vol. 85, # 20794 Full Text Show Details

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Larhed, Mats; Alterman, Mathias; Wan, Yiqian; Hallberg, Anders; Kaiser, Nils-Fredrik

Patent: US2002/161266 A1, 2002 ; Title/Abstract

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1.2:Type I: Carbonylation

Examples 1-2 Type I: Carbonylation The reactions and the results of Examples 1 and 2 are shown in .

General Microwave Procedure for the Synthesis of Amides 2. [Mo(CO)6] (30.0 mg, 0.114 mmol) and 1.375 mL of a fresh toluene solution of palladacycle (8.0 mg, 8.5 μmol) and BINAP (14.0 mg, 22.0 μmol), were charged into a Smith Process Vial (a microwave-tube).

A teflon-coated stirring bar was added.

Utilizing the SmithSynthesizer 0.200 mL 4.0 M K2CO3(aq), 1.00 mL diglyme, 0.290 mmol amine and aryl halide (0.229 mmol, 0.100 mL of a stock solution of 4.59 mmol aryl halide in 2.00 mL diglyme) were dispensed into the microwave tube.

The tube was sealed (Crymper-seal) and the mixture was heated by microwaves at 150° C. for 15 minutes.

The mixture turned black during irradiation.

After cooling, the reaction mixture was filtrated and concentrated at reduced pressure.

The amide 2 was isolated by flash-chromatography.

Instead of the palladacycle and BINAP combination, corresponding amounts of 10percent Pd/C (18.1 mg) were used with aryl iodides. Pd(OAc)2 (3.8 mg) performed equally well with aryl iodides.

Note.

With Pd/C, an alternative fast, but less efficient way of isolating products 2 (~10-15percent lower yields), was to add HCl (2 mL of 2 M concentration) and 3 mL of diethyl ether to the reaction mixture after irradiation.

The mixture was shaken once and the ether phase was saved.

Evaporation gave pure 2.

Microwave Procedure for the Synthesis of p-Methyl Benzoic Acid 3. [Mo(CO)6] (30.0 mg, 0.114 mmol) and 10percent Pd/C (18.1 mg, 17.0 μmol) were charged into a Smith Process Vial (a microwave-tube).

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Cordi, Alex; Desos, Patrice; Lefoulon, Francois; Lestage, Pierre

Patent: US2002/37894 A1, 2002 ; Title/Abstract

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28:5,5-Dioxo-2,3,3a,4-tetrahydro-1 H-pyrrolo[2,1-c][1,2,4]-benzothiadiazin-7-yl 4-methylbenzoate

EXAMPLE 28 5,5-Dioxo-2,3,3a,4-tetrahydro-1 H-pyrrolo[2,1-c][1,2,4]-benzothiadiazin-7-yl 4-methylbenzoate Melting point: 198-200° C.

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E. I. du Pont de Nemours and Company

Patent: US6548698 B1, 2003 ; Title/Abstract

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4.b:(b)

(b) Concentration Effect A mixture of K2S2O8 (1.35 g), trifluoroacetic acid (4 mL), and the catalyst solution as prepared in Example 4(a) (1 mL) was stirred in air for 10 minutes.

After toluene (5 mL) was added, the mixture was stirred under CO (1 atm) at room temperature for 66 hours.

The mixture was diluted with water (5 mL), basified with NaOH, washed with ether, acidified with HCl, and thoroughly extracted with ether.

The combined etherial extracts were evaporated to dryness.

The residue was sublimed under vacuum to give 225 mg (TON=10) of p-toluic acid of >95percent purity (1H NMR).

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E. I. du Pont de Nemours and Company

Patent: US6548698 B1, 2003 ; Title/Abstract

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6:Oxidative Carbonylation of Toluene, Catalyzed by [Rh(CO2(trifluoroacetate)]x

Example 6 Oxidative Carbonylation of Toluene, Catalyzed by [Rh(CO2(trifluoroacetate)]x To a stirring mixture of K2S2O8 (1.40 g) and trifluoroacetic acid (5 mL) was added golden-yellow [Rh(CO)2(trifluoroacetate)]x (17 mg).

The reaction mixture turned deep purple immediately.

Toluene (5 mL) was added, and the dark mixture was stirred under CO (1 atm) at 65° C. (oil bath).

The color changed first to dark-red and then tan-brown in 0.5 and 2 hours, respectively.

After 54 hours water was added to the mixture.

The solution was evaporated, and the resulting mixture was extracted with ether (3*20 mL).

The combined ether extracts were dried with MgSO4 and taken to dryness, leaving 470 mg of toluic acid (TON=55).

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Ethyl Corporation

Patent: US3935216 A1, 1976 ; Title/Abstract

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1:Preparation of Para-Toluic Methane Sulfonic Anhydride

EXAMPLE 1 Preparation of Para-Toluic Methane Sulfonic Anhydride 25.4 g (0.1 mole) of para-toluic anhydride was dissolved in 100 ml of warm nitromethane and then 9.6 g (0.1 mole) of methane sulfonic acid was added.

The reaction mixture was stirred for 20 minutes and then filtered, giving 13.72 g (0.1 mole) of para-toluic acid precipitant.

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Mitsubishi Gas Chemical Company, Inc.

Patent: US3981909 A1, 1976 ; Title/Abstract

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C.3:Comparative Example 3

By distillation of the contents, 11.6 g of propylene oxide, 90.5 g of solvent acetone, and 53.0 g of p-toluic acid as the bottoms are obtained.

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Suntech, Inc.

Patent: US4093647 A1, 1978 ; Title/Abstract

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3:EXAMPLE 3

EXAMPLE 3 A quantity of p-tolylthallium bis(trifluoroacetate) STR1 was prepared by the method of A McKillop and J. D. Hunt as reported in J. Organometallic Chemistry, 24 (1970) 77-88.

A 75 ml Fischer-Porter tube was charged with 0.0188 gms of Pd(OOCCH3)2, 2.6 gms of p-tolyl thallium bis(trifluoroacetate), 5 ml of trifluoroacetic acid, and 5 ml of trifluoroacetic anhydride.

The reaction mixture was stirred at room temperature under 100 psig of CO pressure.

Very little CO uptake was observed until 15 ml of toluene was added to the Fisher-Porter tube after which the run proceeded as in Example 1.

The recovered toluic acid amounted to 0.2794 gms.

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Suntech, Inc.

Patent: US4093647 A1, 1978 ; Title/Abstract

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11:EXAMPLE 11

EXAMPLE 11 The experiment described in Example 1 was repeated except that 0.0117 gms of PdCl2 was used along with 0.866 gms of toluene.

The recovered toluic acid amounted to 0.471 gms.

The isomer distribution was found to be 91.1percent para, 4.5percent ortho and 4.3percent meta.

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Ethyl Corporation

Patent: US4136113 A1, 1979 ; Title/Abstract

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24.A:A.

A. Toluic Acid To a reaction vessel was added 5 grams (0.037 moles) of para toluic acid suspended in about 100 ml of benzene.

Then, 3.14 grams (0.0185 moles) of silicon tetrachloride were added and the reaction mixture stirred at room temperature.

A small amount of HCl gas evolved during this stirring.

Even though a small amount of material remained undissolved, the reaction mixture was distilled at 80° C. and atmospheric pressure.

The overhead condensate contained only benzene and silicon tetrachloride.

The pot residue was further heated until p-toluic acid sublimed.

Analysis of the liquid remaining in the pot showed it to contain what is probably a silicon chloro toluate.

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Suntech, Inc.

Patent: US4093647 A1, 1978 ; Title/Abstract

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4:EXAMPLE 4

EXAMPLE 4 A 75 ml Fisher-Porter tube was charged with 2.5 gms of p-tolyl thallium bis(trifluoroacetate), 10 ml of toluene, 5 ml of trifluoroacetic acid and 5 ml of trifluoroacetic anhydride.

The reaction mixture was stirred at room temperature under 84 psig of CO pressure.

There was no appreciable uptake of CO nor could any toluic acid be isolated from the reaction product after the workup procedure of Example 1.

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Suntech, Inc.

Patent: US4093647 A1, 1978 ; Title/Abstract

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7:EXAMPLE 7

EXAMPLE 7 A 75 ml Fischer-Porter tube was charged with 0.0152 gms of Pd(OOCCH3)2, 2.5 gms of TL(OOCCF3)3 0.5 gms of toluene, 5 ml of trifluoroacetic acid and 5 ml of trifluoroacetic anhydride.

The reaction mixture was pressured to 100 psig with CO and maintained at room temperature.

The reaction mixture turned a milky beige in color and there was essentially no CO uptake.

An additional 0.5 gms of toluene was added to the reaction mixture. CO uptake began and the mixture rapidly turned clear and pale yellow in color and the reaction proceeded as in Example 1.

After the usual workup procedure 0.436 gms of toluic acid were recovered indicating a 69.8percent utilization of the available Tl(III) oxidant.

Conversion of toluene to toluic acid amounted to 29.4percent.

The product contained 93.0percent.

The product contained 93.0percent para, 3.3percent ortho and 3.7percent meta isomers.

AMERICAN CYANAMID COMPANY

Patent: EP158000 B1, 1991 ;

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Title/Abstract

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8:Preparation of (+)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluic acid

The pure p -toluic acid can be obtained by hydrolysis of the corresponding methyl ester (of Example 9) with sodium hydroxide to give the product 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)- p -toluic acid as an amorphous solid with [α] [25/D ] = +6.09° (C = 0.0266 g/ml THF).

Nippon Soda Co., Ltd.; Ono, Kazuo; Kaneko, Masami; Amanokura, Natsuki

Patent: US8653160 B2, 2014 ;

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Title/Abstract

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The aromatic carboxylic acid compound is not particularly limited, and the following can be exemplified: benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2-n-propylbenzoic acid, 3-n-propylbenzoic acid, 4-n-propylbenzoic acid, ...

With sodium hydroxide in ethanol

T=80°C; 8 h; Schlenk technique; Temperature; Hide Experimental Procedure

Zhengzhou University; Niu, Junlong; Zhang, Linbao; Zhang, Shoukun; Hao, Xinqi; Ren, Baozeng; Song, Maoping

Patent: CN104370736 B, 2016 ; Location in patent: Paragraph 0022; 0026 ; Title/Abstract

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2.2:Preparation of 2-ethoxybenzoic acid

General procedure: Preparation of 2-ethoxy-benzoic acid: ethoxylated ortho product (0.2mmol, 52mg) obtained, NaOH (3mmol, 120mg) placed Schlenk tube, was added 1.5mL of ethanol, 80 °C under closed reaction 8h, after completion of the reaction the ethanol was removed under reduced pressure, dilute hydrochloric acid (5mL, 2N) and excess alkali, and then the mixture with CH2Cl2(5 × 4mL) was extracted, dried over anhydrous sodium sulfate, and column chromatography (CH2Cl2/CH3OH) to give 2-ethoxybenzoic acid 27mg, 80percent yield.

A

B

C

D

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A: 98.1% B: 0.2% C: 0.4% D: 0.4%

With hydrogen bromide; oxygen; acetic acid; cobalt(II) acetate; manganese(II) acetate in water

T=190°C; P=16501.7 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 14-15 ; Title/Abstract

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2:

CONTROLS 2-10; For purposes of comparison a bromine-promoted cobalt-manganese catalyst representative of catalysts used in commercial manufacture of terephthalic acid by oxidation of para-xylene was tested in Control 2. Bromine-free catalysts containing various amounts of cobalt and zirconium as in US Patent Application No. 2002/0188155 were used in Controls 3-10.For Control 2, cobalt(II) acetate tetrahydrate, manganese(II) acetate tetrahydrate and a solution of 48 wt percent hydrobromic acid in water were added to a solvent containing 95 wt percent acetic acid and 5 wt percent water in amounts providing 615 parts per million by weight ("ppmw") cobalt, 616 ppmw manganese and 1120 ppmw bromine. The solution was loaded into a stirred 100 mL titanium reactor. The reactor was sealed, pressurized to 22 bara with compressed nitrogen and heated to maintain a constant reactor temperature of 190° C. and, while maintaining those conditions, a gaseous mixture of 8 vol. percent oxygen and 92 vol percent nitrogen was added continuously at a rate of 2.0 grams/minute and para-xylene (>99percent pure) was added continuously at a rate of 0.133 gram/minute. After one hour, addition of para-xylene feed was stopped. Addition of the gaseous mixture was continued for an additional thirty minutes and then stopped. The reactor contents were then cooled and a sample of the total reactor product slurry was removed and analyzed by HPLC. Production of carbon oxides during the reaction was calculated based on concentrations in gas samples removed from the reactor during the last 30 minutes of para-xylene addition.For controls 3-10, cobalt(II) acetate tetrahydrate and a solution of 16.2 wt percent zirconyl(IV) acetate in water were added to an acetic acid and water solvent as in Control 2 in amounts providing varying levels of cobalt and zirconium. The resulting catalysts were loaded into a reactor as used in Control 2 and, while maintaining the reactor at a constant temperature of 195° C. and pressure of 22 bara, a nitrogen and oxygen mixture and para-xylene feed, both as in Control 2, were added continuously over a period of one hour at rates of 2.0 g/min. of the gas mixture and 0.133 g/min. of the para-xylene. Addition of para-xylene feed was discontinued after one hour and addition of the oxygen and nitrogen gas mixture was discontinued after another one-half hour. Reactor contents were then cooled and total product was analyzed as in Control 2. Carbon oxide production was calculated from vent gas samples taken during the last 30 minutes of p-xylene addition.Results of the oxidations with Controls 2-10 are reported in TABLE 3, in which numbers of the Controls are shown in the "No." column. From TABLE 3, it can be seen that the conventional, bromine-promoted cobalt and manganese catalyst of Control 2 was highly selective to TA with only minor production of less fully oxidized intermediates. PTOL, which is an intermediate oxidation product in oxidation of para-xylene to terephthalic acid, was the primary oxidation product produced in the bromine-free cobalt-zirconium catalyzed trials in Controls 3-10. It also can be seen that carbon oxide generation with the cobalt-zirconium-catalyzed controls was very high.

A: 50.3% B: 7.2% C: 6.4% D: 6.2%

With oxygen; acetic acid; palladium diacetate; antimony(III) acetate in water

T=182 - 195°C; P=16501.7 - 20929.4 Torr; 1 - 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 14; 15-16 ; Title/Abstract

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5; 7:

EXAMPLE 5; Weighed amounts of palladium(II) acetate, antimony(III) acetate and tin(II) acetate were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixture was batch loaded into a stirred 100 mL titanium reactor. The reactor was sealed, pressurized to 22 bara with compressed nitrogen and heated to about 190-195° C. and, while maintaining those conditions, a gaseous mixture of 8 vol. percent oxygen with nitrogen was added continuously at a rate of 1.0 gram/minute and greater than 99 wt percent pure para-xylene was added continuously at a rate of 0.133 gram/minute. After one hour, addition of para-xylene feed was stopped. Addition of the gaseous mixture was continued for an additional thirty minutes and then stopped. Vent gas removed from the reactor was sampled at intervals beginning after thirty minutes of para-xylene addition. The reactor contents were then cooled and a sample of product slurry resulting from the reaction was removed and analyzed by HPLC. TABLE 2 reports metals concentrations, yields of products determined by HPLC and carbon oxide production calculated from vent gas samples.From Example 5 and TABLE 2 it is evident that the palladium-antimony-tin composition of the example was active in the absence of bromine for conversion of para-xylene to derivatives with oxidized substituent groups at a yield of about 70 mole percent based on moles of para-xylene feed. Selectivity to carboxyl-substituted derivatives of the p-xylene feed was high, as seen not only from the 62.9percent combined yields of TA, 4CBA and PTOL, each of which includes at least one carboxyl-substituent, but also from the 50.3percent yield of TA. The 50.3percent TA yield based on para-xylene feed corresponds to about 72percent based on moles of para-xylene feed converted to oxidized alkyl aromatic derivatives. TA selectivity of the catalytic composition of Example 5 at the reaction temperature of the example was unexpected. Also as seen from the example and the table, good oxidized alkyl aromatic yield and carboxyl selectivity with the palladium-antimony-tin catalyst were achieved with carbon oxides generated in an amount corresponding to only 19percent of the molar amount of p-xylene added.; EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

A: 4.9% B: 3% C: 1.9% D: 36.9%

With hydrogen bromide; oxygen; acetic acid; zirconium oxyacetate; cobalt(II) acetate in water

T=190°C; P=16501.7 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 14-15 ; Title/Abstract

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3; 4; 5; 6; 7; 8; 9; 10:

CONTROLS 2-10; For purposes of comparison a bromine-promoted cobalt-manganese catalyst representative of catalysts used in commercial manufacture of terephthalic acid by oxidation of para-xylene was tested in Control 2. Bromine-free catalysts containing various amounts of cobalt and zirconium as in US Patent Application No. 2002/0188155 were used in Controls 3-10.For Control 2, cobalt(II) acetate tetrahydrate, manganese(II) acetate tetrahydrate and a solution of 48 wt percent hydrobromic acid in water were added to a solvent containing 95 wt percent acetic acid and 5 wt percent water in amounts providing 615 parts per million by weight ("ppmw") cobalt, 616 ppmw manganese and 1120 ppmw bromine. The solution was loaded into a stirred 100 mL titanium reactor. The reactor was sealed, pressurized to 22 bara with compressed nitrogen and heated to maintain a constant reactor temperature of 190° C. and, while maintaining those conditions, a gaseous mixture of 8 vol. percent oxygen and 92 vol percent nitrogen was added continuously at a rate of 2.0 grams/minute and para-xylene (>99percent pure) was added continuously at a rate of 0.133 gram/minute. After one hour, addition of para-xylene feed was stopped. Addition of the gaseous mixture was continued for an additional thirty minutes and then stopped. The reactor contents were then cooled and a sample of the total reactor product slurry was removed and analyzed by HPLC. Production of carbon oxides during the reaction was calculated based on concentrations in gas samples removed from the reactor during the last 30 minutes of para-xylene addition.For controls 3-10, cobalt(II) acetate tetrahydrate and a solution of 16.2 wt percent zirconyl(IV) acetate in water were added to an acetic acid and water solvent as in Control 2 in amounts providing varying levels of cobalt and zirconium. The resulting catalysts were loaded into a reactor as used in Control 2 and, while maintaining the reactor at a constant temperature of 195° C. and pressure of 22 bara, a nitrogen and oxygen mixture and para-xylene feed, both as in Control 2, were added continuously over a period of one hour at rates of 2.0 g/min. of the gas mixture and 0.133 g/min. of the para-xylene. Addition of para-xylene feed was discontinued after one hour and addition of the oxygen and nitrogen gas mixture was discontinued after another one-half hour. Reactor contents were then cooled and total product was analyzed as in Control 2. Carbon oxide production was calculated from vent gas samples taken during the last 30 minutes of p-xylene addition.Results of the oxidations with Controls 2-10 are reported in TABLE 3, in which numbers of the Controls are shown in the "No." column. From TABLE 3, it can be seen that the conventional, bromine-promoted cobalt and manganese catalyst of Control 2 was highly selective to TA with only minor production of less fully oxidized intermediates. PTOL, which is an intermediate oxidation product in oxidation of para-xylene to terephthalic acid, was the primary oxidation product produced in the bromine-free cobalt-zirconium catalyzed trials in Controls 3-10. It also can be seen that carbon oxide generation with the cobalt-zirconium-catalyzed controls was very high.

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With air; sodium bromide; Co3(O) in acetic acid

T=199.85°C; P=28443.1 Torr; Product distribution; Further Variations:Catalysts;

Chavan; Srinivas; Ratnasamy

Chemical Communications, 2001 , # 12 p. 1124 - 1125 Title/Abstract

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With N -hydroxyphthalimide; oxygen; cobalt(II) acetate in acetic acid

T=70°C; P=760 Torr; Kinetics; Further Variations:CatalystsReagents;

Saha, Basudeb; Koshino, Nobuyoshi; Espenson, James H.

Journal of Physical Chemistry A, 2004 , vol. 108, # 3 p. 425 - 431 Title/Abstract

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With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Industry scaleBubble column reactor; Hide Experimental Procedure

Wonders, Alan George; de Vreede, Marcel; Partin, Lee Reynolds; Strasser, Wayne Scott

Patent: US2006/47145 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

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1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately commingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Bubble column reactorIndustry scale; Hide Experimental Procedure

Wonders, Alan George; Partin, Lee Reynolds; Strasser, Wayne Scott; de Vreede, Marcel; Gupta, Puneet

Patent: US2006/47146 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

Full Text Show Details

1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately commingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel *overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Bubble column reactorIndustry scale; Hide Experimental Procedure

de Vreede, Marcel; Partin, Lee Reynolds; Strasser, Wayne Scott

Patent: US2006/47149 A1, 2006 ; Location in patent: Page/Page column 40-41 ; Title/Abstract

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Wonders, Alan George; Partin, Lee Reynolds; Strasser, Wayne Scott; de Vreede, Marcel

Patent: US2006/47151 A1, 2006 ; Location in patent: Page/Page column 40-41 ; Title/Abstract

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Wonders, Alan George; Jenkins, Howard Wood; Partin, Lee Reynolds; Strasser, Wayne Scott; de Vreede, Marcel

Patent: US2006/47157 A1, 2006 ; Location in patent: Page/Page column 40-41 ; Title/Abstract

Full Text Show Details

1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately commingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Bubble column reactorIndustry scale; Hide Experimental Procedure

Wonders, Alan George; Strasser, Wayne Scott; de Vreede, Marcel; Tidwell, J. Thomas

Patent: US2006/47147 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

Full Text Show Details

1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately coammingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about. 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed

calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Industry scaleBubble column reactor; Hide Experimental Procedure

Wonders, Alan George; de Vreede, Marcel; Partin, Lee Reynolds; Strasser, Wayne Scott

Patent: US2006/47160 A1, 2006 ; Location in patent: Page/Page column 40-41 ; Title/Abstract

Full Text Show Details

Wonders, Alan George; Jenkins, Howard Wood; Partin, Lee Reynolds; Strasser, Wayne Scott; de Vreede, Marcel

Patent: US2006/47162 A1, 2006 ; Location in patent: Page/Page column 40-41 ; Title/Abstract

Full Text Show Details

1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately commingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160°C; P=3900.39 Torr; Industry scaleBubble column reactor; Hide Experimental Procedure

Wonders, Alan George; Partin, Lee Reynolds; Strasser, Wayne Scott; de Vreede, Marcel; Gupta, Puneet

Patent: US2006/47158 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

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1:

This is an operational example from a commercial oxidation of para-xylene in a bubble column reactor. This example demonstrates, for example, that large vertical gradients exist for concentrations of para-xylene when appropriate geometric and process conditions are employed according to aspects of the current invention. This example employed a commercial bubble column oxidizer vessel having a nearly vertical, essentially cylindrical body with an inside diameter of about 2.44 meters.

The height of the bubble column oxidizer vessel was about 32 meters from lower tangent line (TL) to upper TL. The vessel was fitted with about 2:1 elliptical heads at the top and bottom of the cylinder. The operating level was about 25 meters of reaction medium above the lower TL. The feed rate of commercial-purity para-xylene was effectively steady at a rate of about 81 kilograms per minute, entering the reaction vessel through a circular hole located in the wall of the cylindrical section at an elevation of about 4.35 meters above the lower TL. The internal diameter of said wall hole was about 0.076 meters. A filtrate solvent was fed at an effectively steady rate of about 777 kilograms per minute. An unmetered fraction of this filtrate solvent, estimated from conduit sizes and pressure drops to be about 20 kilograms per minute, was feed as a liquid flush to the oxidant sparger. The balance of the filtrate solvent, about 757 kilograms per minute, was fed intimately commingled with the commercial-purity para-xylene. The combined liquid-phase feed stream of filtrate solvent and commercial-purity para-xylene thus amounted to about 838 kilograms per minute giving a superficial velocity of the inlet flow through said wall hole of about 3 meters per second. This filtrate solvent was from a plant recycle system and was comprised above about 97 weight percent of acetic acid and water. The concentration of catalyst components in the filtrate solvent was such that the composition within the liquid phase of the reaction medium was about 1,777 ppmw of cobalt, about 1,518 ppmw of bromine, and about 107 ppmw of manganese. A separate stream of reflux solvent was fed as droplets into the gas-disengaging zone above the operating level of the reaction medium at an effectively steady rate of about 572 kilograms per minute. This reflux solvent was comprised of above about 99 weight percent of acetic acid and water; and the reflux solvent was from a separate plant recycle system that was without significant levels of catalyst components. The combined water content of the filtrate solvent feed and of the reflux solvent feed was such that the concentration of water within the liquid phase of the reaction medium was about 6.0 weight percent. The oxidant was compressed air fed at an effectively steady rate of about 384 kilograms per minute through an oxidant sparger similar to the one illustrated in FIGS. 2-5. This oxidant sparger comprised a mitered flow conduit that was approximately an equal-sided octagon with a crossing member connecting from one side to the opposite side and traversing through the vertical axis of symmetry of the reaction vessel. The mitered flow conduit was made from nominal 12-inch Schedule 10 S piping components. The width of the octagon from the centroid of one side of the flow conduit to the centroid of the opposite side was about 1.83 meters. The octagon lay approximately horizontal, and the mid-elevation of the octagonal conduit was about 0.11 meters above the lower TL of the reaction vessel. The oxidant sparger contained 75 circular holes that were about 0.025 meters in diameter. The holes were situated approximately uniformly around the octagon and cross member, lying near the top of said 12-inch piping. There was one circular hole with diameter of about 0.012 meters near the bottom of one side only of the octagonal conduit. The operating pressure in the reaction vessel overhead gas was steadily about 0.52 megapascal gauge. The reaction was operated in a substantially adiabatic manner so that the heat of reaction elevated the temperature of the incoming feeds and evaporated much of the incoming solvent. Measured near the mid-elevation of the reaction medium, the operating temperature was about 160° C. An exiting slurry comprising crude terephthalic acid (CTA) was removed from near the bottom of the lower elliptical head of the reaction vessel at an effectively steady rate. The flow rate of the exiting slurry was about 408 kilograms per minute. Samples of slurry from the reaction medium were obtained from three elevations in the reaction vessel, as described below. In determining the concentration of various species at various locations within the reaction medium, it was necessary to account for the stochastic nature of the system by taking enough samples to determine a time-averaged value of sufficient resolution. One set of five samples was obtained from the exiting slurry conduit from near the bottom of the lower elliptical head of the reaction vessel. Another set of five samples was obtained from a wall hole located at an elevation of about 12.4 meters above the lower TL of the reaction vessel. The third set of five samples was obtained from a wall hole located at an elevation of about 17.2 meters above the lower TL of the reaction vessel. All slurry samples were analyzed by a calibrated gas chromatography (GC) method for composition of para-xylene and para-tolualdehyde in the liquid phase. Table 5, below, shows the average of the five results that were obtained from the three different column elevations. Results are reported as mass parts of analyte per million mass parts (ppmw) of liquid phase. These results show large gradients occurred vertically in the local concentrations of para-xylene and para-tolualdehyde. For example, the gradient in concentration of paraxylene observed in data of Table 5 was over 20:1 (455:21). These results demonstrate that the inherent fluid mixing of the entering para-xylene feed within the bubble column was importantly slower than the inherent reaction rates. To a lesser extent, vertical gradients also were observed for the concentrations of other related aromatic reactive species in the reaction medium (e.g., para-toluic acid and 4-carboxy benzaldehyde). As is demonstrated in subsequent examples, detailed calculational models show that the actual range of para-xylene concentration within the liquid phase of the reaction medium of this example was well in excess of 100:1. Even without executing a rigorous calculational model, those skilled in the art will recognize that the actual maximum concentration of para-xylene occurred in the region near where the feed para-xylene was introduced to the bubble column reaction vessel through the vessel wall. This elevation of maximum para-xylene concentration is about 4.35 meters above the lower TL, in between the samples take from about 12.4 meters and from the underflow. Similarly, the actual minimum concentration of para-xylene likely occurred at or very near the top of the reaction medium at about 25 meters, well above the highest elevation from where the above samples were taken. Concentrations of para-xylene and other oxidizable compounds can be measured for other locations within the reaction medium by employing suitable mechanical devices for sampling at any position vertically or horizontally within the reaction medium. Optionally, concentrations for positions not physically sampled and chemically analyzed may be calculated with reasonable accuracy using computational models of sufficient intricacy to cope with the highly complex fluid flow patterns, chemical reaction kinetics, energy balance, vapor-liquid-solid equilibriums, and inter-phase exchange rates.

With oxygen; Co 632ppm, Mn 632ppm, Br 1264ppm + Zr 96ppm in water; acetic acid

T=210°C; 0.0213333 - 0.081 h; Conversion of starting material; Hide Experimental Procedure

E.I. DU PONT DE NEMOURS AND COMPANY

Patent: EP1003699 B1, 2003 ; Location in patent: Page/Page column 4-5 ; Title/Abstract

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1.1; 1.2; 1.3; 1.4; 1.5; 1.6:

EXAMPLES; Example 1 Plug Flow Reactor Oxidations; Experiments were performed using a plug flow reactor system comprising two feed vessels, a reaction coil and two product collection vessels. Simultaneous flow from the feed vessels through the reaction coil into either one of the product collection vessels was established by differential gas pressure and appropriate valve operations. The first vessel was charged with a known compositon of paraxylene in acetic acid/water solvent. The second feed vessel was charged with a known composition of catalyst in acetic acid/water solvent. Air was introduced into both feed vessels, through dip pipes, at a pressure to ensure that the desired amount of oxygen (in excess of the stoichiometric paraxylene requirement) went into solution. The feed vessels and reaction coil were immersed in an oil bath to preheat the feeds to the required reaction temperature. Simultaneous flow from the feed vessels through the reaction coil was then established into the first product collection vessel labeled as "off spec". After a predetermined time, the product stream from the reaction coil was switched to the second product collection vessel. After a further predetermined time, the product stream was switched back to the "off-spec" collection vessel. At the end of the experiment, all vessels were cooled, vented, washed out and drained. The solid and liquid contents of the sample product collection vessel were recovered, weighed and analyzed, and the composition of the reaction solution leaving the reaction coil was calculated. In Table 1, the concentrations of the TA precursors paratolualdehyde (ptolald), paratoluic acid (ptol) and 4-carboxybenzaldehyde (4-CBA) are reported. for experiments where the reaction residence time was varied. At this scale, the reactions ran under nearly isothermal conditions, close to the oil bath temperature of 210°C throughout. The Examples demonstrate the effect of residence time on precursor concentrations. At 4.86 minutes residence time, single pass paraxylene conversion to TA was greater than 99.5percent (precursors less than 0.5percent of feed paraxylene). At 1.28 minutes residence time, single pass paraxylene conversion to TA fell to about 84percent. Significantly, however, paraxylene conversion to 4-CBA (the intermediate that tends to coprecipitate with TA in conventional processes) is of the order of 1percent or below throughout. High single pass conversion of paraxylene to TA is not essential to the process so long as the 4-CBA concentration in the reaction stream leaving the reactor is low. During the crystallization step, TA precursors substantially remain in solution in the reaction medium, i.e., dissolved in the mother liquor, and thereby they can be recycled to the plug flow oxidation reactor.

With hydrogen bromide; oxygen; cobalt(II) acetate; manganese(II) acetate; benzoic acid in water

T=234.99°C; P=36961.4 Torr; 0.25 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2008/194866 A1, 2008 ; Location in patent: Page/Page column 4-5 ; Title/Abstract

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3:

Example 3 was conducted as indicated above for Example 2, except that the gas purge during the oxidation step was changed from 21percent O2 to pure N2 as soon as all of the pX feedstock had been added, thereby eliminating the post-oxidation step. The conditions and results from Example 3 are listed below in Table 2 and illustrate that a secondary oxidation step is not essential for high levels of pX conversion. The TA concentration in the reactor of 7.77percent for Example 3 is below the solubility of TA given in Example 1 (10.9percent at 455° F.) indicating that all of the TA formed was in solution and suitable for direct feeding to the purification step without additional process steps and equipment to dissolve TA solids. The formation of only 0.255 mol COx/mol pX illustrates the desirable burning resistance of the solvent and feedstock under these conditions.

With oxygen; acetic acid; palladium diacetate; bismuth(III) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15-16 ; Title/Abstract

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8:

EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

With oxygen; acetic acid; bismuth(III) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15 ; Title/Abstract

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14:

CONTROLS 11-15; Weighed amounts of each of palladium(II) acetate, antimony(III) acetate and tin(II) acetate, bismuth (III) acetate and molybdenum(II) dimer were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixtures were batch loaded individually and in various combinations into a stirred, vented 300 mL titanium reactor. The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C., after which the nitrogen flow was replaced by a mixture of 8 vol. percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and para-xylene feedstock and supplemental solvent were added. The feedstock and supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after the reactor contents had reached 182° C., the temperature set-point was increased to 194° C. and after another 20 minutes the set-point temperature was increased to 195° C. After 60 minutes, feedstock and solvent additions were terminated. For 30 minutes thereafter the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the 30 minutes, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. The vent gas from the reactor was monitored continuously by a bank of on-line analyzers for carbon monoxide, carbon dioxide, and oxygen throughout span of the oxidation. The heating mantel was then removed and the reactor was cooled, depressurized, and unsealed. A representative sample of the reactor effluent was removed for analysis by HPLC. Results of the oxidations are reported in TABLE 4. Conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4-carboxybenzaldehyde ("4CBA"), p-toluic acid ("PTOL") and p-tolualdehyde ("PTOL") respectively, of the converted products weight. Acid Selectivity reported in the Table is the sum of TA, 4CBA and PTOL selectivities. Carbon oxides production was calculated from vent gas samples. Comparing TABLES 3 and 4, it is evident that none of the metals of Controls 11-15 approached the performance of the bromine-promoted cobalt and manganese catalyst of Control 1. Conversion of para-xylene in these trials was greatest with palladium in Control 11 but less than half that in Examples 1 and 2 with combinations of palladium and antimony and palladium and tin, respectively, and far below that in Examples 3-5 using palladium antimony and tin. Among Controls 11-15, only antimony and bismuth, in Controls 12 and 14, showed comparable selectivity to TA as the cobalt-zirconium compositions of Controls 3-10. However, as seen in TABLE 4, conversions in Controls 12 and 14 were only about 1percent.

With oxygen; acetic acid; titanium(IV) oxide bis(2,4pentanedionate); V(acac)3; diacetoxy-platinum in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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12:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate); V(acac)3 in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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10:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; V(acac)3; diacetoxy-platinum in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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11:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; V(acac)3 in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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19:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; tin(II) acetate; antimony(III) acetate in water

BP Corporation North America Inc.

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15-16 ; Title/Abstract

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16:

EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

With oxygen; acetic acid; palladium diacetate; tin(II) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15-16 ; Title/Abstract

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6:

EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

With oxygen; acetic acid; tin(II) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15 ; Title/Abstract

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13:

CONTROLS 11-15; Weighed amounts of each of palladium(II) acetate, antimony(III) acetate and tin(II) acetate, bismuth (III) acetate and molybdenum(II) dimer were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixtures were batch loaded individually and in various combinations into a stirred, vented 300 mL titanium reactor. The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C., after which the nitrogen flow was replaced by a mixture of 8 vol. percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and para-xylene feedstock and supplemental solvent were added. The feedstock and supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after the reactor contents had reached 182° C., the temperature set-point was increased to 194° C. and after another 20 minutes the set-point temperature was increased to 195° C. After 60 minutes, feedstock and solvent additions were terminated. For 30 minutes thereafter the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the 30 minutes, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. The vent gas from the reactor was monitored continuously by a bank of on-line analyzers for carbon monoxide, carbon dioxide, and oxygen throughout span of the oxidation. The heating mantel was then removed and the reactor was cooled, depressurized, and unsealed. A representative sample of the reactor effluent was removed for analysis by HPLC. Results of the oxidations are reported in TABLE 4. Conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4-carboxybenzaldehyde ("4CBA"), p-toluic acid ("PTOL") and p-tolualdehyde ("PTOL") respectively, of the converted products weight. Acid Selectivity reported in the Table is the sum of TA, 4CBA and PTOL selectivities. Carbon oxides production was calculated from vent gas samples. Comparing TABLES 3 and 4, it is evident that none of the metals of Controls 11-15 approached the performance of the bromine-promoted cobalt and manganese catalyst of Control 1. Conversion of para-xylene in these trials was greatest with palladium in Control 11 but less than half that in Examples 1 and 2 with combinations of palladium and antimony and palladium and tin, respectively, and far below that in Examples 3-5 using palladium antimony and tin. Among Controls 11-15, only antimony and bismuth, in Controls 12 and 14, showed comparable selectivity to TA as the cobalt-zirconium compositions of Controls 3-10. However, as seen in TABLE 4, conversions in Controls 12 and 14 were only about 1percent.

With oxygen; acetic acid; tetrakis(acetato)dimolybdenum(II); antimony(III) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15-16 ; Title/Abstract

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17:

EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

With oxygen; acetic acid; antimony(III) acetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15 ; Title/Abstract

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12:

CONTROLS 11-15; Weighed amounts of each of palladium(II) acetate, antimony(III) acetate and tin(II) acetate, bismuth (III) acetate and molybdenum(II) dimer were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixtures were batch loaded individually and in various combinations into a stirred, vented 300 mL titanium reactor. The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C., after which the nitrogen flow was replaced by a mixture of 8 vol. percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and para-xylene feedstock and supplemental solvent were added. The feedstock and supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after the reactor contents had reached 182° C., the temperature set-point was increased to 194° C. and after another 20 minutes the set-point temperature was increased to 195° C. After 60 minutes, feedstock and solvent additions were terminated. For 30 minutes thereafter the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the 30 minutes, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. The vent gas from the reactor was monitored continuously by a bank of on-line analyzers for carbon monoxide, carbon dioxide, and oxygen throughout span of the oxidation. The heating mantel was then removed and the reactor was cooled, depressurized, and unsealed. A representative sample of the reactor effluent was removed for analysis by HPLC. Results of the oxidations are reported in TABLE 4. Conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4-carboxybenzaldehyde ("4CBA"), p-toluic acid ("PTOL") and p-tolualdehyde ("PTOL") respectively, of the converted products weight. Acid Selectivity reported in the Table is the sum of TA, 4CBA and PTOL selectivities. Carbon oxides production was calculated from vent gas samples. Comparing TABLES 3 and 4, it is evident that none of the metals of Controls 11-15 approached the performance of the bromine-promoted cobalt and manganese catalyst of Control 1. Conversion of para-xylene in these trials was greatest with palladium in Control 11 but less than half that in Examples 1 and 2 with combinations of palladium and antimony and palladium and tin, respectively, and far below that in Examples 3-5 using palladium antimony and tin. Among Controls 11-15, only antimony and bismuth, in Controls 12 and 14, showed comparable selectivity to TA as the cobalt-zirconium compositions of Controls 3-10. However, as seen in TABLE 4, conversions in Controls 12 and 14 were only about 1percent.

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate); diacetoxyplatinum in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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21:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate) in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ;

Title/Abstract

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20:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; palladium diacetate; tetrakis(acetato)dimolybdenum(II) in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15-16 ; Title/Abstract

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9:

EXAMPLES 6-9 AND CONTROLS 16-17; Combinations of salt solutions used in Controls 11-15 were used in para-xylene oxidations and reactor liquid product and vent gas samples were analyzed following the procedures of Controls 11-15. Results are reported in TABLE 3. As with Examples 1 and 2, improved conversions in oxidations with the binary metal or metal and metalloid combinations in Examples 6-9 over results with the individual metals or metalloids in Controls 11-15 can be seen from TABLE 5 and comparison thereof with TABLE 4. Although metals concentration in Control 16, using a combination of antimony and tin, was about 4 times that in Control 1, also using antimony and tin, conversion was still low.

With oxygen; acetic acid; palladium diacetate in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15 ; Title/Abstract

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11:

CONTROLS 11-15; Weighed amounts of each of palladium(II) acetate, antimony(III) acetate and tin(II) acetate, bismuth (III) acetate and molybdenum(II) dimer were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixtures were batch loaded individually and in various combinations into a stirred, vented 300 mL titanium reactor. The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C., after which the nitrogen flow was replaced by a mixture of 8 vol. percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and para-xylene feedstock and supplemental solvent were added. The feedstock and supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after the reactor contents had reached 182° C., the temperature set-point was increased to 194° C. and after another 20 minutes the set-point temperature was increased to 195° C. After 60 minutes, feedstock and solvent additions were terminated. For 30 minutes thereafter the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the 30 minutes, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. The vent gas from the reactor was monitored continuously by a bank of on-line analyzers for carbon monoxide, carbon dioxide, and oxygen throughout span of the oxidation. The heating mantel was then removed and the reactor was cooled, depressurized, and unsealed. A representative sample of the reactor effluent was removed for analysis by HPLC. Results of the oxidations are reported in TABLE 4. Conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4-carboxybenzaldehyde ("4CBA"), p-toluic acid ("PTOL") and p-tolualdehyde ("PTOL") respectively, of the converted products weight. Acid Selectivity reported in the Table is the sum of TA, 4CBA and PTOL selectivities. Carbon oxides production was calculated from vent gas samples. Comparing TABLES 3 and 4, it is evident that none of the metals of Controls 11-15 approached the performance of the bromine-promoted cobalt and manganese catalyst of Control 1. Conversion of para-xylene in these trials was greatest with palladium in Control 11 but less than half that in Examples 1 and 2 with combinations of palladium and antimony and palladium and tin, respectively, and far below that in Examples 3-5 using palladium antimony and tin. Among Controls 11-15, only antimony and bismuth, in Controls 12 and 14, showed comparable selectivity to TA as the cobalt-zirconium compositions of Controls 3-10. However, as seen in TABLE 4, conversions in Controls 12 and 14 were only about 1percent.

With oxygen; acetic acid; diacetoxy-platinum in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16 ; Title/Abstract

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18:

CONTROLS 18-21 AND EXAMPLES 10-12; Oxidations were conducted as in Controls 11-15 using weighed amounts of platinum(II) acetate, vanadium(III) acetylacetonate and titanium(IV) oxide acetylacetonate in aqueous 95 wt. percent acetic acid. Results appear in TABLE 6. Oxidations were conducted by the same procedures using combinations of the platinum, vanadium and titanium metal solutions. Results are reported in TABLE 7. As seen from TABLES 6 an 7, oxidations with combinations of vanadium and titanium in Example 10, platinum and vanadium in Example 11 and platinum, titanium and vanadium in Example 12 resulted in higher conversions than when the individual metals were used in Controls 18-20. Conversion in Control 21 using platinum and titanium but lacking a Group 5, 6, 14 or 15 metal or metalloid was less than in Controls 18 and 20 in which platinum and titanium were used individually.

With oxygen; acetic acid; tetrakis(acetato)dimolybdenum(II) in water

T=182 - 195°C; P=20929.4 Torr; 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 15 ; Title/Abstract

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15:

CONTROLS 11-15; Weighed amounts of each of palladium(II) acetate, antimony(III) acetate and tin(II) acetate, bismuth (III) acetate and molybdenum(II) dimer were added to a solvent composed of 95 wt. percent acetic acid and 5 wt. percent water and the resulting mixtures were batch loaded individually and in various combinations into a stirred, vented 300 mL titanium reactor. The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C., after which the nitrogen flow was replaced by a mixture of 8 vol. percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and para-xylene feedstock and supplemental solvent were added. The feedstock and supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after the reactor contents had reached 182° C., the temperature set-point was increased to 194° C. and after another 20 minutes the set-point temperature was increased to 195° C. After 60 minutes, feedstock and solvent additions were terminated. For 30 minutes thereafter the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the 30 minutes, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. The vent gas from the reactor was monitored continuously by a bank of on-line analyzers for carbon monoxide, carbon dioxide, and oxygen throughout span of the oxidation. The heating mantel was then removed and the reactor was cooled, depressurized, and unsealed. A representative sample of the reactor effluent was removed for analysis by HPLC. Results of the oxidations are reported in TABLE 4. Conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4-carboxybenzaldehyde ("4CBA"), p-toluic acid ("PTOL") and p-tolualdehyde ("PTOL") respectively, of the converted products weight. Acid Selectivity reported in the Table is the sum of TA, 4CBA and PTOL selectivities. Carbon oxides production was calculated from vent gas samples. Comparing TABLES 3 and 4, it is evident that none of the metals of Controls 11-15 approached the performance of the bromine-promoted cobalt and manganese catalyst of Control 1. Conversion of para-xylene in these trials was greatest with palladium in Control 11 but less than half that in Examples 1 and 2 with combinations of palladium and antimony and palladium and tin, respectively, and far below that in Examples 3-5 using palladium antimony and tin. Among Controls 11-15, only antimony and bismuth, in Controls 12 and 14, showed comparable selectivity to TA as the cobalt-zirconium compositions of Controls 3-10. However, as seen in TABLE 4, conversions in Controls 12 and 14 were only about 1percent.

With dmap; oxygen; benzyl bromide in acetonitrile

T=160°C; P=7500.75 Torr; 3 h; Autoclave;

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968 Title/Abstract

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With oxygen; ammonium bromide; copper(ll) bromide in water

T=330°C; Flow reactor;

Pérez, Eduardo; Thomas, Morgan L.; Housley, Duncan; Hamley, Paul A.; Fraga-Dubreuil, Joan; Li, Jun; Lester, Edward; Poliakoff, Martyn

RSC Advances, 2016 , vol. 6, # 14 p. 11289 - 11294 Title/Abstract

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With dihydrogen peroxide; manganese (II) acetate tetrahydrate; cobalt(II) diacetate tetrahydrate; potassium bromide

T=100°C; Catalytic behavior; Reagent/catalyst; Hide Experimental Procedure

Nui, Pham Xuan; Dung, Nguyen Nho; Van Thi, Tran Thi

Asian Journal of Chemistry, 2016 , vol. 28, # 7 p. 1486 - 1492 Title/Abstract

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Catalytic oxidation of p-xylene in liquid phase

Oxidation reaction of p-xylene was carried out as follow: 20 mL of p-xylene and precisely weighed catalyst were added into a100 mL tree-neck round bottomed flask fitted with a water condenser and kept in water bath with continuous stirring. Hydrogen peroxide was dropped into the flask at a rate while the temperature was kept at a defined value. The contents of hydrogen peroxide were determined by iodometric method. After the reaction, the mixture was quenched to room temperature and then catalyst was filtered off. The oxidation products of p-xylene were identified by GC-MS 7890A-5975C with a (30 m × 250 μm × 0.25 μm) HP-5MS column, 45-250 °C (45 °C in 2 min, 4 °C/min to 200°C, 15 °C/min to 250 °C and kept in 5 min) and by LC-MS coinjection of standard compound. They were quantified by LCMS Series 2A Shimadzu (Japan) with UV 254 nm) detector and SPD-10ADVP column, eluent consisting of 1 percent acetic acid : acetonitrile with ratio 20:80 to 40:60 (w/w); with flow rate of 1 mL to 1.5 mL min-1. The p-xylene conversion was determined as (moles of reacted p-xylene)/(moles of initial pxylene)× 100 percent. The selectivity of product (terephthalic acid-TA) was determined as (moles of the product)/(moles of reacted p-xylene) × 100 percent.

21

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93%

With toluene-4-sulfonic acid

0.0666667 h; microwave irradiation;

Lee, Jong Chan; Yoo, Eun Sang; Lee, Jin Seo

Synthetic Communications, 2004 , vol. 34, # 16 p. 3017 - 3020 Title/Abstract

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93%

With [Ru3(CO)7(μ3-η2,η3,η5-acenaphthylene)]; Dimethylphenylsilane in DME

T=40°C; 7 h; Inert atmosphere;

Hanada, Shiori; Yuasa, Akihiro; Kuroiwa, Hirotaka; Motoyama, Yukihiro; Nagashima, Hideo

European Journal of Organic Chemistry, 2010 , # 6 p. 1021 - 1025 Title/Abstract

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88%

With high-silica Hβ-75 zeolite in water

T=130°C; 24 h; Reagent/catalyst; Hide Experimental Procedure

Siddiki; Toyao, Takashi; Kon, Kenichi; Touchy, Abeda S.; Shimizu, Ken-ichi

Journal of Catalysis, 2016 , vol. 344, p. 741 - 748 Title/Abstract

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2.4. Catalytic tests

General procedure: The heterogeneous catalysts, stored under ambient conditions,were used for catalytic reactions without any pretreatment. Typically,ester (1 mmol), 1 mL H2O and 10 mg of catalysts and a magneticstarter bar were added to a reaction vessel (Pyrex pressuretube, 13 mL), and the mixture was heated at 130 °C under air withstirring at 300 rpm. For the catalytic tests in Table 1 and kineticstudy, conversions and yields were determined by GC-FID usingn-dodecane as an internal standard as follows. After completionof the reaction, acetone (7 mL) was added to the mixture, andthe catalyst was separated by centrifugation. Then, n-dodecane(0.2 mmol) was added to the reaction mixture, and the mixturewas analyzed by GC-FID and GC-MS. The GC-FID sensitivities ofthe products were determined using commercial carboxylic acidsor the isolated products after the reaction. For some of the productsin Tables 2 and 3, we determined isolated yields of the carboxylicacids as follows. After the filtration of the catalyst, followed bywashing the catalyst with acetone (6 mL), and by evaporation,the product was isolated by column chromatography using silicagel 60 (spherical, 63-210 μm, Kanto Chemical Co. Ltd.) with hexane/ethyl acetate (60/40-80/20) as the eluting solvent, followedby analyses by 1H NMR, 13C NMR and GC-MS equipped with thesame column as GC-FID.

22

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93%

With pyrrolidine; dihydrogen peroxide in toluene

T=25°C; 2 h;

Khan, Shahnawaz; Ahmed, Qazi Naveed

European Journal of Organic Chemistry, 2016 , vol. 2016, # 32 p. 5377 - 5385 Title/Abstract

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90%

With iodine; dimethyl sulfoxide

T=180°C; 0.0833333 h; Inert atmosphereMicrowave irradiation;

Venkateswarlu, Vunnam; Aravinda Kumar; Gupta, Sorav; Singh, Deepika; Vishwakarma, Ram A.; Sawant, Sanghapal D.

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 29 p. 7973 - 7978 Title/Abstract

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Multi-step reaction with 2 steps 2: H2SO4

View Scheme

Kano, Kunio; Scarpetti, David; Anselme, Jean-Pierre

Tetrahedron Letters, 1985 , vol. 26, # 50 p. 6151 - 6154 Title/Abstract

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A

B

C

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23

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A: 37% B: 26% C: 9%

With tert.-butylhydroperoxide in water

T=160 - 180°C; 2 h; Microwave irradiationCooling; Product distribution / selectivity; Hide Experimental Procedure

Hong Kong Baptist University

Patent: US7488843 B1, 2009 ; Location in patent: Page/Page column 9; 10 ; Title/Abstract

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2:

Direct oxidation of the three xylene isomers with 30 equivalents (5 folds in excess) of 70percent aqueous TBHP under simultaneous cooling were also carried out as shown in scheme 4; Results are summarized in Table 4. The use of ionic liquid is not crucial in these cases. The oxidation of xylenes is probably a stepwise process. Various amounts of toluic acids (methylbenzoic) were also obtained in the crude reaction mixtures. This is in line with the fact that the ease of oxidation of substituted methylbenzene parallels the electron density of the aromatic ring (entries 9-13 of table 2). Once one of the methyl groups of xylene is oxidized, the oxidation of the remaining methyl group is deactivated by the electron-withdrawing effect of the carboxyl group24. To our surprise, 5 to 10percent of benzoic acid was also detected.Despite the oxidation of xylene isomers yielding a mixture of products, the isolations of two of the products are still straight forward. In the case of p- and m-xylene, the oxidized benzenedicarboxylic acids (terephthalic 4a and isophthalic 4b) precipitated out from the reaction mixtures (see Supplementary Information). After filtration and recrystallization, purified terephthalic and isophthalic acids can be obtained in moderate yields

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160.3 - 160.4°C; P=4650.47 Torr; 8 h; Pilot scale; Product distribution / selectivity; Hide Experimental Procedure

Wonders, Alan George; Lavoie, Gino Georges; Sumner, Charles Edwan

Patent: US2006/47152 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

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1; 2:

Examples 1-4 pertain to pilot-scale oxidations of para-xylene to terephthalic acid conducted in a pilot-scale system assembled around a mechanically agitated, hot-oil jacketed, 2-gallon, titanium reaction vessel. The gas dispersion type agitator within the reaction vessel was rotated at about 1,500 revolutions per minute (rpm), and the power draw of the agitator was about 220 watts. The pilot-scale system was equipped with means to control the pressure and temperature within the reaction vessel and to control the gas and liquid flow rates entering the reaction vessel. The feed of para-xylene was provided via a syringe pump at an effectively steady rate of about 0.28 kilograms per hour. Catalyst feed solution was pumped from a catalyst feed tank into the reaction vessel at an effectively steady rate of about 3.2 kilograms per hour. Both para-xylene and catalyst feed solution were released into the reaction medium through a dip tube ending below the level of aerated slurry within the reaction vessel. Using a nuclear level measurement system, the reaction mass in the reactor was maintained at an indicated value of around 40 percent by automatic operation of a drain valve located near the bottom of the reactor. By calibration, this indicated level corresponded to approximately 3 kilograms of reaction medium. Compressed air was fed effectively continuously through a tube ending below the level of the gas dispersion impeller within the reaction vessel. The offgas from the reaction vessel was fitted with a condenser system designed to condense most organic vapor from the off-gas. Condensate from the off-gas was removed from the process at a rate of about 1.3 kilogram per hour, and the balance of the off-gas condensate was returned to the reaction vessel. The air feed rate was adjusted to maintain an oxygen concentration in the exiting gas of about 3 to 4 mole percent on a dry basis after the off-gas condenser. The gases exiting the reactor were continuously monitored for oxygen, carbon dioxide, and carbon monoxide using in-line gas analyzers. The product slurry, comprising crude terephthalic acid (CTA) solids, was collected in an unaerated, stirred receiving tank, which was drained batchwise every four hours into a second unaerated tank in which the slurry was cooled to about 40° C. to crystallize additional dissolved product. The resulting cooled slurry was filtered. The filtrate was collected, weighed and analyzed by HPLCMS for low-level organic compounds, by x-ray for metals, by gas chromatography for methyl acetate and xylene, and by near infrared for water. The moist solids were weighed, and a sample was analyzed for moisture content. A portion of the remaining solids was washed with acetic acid, dried and analyzed by HPLC-MS for specific analytes. The reaction condensate was weighed and analyzed by a gas chromatography method calibrated with known concentrations of the specific analytes.

For each oxidation run, the catalyst feed solution was prepared in an agitated catalyst feed tank. The catalyst feed solution contained glacial acetic acid and deionized water. The cobalt in the catalyst feed solution was added as cobaltous acetate tetrahydrate, the manganese was added as manganous acetate tetrahydrate, and the bromine was added as aqueous 48 percent hydrobromic acid. The amounts of each component in the catalyst feed solution were selected to give the reaction slurry compositions shown below. For start-up, the reaction vessel was charged with catalyst feed solution and xylene, was brought to the reaction temperature with a heating oil jacket and pressure, and was concentrated by evaporation to about half volume. Air diluted with nitrogen was introduced into the mixture until an exotherm was observed. Once the reaction was initiated, para-xylene and catalyst feed solution were fed to the reaction at the rates given above. The reaction was sustained at the conditions for about 8 hours before product was retained. Thereafter, slurry product was collected at about 4-hour intervals for the duration of the experiment, and analyses were conducted as stated above. The values for the gas flows, temperature, and pressure were recorded every ten minutes and averaged for each run. For some reactions disclosed below, the as-received, chromatographic (HPLC) grade of para-xylene was further purified by two cycles of partial freezethaw crystallization. The levels of several impurities in the feed para-xylene were as shown in Table 5, as determined by gas chromatographic analysis. Examples 1 and 2 show that some benzoic acid (BA) comes from impurities typically found in impure para-xylene and that some benzoic acid is produced from para-xylene itself during partial oxidation even in a highly agitated and highly aerated reaction medium. Data for Examples 1 and 2 are presented in Table 6. As can be seen in Table 6, the ratio of TPA production compared to the net generation of benzoic acid was only 720 when operated with HPLC grade of impure para-xylene. This ratio rose to 1,180 for Example 2 when using further-purified para-xylene. However, it is important that some benzoic acid was intrinsically generated at these reaction conditions even when fed the further-purified para-xylene, which was essentially devoid of mono-substituted benzene rings. That is, self-generated benzoic acid was formed, perhaps by loss of one alkyl or acyl substituent during the oxidation of the para-xylene itself. Furthermore, the self-generated benzoic acid amount was about the same, within experimental accuracy, whether using the HPLC grade para-xylene or the further-purified para-xylene. That is, the data in Table 2 demonstrate that the total amount of benzoic acid produced with HPLC grade para-xylene was, within experimental accuracy, the sum of self-generated benzoic acid plus benzoic acid made by oxidation of appropriate non-xylene impurities, notably toluene and ethylbenzene.

With oxygen; acetic acid; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate in water

T=160.3 - 160.4°C; P=4650.47 Torr; 8 h; Pilot scale; Product distribution / selectivity; Hide Experimental Procedure

Wonders, Alan George; Lavoie, Gino Georges; Sumner, Charles Edwan; Davenport, Bryan Wayne

Patent: US2006/47153 A1, 2006 ; Location in patent: Page/Page column 39-40 ; Title/Abstract

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1; 2:

Examples 1-4 pertain to pilot-scale oxidations of para-xylene to terephthalic acid conducted in a pilot-scale system assembled around a mechanically agitated, hot-oil jacketed, 2-gallon, titanium reaction vessel. The gas dispersion type agitator within the reaction vessel was rotated at about 1,500 revolutions per minute (rpm), and the power draw of the agitator was about 220 watts. The pilot-scale system was equipped with means to control the pressure and temperature within the reaction vessel and to control the gas and liquid flow rates entering the reaction vessel. The feed of para-xylene was provided via a syringe pump at an effectively steady rate of about 0.28 kilograms per hour. Catalyst feed solution was pumped from a catalyst feed tank into the reaction vessel at an effectively steady rate of about 3.2 kilograms per hour. Both para-xylene and catalyst feed solution were released into the reaction medium through a dip tube ending below the level of aerated slurry within the reaction vessel. Using a nuclear level measurement system, the reaction mass in the reactor was maintained at an indicated value of around 40 percent by automatic operation of a drain valve located near the bottom of the reactor. By calibration, this indicated level corresponded to approximately 3 kilograms of reaction medium. Compressed air was fed effectively continuously through a tube ending below the level of the gas dispersion impeller within the reaction vessel. The offgas from the reaction vessel was fitted with a condenser system designed to condense most organic vapor from the off-gas. Condensate from the off-gas was removed from the process at a rate of about 1.3 kilogram per hour, and the balance of the off-gas condensate was returned to the reaction vessel. The air feed rate was adjusted to maintain an oxygen concentration in the exiting gas of about 3 to 4 mole percent on a dry basis after the off-gas condenser. The gases exiting the reactor were continuously monitored for oxygen, carbon dioxide, and carbon monoxide using in-line gas analyzers. The product slurry, comprising crude terephthalic acid (CTA) solids, was collected in an unaerated, stirred receiving tank, which was drained batchwise every four hours into a second unaerated tank in which the slurry was cooled to about 40° C. to crystallize additional dissolved product. The resulting cooled slurry was filtered. The filtrate was collected, weighed and analyzed by HPLCMS for low-level organic compounds, by x-ray for metals, by gas chromatography for methyl acetate and xylene, and by near infrared for water. The moist solids were weighed, and a sample was analyzed for moisture content. A portion of the remaining solids was washed with-acetic acid, dried and analyzed by HPLC-MS for specific analytes. The reaction condensate was weighed and analyzed by a gas chromatography method calibrated with known concentrations of the specific analytes.

For each oxidation run, the catalyst feed solution was prepared in an agitated catalyst feed tank. The catalyst feed solution contained glacial acetic acid and deionized water. The cobalt in the catalyst feed solution was added as cobaltous acetate tetrahydrate, the manganese was added as manganous acetate tetrahydrate, and the bromine was added as aqueous 48 percent hydrobromic acid. The amounts of each component in the catalyst feed solution were selected to give the reaction slurry compositions shown below. For start-up, the reaction vessel was charged with catalyst feed solution and xylene, was brought to the reaction temperature with a heating oil jacket and pressure, and was concentrated by evaporation to about half volume. Air diluted with nitrogen was introduced into the mixture until an exotherm was observed. Once the reaction was initiated, para-xylene and catalyst feed solution were fed to the reaction at the rates given above. The reaction was sustained at the conditions for about 8 hours before product was retained. Thereafter, slurry product was collected at about 4-hour intervals for the duration of the experiment, and analyses were conducted as stated above. The values for the gas flows, temperature, and pressure were recorded every ten minutes and averaged for each run. For some reactions disclosed below, the as-received, chromatographic (HPLC) grade of para-xylene was further purified by two cycles of partial freezethaw crystallization. The levels of several impurities in the feed para-xylene were as shown in Table 5, as determined by gas chromatographic analysis. Examples 1 and 2 show that some benzoic acid (BA) comes from impurities typically found in impure para-xylene and that some benzoic acid is produced from para-xylene itself during partial oxidation even in a highly agitated and highly aerated reaction medium. Data for Examples 1 and 2 are presented in Table 6. As can be seen in Table 6, the ratio of TPA production compared to the net generation of benzoic acid was only 720 when operated with HPLC grade of impure para-xylene. This ratio rose to 1,180 for Example 2 when using further-purified para-xylene. However, it is important that some benzoic acid was intrinsically generated at these reaction conditions even when fed the further-purified para-xylene, which was essentially devoid of mono-substituted benzene rings. That is, self-generated benzoic acid was formed, perhaps by loss of one alkyl or acyl substituent during the oxidation of the para-xylene itself. Furthermore, the self-generated benzoic acid amount was about the same, within experimental accuracy, whether using the HPLC grade para-xylene or the further-purified para-xylene. That is, the data in Table 2 demonstrate that the total amount of benzoic acid produced with HPLC grade para-xylene was, within experimental accuracy, the sum of self-generated benzoic acid plus benzoic acid made by oxidation of appropriate non-xylene impurities, notably toluene and ethylbenzene.

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With oxygen; ammonium bromide; copper(ll) bromide in water

T=380°C; Flow reactor;

Pérez, Eduardo; Thomas, Morgan L.; Housley, Duncan; Hamley, Paul A.; Fraga-Dubreuil, Joan; Li, Jun; Lester, Edward; Poliakoff, Martyn

RSC Advances, 2016 , vol. 6, # 14 p. 11289 - 11294 Title/Abstract

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24

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90%

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With oxone; trifluoroacetic acid in 1,4-dioxane

10 h; RefluxGreen chemistry; Hide Experimental Procedure

Rx-ID: 28492442 Find similar reactions

Aravinda Kumar; Venkateswarlu, Vunnam; Vishwakarma, Ram A.; Sawant, Sanghapal D.

Synthesis (Germany), 2015 , vol. 47, # 20 art. no. SS-2015-T0238-OP, p. 3161 - 3168 Title/Abstract

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Benzoic Acid (3a); Typical Procedure from Acetophenone or Phenylacetylene

General procedure: To a mixture of acetophenone (100 mg, 1 equiv) or phenylacetylene (1 equiv) in dioxane (5 mL), Oxone (2 equiv) and TFA (2 equiv) were added. The mixture was then heated to reflux for 10 h and then cooled to r.t. H2O (10 mL) was added and the mixture was extracted with EtOAc (2 × 20 mL). The combined organic layers were treated with sat. NaHCO3 solution and the aqueous layer was poured onto crushed ice and treated with 2 M HCl; a colorless solid precipitated out. The precipitate was filtered off and dried in vacuo to give benzoic acid (3a) after column chromatography (silica gel; EtOAc–hexane, 1:9) as a white crystalline solid; yield: 0.096 g (95percent) from 1a; mp 122–123 °C.

78%

With oxone; sodium hydrogencarbonate in water; acetonitrile

T=20°C; 6.5 h;

Vijay Kumar; Prakash Reddy; Sridhar; Srinivas; Rama Rao

Synlett, 2009 , # 5 p. 739 - 742 Title/Abstract

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65%

With hydroxylamine hydrochloride; iodine in dimethyl sulfoxide

T=100°C; 7 h;

Sathyanarayana, Pochampalli; Upare, Atul; Ravi, Owk; Muktapuram, Prathap Reddy; Bathula, Surendar Reddy

RSC Advances, 2016 , vol. 6, # 27 p. 22749 - 22753 Title/Abstract

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52%

With carbon tetrabromide; water; oxygen in ethyl acetate

5 h; Irradiation;

Yamaguchi, Tomoaki; Nobuta, Tomoya; Kudo, Yasuhisa; Hirashima, Shin-Ichi; Tada, Norihiro; Miura, Tsuyoshi; Itoh, Akichika

Synlett, 2013 , vol. 24, # 5 art. no. ST-2013-U0018-L, p. 607 - 610 Title/Abstract

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A

B

C

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25

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A: 56.7%

With oxygen in N,N-dimethyl-formamide

T=100°C; P=760.051 Torr; 12 h;

Tang, Qinghu; Wang, Yanyan; Zhang, Jian; Qiao, Ran; Xie, Xiaopei; Wang, Yi; Yang, Yanhui

Applied Organometallic Chemistry, 2016 , vol. 30, # 6 p. 435 - 440 Title/Abstract

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A: 51%

With C20H24CoN2O6(1+)*NO3(1-)*H2O; oxygen; isobutyraldehyde in acetonitrile

T=60°C; P=760.051 Torr; 8 h; Time; Hide Experimental Procedure

Saha, Debraj; Maity, Tanmoy; Bera, Rajesh; Koner, Subratanath

Polyhedron, 2013 , vol. 56, p. 230 - 236 Title/Abstract

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2.6. Catalytic reactions

General procedure: Catalytic test reactions were performed in a three-necked flask (50 mL) equipped with a reflux condenser, magnetic stirrer and gas inlet. The olefin (10 mmol), isobutyraldehyde (10 mmol) andacetonitrile (20 ml) were added to the flask and immersed in an oil bath kept at 60 C. Bubbling air at atmospheric pressure was passed through the reaction mixture at a flow rate of ca. 5ml/min under vigorous stirring. The mixture was then equilibrated to the desired temperature in an oil bath. The reaction was started after addition of catalyst (1 mg) into the reaction mixture. The products of the epoxidation reactions were collected atdifferent time intervals and were identified and quantified by gas chromatography.

With dihydrogen peroxide

T=70°C; 2 h; Ionic liquid;

Wang, Sa-Sa; Liu, Wei; Wan, Qing-Xia; Liu, Ye

Green Chemistry, 2009 , vol. 11, # 10 p. 1589 - 1594 Title/Abstract

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91%

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With oxygen; sodium hydrogencarbonate in acetonitrile

4 h; Molecular sieveIrradiation; Hide Experimental Procedure

Rx-ID: 32104933 Find similar reactions

Wang, Xiao-Yan; Shang, Zhen-Peng; Zha, Gao-Feng; Chen, Xiao-Qing; Bukhari, Syed Nasir Abbas; Qin, Hua-Li

Tetrahedron Letters, 2016 , vol. 57, # 50 p. 5628 - 5631 Title/Abstract

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Representative procedure for oxidization of 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione (1n) to thiophene-2-carboxylic acid (2n) in 1.0 mmol scale under blue LED irradiation with molecular oxygen

General procedure: Photoredox catalyst [Ru(bpy)3]Cl2·6H2O (6.4mg, 0.01 mmol) was added to a stirred suspension of 2 mL CH3CN, β-diketone 1n (222mg, 1.0 mmol), 4Å molecular sieve (200 mg) and NaHCO3 (84 mg, 1.0 mmol), the mixture was stirred under irradiation of 20W blue LED and charged with oxygen balloon for 4h unless otherwise noticed, after completion of the reaction, the resulted suspension was acidified with 1percent HCl before filtered through celite, the filtrate was concentrated before purified through silica gel chromatography (gradient elution with hexanes/ethyl acetate from 3/1 to 2/1) to yield the carboxylic acid 2n 9 ( 126mg, 0.99 mmol, 99percent) as white solid. (M. p = 125-129 oC) 1H NMR (DMSO-d6, 400 MHz, ppm) δ 13.06 (s, br, 1H), 7.88 (d, 1H, J = 4.8 Hz), 7.74 (d, 1H, J = 3.8 Hz); 13C NMR (DMSO-d6, 100 MHz, ppm) δ 163.4, 135.2, 133.8, 133.7, 128.7.

77%

With iodine; oxygen in ethyl acetate

10 h; Mercury lamp irradiation;

Tada, Norihiro; Shomura, Motoki; Cui, Lei; Nobuta, Tomoya; Miura, Tsuyoshi; Itoh, Akichika

Synlett, 2011 , # 19 art. no. U06311ST, p. 2896 - 2900 Title/Abstract

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72%

With 2-chloroanthracene-9,10-dione; oxygen; caesium carbonate in acetone

20 h; Irradiation; Hide Experimental Procedure

Tachikawa, Yuma; Cui, Lei; Matsusaki, Yoko; Tada, Norihiro; Miura, Tsuyoshi; Itoh, Akichika

Tetrahedron Letters, 2013 , vol. 54, # 46 p. 6218 - 6221 Title/Abstract

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General procedure: A solution of 1-phenyl-1,3-butanedione (1a, 0.3 mmol), 2-chloroanthraquinone (0.03 mmol), and Cs2CO3 (0.15 mmol) in dry acetone (5 mL) in a Pyrex test tube, purged with an O2 balloon, was stirred and irradiated externally with four 22 W fluorescent lamp for 20 h. The aqueous solution was washed with EtOAc, and then acidified with 2 M aq HCl solution, which was extracted with EtOAc. The organic layer was washed with brine and dried over MgSO4, and concentrated in vacuo. The pure product 2a was obtained by acid-base extraction with Et2O. All synthesized compounds (2a–2f) have been reported in the literature3 and were characterized by comparing the corresponding spectroscopic data.

Hide Details

With dihydrogen peroxide in water; acetone

T=10 - 15°C; 5.5 h; Irradiation; Hide Experimental Procedure

East China Normal University; Yang, ping; Gui, chengyi; Zhao, suqing

Patent: CN105777526 A, 2016 ; Location in patent: Paragraph 0059-0060; 0063-0064 ; Title/Abstract

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18:

0. 1g of [TEAH] H2PW12O40 / SBA-15, 20mL of acetone as solvent and 3mmol of p-methylbenzoylacetone were added to the self-made quartz reactor. The reaction temperature was controlled at 10-15 ° C, 30min, then add 1ml 30percent hydrogen peroxide solution, open the 400W high pressure mercury lamp light 5h, centrifuge separation of the catalyst, adding dimethyl sulfoxide (DMS0) As an internal standard, GC detection of aromatic carboxylic acid products. The results are shown in Table 2.

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With vanadia

T=200°C; 1 h; Temperature; Hide Experimental Procedure

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PERSTORP AB; LUNDMARK, Stefan; KANGAS, Matias; HÄGGMAN, Bo

Patent: WO2014/133433 A1, 2014 ; Location in patent: Page/Page column 6 ; Title/Abstract

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1.3:Step 1 - gas phase oxidations

Example 1 (Step 1 - gas phase oxidations) Into a tubular reactor 2.5 cm in internal diameter and 3.5 m in length, the catalyst was packed together with an inert carrier. The tubular reactor was heated and a mixed gas containing p- cymene preheated to at least 135°C and air with an inlet temperature of 170°C, in a ratio of 100 g Nm3 (100 gram of cymene relative to 1 m3 of air at standard temperature and pressure) was fed to into the tubular reactor at a rate of 4.0 Nm3/hr. Results are given in Table 1. Three experiments (Experiment 1-3) were performed using the following reaction temperatures and reaction time: Experiment 1 : 160°C. Experiment 2: 180°C. Experiment 3: 200°C. One hour reaction time. Yielded reaction mixtures are in enclosed Table 1 reported as percent by weight.

With oxygen

T=140°C; P=15001.5 Torr; 24 h; Autoclave; Time;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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28

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81%

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With oxygen; potassium hydoxide

T=20°C; Schlenk technique; chemoselective reaction;

Rx-ID: 41719591 Find similar reactions

Wang, Xing; Chen, Rui-Xi; Wei, Zeng-Feng; Zhang, Chen-Yang; Tu, Hai-Yang; Zhang, Ai-Dong

Journal of Organic Chemistry, 2016 , vol. 81, # 1 p. 238 - 249 Title/Abstract

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Rx-ID: 41719600 Find similar reactions

A: 93% B: 97%

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With oxygen; potassium hydoxide

T=20°C; Schlenk technique; chemoselective reaction;

Find similar

Wang, Xing; Chen, Rui-Xi; Wei, Zeng-Feng; Zhang, Chen-Yang; Tu, Hai-Yang; Zhang, Ai-Dong

Journal of Organic Chemistry, 2016 , vol. 81, # 1 p. 238 - 249 Title/Abstract

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30

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92%

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With zinc diacetate; water; tetra-(n-butyl)ammonium iodide

T=80°C; 24 h;

Rx-ID: 41775290 Find similar reactions

Marcé, Patricia; Lynch, James; Blacker, A. John; Williams, Jonathan M. J.

Chemical Communications, 2016 , vol. 52, # 5 p. 1013 - 1016 Title/Abstract

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A

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31

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With oxygen; sodium t-butanolate in benzene

T=20°C; P=750.075 Torr; 24 h; Overall yield = 84 percent; chemoselective reaction;

Kim, Sun Min; Shin, Hun Yi; Kim, Dong Wan; Yang, Jung Woon

ChemSusChem, 2016 , vol. 9, # 3 p. 241 - 245 Title/Abstract

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C

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32

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With oxygen; sodium t-butanolate in N,N,N,N,N,N-hexamethylphosphoric triamide

T=20°C; P=750.075 Torr; 24 h; Overall yield = 80 percent; chemoselective reaction;

Kim, Sun Min; Shin, Hun Yi; Kim, Dong Wan; Yang, Jung Woon

ChemSusChem, 2016 , vol. 9, # 3 p. 241 - 245 Title/Abstract

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33

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86%

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With oxygen; sodium t-butanolate in tetrahydrofuran

T=20°C; P=750.075 Torr; 22 h; chemoselective reaction;

Rx-ID: 41958388 Find similar reactions

Kim, Sun Min; Shin, Hun Yi; Kim, Dong Wan; Yang, Jung Woon

ChemSusChem, 2016 , vol. 9, # 3 p. 241 - 245 Title/Abstract

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Rx-ID: 41985298 Find similar reactions

With palladium diacetate; p-benozquinone in acetic acid; dimethyl sulfoxide

Fu, Wenqian; Feng, Yu; Fang, Zhongxue; Chen, Qun; Tang, Ting; Yu, Quanyong; Tang, Tiandi

Chemical Communications, 2016 , vol. 52, # 15 p. 3115 - 3118 Title/Abstract

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35

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90%

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With hydroxylamine hydrochloride; iodine in dimethyl sulfoxide

T=100°C; 5 h;

Rx-ID: 42034381 Find similar reactions

Sathyanarayana, Pochampalli; Upare, Atul; Ravi, Owk; Muktapuram, Prathap Reddy; Bathula, Surendar Reddy

RSC Advances, 2016 , vol. 6, # 27 p. 22749 - 22753

Title/Abstract

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36

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Rx-ID: 42452742 Find similar reactions

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Banella, Maria Barbara; Gioia, Claudio; Vannini, Micaela; Colonna, Martino; Celli, Annamaria; Gandini, Alessandro

ChemSusChem, 2016 , vol. 9, # 9 p. 942 - 945 Title/Abstract

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Stage #1: T=140°C; Diels-Alder Cycloaddition; 4 h; Stage #2: With sulfuric acid

T=60 - 130°C; 0.666667 h;

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37

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A: 79% B: 83%

With bis(acetylacetonate)oxovanadium; methyl 3,5-bis((1H-1,2,4-triazol-1yl)methyl)benzoate; oxygen; sodium acetate

T=120°C; 48 h;

Urgoitia, Garazi; SanMartin, Raul; Herrero, María Teresa; Domínguez, Esther

Advanced Synthesis and Catalysis, 2016 , vol. 358, # 20 p. 3307 - 3312 Title/Abstract

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B

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38

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A: 7% B: 93%

With water

T=140°C; 6 h; Sealed tube;

Srinivasa Rao; Srivani; Dhana Lakshmi; Lingaiah

Catalysis Letters, 2016 , vol. 146, # 10 p. 2025 - 2031

Hide Experimental Procedure

Title/Abstract

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2.3 General Reaction Procedure

General procedure: In a typical reaction procedure 1 mmol benzonitrile and3 ml of H2O was taken in a sealed tube. About 80 mg ofcatalyst was added to this reaction mixture and stirred at140 °C on a oil bath for stipulated reaction time. Theprogress of the reaction was monitored by using thin layerchromatography. The products were identified by GC–MS(SHIMADZU-2010) analysis by separating the products ona DB-5 column.

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Multi-step reaction with 2 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Rx-ID: 43879801 Find similar reactions

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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C

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40

Synthesize Find similar Rx-ID: 43879802 Find similar reactions

With oxygen

T=140°C; P=15001.5 Torr; 6 h; Autoclave;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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A

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C

D

E

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41

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With oxygen

T=100°C; P=15001.5 Torr; 24 h; Autoclave; Pressure;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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A

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C

D

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42

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With oxygen

T=100°C; P=26252.6 Torr; 24 h; Autoclave;

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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43

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Rx-ID: 43879814 Find similar reactions

Multi-step reaction with 2 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 2 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Hide Details

Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 4 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr 2: oxygen / 6 h / 100 °C / 26252.6 Torr 3: oxygen / 6 h / 100 °C / 26252.6 Torr 4: oxygen / 6 h / 140 °C / 15001.5 Torr View Scheme

/ / / /

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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|Autoclave |Autoclave |Autoclave |Autoclave

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Rx-ID: 43879817 Find similar reactions

Multi-step reaction with 2 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Multi-step reaction with 3 steps 1: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 2: oxygen / 6 h / 100 °C / 26252.6 Torr / |Autoclave 3: oxygen / 6 h / 140 °C / 15001.5 Torr / |Autoclave View Scheme

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Parvulescu, Vasile I.; Cavani, Fabrizio

ChemSusChem, 2016 , vol. 9, # 21 p. 3102 - 3112 Title/Abstract

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Rx-ID: 43982755 Find similar reactions

Yuanjiang Hualong Catalyst Technology Co., Ltd.; Guo, Cancheng; Guo, Xin

Patent: CN105218344 A, 2016 ; Location in patent: Paragraph 0051; 0052 ;

T=110°C; P=15001.5 Torr; Overall yield = 82 percent; Hide Experimental Procedure

Title/Abstract

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3:Example 3

The benzoic acid product was prepared by air oxidation of the mixture of p-xylene and mesitylene using the reaction separation synchronous reactor shown in Fig.Xylene and mesityleof 30ppm)And nickel acetatne (volume ratio 1: 1)The raw materials were addedFour pairs of chlorophenyl porphyrin iron-dimer(Concentration e(Concentration up to 150 ppm)As the composite catalyst,The mixture is fed from the top of the isothermal settling columnThe temperature of the stirring reaction tower is adjusted to 110 from the gas feed inlet of the stirring reaction tower, and the temperature of the stirring reaction tower is adjusted to 110, and the temperature of the stirring reaction tower is adjusted to 110 , the pressure inside the column to maintain 2.0MPa oxidation reaction, open the cycle of the pipeline valve, open the circulating pump, the reaction of p-methyl benzoic acid and 3,5-dimethyl benzoic acid mixed with the rapid settlement of circulating fluid into Constant temperature settling tower, trapped in the porous plate. When the p-toluic acid and 3,5-dimethylbenzoic acid products are required to be withdrawn, the circulating pump is stopped, the reaction liquid is recovered from the bottom of the thermostat settling column, the thermostatic settling column is taken out and the p-toluic acid And 3,5-dimethylbenzoic acid product. After simple drying of the collected p-toluic acid and 3,5-dimethylbenzoic acid product, the products were tested. The total amount of xylene and mesitylene The conversion was 92.5percentThe product of p-toluic acid andThe overall yield of 3,5-dimethylbenzoic acid was 82percent.The reaction continued and no pipe plugging occurred.

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D: 92%Spectr.

E: 94 %Spectr.

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With copper(II) sulfate in water; acetonitrile

1 h; UV-irradiation; Quantum yield;

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Venkatesh, Yarra; Rajesh; Karthik; Chetan; Mandal, Mahitosh; Jana, Avijit; Singh, N.D. Pradeep

Journal of Organic Chemistry, 2016 , vol. 81, # 22 p. 11168 - 11175 Title/Abstract

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47

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70%

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Stage #1: With ozone in dichloromethane

T=-78°C; Inert atmosphere; Stage #2: With lithium hydroxide monohydrate; dihydrogen peroxide in tetrahydrofuran; water

T=20°C; 24 h; Inert atmosphere;

Rx-ID: 44583297 Find similar reactions

Berger, Martin; Chauhan, Rajan; Rodrigues, Catarina A. B.; Maulide, Nuno

Chemistry - A European Journal, 2016 , vol. 22, # 47 p. 16805 - 16808 Title/Abstract

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48

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Rx-ID: 44783097 Find similar reactions

84%

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With copper(l) iodide; phen; potassium tert-butylate in dimethyl sulfoxide

T=140°C; P=750.075 Torr; 3 h; Schlenk techniqueSealed tube; Hide Experimental Procedure

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Changzhou University; SUN, SONG; CHENG, JIANG; YU, JINTAO; ZHANG, ZHENG; ZHU, SONGJIAN; WANG, LEI; FEI, HAIYANG

Patent: CN104151213 B, 2016 ; Location in patent: Paragraph 0036-0037 ; Title/Abstract

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2:Example 2: Preparation of 4-methylbenzoic acid (4-Me-C6H4C00H

In a 20 mL dehydrated deoxygenated Schlenk tube, sodium p-toluenesulfinate (0.2 mmol,35.6 mg), cuprous iodide(0.62 mmol, 3.81 mg), l, o-o-phenanthroline (0. 06 mmol, 10.8 mg), potassium tert-butoxide (0.6 mmol, 67.3 mg), 2.5 mL dimethyl Sulfone (DMS0), and finally into the reaction tube into 0.1 MPa of C02.The sealed reaction tube was heated and stirred for about 3 hours in a 140 ° C oil bath. The reaction solution was acidified with 2 mL of 1 M hydrochloric acid solution and extracted with ethyl acetate (4 mL X). The organic phases were combined and finally the product was purified by column chromatography and then dried to give a white solid powder 22.8 mg, yield 84percent

49

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Rx-ID: 662097 Find similar reactions

93%

With benzene-1,2-dicarboxylic acid

0.833333 h; microwave-irradiation;

Bratulescu, George

Revue Roumaine de Chimie, 2001 , vol. 46, # 3 p. 207 - 209 Title/Abstract

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90%

With 1-butyl-3-methylimidazolium hydrogen sulfate; water

T=60 - 65°C; 2.45 h; Green chemistry; Hide Experimental Procedure

Kumar, Satyanand; Dixit, Sandeep Kumar; Awasthi, Satish Kumar

Tetrahedron Letters, 2014 , vol. 55, # 28 p. 3802 - 3804 Title/Abstract

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General procedure for the synthesis of carboxylic acids from nitriles

General procedure: Aromatic or aliphatic nitriles (2 mmol) were dissolved in 5 ml of [bmim]HSO4 and the reaction mixture was heated at 60-65 °C for 1-3 h. The progress of reaction was monitored by TLC. After completion of reaction, as checked by TLC, the reaction mixture was poured into water containing crushed ice. The product was precipitated out, filtered and dried. The yield of the final product was high (>90percent) in all cases. All final products obtained were found sufficiently pure so it didn’t need further purification.The filtrate was concentrated under vacuum, washed with diethylether twice and concentrated under high vacuum. After proper drying under reduced pressure, approximately 95percent ionic liquid was recovered from the reaction and compared with the original ionic liquid to check its authenticity. The efficiency of recovered ionic liquid in conversion of nitriles to acids was found unchanged in comparison to the original one and we reused it up to 5-6 cycles without any significant loss of its activity.

82%

With phosphate buffer

T=30°C; 24 h; rhodococcus rhodocrous AJ270, pH 7.0;

Meth-Cohn, Otto; Wang, Mei-Xiang

Tetrahedron Letters, 1995 , vol. 36, # 52 p. 9561 - 9564 Title/Abstract

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82.2%

With potassium phosphate buffer

T=30°C; 24 h; Rhodococcus sp. AJ270 cells;

Meth-Cohn, Otto; Wang, Mei-Xiang

Journal of the Chemical Society - Perkin Transactions 1, 1997 , # 8 p. 1099 - 1104 Title/Abstract

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With hydrogenchloride

unter Druck;

Heim

Chemische Berichte, 1883 , vol. 16, p. 1775 Full Text View citing articles Show Details

With ethanol

unter Druck;

Heim

Chemische Berichte, 1883 , vol. 16, p. 1775 Full Text View citing articles Show Details

With sulfuric acid; water

van Scherpenzeel

Recueil des Travaux Chimiques des Pays-Bas, 1901 , vol. 20, p. 155 Full Text View citing articles Show Details

Herb

Justus Liebigs Annalen der Chemie, 1890 , vol. 258, p. 9 Full Text Show Details

With steam; thorium dioxide

T=420°C;

Mailhe

Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1920 , vol. 171, p. 247 Bulletin de la Societe Chimique de France, 1920 , vol. <4>27, p. 756 Full Text View citing articles Show Details

64

With water in dimethyl sulfoxide

Yousefi; Mohammadi; Habibi; Cheraghi

%Chromat.

T=26°C; pH=7; 24 h; aq. phosphate buffer;

Biocatalysis and Biotransformation, 2011 , vol. 29, # 2-3 p. 54 - 59 Title/Abstract

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With pro-nitro010; water

Enzymatic reaction; Reagent/catalyst;

Black, Gary W.; Brown, Nicola L.; Perry, Justin J. B.; Randall, P. David; Turnbull, Graeme; Zhang, Meng

Chemical Communications, 2015 , vol. 51, # 13 p. 2660 - 2662 Title/Abstract

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With nitrilase from Gordonia terrae in aq. phosphate buffer

T=35°C; pH=8; 1 h; Enzymatic reaction;

Kumar, Vijay; Seth, Amit; Kumari, Vijaya; Kumar, Virender; Bhalla, Tek C.

Protein and Peptide Letters, 2015 , vol. 22, # 1 p. 52 - 62 Title/Abstract

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50

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Rx-ID: 1701644 Find similar reactions

77%

With sodium hydroxide; Glyoxal; copper dichloride

Heating;

Singh, Latika; Ram, Ram N.

Journal of Organic Chemistry, 1994 , vol. 59, # 4 p. 710 - 711 Title/Abstract

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Multi-step reaction with 2 steps 1: sodium hydride / tetrahydrofuran / 24 h / 0 °C 2: sodium hydroxide / water / 12 h / 85 °C View Scheme

Asahara, Haruyasu; Arikiyo, Keita; Nishiwaki, Nagatoshi

Beilstein Journal of Organic Chemistry, 2015 , vol. 11, p. 1241 - 1245 Title/Abstract

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51

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A: 87% B: 7%

With iodine; potassium carbonate; tert-butyl alcohol

T=50°C; 19 h;

Mori, Naoshi; Togo, Hideo

Synlett, 2004 , # 5 p. 880 - 882 Title/Abstract

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A: 87% B: 7%

With iodine; potassium carbonate in tert-butyl alcohol

T=50°C; 19 h;

Mori, Naoshi; Togo, Hideo

Tetrahedron, 2005 , vol. 61, # 24 p. 5915 - 5925 Title/Abstract

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A: 80% B: 9%

With iodine pentoxide; potassium bromide in water

T=20°C; 12 h;

Liu, Zhong-Quan; Zhao, Yankai; Luo, Haiqing; Chai, Lingzhi; Sheng, Qiuju

Tetrahedron Letters, 2007 , vol. 48, # 17 p. 3017 - 3019

Title/Abstract

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A: 11% B: 74%

With 2.9-dimethyl-1,10-phenanthroline; oxygen; sodium hydrogencarbonate; gold(I) chloride in water

T=100°C; P=38002.6 Torr; 24 h;

Li, Huanrong; Guan, Bingtao; Wang, Wenjin; Xing, Dong; Fang, Zhao; Wan, Xiaobing; Yang, Liping; Shi, Zhangjie

Tetrahedron, 2007 , vol. 63, # 35 p. 8430 - 8434 Title/Abstract

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A: 13% B: 59%

With dihydrogen peroxide; methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate in 1,1,2,2-tetrachloroethylene

T=90°C; 4 h;

Venturello, Carlo; Gambaro, Mario

Journal of Organic Chemistry, 1991 , vol. 56, # 20 p. 5924 - 5931 Title/Abstract

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A: 55% B: 37%

With peracetic acid; C24H29INO5 in acetic acid

T=30°C; 24 h;

Yakura, Takayuki; Ozono, Ayaka

Advanced Synthesis and Catalysis, 2011 , vol. 353, # 6 p. 855 - 859 Title/Abstract

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A: 47% B: 53%

With iodine; potassium carbonate

T=50°C; 21 h;

Mori, Naoshi; Togo, Hideo

Synlett, 2004 , # 5 p. 880 - 882 Title/Abstract

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A: 47% B: 53%

With iodine; potassium carbonate in water

T=50°C; 21 h;

Mori, Naoshi; Togo, Hideo

Tetrahedron, 2005 , vol. 61, # 24 p. 5915 - 5925 Title/Abstract

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B: 26%

With tetrapropylammonium perruthennate; 4-methylmorpholine N-oxide in acetonitrile

T=20°C; 3 h;

Schmidt, Andrea-Katharina C.; Stark, Christian B. W.

Organic Letters, 2011 , vol. 13, # 16 p. 4164 - 4167 Title/Abstract

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With bromate; sulfuric acid; mercury(II) diacetate in water; acetic acid

T=40°C; 1.5 h; ΔG(excit.), ΔH(excit.), ΔS(excit.), Ea at 40 deg C; added salts: NaClO4, NaHSO4; Rate constantMechanismThermodynamic data;

Reddy, Ch. Sanjeeva; Sundaram, E. V.

Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1984 , vol. 23, # 11 p. 911 - 916 Title/Abstract

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With air in water-d2

T=20°C; 2 h; Irradiationsolid phase reaction; Reactivity;

Schmaderer, Harald; Hilgers, Petra; Lechner, Robert; Koenig, Burkhard

Advanced Synthesis and Catalysis, 2009 , vol. 351, # 1-2 p. 163 - 174 Title/Abstract

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With CpMo(CO)3(CCPh); dihydrogen peroxide in water

T=80°C; 8 h; chemoselective reaction;

Biradar, Ankush V.; Dongare, Mohan K.; Umbarkar, Shubhangi B.

Tetrahedron Letters, 2009 , vol. 50, # 24 p. 2885 - 2888 Title/Abstract

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With oxygen; nitric acid in 1,4-dioxane; water

T=90°C; 4 h; chemoselective reaction;

Kuang, Yongbo; Islam, Nazrul M.; Nabae, Yuta; Hayakawa, Teruaki; Kakimoto, Masa-Aki

Angewandte Chemie - International Edition, 2010 , vol. 49, # 2 p. 436 - 440 Title/Abstract

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Stage #1: With gold on titanium oxide in water

T=90°C; 0.166667 h; Inert atmosphere; Stage #2: With dihydrogen peroxide in water

T=90°C; 1.08333 h; Inert atmosphere; chemoselective reaction;

Ni, Ji; Yu, Wen-Jian; He, Lin; Sun, Hao; Cao, Yong; He, He-Yong; Fan, Kang-Nian

Green Chemistry, 2009 , vol. 11, # 6 p. 756 - 759 Title/Abstract

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With oxygen in 2,3,4-trifluorotoluene

T=100°C; P=6000.6 Torr; 3 h; UV-irradiationAutoclave;

Su, Fangzheng; Mathew, Smitha C.; Lipner, Grzegorz; Fu, Xianzhi; Antonietti, Markus; Blechert, Siegfried; Wang, Xinchen

Journal of the American Chemical Society, 2010 , vol. 132, # 46 p. 16299 - 16301 Title/Abstract

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With dihydrogen peroxide in acetonitrile

T=20°C; 6 h; chemoselective reaction;

Islam; Roy, Anupam Singha; Mondal, Paramita; Mubarak, Manir; Mondal, Sanchita; Hossain, Dildar; Banerjee, Satabdi; Santra

Journal of Molecular Catalysis A: Chemical, 2011 , vol. 336, # 1-2 p. 106 - 114 Title/Abstract

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With copper(ll) sulfate pentahydrate; sulfuric acid; dihydrogen peroxide in water

T=100°C; 2 h;

Ahmad, Jahir Uddin; Raeisaenen, Minna T.; Leskelae, Markku; Repo, Timo

Applied Catalysis A: General, 2012 , vol. 411-412, p. 180 - 187 Title/Abstract

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A: 74 %Chromat.

B: 26 %Chromat.

With tert.-butylnitrite in DME

T=100°C; 10 h; Inert atmosphere; Hide Experimental Procedure

Hamasaki, Akiyuki; Kuwada, Hideyuki; Tokunaga, Makoto

Tetrahedron Letters, 2012 , vol. 53, # 7 p. 811 - 814 Title/Abstract

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Typical procedure for the oxidation of primary benzylic alcohols (Table 4).

General procedure: To a mixture of alcohol 4 (1 mmol), tridecane (50 μL, 0.205 mmol, internal standard) and DME (1 mL) in a screw cap tube was added t-BuONO (198 μL, 1.5 mmol, 1.5 equiv.) under N2 atmosphere. The solution was stirred under the conditions indicated in table 4. The reaction mixture was analyzed by GC and the product was isolated by column chromatography (SiO2) for the characterization.

With dihydrogen peroxide in water; acetonitrile

T=60°C; 8 h; chemoselective reaction;

Islam, Manirul; Hossain, Dildar; Mondal, Paramita; Tuhina, Kazi; Roy, Anupam Singha; Mondal, Sanchita; Mobarak, Manir

Transition Metal Chemistry, 2011 , vol. 36, # 2 p. 223 - 230 Title/Abstract

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With dihydrogen peroxide in water

T=50°C; 6 h;

Islam, Sk. Manirul; Roy, Anupam Singha; Mondal, Paramita; Salam, Noor

Journal of Molecular Catalysis A: Chemical, 2012 , vol. 358, p. 38 - 48 Title/Abstract

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A: Ca. 80 %Chromat.

With [C4dmim][CH3COO] in water

24 h; RefluxInert atmosphere;

Feng, Bo; Chen, Chen; Yang, Hanmin; Zhao, Xiuge; Hua, Li; Yu, Yinyin; Cao, Ting; Shi, Yu; Hou, Zhenshan

Advanced Synthesis and Catalysis, 2012 , vol. 354, # 8 p. 1559 - 1565 Title/Abstract

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With dihydrogen peroxide in water; acetonitrile

T=60°C; 8 h;

Islam, Sk Manirul; Mobarok, Manir; Mondal, Paramita; Roy, Anupam Singha; Salam, Noor; Hossain, Dildar; Mondal, Sanchita

Transition Metal Chemistry, 2012 , vol. 37, # 1 p. 97 - 107 Title/Abstract

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A: 80 %Spectr.

B: 16 %Spectr.

With oxygen in water

T=30°C; P=760.051 Torr; 10 h;

Ohtaka, Atsushi; Kono, Yuki; Inui, Shigeki; Yamamoto, Syusei; Ushiyama, Tomoki; Shimomura, Osamu; Nomura, Ryoki

Journal of Molecular Catalysis A: Chemical, 2012 , vol. 360, p. 48 - 53 Title/Abstract

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With di-tert-butyl peroxide in water

T=50°C; 6 h; Hide Experimental Procedure

Islam; Roy, Anupam Singha; Mondal, Paramita; Paul, Sumantra; Salam, Noor

Inorganic Chemistry Communications, 2012 , vol. 24, p. 170 - 176 Title/Abstract

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Catalytic oxidation by TBHP

General procedure: The liquid phase oxidation reactions were carried out in a two-necked round bottom flask fitted with a water condenser and placed in an oil bath at different temperatures under vigorous stirring for a certain period of time. Substrates (5 mmol) were taken in water (5 mL) for different sets of reactions together with catalyst in which 10 mmol of TBHP (70percent in aq.) was added. After the reaction, the organic products were separated from the reaction mixture by extraction with dichloromethane (5 mL×2). The combined organic portions were dried and concentrated. Product analysis was performed by Varian 3400 gas chromatograph equipped with a 30 m CP-SIL8CB capillary column and a Flame Ionization Detector using cyclohexanone as internal standard. All reaction products were identified by using Trace DSQ II GC-MS.

With tert.-butylhydroperoxide in acetonitrile

T=60°C; 2.5 h; Kinetics; Hide Experimental Procedure

Mahiya, Kuldeep; Mathur, Pavan

Inorganica Chimica Acta, 2013 , vol. 399, p. 36 - 44 Title/Abstract

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2.6.1 Experimental procedure

General procedure: (a) Oxidation of two alcohols, 4-methyl benzyl alcohol and 2,4-dimethyl benzyl alcohol were studied using the copper(II) metallatriangles as catalyst, heterogeneously in acetonitrile at 60°C. The time duration was 2.5h and ratio of catalyst: substrate: oxidant was fixed as 1:60:60 for each reaction. The progress of reaction was monitored by TLC. The catalyst was filtered, dried and washed with acetonitrile after each reaction and reutilized for the next reaction. The products formed were analyzed by GCMS. (b) The kinetics of the conversion of 4-methylbenzyl alcohol to 4-methylbenzaldehyde was studied spectrophotometrically. 0.16mmol of 4-methylbenzyl alcohol was mixed with 0.0042mmol of the copper(II) metallatriangle (1) in 10ml acetonitrile in the presence of 0.16 mmoles of tert.butyl hydroperoxide (TBHP) at 60°C with rapid stirring. After every 5min, 20μL solution from the reaction mixture was taken in a quartz cuvette containing 2.0mL acetonitrile ant the solution scanned in the UV-range for the development of any new band. It is found that a new band immediately starts to arise at ∼255nm. This band grows in intensity for nearly two hours and also splits into two bands viz at ∼246 and 255nm suggesting the formation of 4-methylbenzoic acid after >1h of reaction. This procedure was repeated with different amount of catalyst (0.0014 and 0.0028 mmol) keeping the amount of 4-methylbenzyl alcohol same (i.e. 0.16 mmol). The rate of formation of 4-methylbenzaldehyde was determined by initial rate method this was obtained from the plot of concentration of aldehyde formed versus time.

With dihydrogen peroxide

T=70°C; Catalytic behavior; Reagent/catalystTemperature;

Rathore, Puran Singh; Thakore, Sonal; Patidar, Rajesh

2014 , vol. 4, # 77 p. 41111 - 41121 Title/Abstract

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With phosphoric acid; dihydrogen peroxide; sodium hydroxide in water

T=50°C; pH=8.5; 2 h;

Wu, Xiaochen; Guo, Shouwu; Zhang, Jingyan

Chemical Communications, 2015 , vol. 51, # 29 p. 6318 - 6321 Title/Abstract

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A: 25 %Chromat.

B: 75 %Chromat.

With oxygen; potassium carbonate in water

T=90°C; P=760.051 Torr; 24 h; Reagent/catalyst;

Karimi, Babak; Khorasani, Mojtaba; Vali, Hojatollah; Vargas, Carolina; Luque, Rafael

ACS Catalysis, 2015 , vol. 5, # 7 p. 4189 - 4200 Title/Abstract

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52

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100%

With potassium carbonate; palladium diacetate in water; N,N-dimethyl-formamide

T=25°C; P=760 Torr; 4 h;

Bumagin, N. A.; Nikitin, K. V.; Beletskaya, I. P.

Journal of Organometallic Chemistry, 1988 , vol. 358, p. 563 - 566 Title/Abstract

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100%

With potassium hydroxide; amphiphilic resin-supported phosphine-palladium; water

Uozumi, Yasuhiro; Watanabe, Toshihiro

Journal of Organic Chemistry, 1999 , vol. 64, # 18 p. 6921 - 6923 Title/Abstract

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92%

T=25°C; hydroxycarbonylation; P=760 Torr; 12 h; Product distribution; Further Variations:Reagents;

With dichloro bis(acetonitrile) palladium(II); sodium lauryl sulfate; potassium carbonate in water; toluene; butan-1-ol

T=50°C; P=760 Torr; 4 h;

Cheprakov, Andrei V.; Ponomareva, Natalia V.; Beletskaya, Irina P.

Journal of Organometallic Chemistry, 1995 , vol. 486, # 1-2 p. 297 - 300 Title/Abstract

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87%

With water; palladium diacetate; potassium carbonate

T=20°C; P=760.051 Torr; 12 h; Hide Experimental Procedure

Han, Wei; Jin, Fengli; Zhou, Qing

Synthesis (Germany), 2015 , vol. 47, # 13 art. no. SS-2015-H0033-OP, p. 1861 - 1868 Title/Abstract

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4-Nitrobenzoic Acid (2a)

General procedure: A 25-mL flask was charged with Pd(OAc)2 (1.2 mg, 0.005 mmol), 1-iodo-4-nitrobenzene (1a, 127.0 mg, 0.5 mmol), K2CO3 (141.0 mg, 1.0 mmol), H2O (0.5 mL), and PEG 400 (2.0 mL); the flask was subjected to standard cycles (3 ×) of evacuation and back-filling with dry and pure CO. The mixture was stirred at r.t. for the indicated time. The mixture was poured into sat. aq NaCl (15 mL), acidified to pH 3 with 3 M aq HCl, and extracted with EtOAc (3 × 15 mL). The solvent was removed from the combined organic phases on a rotary evaporator. The crude product was purified by column chromatography (silica gel, PE–EtOAc–HCO2H, 25:1:1) to afford 2a as a light yellow solid; yield: 75mg (90percent); mp 238.0–239.3 °C. 1H NMR (400 MHz, DMSO-d6): δ = 13.68 (br s, 1 H), 8.30 (d, J = 8.0 Hz,2 H), 8.14 (d, J = 8.0 Hz, 2 H). 13C NMR (100 MHz, DMSO-d6): δ = 165.9, 150.0, 136.4, 130.7, 123.8.

82%

With 4,4'-bis(trimethylaminomethyl)-2,2'-bipyridine dihydrobromide; bistriphenylphosphine-palladium(II) chloride; water; sodium carbonate in water

T=100°C; P=7600.51 Torr; 24 h; Autoclave; Catalytic behavior;

Tsai, Sheng-Wen; Huang, Shao-Hsien; Lee, Han-Sheng; Tsai, Fu-Yu

Journal of the Chinese Chemical Society, 2013 , vol. 60, # 7 p. 769 - 772 Title/Abstract

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80%

With water; sodium carbonate; trans-di(μ-acetato)bis[o-(di-otolylphosphino)benzyl]dipalladium(II)

T=20 - 165°C; P=22502.3 Torr; 0.333333 h; microwave irradiation;

Kormos, Chad M.; Leadbeater, Nicholas E.

Synlett, 2006 , # 11 p. 1663 - 1666 Title/Abstract

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A

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53

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With oxygen; vanadium pentaoxide; antimony trioxide; Titanium(IV) oxide in water

T=340°C; P=750.06 Torr; other temperatures; Product distribution;

Antol, Marcel; Cvengrosova, Zuzana; Vrabel, Imrich; Lesko, Jan; Hronec, Milan

Collection of Czechoslovak Chemical Communications, 1997 , vol. 62, # 9 p. 1481 - 1490 Title/Abstract

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With air; acetic acid; sodium bromide; anhydrous cobalt diacetate; Manganese (II) acetate

T=199.85°C; P=28443.1 Torr; 0.75 h; Product distribution; Further Variations:CatalystsReagentsSolvents;

Ratnasamy; Chavan; Srinivas

Journal of Catalysis, 2001 , vol. 204, # 2 p. 409 - 419 Title/Abstract

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With hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [1,3-butylmethylimidazolium]Br; acetic acid; [C4C1im][MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0068; 0078 ; Title/Abstract

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1:Comparative Example No Ammonium Acetate

Comparative Example No Ammonium Acetate 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g Hbr. The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180° C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way had 4-CBA content of 20278 ppm, and toluic acid content of 2295 ppm.

On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The results are shown in Table 1. The 4-CBA content of the solid products for this example and examples 1 and 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.

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With hydrogen bromide; oxygen; anhydrous cobalt diacetate; Manganese (II) acetate; acetic acid

T=175 - 225°C; P=11251.1 - 22502.3 Torr;

Rezaei, Vahid; Sajadi, Seyed Ali Akbar

Russian Journal of Applied Chemistry, 2015 , vol. 88, # 7 p. 1201 - 1206 Title/Abstract

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A: 89%

With dihydrogen peroxide; methyltrioxorhenium(VII); acetic acid; sodium bromide

10 h; Ambient temperature;

Espenson; Zhu; Zauche

Journal of Organic Chemistry, 1999 , vol. 64, # 4 p. 1191 - 1196 Title/Abstract

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A: 65%

With dihydrogen peroxide; magnesium chloride

T=65°C; 40 h; Reagent/catalyst;

Feng, Jian-Bo; Gong, Jin-Long; Li, Qin; Wu, Xiao-Feng

Tetrahedron Letters, 2014 , vol. 55, # 9 p. 1657 - 1659 Title/Abstract

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A: 42% B: 10%

With dihydrogen peroxide; calcium chloride

T=20 - 70°C; 24 h; Reagent/catalyst;

Kashyap, Rajarshi; Talukdar, Dhruba Joyti; Pratihar, Sanjay

New Journal of Chemistry, 2015 , vol. 39, # 2 p. 1430 - 1437 Title/Abstract

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With dihydrogen peroxide

T=80°C; 6 h; Dean-Stark; Catalytic behavior;

Singh, Sukriti; Patel, Anjali

Catalysis Letters, 2014 , vol. 144, # 9 p. 1557 - 1567,11 Title/Abstract

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60%

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With oxone; trifluoroacetic acid in 1,4-dioxane

10 h; RefluxGreen chemistry; Hide Experimental Procedure

Rx-ID: 12603819 Find similar reactions

Aravinda Kumar; Venkateswarlu, Vunnam; Vishwakarma, Ram A.; Sawant, Sanghapal D.

Synthesis (Germany), 2015 , vol. 47, # 20 art. no. SS-2015-T0238-OP, p. 3161 - 3168 Title/Abstract

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Benzoic Acid (3a); Typical Procedure from Acetophenone or Phenylacetylene

General procedure: To a mixture of acetophenone (100 mg, 1 equiv) or phenylacetylene (1 equiv) in dioxane (5 mL), Oxone (2 equiv) and TFA (2 equiv) were added. The mixture was then heated to reflux for 10 h and then cooled to r.t. H2O (10 mL) was added and the mixture was extracted with EtOAc (2 × 20 mL). The combined organic layers were treated with sat. NaHCO3 solution and the aqueous layer was poured onto crushed ice and treated with 2 M HCl; a colorless solid precipitated out. The precipitate was filtered off and dried in vacuo to give benzoic acid (3a) after column chromatography (silica gel; EtOAc–hexane, 1:9) as a white crystalline solid; yield: 0.096 g (95percent) from 1a; mp 122–123 °C.

Multi-step reaction with 2 steps 1: 1-butyl-3-methylimidazolium tetrafluoroborate / 1 h / 60 °C 2: urea; hydrogen peroxide; 1-butyl-3-methylimidazolium tetrafluoroborate View Scheme

Jong, Chan Lee; Jang, Mi Lee

Synthetic Communications, 2006 , vol. 36, # 8 p. 1071 - 1074 Title/Abstract

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A

B

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57

A: 73 %Chromat.

B: 12 %Chromat.

With tert.-butylnitrite; oxygen in carbon dioxide

T=80°C; P=97509.8 Torr; 18 h; AutoclaveSupercritical conditions;

Miao, Cheng-Xia; Yu, Bing; He, Liang-Nian

Green Chemistry, 2011 , vol. 13, # 3 p. 541 - 544 Title/Abstract

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With ammonium cerium (IV) nitrate; oxygen in 1,4-dioxane

T=80°C; 24 h; Green chemistry; Overall yield = 70 percent;

Yu, Lei; Huang, Yaping; Bai, Zengbing; Zhu, Bingchun; Ding, Kehong; Chen, Tian; Ding, Yuanhua; Wang, Yuguang

Journal of the Chinese Chemical Society, 2015 , vol. 62, # 6 p. 479 - 482 Title/Abstract

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Multi-step reaction with 2 steps 1: 4 h / 95 °C / |Sealed tube 2: sulfuric acid / 0.25 h / 100 °C View Scheme

Wang, Fei; Tong, Zhaohui

RSC Advances, 2014 , vol. 4, # 12 p. 6314 - 6317 Title/Abstract

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Multi-step reaction with 3 steps 1.1: AlCl3, aluminium chloride / neat (no solvent) / 2 h / 0 °C / |Cooling with ice 2.1: 0.5 Pd/Al2O3 / triglyme (triethylene glycol dimethyl ether) / 10 h / 210 °C / |Reflux 3.1: sodium hydroxide / diethyl ether; methanol / 20 h / 20 °C 3.2: pH 2 - 3 View Scheme

Far Eastern New Century Corporation; Chen, Guei-San; Chi, Fa-Chen; Chou, Cheng-Han; Lu, Xin-An

Patent: US9061989 B1, 2015 ; Title/Abstract

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With 5C16H36N(1+)*(x)H2O*FeO39SiW11(5-); dihydrogen peroxide in water; acetonitrile

T=80°C; 6 h;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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Rx-ID: 39244583 Find similar reactions

With 5C16H36N(1+)*(x)H2O*CoO39PW11(5-); dihydrogen peroxide in water; acetonitrile

T=80°C; 6 h;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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With 6C16H36N(1+)*(x)H2O*BFeO39W11(6-); dihydrogen peroxide in water; acetonitrile

T=80°C; 6 h; Reagent/catalyst;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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With 4C16H36N(1+)*(x)H2O*FeO39PW11(4-); dihydrogen peroxide in water; acetonitrile

T=80°C; 6 h;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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With 6C16H36N(1+)*(x)H2O*BMnO39W11(6-); dihydrogen peroxide in water; acetonitrile

T=60°C; 6 h;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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With 6C16H36N(1+)*(x)H2O*CoO39SiW11(6-); dihydrogen peroxide in water; acetonitrile

T=80°C; 6 h;

Duarte, Tiago A. G.; Estrada, Ana C.; Simes, Mrio M. Q.; Santos, Isabel C. M. S.; Cavaleiro, Ana M. V.; Neves, M. Graca P. M. S.; Cavaleiro, Jos A. S.

Catalysis Science and Technology, 2015 , vol. 5, # 1 p. 351 - 363 Title/Abstract

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A

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C: 19.8 %Chromat.

With ammonium acetate; water; hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [N-butylthiazolium][Br]; acetic acid; [C4C1im]

UOP LLC; BUCHBINDER, Avram M.; BHATTACHARYYA, Alakananda; EDIRISINGHE, Praneeth D.; WALENGA, Joel T.

Patent: WO2015/47647 A1, 2015 ;

Location in patent: Page/Page column 15; 16 ;

[MeCO2]

T=206 - 215°C; 3 h; Autoclave; Hide Experimental Procedure

Title/Abstract

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3:

In separate examples, ionic liquid was subjected to an oxidative aging treatment for 21 hours at 215°C, similar to the thermal treatment but under flowing air and including Co, Mn, HBr catalyst but no methyl aromatic reactant (or intermediate). This process resulted in generation of all of the products that result from thermal treatment (in examples 1 and 2), plus significant amounts of compound (5), and trace amounts of compounds (2), (8), (11), and (13) observed in mass spectrometry.

Compound (1) was also only observed in trace amounts. However, when conducted in the presence of para-xylene, even the trace amounts of oxygenated BMIm, compounds (2) and (11), were not observed. Similar results were obtained when the oxidation was conducted for only 3 hours. High performance liquid chromatography (HPLC) with UV-vis detection shows that no overall loss of imidazolium compounds occurred. The amounts of BMIm, and compounds (6), (1), (5), (7) and (10) as a percentage of moles of ionic liquid cations are shown in Table 2. The quantification of compound (10) is an estimate assuming similar UV-vis molar absorptivity as other cations. Table 2 Subsequently, 70 g of the product of this reaction was used as a solvent for para-xylene oxidation, after addition of 0.4 g HBr, 33.8 g acetic acid (to make up for loss during the initial oxidation), and 20 g para-xylene. The reaction was run by heating to a target temperature 215°C with 2500 seem air flow for three hours, although the temperature dropped to 206°C after the initial exotherm. After isolating the products by filtration and washing, the solid portion of the products of this reaction (as analyzed by HPLC) contained 6669 ppm 4-CBA, 19.8percent toluic acid and 5.0percent toluamide, with the remainder consisting of terephthalic acid and terephthalic acid-monoamide in a ratio of 1.2: 1. The high amount of toluic acid and toluamide indicate reaction did not reach full conversion, which may also be the reason for high 4-CBA.

With ammonium acetate; hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [N-butylthiazolium][Br]; acetic acid; [C4C1im] [MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0069; 0078 ; Title/Abstract

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1; 1A:Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products

Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180° C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18percent. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.

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With ammonium acetate; hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [N-butylthiazolium][Br]; acetic acid; [C4C1im] [MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0069; 0078 ; Title/Abstract

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1; 1C:Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products

Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180° C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18percent. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.

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Rx-ID: 39829239 Find similar reactions

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With ammonium acetate; hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [N-butylthiazolium][Br]; acetic acid; [C4C1im] [MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

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UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0069; 0078 ; Title/Abstract

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1; 1E:Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products

Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180° C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18percent. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.

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With ammonia; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [Nbutylthiazolium][Br]; acetic acid; [C4C1im][MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0070; 0072; 0078 ; Title/Abstract

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1; 2B:Example 2 Oxidation in the Presence of Ammonia Gas Feed to Generate Amide Containing Products

Example 2 Oxidation in the Presence of Ammonia Gas Feed to Generate Amide Containing Products In another set of examples, ammonia was introduced in the gas phase instead of including ammonium acetate. In all of these examples, the catalyst was composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g BBL The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air/ammonia mixture at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The detailed data is shown in Table 2. The 4-CBA content of the solid products for this example, the comparative example and example 1, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor. In example 2B, 20 g para-xylene was oxidized in a mixture of 62.5 g acetic acid, 25 g BMImBr, 12.6 g BMImOAc, and 0.4 g water. The air/ammonia mixture contained 2.5 volume percent ammonia. The solid terephthalic acid reaction products produced in this had 4-CBA content of 22 ppm, toluic acid content of 536 ppm, toluamide content of 5666 ppm and terephthalic acid monoamide content of 20.9percent.

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With ammonium acetate; hydrogen bromide; oxygen; Manganese (II) acetate; [Co(O2CCH3)2]*4H2O; [1,3-butylmethylimidazolium]Br; acetic acid; [C4C1im][MeCO2] in water

T=215°C; 3 h; Hide Experimental Procedure

UOP LLC; Buchbinder, Avram M.; Bhattacharyya, Alakananda; Jarusiripipat, Tatsamai T.; Shih, Raymond; Walenga, Joel T.; Kuznetsova, Nina

Patent: US2015/99898 A1, 2015 ; Location in patent: Paragraph 0013; 0069; 0078 ; Title/Abstract

Full Text Show Details

1; 1G:Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products

Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215° C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180° C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80° C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18percent. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.

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With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical; laccasefrom Trametes versicolor; oxygen in water

T=30°C; pH=4.5; 168 h; Enzymatic reaction;

Galletti, Paola; Funiciello, Federica; Soldati, Roberto; Giacomini, Daria

Advanced Synthesis and Catalysis, 2015 , vol. 357, # 8 p. 1840 - 1848 Title/Abstract

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With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical; laccasefrom Trametes versicolor; oxygen in water

T=30°C; pH=4.5; 240 h; Enzymatic reaction;

Galletti, Paola; Funiciello, Federica; Soldati, Roberto; Giacomini, Daria

Advanced Synthesis and Catalysis, 2015 , vol. 357, # 8 p. 1840 - 1848 Title/Abstract

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Multi-step reaction with 2 steps 1.1: 0.5 Pd/Al2O3 / triglyme (triethylene glycol dimethyl ether) / 10 h / 210 °C / |Reflux 2.1: sodium hydroxide / diethyl ether; methanol / 20 h / 20 °C 2.2: pH 2 - 3 View Scheme

Rx-ID: 40330229 Find similar reactions

Far Eastern New Century Corporation; Chen, Guei-San; Chi, Fa-Chen; Chou, Cheng-Han; Lu, Xin-An

Patent: US9061989 B1, 2015 ; Title/Abstract

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Rx-ID: 40470900 Find similar reactions

84%

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Stage #1: With copper(l) iodide; potassium tert-butylate; o-phenanthroline in dimethyl sulfoxide

T=140°C; P=760.051 Torr; 12 h; Schlenk technique; Stage #2: With hydrogenchloride in water; dimethyl sulfoxide

Schlenk technique;

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Sun, Song; Yu, Jin-Tao; Jiang, Yan; Cheng, Jiang

Advanced Synthesis and Catalysis, 2015 , vol. 357, # 9 p. 2022 - 2026 Title/Abstract

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With ammonium cerium (IV) nitrate; oxygen in 1,4-dioxane

T=80°C; 24 h; Green chemistry; Overall yield = 63 percent;

Yu, Lei; Huang, Yaping; Bai, Zengbing; Zhu, Bingchun; Ding, Kehong; Chen, Tian; Ding, Yuanhua; Wang, Yuguang

Journal of the Chinese Chemical Society, 2015 , vol. 62, # 6 p. 479 - 482 Title/Abstract

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Rx-ID: 40532342 Find similar reactions

A: 18 %Spectr.

B: 43%

With oxygen; sodium hydroxide in tetrahydrofuran; water

T=20°C; 18 h;

Miyamura, Hiroyuki; Min, Hyemin; Soulé, Jean-François; Kobayashi, Shu

Angewandte Chemie - International Edition, 2015 , vol. 54, # 26 p. 7564 - 7567 Angew. Chem., 2015 , vol. 127, p. 7674 - 7677 Title/Abstract

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A: 20% B: 35%

With PMe(t-Bu)2.HBF4; copper diacetate; palladium diacetate; potassium carbonate in N,N-dimethyl acetamide

T=100°C; 6 h; Reagent/catalystSolvent;

Tan, Hongyu; Houpis, Ioannis; Liu, Renmao; Wang, Youchu; Chen, Zhilong

Organic Letters, 2015 , vol. 17, # 14 p. 3548 - 3551 Title/Abstract

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A: 22% B: 8% C: 59%

With palladium diacetate; potassium carbonate; 1,4-di(diphenylphosphino)butane in acetonitrile

T=100°C; 6 h; Reagent/catalystSolvent;

Tan, Hongyu; Houpis, Ioannis; Liu, Renmao; Wang, Youchu; Chen, Zhilong

Organic Letters, 2015 , vol. 17, # 14 p. 3548 - 3551 Title/Abstract

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A: 9% B: 31% C: 45%

With PMe(t-Bu)2.HBF4; silver(I) acetate; palladium diacetate; potassium carbonate in N,N-dimethyl acetamide

T=100°C; 6 h; Reagent/catalystSolvent;

Tan, Hongyu; Houpis, Ioannis; Liu, Renmao; Wang, Youchu; Chen, Zhilong

Organic Letters, 2015 , vol. 17, # 14 p. 3548 - 3551 Title/Abstract

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Rx-ID: 40545560 Find similar reactions

A: 8% B: 60% C: 11% D: 25%

With PMe(t-Bu)2.HBF4; palladium diacetate; potassium carbonate in N,N-dimethyl acetamide

T=100°C; 6 h; Reagent/catalystSolvent;

Tan, Hongyu; Houpis, Ioannis; Liu, Renmao; Wang, Youchu; Chen, Zhilong

Organic Letters, 2015 , vol. 17, # 14 p. 3548 - 3551 Title/Abstract

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Rx-ID: 40593783 Find similar reactions

A: 8%

With trifluorormethanesulfonic acid in dichloromethane

T=30°C; 18 h; chemoselective reaction;

Guo, Biao; Zhou, Yiming; Zhang, Lei; Hua, Ruimao

Journal of Organic Chemistry, 2015 , vol. 80, # 15 p. 7635 - 7641 Title/Abstract

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Multi-step reaction with 2 steps 1: bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine / 24 h / 90 °C / |Inert atmosphere; |Sealed tube 2: trifluorormethanesulfonic acid / dichloromethane / 18 h / 30 °C View Scheme

Rx-ID: 40593798 Find similar reactions

Guo, Biao; Zhou, Yiming; Zhang, Lei; Hua, Ruimao

Journal of Organic Chemistry, 2015 , vol. 80, # 15 p. 7635 - 7641 Title/Abstract

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Rx-ID: 40846291 Find similar reactions

48%

With copper(l) iodide; hydroxylamine hydrochloride; oxygen in dimethyl sulfoxide

T=100°C; 18 h;

Sathyanarayana, Pochampalli; Ravi, Owk; Muktapuram, Prathap Reddy; Bathula, Surendar Reddy

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 37 p. 9681 - 9685 Title/Abstract

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With sodium hydroxide in water

T=85°C; 12 h; Hide Experimental Procedure

Rx-ID: 40846857 Find similar reactions

Asahara, Haruyasu; Arikiyo, Keita; Nishiwaki, Nagatoshi

Beilstein Journal of Organic Chemistry, 2015 , vol. 11, p. 1241 - 1245 Title/Abstract

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General procedure: To a solution of amide 3 (101 mg, 0.5 mmol) in THF (1 mL), asuspension of 60 wt percent sodium hydride (100 mg, 2.5 mmol) inTHF (3 mL) was added under argon. After the mixture wasstirred vigorously for 10 min, the mixture was cooled to 0 °Cand then a solution of tosyl chloride (191 mg, 1 mmol) in THF(1 mL) was slowly added. After the mixture was stirred for 3 hat 0 °C, propylamine (164 μL, 2 mmol) was added, and then themixture was stirred at room temperature for 12 h. After evaporation of the solvent, the residue was dissolved into diethyl ether(5 mL), washed with water (5 mL), and the aqueous layer wasextracted with diethyl ether (2 × 5 mL). The combined organiclayer was dried over magnesium sulfate, and concentrated, andthe residue was subjected to column chromatography on silicagel to afford N-propylcarboxamide 5c (85 mg, 0.37 mol, 74percentyield), A

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Rx-ID: 40966527 Find similar reactions

Fan, Wenyou; Yang, Youqing; Lei, Jianhua; Jiang, Qijian; Zhou, Wang

Journal of Organic Chemistry, 2015 , vol. 80, # 17 p. 8782 - 8789 Title/Abstract

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With phen; CuCl2*2H2O; oxygen in acetonitrile

P=760.051 Torr; 2 h; Reflux;

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Rx-ID: 40968298 Find similar reactions

A: 85% B: 10%

With sodium cyanide in DMFA

T=80°C; 24 h; Molecular sieve; Hide Experimental Procedure

Kim, Yoo-Jin; Cheon, Cheol-Hong

Bulletin of the Korean Chemical Society, 2015 , vol. 36, # 8 p. 2055 - 2061 Title/Abstract

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General Procedure for Metal-Free Aerobic Oxidative Esterification (Tables 2 and 3).

General procedure: Aldehyde 1 (1.0 mmol; 1.0 equiv.) and 4 Å molecular sieves (300 mg) were added to a mixture of DMF (3.0 mL) and an appropriate alcohol (or a thiol) (3.0 mL). To the above solution was added sodium cyanide (1.5 mmol; 1.5 equiv). The reaction mixture was stirred in an open flask at 50 C and monitored by TLC. After the complete consumption of 1, the mixture was poured into water (25 mL) and extracted with diethyl ether (5 × 10 mL). The organic layers were combined, dried over anhydrous magnesium sulfate, and concentrated. The crude mixture was further purified by column chromatography on silica gel using ethyl acetate/hexane as the eluent to furnish the desired ester compound 3. The aqueous layer was acidified with HCl, extracted with ether, and concentrated to yield the corresponding carboxylic acid 6, which was sufficiently pure needing no further purification.

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With oxone; trifluoroacetic acid in 1,4-dioxane

10 h; RefluxGreen chemistry; Hide Experimental Procedure

Rx-ID: 41068301 Find similar reactions

Aravinda Kumar; Venkateswarlu, Vunnam; Vishwakarma, Ram A.; Sawant, Sanghapal D.

Synthesis (Germany), 2015 , vol. 47, # 20 art. no. SS-2015-T0238-OP, p. 3161 - 3168 Title/Abstract

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Benzoic Acid (3a); Typical Procedure from Acetophenone or Phenylacetylene

General procedure: To a mixture of acetophenone (100 mg, 1 equiv) or phenylacetylene (1 equiv) in dioxane (5 mL), Oxone (2 equiv) and TFA (2 equiv) were added. The mixture was then heated to reflux for 10 h and then cooled to r.t. H2O (10 mL) was added and the mixture was extracted with EtOAc (2 × 20 mL). The combined organic layers were treated with sat. NaHCO3 solution and the aqueous layer was poured onto crushed ice and treated with 2 M HCl; a colorless solid precipitated out. The precipitate was filtered off and dried in vacuo to give benzoic acid (3a) after column chromatography (silica gel; EtOAc–hexane, 1:9) as a white crystalline solid; yield: 0.096 g (95percent) from 1a; mp 122–123 °C.

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With oxone; trifluoroacetic acid in 1,4-dioxane

10 h; RefluxGreen chemistry; Hide Experimental Procedure

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Rx-ID: 41068304 Find similar reactions

Aravinda Kumar; Venkateswarlu, Vunnam; Vishwakarma, Ram A.; Sawant, Sanghapal D.

Synthesis (Germany), 2015 , vol. 47, # 20 art. no. SS-2015-T0238-OP, p. 3161 - 3168 Title/Abstract

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Benzoic Acid (3a); Typical Procedure from Acetophenone or Phenylacetylene

General procedure: To a mixture of acetophenone (100 mg, 1 equiv) or phenylacetylene (1 equiv) in dioxane (5 mL), Oxone (2 equiv) and TFA (2 equiv) were added. The mixture was then heated to reflux for 10 h and then cooled to r.t. H2O (10 mL) was added and the mixture was extracted with EtOAc (2 × 20 mL). The combined organic layers were treated with sat. NaHCO3 solution and the aqueous layer was poured onto crushed ice and treated with 2 M HCl; a colorless solid precipitated out. The precipitate was filtered off and dried in vacuo to give benzoic acid (3a) after column chromatography (silica gel; EtOAc–hexane, 1:9) as a white crystalline solid; yield: 0.096 g (95percent) from 1a; mp 122–123 °C.

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Rx-ID: 41118513 Find similar reactions

Battula, Satyanarayana; Kumar, Atul; Ahmed, Qazi Naveed

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 39 p. 9953 - 9956 Title/Abstract

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With tert -butyl hydrogen peroxide in toluene

T=20°C; 4 h;

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With tert -butyl hydrogen peroxide in toluene

T=20°C; 4 h;

Rx-ID: 41118514 Find similar reactions

Battula, Satyanarayana; Kumar, Atul; Ahmed, Qazi Naveed

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 39 p. 9953 - 9956 Title/Abstract

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84

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80%

With tert -butyl hydrogen peroxide in toluene

T=20°C; 4 h;

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Rx-ID: 41118515 Find similar reactions

Battula, Satyanarayana; Kumar, Atul; Ahmed, Qazi Naveed

Organic and Biomolecular Chemistry, 2015 , vol. 13, # 39 p. 9953 - 9956 Title/Abstract

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85

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Rx-ID: 41287079 Find similar reactions

90%

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With 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene; cesium fluoride in DMFA

T=0 - 20°C; P=760.051 Torr; 2 h;

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Mita, Tsuyoshi; Suga, Kenta; Sato, Kaori; Sato, Yoshihiro

Organic Letters, 2015 , vol. 17, # 21 p. 5276 - 5279 Title/Abstract

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Rx-ID: 41436910 Find similar reactions

A: 20% B: 65%

With Polystyrene-supported palladium(0) nanoparticles T=130°C; P=5171.62 Torr; 0.75 h; Microwave irradiationSealed tube; Reagent/catalystSolventTemperatureTime;

Shil, Arun K.; Kumar, Sandeep; Reddy, C. Bal; Dadhwal, Sumit; Thakur, Vandna; Das, Pralay

Organic Letters, 2015 , vol. 17, # 21 p. 5352 - 5355 Title/Abstract

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Rx-ID: 41436926 Find similar reactions

A: 15% B: 58%

With N-iodo-succinimide in 1,4-dioxane

T=130°C; P=5171.62 Torr; Microwave irradiationSealed tube;

Shil, Arun K.; Kumar, Sandeep; Reddy, C. Bal; Dadhwal, Sumit; Thakur, Vandna; Das, Pralay

Organic Letters, 2015 , vol. 17, # 21 p. 5352 - 5355 Title/Abstract

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88

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Rx-ID: 41675851 Find similar reactions

44%

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With palladium on activated charcoal in 1,4-dioxane

T=130°C; P=5171.62 Torr; 0.75 h; Microwave irradiationSealed tube;

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Shil, Arun K.; Kumar, Sandeep; Reddy, C. Bal; Dadhwal, Sumit; Thakur, Vandna; Das, Pralay

Organic Letters, 2015 , vol. 17, # 21 p. 5352 - 5355 Title/Abstract

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A

B

C

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89

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Rx-ID: 9149389 Find similar reactions

B: 69%

With aluminium trichloride; aluminium

T=60°C; P=42753.4 Torr; 18 h;

Olah, George A.; Toeroek, Bela; Joschek, Jens P.; Bucsi, Imre; Esteves, Pierre M.; Rasul, Golam; Prakash, G. K. Surya

Journal of the American Chemical Society, 2002 , vol. 124, # 38 p. 11379 - 11391 Title/Abstract

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Stage #1: With [RhCl(1,2-bis(dicyclohexylphosphino)ethane)]2 ; Al(3+)*1.5CH3(1)*1.5C H O(1-); tetramethylurea in DMAA

2 5

Suga, Takuya; Mizuno, Hajime; Takaya, Jun; Iwasawa, Nobuharu

Chemical Communications, 2014 , vol. 50, # 92 p. 14360 - 14363 Title/Abstract

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T=20 - 120°C; P=760.051 Torr; 6 h; Inert atmosphere; Stage #2: With hydrochlorid acid in diethyl ether; DMAA; water

Inert atmosphere; Catalytic behavior; regioselective reaction;

90

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Rx-ID: 33406225 Find similar reactions

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99%

Stage #1: With [Ni(N,N'-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2ylidene)(allyl)Cl]; potassium tert-butylate in toluene

T=100°C; P=760.051 Torr; 15 h; Schlenk techniqueInert atmosphere; Stage #2: With hydrogenchloride in water; ethyl acetate; toluene

T=20°C;

Makida, Yusuke; Marelli, Enrico; Slawin, Alexandra M. Z.; Nolan, Steven P.

Chemical Communications, 2014 , vol. 50, # 59 p. 8010 - 8013 Title/Abstract

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83%

Stage #1: With potassium tert-butylate; silver(I) acetate; triphenylphosphine in tetrahydrofuran

T=70°C; P=15201 Torr; 16 h; Inert atmosphereAutoclave; Stage #2: With hydrogenchloride in tetrahydrofuran; water

Inert atmosphere;

Zhang, Xiao; Zhang, Wen-Zhen; Shi, Ling-Long; Guo, Chun-Xiao; Zhang, Ling-Ling; Lu, Xiao-Bing

Chemical Communications, 2012 , vol. 48, # 50 p. 6292 - 6294 Title/Abstract

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91

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90%

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With sulfuric acid

T=100°C; 0.25 h;

Rx-ID: 37110503 Find similar reactions

Wang, Fei; Tong, Zhaohui

RSC Advances, 2014 , vol. 4, # 12 p. 6314 - 6317 Title/Abstract

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A

B

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92

Synthesize Find similar Rx-ID: 37110505 Find similar reactions

A: 16% B: 24%

With sulfuric acid

T=100°C; 0.25 h; Overall yield = 40 percentSpectr.;

Wang, Fei; Tong, Zhaohui

RSC Advances, 2014 , vol. 4, # 12 p. 6314 - 6317 Title/Abstract

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A

93

B

C

Synthesize Find similar Rx-ID: 37431845 Find similar reactions

A: 27% B: 3% C: 16%

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With Oxonereg; in water; acetonitrile

24 h; Reflux; Hide Experimental Procedure

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Parida, Keshaba Nanda; Moorthy, Jarugu Narasimha

Tetrahedron, 2014 , vol. 70, # 13 p. 2280 - 2285 Title/Abstract

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1:5.2 General procedure for the oxidative cleavage of olefins

General procedure: To a solution of the olefin (0.5–1.2 mmol) in 16 mL of acetonitrile–water (1:1) mixture at reflux was introduced oxone incrementally over the entire duration of the reaction. Progress of the reaction in each case was monitored by TLC analysis. After completion of the reaction as judged by TLC analysis, the reaction mixture was cooled to rt, and the organic matter was extracted with ethyl acetate. The combined organic extract was dried over anhyd Na2SO4 and concentrated in vacuo. The residue was subjected to a short-pad silica gel column chromatography to isolate pure product/s. All the products were characterized by their 1H NMR spectral data.

A

B

C

D

E

F

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94

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Rx-ID: 37758570 Find similar reactions

B: 35% D: 14%

Stage #1: para-bromotoluene With tert.-butyl lithium in diethyl ether

T=-78°C; 0.5 h; Inert atmosphere; Stage #2: 1,1,3,3-tetramethyl-indan-2-carboxylic acid in diethyl ether

T=20°C; 18 h; Inert atmosphere; Stage #3: carbon dioxide in diethyl ether

Heating; Hide Experimental Procedure

Knorr, Rudolf; Menke, Thomas; Freudenreich, Johannes; Pires, Claudio

Beilstein Journal of Organic Chemistry, 2014 , vol. 10, p. 307 - 315 Title/Abstract

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2-(p-Methylbenzoyl)-1,1,3,3-tetramethylindane (38a)

Around-bottomed Schlenk flask (50 mL) was charged with 4-bromotoluene (0.563 mL, 4.58 mmol), anhydrous Et2O (10 mL), and a magnetic stirring bar. The contents were stirred and cooled at −78 °C under argon gas cover during the dropwise addition of t-BuLi (9.16 mmol) in pentane (6.10 mL), then stirred without cooling for 30 min. After the dropwise addition of acid 10 (400 mg, 1.83 mmol) in anhydrous Et2O (10 mL) to this solution of p-methylphenyllithium (34a) and further stirringat rt for 18 hours, the mixture was poured onto solid CO2, warmed up, and diluted with aqueous NaOH (1 M, 20 mL). Th eaqueous layer was shaken with Et2O (3 × 20 mL) and the combined four Et2O layers were washed with distilled water until neutral, dried over Na2SO4, and concentrated to leave the crude nonacidic material (455 mg) consisting mainly of 38a, 39a, and toluene (9:1:9). Repeated crystallizations from pentanea fforded white needles of 38a (isolated yield up to 35percent) A

95

B

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With sodium cyanide in water; dimethyl sulfoxide

T=20°C;

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Kim, Yoo-Jin; Kim, Na Yeun; Cheon, Cheol-Hong

Organic Letters, 2014 , vol. 16, # 9 p. 2514 - 2517 Title/Abstract

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A

B

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96

Synthesize Find similar Rx-ID: 37867799 Find similar reactions

B: 90%

Ikbal; Saha, Biswajit; Barman, Shrabani; Atta, Sanghamitra; Banerjee, Deb Ranjan; Ghosh, Sudip Kumar; Singh, N. D. Pradeep

Organic and Biomolecular Chemistry, 2014 , vol. 12, # 21 p. 3459 - 3469 Title/Abstract

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in water; acetonitrile

6 h; PhotolysisInert atmosphere; Quantum yield;

97

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60%

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Stage #1: With oxygen; sodium t-butanolate in tetrahydrofuran

T=20°C; P=760.051 Torr; 5 h; Stage #2: With hydrogenchloride in tetrahydrofuran; water

pH=1; chemoselective reaction;

Rx-ID: 38002687 Find similar reactions

Kim, Sun Min; Kim, Dong Wan; Yang, Jung Woon

Organic Letters, 2014 , vol. 16, # 11 p. 2876 - 2879 Title/Abstract

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A

B

98

Synthesize Find similar Rx-ID: 38110312 Find similar reactions

B: 85 %Spectr.

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With water in methanol

1.33333 h; Inert atmospherePhotolysis;

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Ikbal, Mohammed; Banerjee, Rakesh; Barman, Shrabani; Atta, Sanghamitra; Dhara, Dibakar; Singh, N.D. Pradeep

Journal of Materials Chemistry C, 2014 , vol. 2, # 23 p. 4622 - 4630 Title/Abstract

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99

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Multi-step reaction with 2 steps 1.1: magnesium sulfate / dichloromethane / 20 °C / |Inert atmosphere 2.1: [Ni(N,N'-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene) (allyl)Cl]; potassium tert-butylate / toluene / 15 h / 100 °C / 760.05 Torr / |Schlenk technique; |Inert atmosphere 2.2: 20 °C View Scheme

Rx-ID: 38188420 Find similar reactions

Makida, Yusuke; Marelli, Enrico; Slawin, Alexandra M. Z.; Nolan, Steven P.

Chemical Communications, 2014 , vol. 50, # 59 p. 8010 - 8013 Title/Abstract

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