Benzo[d][1,3]dioxole-5-carbaldehyde (Piperonal)

Query Query O

O

1. Query O

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181 reactions in Reaxys

2016-07-07 15h:04m:49s (EST)

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HO

O

O

O

O O

Rx-ID: 1760409 View in Reaxys 1/181 Yield 100 %

Conditions & References With bis(2,2'-bipyridyl) copper(II) permanganate in dichloromethane, Time= 0.5h, Ambient temperature Firouzabadi, H.; Sardarian, A. R.; Naderi, M.; Vessal, B.; Tetrahedron; vol. 40; nb. 23; (1984); p. 5001 - 5004 View in Reaxys

100 %

With 2,2'-bipyridylchromium peroxide in benzene, Time= 1.25h, Heating Firouzabadi, H.; Iranpoor, N.; Kiaeezadeh, F.; Toofan, J.; Tetrahedron; vol. 42; nb. 2; (1986); p. 719 - 726 View in Reaxys

100 %

With dipyridinium dichromate, chloro-trimethyl-silane in dichloromethane, Time= 0.25h Cossio, Fernando P.; Aizpurua, Jesus M.; Palomo, Claudio; Canadian Journal of Chemistry; vol. 64; (1986); p.

225 - 231 View in Reaxys

100 %

With tetrakis(pyridine)silver dichromate in benzene, Time= 1h, Heating Firouzabadi, H.; Sardarian, A.; Gharibi, H.; Synthetic Communications; vol. 14; nb. 1; (1984); p. 89 - 94 View in Reaxys

100 %

With 2,2'-bipyridylchromium peroxide in benzene, Time= 1.25h, Heating, effect of various chromium(VI) based oxidants, Product distribution Firouzabadi, H.; Iranpoor, N.; Kiaeezadeh, F.; Toofan, J.; Tetrahedron; vol. 42; nb. 2; (1986); p. 719 - 726 View in Reaxys

100 %

With silica gel, Bobbitt's oxidant in dichloromethane Bobbitt, James M.; Journal of Organic Chemistry; vol. 63; nb. 25; (1998); p. 9367 - 9374 View in Reaxys

100 %

With polymer-supported iodoxybenzoic acid in dichloromethane, Time= 5h, T= 25 °C Lei; Denecker; Jegasothy; Sherrington; Slater; Sutherland; Tetrahedron Letters; vol. 44; nb. 8; (2003); p. 1635 1637 View in Reaxys

100 %

With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in toluene, Time= 1.5h, T= 80 °C Ozanne, Aurelie; Pouysegu, Laurent; Depernet, Dominique; Francois, Bruno; Quideau, Stephane; Organic Letters; vol. 5; nb. 16; (2003); p. 2903 - 2906 View in Reaxys

100 %

1 :Example 1 (Synthesis of piperonal using a molybdenum compound: sodium molybdate was used, pH value of the reaction solution; 4.0 to 5.0); In a glass-made reaction vessel equipped with a thermometer, a temperature controller, a dropping device and a stirring device were charged 213 g of toluene, 127.7 g (839 mmol) ofpiperonyl alcohol, 3.07 g (12.7 mmol) of sodium molybdate-dihydrate (Na2MoO4*2H2O), 4.32 g (12.7 mmol) of tetrabutyl ammonium hydrogen sulfate and 18.0 g of water. Then, to the mixture were added 0.50 g (3.20 mmol) of sodium dihydrogen phosphate*dihydrate and 2.05 g (5.72 mmol) of disodium hydrogen phosphate*1 dihydrate (a pH value at this time was 4.87.). An inner temperature of the reaction mixture was maintained from 84 to 85°C, and 52.0 g (0.92 mol) of 60percent aqueous hydrogen peroxide was added dropwise to the mixture with 230 mmol/hr, while maintaining the pH of the reaction mixture to 4.0 to 5.0. After completion of the dropwise addition, the mixture was reacted for further one hour. After completion of the reaction, the resulting reaction mixture was cooled to room temperature, and when the organic layer solution was quantitatively analyzed by HPLC (measured wavelength: 256 nm: absolute calibration method), then, the reaction yield of piperonal was 100.0percent (Conversion ofpiperonyl alcohol: 99.0percent). Next, the solvent was distilled off from the organic layer solution, and the resulting white solid (piperonal) was analyzed, then, the physical properties thereof were as follows. MS spectrum (CI-MS); 151 [M]+ 1H-NMR spectrum (300 mHz, CDCl3) δ (ppm); 6.07 (2H, s), 6.93 (1H, d, J=7.8Hz), 7.32 (1H, d, J=1.5Hz), 7.40, 7.42 (1H, dd, J=1.5Hz), 9.81 (1H, s)

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With sodium phosphate dibasic dihydrate, sodium dihydrogenphosphate dihydrate, dihydrogen peroxide, sodium molybdate dihydrate, tetra(n-butyl)ammonium hydrogensulfate in water, toluene, T= 84 - 85 °C , pH= 4 - 5, Product distribution / selectivity Patent; Ube Industries, Ltd.; EP2351728; (2011); (A1) English View in Reaxys 100 %

With potassium osmate(VI) dihydrate, potassium carbonate, potassium hexacyanoferrate(III) in water, acetonitrile, Time= 0.416667h, T= 60 °C , chemoselective reaction Fernandes, Rodney A.; Bethi, Venkati; RSC Advances; vol. 4; nb. 76; (2014); p. 40561 - 40568 View in Reaxys

99.3 %

1 :20.0 g (0.136 mols) of piperonyl alcohol, 200 g of toluene and 2.7 g (0.013 mols) of aluminium isopropoxide (homogeneous catalyst) are introduced into a 1000 ml flask. The solution is heated under reflux and 8.00 g (0.263 mois) of p- formaidehyde are slowly added. At the end of the addition the mixture is left for about 2 hours under reflux, after which it is cooled and 300 ml of an aqueous 1 M sodium hydroxide solution are added. The phases are separated and the organic solution evaporated under vacuum (at 30°C/21 mbar) to obtain a crude reaction product containing 3,4-methylenedioxybenzaldehyde with a GC yield of 99.3percent and a conversion of 100percent.

With formaldehyd, aluminum isopropoxide in toluene, Time= 2h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys

99 %

2 :2.5 g of zirconium (Zrψ2)XZO 632/03 from Melcat (heterogeneous catalyst) and100 g of toluene are introduced into a 500 mi flask. The mixture is heated under reflux to azeotropically eliminate the water present, then, after cooling, 10.0 g(0.066 mols) of piperony. alcohol are added. After heating under reflux, 4.93 g(0.164 mois) of p-formaldehyde are slowly added.At the end of the addition, the solution is maintained for about 4 hours under reflux, then cooled and the catalyst filtered off. The organic solution is evaporated under vacuum (at 30°C/21 mbar) to obtain a crude reaction product containing3,4-methylenedioxybenzaldehyde with a 99percent GC yield and a conversion of 100percent.

With formaldehyd, (ZrO2)XZO 632/03 in toluene, Time= 4h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys

99.8 %

3 :Foilowing the method described in example 2, 10.0 g (0.164 mols) of piperonyl alcohol in 100 g of toluene are reacted with 4.93 g (0.164 mols) of p-formaldehyde in the presence of 2.5 g Pural MG61 from Sasol (a hydrotaicite) (heterogeneous catalyst). After evaporating the organic solution under vacuum (at 30°C/21 mbar) a crude reaction product containing 3,4-methylenedioxybenzaldehyde is obtained with a 99.8percent GC yield and a conversion of 100percent.

With formaldehyd, Pural MG61 in toluene, Time= 4h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys

99 %

With oxalyl dichloride, 3-methyl-1-[6-(methanesulfinyl)hexan-1-yl]-1H-imidazolium p-toluenesulfonate, triethylamine in dichloromethane, T= -78 - 20 °C , Swern oxidation Tsuchiya, Daisuke; Moriyama, Katsuhiko; Togo, Hideo; Synlett; nb. 18; (2011); p. 2701 - 2704 View in Reaxys

99 %

4.7. General procedure for the Swern oxidation using ion-supported methyl sulfoxide A-1 or B-1 General procedure: Oxalyl chloride (0.34 mL) was added dropwise to a solution of ion-supported methyl sulfoxide A-1 (C6) (1.60 g, 4.0 mmol) in CH2Cl2 (6 mL) at -70 °C and the mixture was stirred for 30 min at the same temperature. Then, a solution of alcohol (2.0 mmol) in CH2Cl2 (3 mL) was added dropwise at -70 °C and the obtained mixture was stirred for 30 min. Triethylamine (1.66 mL, 12 mmol) was added dropwise at -70 °C and the mixture was stirred for 1 h at the same temperature. The resulting mixture was warmed to -60 °C and stirred for 1.5 h at the same temperature. Then, the mixture was warmed to -50 °C and stirred for 1 h at the same temperature. Finally, the mixture was warmed to room temperature and stirred for 2 h at the same temperature. The reaction mixture was quenched with water (10 mL), neutralized (pH=6-7) with aq 1 M HCl solution, and extracted with diethyl ether (40 mL.x.2). The

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organic layer was washed with water (10 mL), dried over Na2SO4, and filtered. After removal of the solvent, aldehyde or ketone was obtained. The purity was estimated by 1H NMR measurements.

Stage 1: With oxalyl dichloride, 3-methyl-1-[6-(methanesulfinyl)hexan-1-yl]-1H-imidazolium p-toluenesulfonate in dichloromethane, Time= 0.5h, T= -70 °C , Swern oxidation Stage 2: With triethylamine in dichloromethane, Time= 5.5h, T= -70 - 20 °C , Swern oxidation Tsuchiya, Daisuke; Tabata, Masayuki; Moriyama, Katsuhiko; Togo, Hideo; Tetrahedron; vol. 68; nb. 34; (2012); p. 6849 - 6855 View in Reaxys 98 %

With 4-(N,N-dimethylamino)pyridinium chlorochromate in dichloromethane, Time= 15h Guziec, Frank S.; Luzzio, Frederick A.; Journal of Organic Chemistry; vol. 47; nb. 9; (1982); p. 1787 - 1789 View in Reaxys

98 %

With N-methyl-2-indolinone, lt;RuCl2(PPh3)2(Hacbh)gt;*2MeOH in dichloromethane, Time= 3h, T= 55 °C El-Hendawy, A. M.; Al-Kubaisi, A. H.; Shoair, A. F.; Monatshefte fuer Chemie; vol. 126; nb. 12; (1995); p. 1291 1302 View in Reaxys

98 %

With 4-(N,N-dimethylamino)pyridinium chlorochromate in dichloromethane, Time= 15h, other benzylic alcohols, Product distribution Guziec, Frank S.; Luzzio, Frederick A.; Journal of Organic Chemistry; vol. 47; nb. 9; (1982); p. 1787 - 1789 View in Reaxys

98 %

A :PREPARATION A : benzo[1,3]dioxole-5-carbaldehyde or piperonal; [Show Image] A 100 mL one-necked round bottomed flask was charged with piperonyl alcohol (1.03 g, 6.66 mmol) in dichloromethane (30 mL) and with manganese IV dioxide (6.43 g, 66.66 mmol). The reaction mixture was stirred at ambient temperature during 2 days. After evaporation of dichloromethane under reduced pressure, the suspension was filtered off on celite and washed with boiled dimethylformamide. After evaporation of the solvents under reduced pressure, the product crystallized and was dried under high vacuum yielding piperonal (983 mg, 98percent) as yellow crystals. 1H NMR (300 MHz, CHCl3d): δ 9.80 (s, 1H), 7.40 (m, 1H), 7.32 (m, 1H), 6.92 (d, 1H, J=7.9 Hz), 6.07 (s, 2H). MS (ESI-) m/z: 184.2 (M+Na)+.

With manganese(IV) oxide in dichloromethane, Time= 48h, T= 20 °C Patent; Hybrigenics S.A.; EP2208725; (2010); (A1) English View in Reaxys

98 %

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, N-methyl-N-[3-(4'-diacetoxyiodo)phenyl-1-propyl]-pyrrolidinium 4-methylbenzenesulfonate in dichloromethane, Time= 3.5h, T= 20 °C Suzuki, Yusuke; Iinuma, Masataka; Moriyama, Katsuhiko; Togo, Hideo; Synlett; vol. 23; nb. 8; (2012); p. 1250 1256 View in Reaxys

98 %

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, [{(MeOH)Cu(OAc)}(μ-k2:k1-2-(3-(pyridin-2-yl)-1H-pyrazol-1yl)acetic acid(-H))]2*0.5H2O, tetraethylammonium iodide, oxygen, potassium carbonate in water, Time= 24h, T= 40 °C , p= 760.051Torr Xie, Jing-Bo; Bao, Jia-Jing; Li, Hong-Xi; Tan, Da-Wei; Li, Hai-Yan; Lang, Jian-Ping; RSC Advances; vol. 4; nb.

96; (2014); p. 54007 - 54017 View in Reaxys

97 %

With molecular sieve, oxygen, lt;Ru2O6(py)4gt;*3.5H2O in acetonitrile, Time= 3h, Ambient temperature Dengel, Andrew C.; El-Hendawy, Ahmed M.; Griffith, William P.; O'Mahoney, Caroline A.; Williams, David J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 3; (1990); p. 737 - 742 View in Reaxys

97 %

With 3 A molecular sieve, oxygen, triethylamine, palladium diacetate in tetrahydrofuran, toluene, Time= 12h, T= 25 °C

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Schultz, Mitchell J.; Park, Candice C.; Sigman, Matthew S.; Chemical Communications; nb. 24; (2002); p. 3034 3035 View in Reaxys 97 %

With palladium diacetate, oxygen, triethylamine in tetrahydrofuran, toluene, Time= 12h, T= 20 °C Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.; Journal of Organic Chemistry; vol. 70; nb. 9; (2005); p. 3343 - 3352 View in Reaxys

97 %

With 1-butyl-3-methylimidazolium Tetrafluoroborate, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione, Time= 3.5h, T= 20 °C Yadav; Reddy; Basak; Venkat Narsaiah; Tetrahedron; vol. 60; nb. 9; (2004); p. 2131 - 2135 View in Reaxys

97 %

With acetic acid, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in acetonitrile, Time= 2h, T= 20 °C Lin, Cheng-Kun; Lu, Ta-Jung; Tetrahedron; vol. 66; nb. 51; (2010); p. 9688 - 9693 View in Reaxys

97 %

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, N-methyl-N-[3-(4-diacetoxyiodo)phenoxy-1-propyl]pyrrolidinium 4-methylbenzenesulfonate in dichloromethane, Time= 3.5h, T= 20 °C , Inert atmosphere Iinuma, Masataka; Moriyama, Katsuhiko; Togo, Hideo; Tetrahedron; vol. 69; nb. 14; (2013); p. 2961 - 2970 View in Reaxys

97 %

With 1-methyl-1H-imidazole, [2,2]bipyridinyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, TPGS–750–M, copper(I) bromide in water, Time= 7h, T= 20 °C Lipshutz; Hageman; Fennewald; Linstadt; Slack; Voigtritter; Chemical Communications; vol. 50; nb. 77; (2014); p. 11378 - 11381 View in Reaxys

96 %

in dichloromethane, Time= 3h El-Hendawy, Ahmed M.; Griffith, William P.; Taha, Fatma I.; Moussa, Mahmoud N.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); (1989); p. 901 - 906 View in Reaxys

96 %

With manganese(IV) oxide, Time= 10h, T= 90 °C , Oxidation Firouzabadi, Habib; Karimi, Babak; Abbassi, Mohammad; Journal of Chemical Research - Part S; nb. 3; (1999); p. 236 - 237 View in Reaxys

96 %

General Procedure-2 [For the open air oxidation of alcohols to carbonyl compounds; GP-2(method B)]: General procedure: In an oven dried Schlenk tube, were added alcohol 1 (69.0–199.5 mg, 0.5 mmol), CuI (10 molpercent)and 1,10-Phenanthroline (20 molpercent) and K3PO4 (2 mmol) followed by the addition of dioxane (2mL) at room temperature under open air atmosphere. The stirred reaction mixture was heated inan oil bath at 80 C for 7–48 h. Progress of the reaction was monitored by TLC till the reaction iscompleted. Then, the reaction mixture was cooled to room temperature, quenched with aqueousNH4Cl solution and then extracted with CH2Cl2 (3 10 mL). The organic layer was washed withsaturated NaCl solution, dried (Na2SO4), and filtered. Evaporation of the solvent under reducedpressure and purification of the crude material by silica gel column chromatography (petroleumether/ ethyl acetate) furnished the aldehyde/ketone 2 (61–97percent).

With potassium phosphate, copper(l) iodide, phen in 1,4-dioxane, T= 80 °C , Schlenk technique, Solvent, Time Reddy, Alavala Gopi Krishna; Mahendar, Lodi; Satyanarayana, Gedu; Synthetic Communications; vol. 44; nb.

14; (2014); p. 2076 - 2087 View in Reaxys

96 %

With hexaammonium heptamolybdate tetrahydrate, dihydrogen peroxide in water, methyl cyclohexane, Time= 2h, T= 50 °C , Ionic liquid, Green chemistry Hu, Yu-Lin; Lu, Ming; Ge, Xiu-Tao; Journal of the Iranian Chemical Society; vol. 10; nb. 3; (2013); p. 453 - 460

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View in Reaxys 95 %

With trimethylamine-N-oxide, 4 A molecular sieve, polymer supported perruthenate in dichloromethane, Time= 14h, Ambient temperature Hinzen, Berthold; Ley, Steven V.; Journal of the Chemical Society - Perkin Transactions 1; nb. 13; (1997); p. 1907 1908 View in Reaxys

95 %

With polymeric complex of oxodiperoxochromium(VI) compound and pyrazine (Pyz-CrO5)n in dichloromethane, Time= 0.3h, Ambient temperature Tamami, Bahman; Yeganeh, Hamid; Tetrahedron; vol. 53; nb. 23; (1997); p. 7889 - 7896 View in Reaxys

95 %

With manganese(IV) oxide in dichloromethane, Time= 24h, Ambient temperature Aoyama, Toyohiko; Sonoda, Naoko; Yamauchi, Mariko; Toriyama, Kyoko; Anzai, Masahiro; Ando, Akira; Shioiri, Takayuki; Synlett; nb. 1; (1998); p. 35 - 36 View in Reaxys

95 %

With dihydrogen peroxide, 1-butyl-3-methylimidazolium Tetrafluoroborate, 1-methyl-3-butylimidazolium decatungstate, Time= 1.5h, Heating Chhikara, Bhupender S.; Tehlan, Sarita; Kumar, Anil; Synlett; nb. 1; (2005); p. 63 - 66; Art.No: S08604ST View in Reaxys

95 %

With sodium periodate, 2,2,6,6-tetramethyl-piperidine-N-oxyl, sodium bromide in dichloromethane, water, Time= 15h, T= 20 °C Lei, Ming; Hu, Rui-Jun; Wang, Yan-Guang; Tetrahedron; vol. 62; nb. 38; (2006); p. 8928 - 8932 View in Reaxys

95 %

With 2,2,6,6-tetramethyl-piperidine-N-oxyl, iodosylbenzene, ytterbium(III) triflate in dichloromethane, Time= 0.25h, T= 20 °C Vatele, Jean-Michel; Synlett; nb. 13; (2006); p. 2055 - 2058 View in Reaxys

95 %

With tetraphenylphosphonium peroxymonosulfate, iodobenzoic acid in acetonitrile, Time= 8h, T= 80 °C Bulman Page, Philip C.; Appleby, Louise F.; Buckley, Benjamin R.; Allin, Steven M.; McKenzie, Michael J.; Synlett; nb. 10; (2007); p. 1565 - 1568 View in Reaxys

94 %

With 1-oxo-3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolinium nitrate in acetonitrile, 0 deg C, 30 min then room temp., 5 h Ma, Zhenkun; Huang, Qingtao; Bobbitt, James M.; Journal of Organic Chemistry; vol. 58; nb. 18; (1993); p. 4837 - 4843 View in Reaxys

94 %

With cycloheptaamylose, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in water, acetone, Time= 12h, T= 20 °C Surendra; Srilakshmi Krishnaveni; Arjun Reddy; Nageswar; Rama Rao; Journal of Organic Chemistry; vol. 68; nb. 5; (2003); p. 2058 - 2059 View in Reaxys

94 %

With N-Bromosuccinimide, cycloheptaamylose in methanol, water, acetone, Time= 8h, T= 20 °C Krishnaveni, N. Srilakshmi; Surendra; Rao, K. Rama; Advanced Synthesis and Catalysis; vol. 346; nb. 2-3; (2004); p. 346 - 350 View in Reaxys

94 %

6 : 4.5. General procedure for the aerobic alcohol oxidation General procedure: Under an air atmosphere, a Schlenk tube was charged with MCM-41-bpy-CuI (40 mg, 0.025 mmol), alcohol (0.5 mmol), TEMPO (4 mg, 0.025 mmol), aqueous ammonia (0.5 mmol, 25e28percent, w/w) and

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EtOH (1.0 mL). The mixture was stirred at 50 °C for 18-48 h. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ethyl acetate (10 mL), and filtered. The MCM-41-bpy-CuI complex was washed with EtOH (2*5 mL), and Et2O (5 mL) and reused in the next run. The filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography on silica gel (petroleum/ethyl acetate=15:1 to 10:1) to provide the desired product.

With ammonium hydroxide, 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, oxygen in ethanol, Time= 30h, T= 50 °C Zhao, Hong; Chen, Qiurong; Wei, Li; Jiang, Yuanyuan; Cai, Mingzhong; Tetrahedron; vol. 71; nb. 46; (2015); p.

8725 - 8731; Art.No: 27151 View in Reaxys 93 %

With 4,4'-bis-(dichloroiodo)-biphenyl, tetraethylammonium bromide in chloroform, Time= 0.416667h, T= 20 °C Telvekar, Vikas N.; Herlekar, Omkar P.; Synthetic Communications; vol. 37; nb. 5; (2007); p. 859 - 863 View in Reaxys

93 %

With [Rh((5-H-dibenzo[a,d]cyclohepten-5-yl)2NH)(PPh3)]OTf, potassium carbonate, Nitrosobenzene in tetrahydrofuran, T= 20 °C Annen, Samuel P.; Gruetzmacher, Hansjoerg; Dalton Transactions; vol. 41; nb. 46; (2012); p. 14137 - 14145 View in Reaxys

92 %

With lt;PPh4gt;2lt;Mo2O3(O2)4gt; in dichloromethane, Time= 3h, Ambient temperature Campbell, Nicholas J.; Dengel, Andrew C.; Edwards, Catherine J.; Griffith, William P.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); (1989); p. 1203 - 1208 View in Reaxys

92 %

With 1-(benzoylamino)-3-methylimidazolium chlorochromate in dichloromethane, Time= 25h, Heating Martinez, Yolanda; De Las Heras, Maria A.; Vaquero, Juan J.; Garcia-Navio, Jose L.; Alvarez-Builla, Julio; Tetrahedron Letters; vol. 36; nb. 46; (1995); p. 8513 - 8516 View in Reaxys

92 %

With oxygen, Mg6Al2Ru0.5(OH)16CO3 in toluene, Time= 8h, T= 60 °C Kaneda, Kiyotomi; Yamashita, Toyokazu; Matsushita, Tsuyoshi; Ebitani, Kohki; Journal of Organic Chemistry; vol. 63; nb. 6; (1998); p. 1750 - 1751 View in Reaxys

92 %

With potassium phosphate, chlorobenzene, CyJohnPhos, bis(dibenzylideneacetone)-palladium(0) in toluene, Time= 14h, T= 105 °C Guram, Anil S.; Bei, Xiaohong; Turner, Howard W.; Organic Letters; vol. 5; nb. 14; (2003); p. 2485 - 2487 View in Reaxys

92 %

With (S)-2-aminopropanoic acid, silica gel, chlorochromic acid in dichloromethane, Time= 2.5h, T= 20 °C Salehi, Peyman; Khodaei, Mohammad Mehdi; Rostami, Amin; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 179; nb. 11; (2004); p. 2235 - 2243 View in Reaxys

92 %

With potassium carbonate, chlorobenzene in toluene, Time= 14h, T= 105 °C Patent; Symyx Technologies, Inc.; US6350916; (2002); (B1) English View in Reaxys

92 %

8 :Following the method described in example 2, 5.0 g (0.0003 mols) of piperonyl alcohol are reacted with 2.5 g (0.083 mois) of p-formaldehyde in 50.0 g of toluene in the presence of 1.25 g of Sorbacide 696 (a hydrotalcite produced bySudChemie, previously calcinated at 4000C).The mixture is maintained under reflux for 2 hours. The catalyst is cooled and filtered off. The organic solution is evaporated under vacuum (at 30°C/21 mbar) to obtain a crude reaction product containing 3,4-methy.enedioxybenzaldehyde with a 92percent GC yield and a conversion of 99.5percent.

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With formaldehyd, Sorbacide 696 in toluene, Time= 2h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys 92 %

Stage 1: With copper(I) bromide in acetonitrile, Time= 0.05h, T= 20 °C , Inert atmosphere Stage 2: With N,N'-di-tert-butyldiaziridinone in acetonitrile, Time= 2h, T= 60 °C Zhu, Yingguang; Zhao, Baoguo; Shi, Yian; Organic Letters; vol. 15; nb. 5; (2013); p. 992 - 995 View in Reaxys

92 %

With ANBX in N,N-dimethyl-formamide, Time= 24h, T= 65 °C Iinuma, Masataka; Moriyama, Katsuhiko; Togo, Hideo; Synlett; vol. 24; nb. 13; (2013); p. 1707 - 1711; Art.No: ST-2013-U0386-L View in Reaxys

91 %

With potassium permanganate, Tris(3,6-dioxaheptyl)amine in dichloromethane, Time= 2h, Ambient temperature McKillop, Alexander; Mills, Lester S.; Synthetic Communications; vol. 17; nb. 6; (1987); p. 647 - 656 View in Reaxys

91 %

With sodium hypochlorite, cycloheptaamylose, potassium bromide in methanol, water, acetone, Time= 8h, T= 20 °C Surendra; Krishnaveni, N. Srilakshmi; Rao, K. Rama; Canadian Journal of Chemistry; vol. 82; nb. 7; (2004); p.

1230 - 1233 View in Reaxys

91 %

With sodium iodide dichloride in water, Time= 3.5h, T= 20 °C Telvekar, Vikas N.; Jadhav, Nikhil C.; Synthetic Communications; vol. 38; nb. 18; (2008); p. 3107 - 3111 View in Reaxys

91 %

General Procedures for the Copper-Catalyzed Primary BenzylicAlcohol Oxidation under Air in Water (pMethylbenzylAlcohol) General procedure: A mixture of p-methylbenzyl alcohol (1.0 mmol), N-phenylglycine(0.0076 g, 0.05 mmol), CuBr2 (0.0112 g, 0.05 mmol),Na2CO3 (0.1060 g, 1.0 mmol), TEMPO (0.0078 g, 0.05 mmol),H2O (3.0 mL) were added to a 100 mL Schlenk tube, which wasvigorously stirred in air under reflux for 0.5 h. After the reaction,the product was extracted with CH2Cl2 (3 × 2.0 mL). Thecombined organic phase was washed with H2O (3.0 mL) anddried over anhydrous MgSO4. After concentration undervacuum, the residue was purified by column chromatography toafford pmethylbenzaldehyde.Isolated yield: 0.1080 g (90percent).

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, sodium carbonate, N-Phenylglycine, copper(ll) bromide in water, Time= 8h, Reflux, Schlenk technique Zhang, Guofu; Lei, Jie; Han, Xingwang; Luan, Yuxin; Ding, Chengrong; Shan, Shang; Synlett; vol. 26; nb. 6; (2015); p. 779 - 784 View in Reaxys

90 %

With barium permanganate in acetonitrile, Time= 2.5h, Heating Firouzabadi, H.; Mottghinejad, E.; Seddighi, M.; Synthesis; nb. 5; (1989); p. 378 - 380 View in Reaxys

90 %

With selenium(IV) oxide, bis-{4-methoxy-phenyl}-selenoxyde in 1,4-dioxane, Time= 24h, Heating Ogura, Fumio; Otsubo, Tetsuo; Ariyoshi, Kimio; Yamaguchi, Hachiro; Chemistry Letters; (1983); p. 1833 - 1834 View in Reaxys

90 %

With cerous hydroxide in benzene, Time= 1h, Heating Firouzabadi, H.; Iranpoor, N.; Synthetic Communications; vol. 14; nb. 9; (1984); p. 875 - 882 View in Reaxys

90 %

With oxoammonium resin in dichloromethane, Time= 1h, T= 20 °C

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Weik, Steffen; Nicholson, Graeme; Jung, Gnther; Rademann, Jrg; Angewandte Chemie - International Edition; vol. 40; nb. 8; (2001); p. 1436 - 1439 View in Reaxys 90 %

With 1-butyl-3-methylimidazolium chloride, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione, Time= 0.25h, T= 20 °C Karthikeyan, Ganesan; Perumal, Paramasivan T.; Synlett; nb. 14; (2003); p. 2249 - 2251 View in Reaxys

90 %

With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in ethyl acetate, Time= 3.25h, T= 80 °C More, Jesse D.; Finney, Nathaniel S.; Organic Letters; vol. 4; nb. 17; (2002); p. 3001 - 3003 View in Reaxys

90 %

With oxygen, potassium carbonate in toluene, Time= 10h, T= 90 °C , p= 760.051Torr Zhang, Lei; Li, Pinhua; Yang, Jin; Wang, Min; Wang, Lei; ChemPlusChem; vol. 79; nb. 2; (2014); p. 217 - 222 View in Reaxys

89 %

With potassium nitrososulfonate, adogen 464 in benzene, Time= 12h Morey, Jeronimo; Dzielenziak, Adam; Saa, Jose Manuel; Chemistry Letters; (1985); p. 263 - 264 View in Reaxys

89 %

With chromium(VI) oxide, tert.-butylhydroperoxide, silica gel in dichloromethane, Time= 0.166667h, microwave irradiation, Oxidation Singh; Sharma; Chhibber; Kaur; Kad; Synthetic Communications; vol. 30; nb. 21; (2000); p. 3941 - 3945 View in Reaxys

89 %

(ii) Procedure for alcohols containing acid-sensitive groups.

General procedure: To a mixture of alcohol in dry DMSO/THF (10 volume, 50:50 mixture) was added 1 equiv of polymer bromide and the reaction mixture was stirred at room temperature for a given period of time (Table 1). After completion of the reaction, the reaction mixture was filtered and the polymer bed was washed with THF. Combined DMSO/THF layers were quenched with ice-water mixture and extracted with ether. The ether layer was given water wash, brine wash, dried over anhydrous sodium sulphate, and concentrated to get the pure carbonyl compounds.

With Br3 (1-)*C10H15NPol(1+), dimethyl sulfoxide in tetrahydrofuran, Time= 5h, T= 20 °C Prasanna; Mohanaraju; Tetrahedron Letters; vol. 52; nb. 51; (2011); p. 6971 - 6973 View in Reaxys

88 %

With N-iodo-succinimide, tetra-(n-butyl)ammonium iodide in dichloromethane, Time= 4h, Ambient temperature Hanessian, Stephen; Wong, David Hin-chor; Therien, Michel; Synthesis; nb. 5; (1981); p. 394 - 396 View in Reaxys

88 %

With Merrifield's resin-bound N-aminoimidazolium chlorochromate in dichloromethane, Time= 2.2h, Heating Linares; Sanchez; Alajarin; Vaquero; Alvarez-Builla; Synthesis; nb. 3; (2001); p. 382 - 388 View in Reaxys

86 %

With acetic anhydride, sodium nitrite, T= 25 °C Bandgar, Babasaheb P.; Sadavarte, Vaibhav S.; Uppalla, Lavkumar S.; Journal of the Chemical Society, Perkin Transactions 1; nb. 21; (2000); p. 3559 - 3560 View in Reaxys

85 %

With oxygen, 2,2,6,6-tetramethyl-piperidine-N-oxyl, copper(l) chloride in N,N-dimethyl-formamide, Time= 16h, T= 25 °C Semmelhack, M. F.; Schmid, Christopher R.; Cortes, David A.; Chou, Chuen S.; Journal of the American Chemical Society; vol. 106; nb. 11; (1984); p. 3374 - 3376 View in Reaxys

85 %

With zinc(II) chlorosulphate in dichloromethane, Time= 2h, Ambient temperature Firouzabadi, H.; Sharifi, A.; Synthesis; nb. 10; (1992); p. 999 - 1002

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View in Reaxys 85 %

With lt;Ce(NO3)3gt;2CrO4 in benzene, Time= 0.6h, Heating Firouzabadi, H.; Iranpoor, N.; Parham, H.; Tootan, J.; Synthetic Communications; vol. 14; nb. 7; (1984); p. 631 638 View in Reaxys

84 %

With polystyrene-supported 5-hydroxy-2-iodoxybenzoic acid in dichloromethane, Time= 3h, T= 20 °C Sorg; Mengel; Jung; Rademann; Angewandte Chemie - International Edition; vol. 40; nb. 23; (2001); p. 4395 4397 View in Reaxys

84 %

3.1. Oxidation of benzhydrol 1a in the presence of substoichiometric amounts of activated MnO2: preparation of benzophenone 2 (Table 1, entry 6). General procedure#10; General procedure: Benzhydrol 1 (0.3831 g, 2.08 mmol) was dissolved in toluene (15 mL) and activated MnO2 (purchased from Aldrich, 0.106 g, 1.92 mmol, 50 mg/mmol) was added to the solution. The reaction mixture was heated at 110 °C under oxygen atmosphere for 4 h. Supernatant of the reaction mixture was scooped by pipet. Additional toluene (5 mL) was added to solid residue and washed the solid then the supernatant was scooped by pipet. This washing procedure was repeated for four times. All of toluene solution was combined and concentrated. Crude product was purified by flash chromatography (silica gel/hexane-EtOAc 3:1) to give 2 in 98percent yield (0.373 g, 2.05 mmol). MnO2 residue was examined for the recycling use of the oxidant (Scheme 4, see below).

With manganese(IV) oxide, oxygen in toluene, Time= 8h, T= 110 °C , Green chemistry Kamimura, Akio; Komatsu, Hiroyuki; Moriyama, Takaaki; Nozaki, Yuichiro; Tetrahedron; vol. 69; nb. 29; (2013); p. 5968 - 5972 View in Reaxys

84 %

General Procedure General procedure: A mixture of benzylic alcohol (1.0mmol), urea hydrogen peroxide (1.5 mmol) and calciumchloride (0.5 mmol) was stirred in PEGDME250 (2 mL) at 70oC for 4 h. After cooling the mixture to room temperature theproduct is extracted into diethyl ether (3 × 20 mL), washedwith water and dried over MgSO4. The combined etherextracts were concentrated under reduced pressure and thecrude product was purified by flash column chromatography(ethyl acetate/n-hexane = 1:3, v/v) to give the desired carbonylcompound.

With urea hydrogen peroxide adduct, calcium chloride, Time= 4h, T= 70 °C Ha, Su Jeong; Jung, Eun-Young; Kim, Won Mi; Lee, Jong Chan; Bulletin of the Korean Chemical Society; vol.

35; nb. 2; (2014); p. 629 - 630 View in Reaxys

83 %

With γ-picolinium chlorochromate, silica gel in dichloromethane, Time= 4h, T= 20 °C Salehi; Khodaei; Yazdanipoor; Polish Journal of Chemistry; vol. 77; nb. 10; (2003); p. 1281 - 1286 View in Reaxys

83 %

4 :In this case the formaldehyde is replaced by benzaldehyde. Operating as described in example 1 , 15.2 g (0.1 mols) of piperonyi alcohol are reacted in 200 g of toluene with 31.2 g (0.3 mols) of benzaldehyde in the presence of 2.04 g (0.01 mols) of aluminium isopropoxide.After cooling and adding 300 ml of an aqueous 1 IvI sodium hydroxide solution, the phases are separated and the organic solution evaporated under vacuum (at 30°C/21 mbar) to obtain a crude reaction product containing 3,4- methylenedioxybenzaldehyde with a 83percent GC yield and a conversion of 95percent.

With benzaldehyde, aluminum isopropoxide in toluene, Time= 2h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys

82 %

With pyridiniumchlorochromate on aluminumoxide, Time= 2h, T= 20 °C Bhar, Sanjay; Chaudhuri, Subrata Kumar; Tetrahedron; vol. 59; nb. 19; (2003); p. 3493 - 3498 View in Reaxys

82 %

With chromium(VI) oxide, 1-butyl-3-methylimidazolium Tetrafluoroborate, Time= 2h, T= 20 °C

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Zheng, Yun-Fa; Du, Xing-Fen; Bao, Wei-Liang; Journal of Chemical Research; nb. 12; (2005); p. 753 - 754 View in Reaxys 82.3 %

d :(d) Oxidation of the piperonyl alcohol/1, 3-benzodioxole mixture The previously obtained crude piperonyl alcohol synthesis product is introduced into a 1 litre flask. 50.1 g NaOH pellets (97percent) (1.21 moles) dissolved in 750 ml H20 and 24 g of 5percent Pt catalyst wetted to 53.6percent are added. The temperature is brought to 80-85°C under N2 flow, after which a flow of air is supplied at about 540 ml/min measured on leaving the reaction environment. Alcohol conversion is essentially complete after 10 hours of reaction time. The air flow is stopped and the reaction mixture is brought to ambient temperature under N2 flow. The catalyst is filtered off and the phases are then separated.

A crude product weighing 1035.45 g is obtained composed of the following: piperonyl alcohol 0. 08percent w/w (0.828 g) heliotropine 14.48percent w/w (150 g) 1, 3-benzodioxole 11.9percent w/w (123.22 g) Conversion of piperonyl alcohol = 99.6percent Yield of heliotropine = 82.3percent With sodium hydroxide, 5percent Pd catalyst in water, Time= 10h, T= 80 - 85 °C , Conversion of starting material Patent; ENDURA S.P.A.; WO2005/42512; (2005); (A1) English View in Reaxys

81 %

With [Ag(py)2MnO4] in benzene, Time= 1h Firouzabadi, H.; Vessal, B.; Naderi, M.; Tetrahedron Letters; vol. 23; nb. 17; (1982); p. 1847 - 1850 View in Reaxys

80 %

With methanol, palladium on activated charcoal, Time= 3h, Heating, Oxidation Itaya, Taisuke; Kanai, Tae; Ohyama, Shin-Ichi; Shirasaki, Yoshihisa; Muramoto, Nobuhiro; Ono, Yukiko; Chemical and Pharmaceutical Bulletin; vol. 47; nb. 10; (1999); p. 1464 - 1472 View in Reaxys

80 %

Typical experimental procedure for the synthesis of Piperonal: (entry 4, Table 1) In a typical experimental procedure a mixture of benzo[d][1,3]dioxol-5-ylmethanol (1 mmol, 152 mg), NaIO4 (1 mmol, 213 mg) in 2 ml of DCM was taken in an open round bottomed flask at room temperature and then NH2OH*HCl (1.5 mmol, 105 mg) was added by portion for 5 min. After completion (TLC), the reaction mixture was diluted with a 1:1 mixture of water/DCM (10 mL) and washed with 10percent (w/v) Na2S2O3 (3 .x. 5 ml). Then the combined organic layer was dried over anhydrous Na2SO4. Evaporation of solvent furnished the crude product which was subjected to column chromatography using ethyl acetate-petroleum ether (1:10) to obtain the analytically pure product as a white solid (122 mg, 80percent).mp.

36-38 °C; IR (KBr) cm-1 2966, 1676, 1598, 1481, 1440 cm-1; 1H NMR (300 MHz, CDCl3) δ 9.80 (s, 1H), 7.41 (dd, J = 1.5, 1.5 Hz, 1H), 7.33 (d, J = 1.2 Hz, 1H), 6.93 (d, J = 8.1 Hz, 1H), 6.09 (s, 2H); 13C NMR (75 MHz, CDCl3) δ 190.2, 152.9, 148.6, 131.7, 128.5, 108.2, 106.7, 102.0.

With sodium periodate, hydroxylamine hydrochloride in dichloromethane, T= 20 °C , chemoselective reaction Majee, Adinath; Kundu, Shrishnu Kumar; Santra, Sougata; Hajra, Alakananda; Tetrahedron Letters; vol. 53; nb.

33; (2012); p. 4433 - 4435 View in Reaxys

80%

With C32H18CuN4O6*H2O, dihydrogen peroxide in water, acetonitrile, Time= 2h, T= 20 °C Shoair, Abdel Ghany F.; Journal of Coordination Chemistry; vol. 65; nb. 20; (2012); p. 3511 - 3518 View in Reaxys

79 %

Typical procedure for the formation of aldehydes (3a-q) General procedure: A test tube equipped with a magnetic stirring bar was charged with 1 (5 mg, 0.005 mmol, 0.25 molpercent), TEMPO (16 mg, 0.10 mmol, 5 molpercent), and K2CO3 (69 mg, 0.50 mmol, 25 molpercent). Alcohols (2a-q, 2.0 mmol), H2O (5 mL) and H2O2 (30percent, 1 mL) were added. The mixed light green solution was stirred at 60°C for 12 h, cooled to room temperature, and then extracted by Et2O (3 × 5mL). The organic layers were combined, washed with brine (20 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. On elution with petroleum ether and ethyl acetate, the crude product was further purified by column chromatography on silica. All aldehyde products synthesized in this work are known and confirmed by 1H NMR spectra.

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, C40H54CuN4O5 (2+)*2I(1-), dihydrogen peroxide, potassium carbonate in water, Time= 12h, T= 60 °C

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Gao, Jun; Ren, Zhi-Gang; Lang, Jian-Ping; Journal of Organometallic Chemistry; vol. 792; (2015); p. 88 - 92; Art.No: 18908 View in Reaxys 78 %

With molecular sieve, lt;PPh4gt;lt;RuO2(OCOMe)Cl2gt; in dichloromethane, Time= 1h, Ambient temperature Griffith, William P.; Jolliffe, Jennifer M.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 24; (1992); p. 3483 - 3488 View in Reaxys

78 %

Experimental Procedures for oxidation of Various alcohols: General procedure: A CH3CN solution of alcohol (1 mmol), ZnBr2 (45 mg, 0.2 mmol), and chloramine-T (282 mg, 1 mmol) was placed in a three necked flask with a reflux condenser. After the mixture was stirred under reflux for 1.5-5 h. After cooling to room temperature, the solution was quenched by adding water and the resulting mixture was extracted with AcOEt. Removal of the solvent under reduced pressure gave the crude product, which was purified by column chromatography on silica gel to give the corresponding carbonyls.

With chloroamine-T, zinc dibromide in acetonitrile, Time= 4h, Reflux Wang, Peng; Cai, Jin; Yang, Jiabin; Sun, Chunlong; Li, Lushen; Hu, Huayou; Ji, Min; Tetrahedron Letters; vol.

54; nb. 6; (2013); p. 533 - 535 View in Reaxys

77.5 %

With [Bmim][Br3], sodium acetate, Time= 1.5h, T= 60 °C Zhang, Yu; Bao, Weiliang; Journal of Chemical Research; nb. 4; (2006); p. 263 - 266 View in Reaxys

75 %

With dinitratocerium (IV) chromate in benzene, Time= 2h, Heating Firouzabadi, H.; Iranpoor, N.; Kiaeezadeh, F.; Toofan, J.; Synthetic Communications; vol. 14; nb. 10; (1984); p.

973 - 982 View in Reaxys

75 %

With pyridinium chlorochromate Hirano; Osawa; Yamaoka; Yokoi; Biological and Pharmaceutical Bulletin; vol. 24; nb. 11; (2001); p. 1277 - 1281 View in Reaxys

72 %

With bis(p-methoxyphenyl)tellurone Engman, Lars; Cava, Michael P.; Journal of the Chemical Society, Chemical Communications; nb. 3; (1982); p. 164 - 165 View in Reaxys

71 %

With Candida antarctica lipase B immobilized, urea hydrogen peroxide adduct in water, Time= 8h, T= 60 °C , Ionic liquid, Enzymatic reaction, chemoselective reaction Sharma, Upendra K.; Sharma, Nandini; Kumar, Rakesh; Kumar, Rajesh; Sinha, Arun K.; Organic Letters; vol.

11; nb. 21; (2009); p. 4846 - 4848 View in Reaxys

70 %

With 4-methylmorpholine N-oxide, tetrapropylammonium perruthennate in dichloromethane, Time= 1h, Ambient temperature Griffith, William P.; Ley, Steven V.; Whitcombe, Gwynne P.; White, Andrew D.; Journal of the Chemical Society, Chemical Communications; (1987); p. 1625 - 1627 View in Reaxys

60 %

With barium permanganate in benzene, Time= 1.5h, Heating Firouzabadi; Mostafavipoor; Bulletin of the Chemical Society of Japan; vol. 56; nb. 3; (1983); p. 914 - 917 View in Reaxys

58 %

5 :In this case the formaldehyde is replaced by cyclohexanone. Similarly to that described in example 4 and using the same quantities, the reaction is conducted with 19.6 g (0.2 mols) of cyclohexanone as hydrogen acceptor. The

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crude reaction product contained 3,4-methylenedioxybenzaldehyde with a 58percent GC yield and a conversion of 70percent.

With cyclohexanone, aluminum isopropoxide in toluene, Time= 2h, Heating / reflux, Conversion of starting material Patent; ENDURA S.P.A.; WO2007/12641; (2007); (A1) English View in Reaxys 57 %

With 1-[4-(diacetoxyiodo)benzyl]-3-methylimidazolium BF4, 1-ethyl-3-methylimidazolium tetrafluoroborate, Time= 3h, T= 30 °C Qian, Weixing; Jin, Erlei; Bao, Weiliang; Zhang, Yongmin; Angewandte Chemie - International Edition; vol. 44; nb. 6; (2005); p. 952 - 955 View in Reaxys

37 %

With tetrabutylammomium bromide, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in dichloromethane, water, Time= 4h, T= 20 °C Kuhakarn, Chutima; Kittigowittana, Krisada; Ghabkham, Pattama; Pohmakotr, Manat; Reutrakul, Vichai; Synthetic Communications; vol. 36; nb. 19; (2006); p. 2887 - 2892 View in Reaxys

35 %

With dihydrogen peroxide, lt;NMe4gt;3lt;(MePO3)lt;MePO2(OH)gt;W6O13(O2)4(OH)2(OH2)gt;*4H2O, Time= 3h, T= 70 °C Griffith, William P.; Parkin, Bernardeta C.; White, Andrew J. P.; Williams, David J.; Journal of the Chemical Society, Chemical Communications; nb. 21; (1995); p. 2183 - 2184 View in Reaxys

34 %

With dihydrogen peroxide, lt;NMe4gt;2lt;(PhPO3)lt;WO(O2)2gt;2lt;WO(O2)2(H2O)gt;gt; in benzene, Time= 3h, T= 70 °C Griffith, William P.; Parkin, Bernadeta C.; White, Andrew J. P.; Williams, David J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 19; (1995); p. 3131 - 3138 View in Reaxys

19 %

With hydrogenchloride, platinum, sodium chloride in chloroform, water, T= 30 °C , Electrolysis Bosco, A. John; Lawrence; Christopher; Radhakrishnan; Joseph Rosario, A. Arul; Raja; Vasudevan; Journal of Physical Organic Chemistry; vol. 28; nb. 9; (2015); p. 591 - 595 View in Reaxys With 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, toluene-4-sulfonic acid in dichloromethane, 1) 0 deg C, 1 h, 2) r.t., 1 h, Yield given Ma, Zhenkun; Bobbitt, James M.; Journal of Organic Chemistry; vol. 56; nb. 21; (1991); p. 6110 - 6114 View in Reaxys

23 % Spectr.

With dihydrogen peroxide, lt;N(C6H13)4gt;3lt;PO4lt;WO(O2)2gt;4gt; in benzene, Time= 3h, Ambient temperature Dengel, Andrew C.; Griffith, William P.; Parkin, Bernardeta C.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 18; (1993); p. 2683 - 2688 View in Reaxys With n-Butylammonium chlorochromate in chloroform, Time= 0.75h, Yield given Kasmai, Hamid S.; Mischke, Steve G.; Blake, Travis J.; Journal of Organic Chemistry; vol. 60; nb. 7; (1995); p.

2267 - 2270 View in Reaxys

72 % Chromat.

With acetyl nitrate on montmorillonite K10, Time= 2h, Ambient temperature De Oliveira Filho; Moreira; Moran, Paulo J. S.; Rodrigues, J. Augusto R.; Tetrahedron Letters; vol. 37; nb. 29; (1996); p. 5029 - 5032 View in Reaxys

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With 1-bromo-butane, N-chloro-succinimide, magnesium, tert-butyl alcohol, 1.) THF, 10 min, 2.) THF, RT, 25 min, Yield given. Multistep reaction Lee, Adam Shih-Yuan; Kung, Chih-Chun; Journal of the Chinese Chemical Society; vol. 44; nb. 1; (1997); p. 65 69 View in Reaxys With manganese(IV) oxide, molecular sieve in hexane, Time= 2h, Heating, Yield given Hirano, Masao; Yakabe, Sigetaka; Chikamori, Hideki; Clark, James H.; Morimoto, Takashi; Journal of Chemical Research - Part S; nb. 6; (1998); p. 308 - 309 View in Reaxys With tert.-butylhydroperoxide, titanium(IV) isopropylate, Time= 0.5h, T= 40 °C , in the presents of 4-NO2-C6H4-CHO; at diff. times; other benzyl alcohols Krohn, Karsten; Khanbabaee, Karamali; Rieger, Hagen; Chemische Berichte; vol. 123; nb. 6; (1990); p. 1357 1364 View in Reaxys With dihydrogen peroxide, ligninase, Ambient temperature, pH 3.0, Product distribution Ageorges, Agnes; Pelter, Andrew; Ward, Robert S.; Phytochemistry (Elsevier); vol. 30; nb. 1; (1991); p. 121 - 126 View in Reaxys 94 % Chromat.

With Pd-hydroxyapatite-0, oxygen in various solvent(s), Time= 3h, T= 90 °C , p= 760Torr Mori, Kohsuke; Hara, Takayoshi; Mizugaki, Tomoo; Ebitani, Kohki; Kaneda, Kiyotomi; Journal of the American Chemical Society; vol. 126; nb. 34; (2004); p. 10657 - 10666 View in Reaxys With potassium phosphate, chlorobenzene, CyJohnPhos, bis(dibenzylideneacetone)-palladium(0) in toluene, Time= 14h, T= 105 °C Bei, Xiaohong; Hagemeyer, Alfred; Volpe, Anthony; Saxton, Robert; Turner, Howard; Guram, Anil S.; Journal of Organic Chemistry; vol. 69; nb. 25; (2004); p. 8626 - 8633 View in Reaxys With manganese(IV) oxide in dichloromethane, Time= 24h, T= 20 °C Poli, Giovanni; Giambastiani, Giuliano; Journal of Organic Chemistry; vol. 67; nb. 26; (2002); p. 9456 - 9459 View in Reaxys With Ag/hydrotalcite in para-xylene, Time= 31h, T= 130 °C Mitsudome, Takato; Mikami, Yusuke; Funai, Hisashi; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi; Angewandte Chemie - International Edition; vol. 47; nb. 1; (2008); p. 138 - 141 View in Reaxys With dihydrogen peroxide, Time= 6h, T= 75 - 80 °C Polshettiwar, Vivek; Varma, Rajender S.; Organic and Biomolecular Chemistry; vol. 7; nb. 1; (2009); p. 37 - 40 View in Reaxys 2.2 :Piperonyl alcohol (4.08 g, 0.026 mmoles) , aluminium isopropoxide 98percent and toluene (45 ml) are added in a round bottom flask under nitrogen atmosphere . The mixture is heated to -1100C and after addition of 1.6 g of pformaldehyde, refluxed for 2 hours. Thereafter the mixture is cooled and 60 ml of 1 M NaOH are added. The 2 phases are separated; the organic phase is dried with Na2SO4, filtered and evaporated maintaining the bath temperature at 3O0C. The product is purified by chromatography (silica, cyclohexane/ethyl acetate, 90:10).

Stage 1: With aluminum isopropoxide in toluene, T= 110 °C Stage 2: With formaldehyd in toluene, Time= 2h, Heating / reflux Patent; CTG PHARMA S.R.L.; WO2009/37556; (2009); (A1) English View in Reaxys

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99 %Chromat.

With N-Bromosuccinimide in polyethylene glycol 400, Time= 2h, T= 60 °C Fan, Ji-Cai; Shang, Zhi-Cai; Liang, Jun; Liu, Xiu-Hong; Liu, Yang; Journal of Physical Organic Chemistry; vol.

21; nb. 11; (2008); p. 945 - 953 View in Reaxys

93 %Chromat.

2-9 :Example 2-9 A mixture of 1 mmol of 1,3-benzodioxole-5-methanol (piperonyl alcohol), 5 mL of toluene, and 0.1 g of the catalyst prepared from Example 2-0 and including Ag particles immobilized on a hydrotalcite surface was stirred at 110° C. in an argon atmosphere for 45 hours and thereby yielded a corresponding carbonyl compound (1,3-benzodioxole-5-carbaldehyde) in a yield equivalent to a gas chromatographic (GC) yield of 93percent, with a selectivity for 1,3-benzodioxole-5-carnaldehyde of 99percent or more.

With Ag/HT in toluene, Time= 45h, T= 110 °C , Inert atmosphere Patent; Kaneda, Kiyotomi; Yamasaki, Noritsugu; US2010/130758; (2010); (A1) English View in Reaxys

51 %Chromat.

With acetaldehyde, Time= 24h, T= 30 °C , pH= 7.5, aq. phosphate buffer, Microbiological reaction, Combinatorial reaction / High throughput screening (HTS), Oppenauer oxidation, chemoselective reaction Orbegozo, Thomas; De Vries, Johannes G.; Kroutil, Wolfgang; European Journal of Organic Chemistry; nb. 18; (2010); p. 3445 - 3448 View in Reaxys With Au/CeO2, oxygen in 2,3,4-trifluorotoluene, T= 90 °C , p= 3750.38Torr , Autoclave Ruiz, Violeta R.; Corma, Avelino; Sabater, Maria J.; Tetrahedron; vol. 66; nb. 3; (2010); p. 730 - 735 View in Reaxys With Ru/Al2O3, oxygen in toluene, Time= 1h, T= 90 °C , p= 3750.38Torr , chemoselective reaction Zotova, Natalia; Hellgardt, Klaus; Kelsall, Geoffrey H.; Jessiman, Alan S.; Hii, King Kuok Mimi; Green Chemistry; vol. 12; nb. 12; (2010); p. 2157 - 2163 View in Reaxys

81 %Chromat.

With hydrotalcite-supported gold nanoparticles (Au/HT), air in toluene, Time= 8h, T= 40 °C , p= 760.051Torr Mitsudome, Takato; Noujima, Akifumi; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi; Advanced Synthesis and Catalysis; vol. 351; nb. 11-12; (2009); p. 1890 - 1896 View in Reaxys With oxygen, potassium carbonate in toluene, Time= 6h, T= 110 °C , p= 3800.26Torr , chemoselective reaction Oliveira, Rafael L.; Zanchet, Daniela; Kiyohara, Pedro K.; Rossi, Liane M.; Chemistry - A European Journal; vol.

17; nb. 16; (2011); p. 4626 - 4631 View in Reaxys With lead acetate, sodium hydroxide, Time= 1h, T= 60 - 80 °C Tarasov; Kustov; Isaeva; Kalenchuk; Mishin; Kapustin; Bogdan; Kinetics and Catalysis; vol. 52; nb. 2; (2011); p.

273 - 276 View in Reaxys With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in acetonitrile, Inert atmosphere, Reflux Drouet, Fleur; Masson, Geraldine; Zhu, Jieping; Organic Letters; vol. 15; nb. 11; (2013); p. 2854 - 2857 View in Reaxys With cis-IrCl(CO)(PPh3)2, potassium hydoxide in benzene-d6, Time= 1h, T= 65 °C Huang, Jian-Lin; Dai, Xi-Jie; Li, Chao-Jun; European Journal of Organic Chemistry; nb. 29; (2013); p. 6496 - 6500 View in Reaxys

141 mg

With ABBX in chloroform, Time= 24h, T= 60 °C , Reagent/catalyst Iinuma, Masataka; Moriyama, Katsuhiko; Togo, Hideo; European Journal of Organic Chemistry; vol. 2014; nb. 4; (2014); p. 772 - 780

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View in Reaxys Prerjaration of intermediate I-59a: Benzo[dl[1 ,3ldioxole-5-carbaldehyde A solution of the commercially available piperonol (5, 100 g, 0.66 mmol) and active Mn02 (572 g, 6.6 mmol) in DCM (1000 ml) was stirred at r.t overnight. The reaction mixture was filtrated and the filtrate were washed with brine, dried over anhydrous Na2504 and concentrated to give crude I-59a (80 g, 80percent yield) as white solid. ESI-MS (Mi-i): 151 calc. for C8H603: 150.1 With manganese(IV) oxide in dichloromethane, T= 20 °C Patent; FUNDACIÓN PARA LA INVESTIGACIÓN MÉDICA APLICADA; CUADRADO TEJEDOR, María Del Mar; FRANCO FERNÁNDEZ, Rafael; GARCÍA OSTA, Ana María; OYARZABAL SANTAMARINA, Julen; RABAL GRACIA, Maria Obdulia; WO2014/131855; (2014); (A1) English View in Reaxys With ABBX in chloroform, Time= 24h, T= 60 °C , Reagent/catalyst Iinuma, Masataka; Moriyama, Katsuhiko; Togo, Hideo; European Journal of Organic Chemistry; vol. 2014; nb. 4; (2014); p. 772 - 780 View in Reaxys Synthesis of (E)-3-(benzo[d][1,3]dioxol-5-ylmethylene)dihydrofuran-2(3H)-one (9). Step 1.

A solution of piperonyl alcohol (1 g, 6.6 mmol) in dry dichloromethane (10 ml) was added to a solution of Dess-Martin reagent (3.35 g, 7.9 mmol) in dichloromethane (10 ml) at 0°C . The reaction was stirred at room temperature for about 72 hours. After a filtration on celite, the organic solution was extracted 3 times with water. The organic layers were dried on Na2SO4 and the solvent was evaporated in vacuo, obtaining a brown solid (benzo[d][1,3]dioxole-5carbaldehyde).Yield: 96percent. Mp: 44°C. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 6.06 (s, 2 H) 6.91 (d, J=7.88 Hz, 1 H) 7.32 (d, J=1.58 Hz, 1 H) 7.39 (dd, J=7.88, 1.58 Hz, 1 H) 9.79 (s, 1 H). 13C NMR (126 MHz, CHLOROFORM-d) δ ppm 102.09 (s, 1 C) 106.92 (s, 1 C) 108.34 (s, 1 C) 128.66 (s, 1 C) 131.87 (s, 1 C) 148.70 (s, 1 C) 153.09 (s, 1 C) 190.28 (s, 1 C). LC-MS (ESI): m/z MH+ = 151.

With Dess-Martin periodane in dichloromethane, Time= 72h, T= 0 - 20 °C Mariano, Marica; Hartmann, Rolf W.; Engel, Matthias; European Journal of Medicinal Chemistry; vol. 112; (2016); p. 209 - 216 View in Reaxys Preparation of intermediate l-69a: Benzo[c 1[1 ,31dioxole-5-carbaldehyde Preparation of intermediate l-69a: Benzo[c 1[1 ,31dioxole-5-carbaldehyde A solution of the commercially available piperonol (5, 100 g, 0.66 mmol) and active MnO2 (572 g, 6.6 mmol) in DCM (1000 ml) was stirred at r.t overnight.

The reaction mixture was filtrated and the filtrate were washed with brine, dried over anhydrous Na2SO4 and concentrated to give crude l-69a (80 g, 80 percent yield) as white solid. ESI-MS (M+1 ): 151 calc. for C8H6O3: 150.1 With manganese(IV) oxide in dichloromethane, T= 20 °C Patent; FUNDACIÓN PARA LA INVESTIGACIÓN MÉDICA APLICADA; CUADRADO TEJEDOR, María del Mar; GARCÍA OSTA, Ana María; OYARZABAL SANTAMARINA, Julen; RABAL GRACIA, Maria Obdulia; SÁNCHEZ ARIAS, Juan Antonio; UGARTE BAZTÁN, Ana; (112 pag.); WO2016/20307; (2016); (A1) English View in Reaxys 9 : Synthesis of 3,4-(methylenedioxy)benzaldehyde To a solution of piperonyl alcohol (10 g, 65.73 mmol) in CH2Cl2 (250 mL), MnO2 (49.3 g, 567.32 mmol) was added in one portion.

The resulting dark suspension was stirred at room temperature for 24 h, and then filtered off throw a celite pad washing with CH2Cl2.

The solvent was removed in vacuum and the resulting crude crystalline yellow pale solid was used without further purification. m.p. 338° C. ESI-MS (Mw 150.03): 151.1 (M+H+).

1H-NMR

(DMSO-d6): δ 9.80 (s, 1H), 7.40 (m, 2H), 6.92 (d, 1H), 6.07 (s, 2H).

With manganese(IV) oxide in dichloromethane, Time= 24h, T= 20 °C

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Patent; BIOLAB SANUS FARMACEUTICA LTDA; De Nucci, Gilberto; (25 pag.); US2016/75702; (2016); (A1) English View in Reaxys

O

O

O

O

O

Rx-ID: 41921392 View in Reaxys 2/181 Yield

Conditions & References

75 %

With carbon tetrabromide, oxygen in acetonitrile, Time= 4h, T= 20 °C , Irradiation, Green chemistry Tripathi, Shubhangi; Singh, Sachchida N.; Yadav, Lal Dhar S.; RSC Advances; vol. 6; nb. 18; (2016); p. 14547 14551 View in Reaxys O O

HO

O

O

O

O

O

O O

O O

Rx-ID: 41955412 View in Reaxys 3/181 Yield

Conditions & References With [Rh(1,3,4,5-tetramethylimidazole-2-ylidene)(trop2NH)][trifluoromethanesulfonate], potassium tert-butylate, Nitrous oxide in tetrahydrofuran, water, toluene, T= 50 °C , p= 750.075Torr , Schlenk technique, Molecular sieve, Overall yield = 87 percent; Overall yield = 164 mg Gianetti, Thomas L.; Annen, Samuel P.; Santiso-Quinones, Gustavo; Reiher, Markus; Driess, Matthias; Grützmacher, Hansjörg; Angewandte Chemie - International Edition; vol. 55; nb. 5; (2016); p. 1854 - 1858; Angew.

Chem.; vol. 128; nb. 5; (2015); p. 1886 - 1890,5 View in Reaxys

O O

O

O O

Rx-ID: 80599 View in Reaxys 4/181 Yield

Conditions & References With hydrochlorid acid, hexamethylenetetraamine, N,N-dimethyl-4-nitrosoaniline, Reagens 4: Zinkchlorid, Erwaermen des Reaktionsgemisches mit Wasser Eliseewa; Debizkaja; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 29; (1956); p. 1894; engl. Ausg. S. 2043 View in Reaxys Reaction Steps: 2 1: petroleum ether; zinc chloride; water; hydrochloric acid 2: hexamethylenetetramine; aqueous ethanol With hydrochlorid acid, ethanol, hexamethylenetetraamine, water, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p.

2178 View in Reaxys Reaction Steps: 2 1: paraformaldehyde; zinc chloride; petroleum ether / Reagens 4: Chlorwasserstoff 2: hexamethylenetetramine; aqueous ethanol With formaldehyd, ethanol, hexamethylenetetraamine, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p.

2178

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View in Reaxys Reaction Steps: 2 1: sulfuric acid / water / 20 h / 0 - 5 °C 2: silver nitrate; sodium peroxodisulphate / water; dichloromethane / 5 h / |Reflux With sodium peroxodisulphate, sulfuric acid, silver nitrate in dichloromethane, water Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco; Organic Process Research and Development; vol. 4; nb. 6; (2000); p. 534 - 543 View in Reaxys Reaction Steps: 2 1: hydrochlorid acid / water / 20 °C 2: sodium hydrogencarbonate / dimethyl sulfoxide / 90 °C With hydrochlorid acid, sodium hydrogencarbonate in water, dimethyl sulfoxide Zhang, Bingyu; Lv, Chao; Li, Weibo; Cui, Zhiming; Chen, Dongdong; Cao, Fangjun; Miao, Fang; Zhou, Le; Chemical and Pharmaceutical Bulletin; vol. 63; nb. 4; (2015); p. 255 - 2625 View in Reaxys

Cl

O

O

O

O

O

Rx-ID: 128455 View in Reaxys 5/181 Yield 95 %

Conditions & References With [C12mim][FeCl4], periodic acid, Time= 1.5h, T= 30 °C Hu, Yu Lin; Liu, Qi Fa; Lu, Ting Ting; Lu, Ming; Catalysis Communications; vol. 11; nb. 10; (2010); p. 923 - 927 View in Reaxys

89 %

With KNO2, 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, oxygen, potassium bromide in water, Time= 2h, Reflux Liu, Qifa; Lu, Ming; Yang, Fei; Wei, Wei; Sun, Feng; Yang, Zhenbang; Huang, Sufeng; Synthetic Communications; vol. 40; nb. 8; (2010); p. 1106 - 1114 View in Reaxys

84 %

With 4-methylmorpholine N-oxide in tetrahydrofuran, Time= 12h, T= 20 °C , Reflux Tabata, Masayuki; Moriyama, Katsuhiko; Togo, Hideo; European Journal of Organic Chemistry; vol. 2014; nb.

16; (2014); p. 3402 - 3410 View in Reaxys

48 %

With sodium hydrogencarbonate in dimethyl sulfoxide, T= 90 °C Zhang, Bingyu; Lv, Chao; Li, Weibo; Cui, Zhiming; Chen, Dongdong; Cao, Fangjun; Miao, Fang; Zhou, Le; Chemical and Pharmaceutical Bulletin; vol. 63; nb. 4; (2015); p. 255 - 2625 View in Reaxys With ethanol, hexamethylenetetraamine Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p.

2178 View in Reaxys

H 2N

O

O

O

O O

Rx-ID: 1772030 View in Reaxys 6/181 Yield 84 %

Conditions & References With 2,6-dimethylpyridine, 2,2,6,6-tetramethyl-piperidine-N-oxyl, water, lithium perchlorate in acetonitrile, T= 23 °C , electrolysis, a platinum gauze electrode, +0.33 V (vs. Ag/Ag(1+))

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Semmelhack, M. F.; Schmid, Christopher R.; Journal of the American Chemical Society; vol. 105; nb. 22; (1983); p. 6732 - 6734 View in Reaxys 50 %

With piperidine, Fremy’s salt, sodium carbonate in tetrahydrofuran, water Castedo, Luis; Riguera, Ricardo; Rodriguez, M. Jesus; Tetrahedron; vol. 38; nb. 11; (1982); p. 1569 - 1570 View in Reaxys With dipotassium peroxodisulfate, [Ru(tris(2,2'-bipyridyl))3]Cl2·6H2O, water in acetonitrile, Time= 12h, T= 20 °C , Sealed tube, Irradiation, Green chemistry Iqbal, Naeem; Cho, Eun Jin; Advanced Synthesis and Catalysis; vol. 357; nb. 10; (2015); p. 2187 - 2192 View in Reaxys

O O

O

O

O O

O

Rx-ID: 4766834 View in Reaxys 7/181 Yield

Conditions & References

94 %

With carbon tetrabromide in water, acetonitrile, Time= 2h, T= 45 °C , sonication Lee, Adam S.-Y.; Cheng; Tetrahedron; vol. 53; nb. 42; (1997); p. 14255 - 14262 View in Reaxys

91 %

With lithium chloride in water, dimethyl sulfoxide, Time= 6h, T= 90 °C Mandal, Pijus Kumar; Dutta, Pinak; Roy, Subhas Chandra; Tetrahedron Letters; vol. 38; nb. 41; (1997); p. 7271 7274 View in Reaxys

90 %

With aluminum oxide, Oxonereg;, Time= 0.025h, Microwave irradiation, Hydrolysis Bose, D. Subhas; Jayalakshmi; Narsaiah, A. Venkat; Synthesis; nb. 1; (2000); p. 67 - 68 View in Reaxys

89 %

With indium(III) chloride in methanol, water, Time= 0.833333h, Heating Ranu, Brindaban C.; Jana, Ranjan; Samanta, Sampak; Advanced Synthesis and Catalysis; vol. 346; nb. 4; (2004); p. 446 - 450 View in Reaxys

86 %

With sodium tetrahydroborate, NiCl2·6H2O in methanol, Time= 0.25h, chemoselective reaction Khurana, Jitender M.; Dawra, Kiran; Sharma, Purnima; RSC Advances; vol. 5; nb. 16; (2015); p. 12048 - 12051 View in Reaxys

98 % Chromat.

With Ti(4+)-exchanged montmorillonite in water, acetone, Time= 1h, T= 60 °C Kawabata, Tomonori; Kato, Masaki; Mizugaki, Tomoo; Ebitani, Kohki; Kaneda, Kiyotomi; Chemistry Letters; vol. 32; nb. 7; (2003); p. 648 - 649 View in Reaxys

O O

O

O

O

O O

Rx-ID: 8675202 View in Reaxys 8/181 Yield 98 %

Conditions & References With Bi(1+)*NO3 (1-)=BiNO3 in dichloromethane, Time= 2h, T= 20 °C Eash; Pulia; Wieland; Mohan; Journal of Organic Chemistry; vol. 65; nb. 24; (2000); p. 8399 - 8401

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View in Reaxys 94 %

With indium(III) chloride in methanol, water, Time= 1.25h, Heating Ranu, Brindaban C.; Jana, Ranjan; Samanta, Sampak; Advanced Synthesis and Catalysis; vol. 346; nb. 4; (2004); p. 446 - 450 View in Reaxys

90 %

With water in methanol, Time= 0.2h, T= 25 - 30 °C Kumar, Dinesh; Kumar, Raj; Chakraborti, Asit K.; Synthesis; nb. 8; (2008); p. 1249 - 1256 View in Reaxys

85 %

With β-cyclodextrin in methanol, water, Time= 8h, T= 50 °C Srilakshmi Krishnaveni; Surendra; Arjun Reddy; Nageswar; Rama Rao; Journal of Organic Chemistry; vol. 68; nb. 5; (2003); p. 2018 - 2019 View in Reaxys

72 %

With sodium tetrahydroborate, NiCl2·6H2O in methanol, Time= 3h, Reflux, chemoselective reaction Khurana, Jitender M.; Dawra, Kiran; Sharma, Purnima; RSC Advances; vol. 5; nb. 16; (2015); p. 12048 - 12051 View in Reaxys With bismuth trifluoromethanesulphonate in tetrahydrofuran, water, Time= 2h, T= 20 °C Carrigan, Marc D.; Sarapa, Dusan; Smith, Russell C.; Wieland, Laura C.; Mohan, Ram S.; Journal of Organic Chemistry; vol. 67; nb. 3; (2002); p. 1027 - 1030 View in Reaxys

O O

O

O

O

O

Br

Rx-ID: 10517496 View in Reaxys 9/181 Yield

Conditions & References

98 %

With potassium carbonate, butan-1-ol, palladium diacetate, triphenylphosphine, Time= 1h, T= 100 °C Chen, Jingbo; Zhang, Yushun; Yang, Liquan; Zhang, Xiang; Liu, Jianping; Li, Liang; Zhang, Hongbin; Tetrahedron; vol. 63; nb. 20; (2007); p. 4266 - 4270 View in Reaxys

88 %

Stage 1: With [1,1‘-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II), triethylamine in water, Time= 0.0333333h, T= 20 °C Stage 2: With 1,1,3,3-Tetramethyldisiloxane, Time= 0.133333h Bhattacharjya, Anish; Klumphu, Piyatida; Lipshutz, Bruce H.; Organic Letters; vol. 17; nb. 5; (2015); p. 1122 1125 View in Reaxys

Cl

Cl

HO

HO

O O

O O

Rx-ID: 10879776 View in Reaxys 10/181 Yield 84.6 %

Conditions & References 1a :3,4-Dihydroxy benzaldehyde (25 g, 0.181 mol), cesium carbonate (88.29 g, 0.271 mol) and dibromomethane (19.0 ml_, 0.271 mol) were dissolved in N, N- dimethylformamide (400 ml.) and the reaction mixture was heated to 1 10 0C for 1.5 h. N,N-dimethylformamide was evaporated under reduced pressure, and the reaction mixture was diluted using ethyl acetate (500 ml_), washed with water (2 x 250 ml.) and brine (2 x 100 ml_). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the title compound. Yield: 23.0 g (84.6 percent). 1H NMR (CDCI3): δ 9.8 (s, 1 H), 7.42 (d, 1 H), 7.34 (d, 1 H), 6.94 (d, 1 H), 6.09 (s, 2H).

With caesium carbonate in N,N-dimethyl-formamide, Time= 1.5h, T= 110 °C

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Patent; NICHOLAS PIRAMAL INDIA LIMITED; WO2008/26125; (2008); (A2) English View in Reaxys < 20 %

With tetrabutylammomium bromide, sodium hydroxide Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco; Organic Process Research and Development; vol. 4; nb. 6; (2000); p. 534 - 543 View in Reaxys 6.1.2. Synthesis of 1,3-benzodioxole-5-carbaldehyde (5, Piperonal) [17] A solution of 3,4-dihydroxybenzaldehyde (10 g, 0.073 mol) in DMF (150 mL) was added dropwise to a suspension of CH2Cl2 (7 mL, 0.108 mol) and K2CO3 (20 g, 0.144 mol) in DMF (300 mL). The mixture was stirred and heated to reflux for 4 h then cooled and filtered. The filtrate was concentrated, diluted with water and extracted with diethyl ether (3 .x. 100 mL). The filtered cake was washed with diethyl ether (100 mL). The ethereal extracts were combined, washed with 10percent NaOH (100 mL), water (100 mL), dried (Na2SO4) and evaporated to afford 7.0 g (64percent) of 5 as light brown solid mp 37 °C. The crude 5 was used in the next step without any further purification.

With potassium carbonate in N,N-dimethyl-formamide, Time= 4h, Reflux Aboul-Enein, Mohamed N.; El-Azzouny, Aida A.; Attia, Mohamed I.; Maklad, Yousreya A.; Amin, Kamilia M.; Abdel-Rehim, Mohamed; El-Behairy, Mohammed F.; European Journal of Medicinal Chemistry; vol. 47; nb. 1; (2012); p. 360 - 369 View in Reaxys 1 : 4.1.1. Synthesis of 1,3-benzodioxole-5-carbaldehyde (12) [22] A solution of 3,4-dihydroxybenzaldehyde (10 g, 0.073 mol, 11) in DMF (150 mL) was added dropwise to a suspension of CH2Cl2 (7 mL, 0.108 mol) and K2CO3 (20 g, 0.144 mol) in DMF (300 mL). The mixture was stirred and heated to reflux for 4 h then cooled and filtered. The filtrate was concentrated, diluted with water and extracted with diethyl ether (3100 mL). The filtered cake was washed with diethyl ether (100 mL). The ethereal extracts were combined, washed with 10percent NaOH (100 mL), water (100 mL), dried (Na2SO4) and evaporated to give 1, 3-benzodioxole-5-carbaldehyde (12) a light brown solid. The crude 12 was used in the next step without any further purification.

With potassium carbonate in N,N-dimethyl-formamide, Time= 4h, Reflux Qin, Ya-Juan; Li, Yu-jing; Jiang, Ai-Qin; Yang, Meng-Ru; Zhu, Qi-Zhang; Dong, Hong; Zhu, Hai-Liang; European Journal of Medicinal Chemistry; vol. 94; (2015); p. 447 - 457; Art.No: 7740 View in Reaxys

2H

2H

Cl

Cl

HO

HO

O

2H

O

2H

O

O

Rx-ID: 25667603 View in Reaxys 11/181 Yield 91 %

Conditions & References 2.1 :EXAMPLE 2(.pound.>l-(Benzo[d] [1, 3]-dioxol-2,2-rf2-5-yl)-4, 4-dimethylpent-l-en-3-ol(rf2-stiripentol)[00105] Benzordiri,31-dioxole-2,2-J2-5-carbaldehyde: Cesium carbonate (8.1 g, 25.00 mmol, 1.72 equiv.) and J2-dichloromethane (2.04 g, 23.7 mmol, 1.63 equiv.) were added to a solution of 3,4-dihydroxybenzaldehyde (2 g, 14.5 mmol, 1.00 equiv.) in (25 mL). The solution was stirred at about 120 0C for about 16 hours and then the solids were removed by filtration. Following standard extractive workup with ethyl acetate (2 x 30 mL), the crude residue was purified by silica gel column chromatography (ethyl acetate / petroleum ether (1:10)) to give the title product as a light yellow solid (2 g; yield = 91percent).

With caesium carbonate in dimethylsulfoxide-d6, Time= 16h, T= 120 °C Patent; AUSPEX PHARMACEUTICALS, INC.; RAO, Tadimeti; ZHANG, Chengzhi; WO2011/11420; (2011); (A2) English View in Reaxys

80 %

2; 6 :[00229] To a solution of 3,4-dihydroxybenzaldehyde (25 g, 181 mmol) in N5N- dimethylformamide was added d2-dichloromethane (25 g, 289 mmol) and cesium carbonate(94.5 g, 289 mmol). The mixture was stirred at 1200C for 12 hours. After that time, <n="66"/>the solution was filtered through a Celite pad and the solvent was removed under vacuum. The residue was then dissolved in 1000 mL of ethyl acetate and washed with water (2 x 250 mL) and

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brine (250 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed.

The crude product was purified by column chromatography to give 18 g (80percent yield) of the title product as yellow crystals. 1HNMR (300MHz, CDCl3): δ 9.80 (s, IH), 7.42-7.27 (m, 2H), 6.92 (d, J= 7.8 Hz, IH).

With caesium carbonate in DMFA, Time= 12h, T= 120 °C Patent; AUSPEX PHARMACEUTICALS, INC.; WO2008/16677; (2008); (A2) English View in Reaxys 61 %

6 :Example 6; d7-Benzori.31dioxole-5-carbaldehyde; d2-Dichloromethane (0.96 mL, 0.015 mol) was added dropwise to a mixture of cesium carbonate (4.9 g, 0.015 mol) and 3,4-dihydroxybenzaldehyde (1.38 g, 0.01 mol) in dimethylformamide (30 mL) at ambient temperature under nitrogen atmosphere. The reaction mixture was heated to 110 0C for 2 hr, cooled to ambient temperature, diluted with water, and extracted with ether-hexane (1 :1). The combined organic phases were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to afford the title product (0.922 g, 61percent) as a pale yellow solid. 1H NMR (300 MHz, CDCl3) δ 7.09 (m, 1 H), 7.40 (s, 1 H)5 7.60 (m, IH), 9.86 (s, IH).

With caesium carbonate in DMFA, Time= 2h, T= 20 - 110 °C Patent; AUSPEX PHARMACEUTICALS, INC.; WO2007/146124; (2007); (A2) English View in Reaxys

61 %

1 :To a suspension of Cs2CO3 (11.6 g, 35.6 mmol) in DMF (60 mL) was added 3,4-dihydroxybenzaldehyde (3.30 g, 23.9 mmol). The mixture was evacuated and flushed with nitrogen three times. Next was added CD2Cl2 (2.29 mL, 26.3 mmol, 99.9percent D) at ambient temperature. The reaction mixture was heated at 110° C. for 2 hours, cooled to ambient temperature and partitioned between water and ether-pentane. The organic layer was washed three more times with water, dried (MgSO4), and concentrated to afford the desired product, d2-piperonal, as an off-white solid.

Yield: 2.21 g (14.5 mmol, 61percent, 94percent D-incorporation at methylenedioxy group). 1H-NMR (CDCl3) δ ppm: 6.06 (s, 0.12H); 6.93 (m, 1H); 7.33 (m, 1H); 7.41 (m, 1H); 9.80 (s, 1H).

Stage 1: With caesium carbonate in DMFA Stage 2: in DMFA, Time= 2h, T= 20 - 100 °C Patent; Gant, Thomas G.; Sarshar, Sepehr; US2007/112031; (2007); (A1) English View in Reaxys 21 :EXAMPLE 21 2,2-dideuterobenzo[d][1,3]dioxole-5-carbaldehyde (Formula XII wherein X1 is D and X2 is H). A solution of A solution of 3,4-dihydroxybenzaldehyde (150 mmol) in 110 mL of dimethylformamide (DMF) is treated under argon with 600 mmol of dideuterodichloromethane (Aldrich Chemicals) and 720 mmol of CsF. The mixture is heated under reflux for 3 h with vigorous stirring. The mixture is then filtered, concentrated in vacuo, and the residue is purified by silica gel flash chromatography (ether/hexanes eluant), yielding the title product.

With cesium fluoride in DMFA, Time= 3h, Heating / reflux Patent; Tung, Roger; US2007/37815; (2007); (A1) English View in Reaxys 5 :Example 5: 2,2-dideuterobenzo[cT][l,3]dioxole-5-carbaldehyde (Formula V wherein Y = D and R = formyl).; A simple distillation apparatus with a dry ice condenser is charged in the distillation bulb with 50 mL of l-methyl-2-pyrrolidinone EPO <DP n="55"/>and 125 mmol OfK2CO3. The mixture is heated at 130 °C and to it is added, during 4.5 h with vigorous stirring, 100 mmol of 3,4-dihydroxybenzaldehyde as a solution in 15 mL of l-methyl-2-pyrrolidinone. Simultaneously, during 3 h, 25 g of dideuterodichloromethane is added via a pressure-tight syringe with the delivery needle well within the stirred solvent. At 3 h, the distilled excess dideuterodichloromethane is drawn from the receiver bulb and re-injected into the reaction in the same manner as above during 1.5 h. This recycling procedure is repeated twice more at one hour intervals (6.5 h reaction time total). The mixture is cooled and filtered, and distilled, first at atmospheric pressure to separate remaining dissolved dideuterodichloromethane, then at approximately 12 torr, yielding the title compound.

With potassium carbonate in N-Methyl-2-pyrrolidone, Time= 6.5h, T= 130 °C Patent; CONCERT PHARMACEUTICALS INC.; WO2007/16431; (2007); (A2) English View in Reaxys 9.A : Step A:

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Step A: 2,2-Dideuterio-1,3-benzodioxole-5-carbaldehyde To a solution of 30 g of 3,4-dihydroxybenzaldehyde (217 mmol) in 110 mL of anhydrous DMF there are added in succession 114 g of caesium carbonate (347 mmol) and 22 mL of dideuterated methylene chloride (347 mmol).

The reaction mixture is subsequently stirred at ambient temperature overnight.

After filtering off the insoluble portion over Celite, the residual filtrate is subsequently hydrolysed by addition of 200 mL of water and then extracted with ethyl acetate.

The organic phases are then combined, washed with a saturated LiCl solution and then dried over MgSO4.

After concentration to dryness, the residue is purified by chromatography over silica gel (petroleum ether/AcOEt gradient).

The title product is obtained in the form of a solid.

1H-NMR: δ: (400 MHz; dmso-d6; 300° K): 9.8 (s, 1H, H aldehyde); 7.4-6.95 (m, 3H, H aromatic) IR: ν: C=O aldehyde: 1670 cm-1 With caesium carbonate in DMFA, T= 20 °C Patent; Le Diguarher, Thierry; Casara, Patrick; Starck, Jérôme-Benoît; Henlin, Jean-Michel; Davidson, James Edward Paul; Murray, James Brooke; Graham, Christopher John; Chen, I-Jen; Geneste, Olivier; Hickman, John; Depil, Stéphane; Le Tiran, Arnaud; Nyerges, Miklos; De Nanteuil, Guillaume; US2015/51189; (2015); (A1) English View in Reaxys

2H

2H

Cl

Cl

O

O

O

2H

2H

O

2H

2H

O

O

Rx-ID: 28374758 View in Reaxys 12/181 Yield 87 %

Conditions & References With 1-methyl-pyrrolidin-2-one, potassium carbonate, Time= 2.25h, T= 110 °C , Inert atmosphere Uttamsingh, Vinita; Gallegos, Richard; Liu, Julie F.; Harbeson, Scott L.; Bridson, Gary W.; Cheng, Changfu; Wells, David S.; Graham, Philip B.; Zelle, Robert; Tung, Roger; Journal of Pharmacology and Experimental Therapeutics; vol. 354; nb. 1; (2015); p. 43 - 54 View in Reaxys

82 - 87 %

5; 7 :A suspension OfK2CO3 (29.6 g, 0.22 mol) in JV-methylpyrrolidinone (NMP) (270 mL) was heated to 110 °C and stirred under N2. A solution of 3,4- dideuteroxybenzaldehyde (XI) (15 g, 0.11 mol) in CD2Cl2 (68 mL, 1.1 mol) and NMP (30 mL) was added dropwise over 45 minutes (min). The reaction mixture was stirred at 110 °C for an additional 90 min. The mixture was allowed to cool, was filtered, and the filtrate was poured into water (900 mL) and extracted with EtOAc (3 x 600 mL). The combined organics were washed with water (2 x 600 mL), dried <n="54"/ >(MgSO4), filtered and concentrated in vacuo. The residue was purified by silica-gel chromatography (4:1 Hexane/ EtOAc) to give 14.2 g (87percent) of XIV as a pale brown oil that solidified on standing. The level of CHD and CH2 present was determined to be approximately 0.5percent and approximately 0.03percent respectively. Example 7. Alternate synthesis of 2,2-d?-Benzo|'d'||T,31dioxole-5- carbaldehyde (XIV). Compound XIV was prepared as generally outlined in Scheme 5 above. Details of the synthesis are set forth below.Synthesis of 2,2-d2-benzo[d][l,3]dioxole-5carbaldehyde (XIV). A 100-L, jacketed reactor equipped with a temperature probe, nitrogenous atmosphere, and reflux condenser was charged with powdered potassium carbonate (4236 g) and NMP (38.7 L). The resulting suspension was heated to 110 °C. A pre-mixed solution of 3,4-dideuteroxybenzaldehyde (2150 g), d2-methylene chloride (13.33 Kg) and NMP (4.3 L) was added via an addition funnel. The solution was added over 20 min via subsurface addition. The temperature of the batch had decreased from 110 °C to 100.6 0C over the course of the addition. The batch was allowed to warm back to 110 0C, and after 90 min HPLC indicated less than 1percent of 3,4- dideuteroxybenzaldehyde. The green-gray suspension was cooled to ambient temperature for 18 h (overnight), and then filtered over a pad of celite. The pad was washed with 4:1 EtO Ac/heptane (21.5 L), and the combined filtrates were added to deionized water (54 L). The resulting aqueous mixture was extracted with 4: 1 EtO Ac/heptane twice (1 x 32 L, 1 x 54 L). The combined organic layers were washed with deionized water (3 x 43 L) and brine (43 L), dried (MgSO4), filtered over celite, and concentrated in vacuo. Crude XIV was isolated as an orange oil which solidified upon standing (2340 g, quantitative yield, 97.6percent AUC by HPLC, CHD impurity as determined by 300 MHz 1H NMR was 0.41percent). The material was further was purified via column chromatography (10.0 kg SiO2 gel, 10 to 20percent EtO Ac/heptane). The product-containing fractions were concentrated to provide d2- piperonal as light yellow solid (1775 g, 82percent yield from 3,4- dideuteroxybenzaldehyde, greater than 99.9percent AUC by HPLC, CHD impurity

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as <n="56"/>determined by 300 MHz 1H NMR was 0.50percent). The level of the CH2 peak was determined to be at the limit of quantification by 300 MHz 1H NMR. With potassium carbonate in 1-methyl-pyrrolidin-2-one, Time= 1.83333 - 2.25h, T= 100.6 - 110 °C , Product distribution / selectivity Patent; CONCERT PHARMACEUTICALS, INC.; WO2009/35652; (2009); (A1) English View in Reaxys 6 :A solution of 3,4-dideuteroxybenzaldehyde (XI) (5g, leq) in N-methylpyrrolidinone (NMP) (10 mL) and CD2Cl2 (22.3 mL, 10 eq) was added over 1 h to a stirring suspension Of K2CO3 (4.9 g, 2 eq) in NMP (100 mL) and D2O (1.5 mL, 2.1 eq) at 110 0C under nitrogen. Stirring was continued at 110 0C for 1.5 h after which time the reaction mixture was cooled to rt, filtered and the solid was washed with ethyl <n="55"/>acetate (10 mL). The combined reaction mixture and wash was partitioned between water (50 mL) and ethyl acetate/heptane (4:1, 50 mL). The aqueous layer was separated and extracted with ethyl acetate/heptane (4:1, 3 x 50 mL). The organic extracts were combined and washed with water (3 x 60 mL), dried over magnesium sulfate and concentrated in vacuo to a brown oil. The residue was purified by chromatography using ethyl acetate/heptane (1 :8) to afford 1.99g of XIV with a CHD level of 0.59percent by 300 MHz 1H NMR. The level of the CH2 peak was determined to be at the limit of quantification by 300 MHz 1H NMR. With water-d2, potassium carbonate in 1-methyl-pyrrolidin-2-one, Time= 2.5h, T= 110 °C , Product distribution / selectivity Patent; CONCERT PHARMACEUTICALS, INC.; WO2009/35652; (2009); (A1) English View in Reaxys

HO

HO

Br

Br

O

O

O O

Rx-ID: 31108265 View in Reaxys 13/181 Yield 90 %

Conditions & References With potassium carbonate in acetonitrile, Time= 24h, T= 90 °C Wang, Fang; Wang, Xue; Zhang, Min-Xia; Yang, Yong-Hua; Zhu, Hai-Liang; RSC Advances; vol. 5; nb. 91; (2015); p. 74425 - 74437 View in Reaxys

85 %

General Procedure for Synthesis of Compounds (2a) Firstly, a solution of 3,4-dihydroxybenzaldehyde (13.8 g,100 mmol) in 250 mL cool acetonitrile (CH3CN), was addedwith K2CO3 (40 g), dibromomethane (120 mmol, 10.4 mL). Thereaction mixture was then stirred at 90°C for 24 h.

After thereaction completed, reaction mixture was filtered and concentrated,then the concentration was extracted with ethyl acetateand water. The combined extracts were dried with anhydrousNa2SO4 and concentrated. The pure white solid benzo[d] [1,3]-dioxole-5-carbaldehyde (2a) was gained with the yield of 85percent.

With potassium carbonate in acetonitrile, Time= 24h, T= 90 °C Sun, Zhi-Gang; Zhou, Xiao-Jing; Zhu, Ming-Li; Ding, Wen-Ze; Li, Zhen; Zhu, Hai-Liang; Chemical and Pharmaceutical Bulletin; vol. 63; nb. 8; (2015); p. 603 - 607 View in Reaxys

78 %

Preparation of Benzo[d][1,3]dioxole-5-carbaldehyde (3,4- methylenedioxy benzaldehyde) (1n) To a solution of 3,4-dihydroxy benzaldehyde (50 mmol), in DMF (100 ml) was added Cs2CO3 (75 mmol) and dibromomethane (75 mmol). The reaction mixture was heated at 110°C for 2 h. DMF was concentrated under reduced pressure. The reaction mass obtained was dissolved in ethyl acetate, washed with water followed by washing with brine. The organic layer was dried over anhydrous Na2SO4 and concentrated to give the pure product. 78 percent, MS : 151 (M+H) (ES+) 1H-NMR (300 MHz, CDCl3) : d 6.097 (s, O-CH2-O), 6.920 - 6.947 (d, J = 8.1 Hz, H5), 7.340 7.399 (d, J = 17.7 Hz, H2), 7.404 - 7.430 (dd, J = 7.8 Hz, H6) 13C-NMR (CDCl3): d 102.124 (O-CH2-O), 106.917 (C5), 108.372 (C2), 128.728 (C6), 131.876 (C1), 148.722 (C3), 153.124 (C4), 190.346 (CHO).

With caesium carbonate in N,N-dimethyl-formamide, Time= 2h, T= 110 °C

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Dhuru, Sameer; Bhedi, Dilip; Gophane, Dnyaneshwar; Hirbhagat, Kiran; Nadar, Vijaya; More, Dattatray; Parikh, Sapna; Dalal, Roda; Fonseca, Lyle C.; Kharas, Firuza; Vadnal, Prashant Y.; Vishwakarma, Ram A.; Sivaramakrishnan; Bioorganic and Medicinal Chemistry Letters; vol. 21; nb. 12; (2011); p. 3784 - 3787 View in Reaxys 75 %

With potassium carbonate in N,N-dimethyl-formamide, Time= 24h, Reflux Lu, Zi-Ming; Tu, Peng-Fei; Liang, Jun-Qing; Wang, Hong-Tao; Zhao, Shao-Hua; Zhang, Hao; Journal of Asian Natural Products Research; vol. 14; nb. 9; (2012); p. 873 - 876,4 View in Reaxys Lu, Zi-Ming; Liang, Jun-Qing; Wang, Hong-Tao; Zhao, Shao-Hua; Zhang, Hao; Tu, Peng-Fei; Journal of Asian Natural Products Research; vol. 14; nb. 9; (2012); p. 873 - 876 View in Reaxys

74 %

67 : Compound 67.1. 2H-1,3-benzodioxole-5-carbaldehyde To a stirred solution of 3,4-dihydroxybenzaldehyde (10 g, 72.40 mmol, 1.00 equiv) in DMF (150 mL) was added cesium carbonate (35.4 g, 108.31 mmol, 1.50 equiv) and dibromomethane (18.7 g, 107.57 mmol, 1.50 equiv). The resulting solution was stirred for 2 h at 110 °C. The solution was cooled to room temperature and the solid was removed by filtration. The filtrate was diluted with H20 (300 mL). The resulting solution was extracted with EtOAc (2 x 300 mL).

The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography, eluted with with EtO Ac/petroleum ether (1 :9) to afford 8 g (74percent) of the title compound as a yellow solid. 1H-NMR (300 MHz, CDC13): δ ppm 9.81 (s, 1H), 7.41 (d, J = 8.1 Hz, 1H), 7.34 (s, 1H), 6.93 (d, J = 8.1 Hz, 1H), 6.08 (s, 2H).

With caesium carbonate in N,N-dimethyl-formamide, Time= 2h, T= 110 °C Patent; MYOKARDIA, INC.; OSLOB, Johan; ANDERSON, Robert; AUBELE, Danielle; EVANCHIK, Marc; FOX, Jonathan Charles; KANE, Brian; LU, Puping; MCDOWELL, Robert; RODRIGUEZ, Hector; SONG, Yonghong; SRAN, Arvinder; WO2014/205223; (2014); (A1) English View in Reaxys

67 %

With caesium carbonate in N,N-dimethyl-formamide, Time= 24h, T= 100 °C , Inert atmosphere, Schlenk technique Xiong, Ya-Ping; Wu, Ming-Yue; Zhang, Xiang-Yu; Ma, Can-Liang; Huang, Lin; Zhao, Li-Jiao; Tan, Bin; Liu, XinYuan; Organic Letters; vol. 16; nb. 3; (2014); p. 1000 - 1003 View in Reaxys Synthesis of compounds with dioxygenated rings 7-10 General procedure: According to the method, 1716 we had improved this strategy. As to 8, 9, and 10, the corresponding liquid of dibromoalkane (1,2-Dibromomethane for 8, 1,3-Dibromopropane for 9, 1,4-Dibromobutane for 10; 10 mmol, 1.0 equiv) was added to 3,4-dihydroxy benazaldehyde (12mmol, 1.2 equiv) and potassium carbonate (2 g) in acetone (60 ml) with stirring at 70-80 ℃. After 20 h reflux, the reaction mixture was cooled and evaporated in reduced pressure, then poured into water and extracted with EtOAc three times. The extraction liquid was purified by a flash chromatography with EtOAc/petroleum ether. As to 7, 3,4-dihydroxy benzaldehyde (12 mmol, 1.2 equiv) dissolved in N’N-dimethylformamide (40 ml) containing potassium carbonate (2 g) and dibromomethane (10 mmol, 1.0 equiv) were heated under reflux at 70-80 ℃ overnight. The mixture was pour into ice water (160 ml) and extracted with EtOAc three times. The organic phase was purified by a flash chromatography with EtOAc/petroleum ether to give the intermediate 7. Due to a number of studies referred to the intermediate compounds 7, 8, 9, and 10, we could identify these compounds by their melting points.

With potassium carbonate in N,N-dimethyl-formamide, T= 70 - 80 °C Li, Dong-Dong; Fang, Fei; Li, Jing-Ran; Du, Qian-Ru; Sun, Jian; Gong, Hai-Bin; Zhu, Hai-Liang; Bioorganic and Medicinal Chemistry Letters; vol. 22; nb. 18; (2012); p. 5870 - 5875 View in Reaxys 20 : 4.2.1. General synthetic procedure of benzodioxole compounds (benzo[d][1,3]dioxole-5-carbaldehyde and 2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde) General procedure: Equimolar portions of the appropriately protocatechuic aldehydes (50 mmol, 1 equiv) and dibromomethane or 1, 2-dibromoethane (50 mmol, 1 equiv) were dissolved in acetonitrile. The mixture was allowed to stir for several minutes at 90 °C to let dissolve. Then potassium carbonate (20.7 g, 3 equiv) was slowly added to the reaction as acid binding agent. The reaction solution was refluxed approximately 24 h. Most commonly, filtered and removed the precipitation, spin dry the solvent, extraction and recrystallization, then you will get benzodioxole compounds as reaction raw materials.

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With potassium carbonate in acetonitrile, Time= 24h, Reflux Wang, Hai-Hong; Qiu, Ke-Ming; Cui, Hong-En; Yang, Yu-Shun; Yin-Luo; Xing, Man; Qiu, Xiao-Yang; Bai, LiFei; Zhu, Hai-Liang; Bioorganic and Medicinal Chemistry; vol. 21; nb. 2; (2013); p. 448 - 455 View in Reaxys General procedure for synthesis of compounds 1-3 General procedure: In the three-necked flask under a nitrogen atmosphere, 3, 4-dihydroxybenzaldehyde (0.828 g, 6 mmol) was dissolved in dry acetone (10 ml), then added anhydrous potassium carbonate (2.5 g). After that, the acetone solution containing dibromomethane or 1,2-dibromoethane or 1,3- dibromopropane (6 mmol) was added dropwise then refluxed for 24 h. The reaction solution was evaporated reduced pressure distillation. The appropriate amount of water was added in the residue, and extracted with ethyl acetate (3×40 ml). Combined organic layer and dried with anhydrous magnesium sulfate. Then the solvent was removed by reduced pressure steam to give the crude product The crude product is purified by column chromatography [eluent: V (petroleum ether) : V (ethyl acetate) = 4: 1] to give white solid (compounds 1-3).

With potassium carbonate in acetone, Time= 24h, Inert atmosphere, Reflux Luo, Yin; Zhang, Shuai; Qiu, Ke-Ming; Liu, Zhi-Jun; Yang, Yu-Shun; Fu, Jie; Zhong, Wei-Qing; Zhu, HaiLiang; Bioorganic and Medicinal Chemistry Letters; vol. 23; nb. 4; (2013); p. 1091 - 1095 View in Reaxys With potassium carbonate in acetone, Time= 24h, Inert atmosphere, Reflux Luo, Yin; Zhou, Yang; Fu, Jie; Zhu, Hai-Liang; RSC Advances; vol. 4; nb. 45; (2014); p. 23904 - 23913 View in Reaxys

HO O

HO

2H

O

2H

O

O

Rx-ID: 39325792 View in Reaxys 14/181 Yield

Conditions & References Reaction Steps: 2 1: water-d2 / tetrahydrofuran / 20 °C / |Inert atmosphere 2: potassium carbonate; 1-methyl-pyrrolidin-2-one / 2.25 h / 110 °C / |Inert atmosphere With 1-methyl-pyrrolidin-2-one, water-d2, potassium carbonate in tetrahydrofuran Uttamsingh, Vinita; Gallegos, Richard; Liu, Julie F.; Harbeson, Scott L.; Bridson, Gary W.; Cheng, Changfu; Wells, David S.; Graham, Philip B.; Zelle, Robert; Tung, Roger; Journal of Pharmacology and Experimental Therapeutics; vol. 354; nb. 1; (2015); p. 43 - 54 View in Reaxys

O O

O

O

O

O

HO

O

O

O

Rx-ID: 39991823 View in Reaxys 15/181 Yield

Conditions & References

61 %, 28 %

With sodium tetrahydroborate, NiCl2·6H2O in methanol, Time= 0.25h, chemoselective reaction Khurana, Jitender M.; Dawra, Kiran; Sharma, Purnima; RSC Advances; vol. 5; nb. 16; (2015); p. 12048 - 12051 View in Reaxys

Br

O

O

C O

N

O O

Rx-ID: 38112140 View in Reaxys 16/181

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Yield

Conditions & References

62 %

Stage 1: With triethylsilane, palladium diacetate, sodium carbonate, 2-dicyclohexylphosphino-1,1'-biphenyl in N,Ndimethyl-formamide, Time= 8h, T= 65 °C , Inert atmosphere, Sealed tube, Green chemistry Stage 2: With water, Green chemistry Jiang, Xiao; Wang, Jin-Mei; Zhang, Ying; Chen, Zhong; Zhu, Yong-Ming; Ji, Shun-Jun; Organic Letters; vol. 16; nb. 13; (2014); p. 3492 - 3495 View in Reaxys

O

O

H

O

O

HO

Rx-ID: 38956452 View in Reaxys 17/181 Yield

Conditions & References 4 : Example 4 Oxidative Decomposition of Benzyl Ethers General procedure: A series of paper blotters (6 x 0.7 cm) were each loaded with 40 μ of a benzyl ether using a positive displacement pipette. The following benzyl ethers were tested: Ex. 1.1, 1.3, 1.4, 1.7. 1.10, 1.11, 1.12, 1.14.

Each blotter was placed inside a transparent 15 ml clear vial (Supelco, 27159) and sealed with a septum-equipped screw cap. The vials were purged with oxygen (20-26 ml/min) for one minute and then placed 10 inches away from a 365 nm UV-A lamp (UVP, 95-0042-07). Periodically a vial was retrieved and 1 ml of the internal standard solution (40 mg/ml of dodecane in acetone) was injected through the septum into the vial. After shaking the vial by hand, the cap was removed and another 15 ml of acetone (graduated cylinder) was added. The vial was recapped, agitated by hand for 1 minute, and then allowed to sit for another 9 minutes. The acetone solution was analyzed by GC-FID utilizing a 30 m x 0.25 mm (25 μιη film) HP-1 column and an Agilent 6850 gas chromatograph. The oven temperature was set to 100°C and raised 30°C/minute to 140°C, then by 2°C/minute to 150°C, then by 40°C/minute to 280°C and finally held for 3 minutes at this temperature. The amount of remaining benzyl ether was determined by a comparison of the GC peak areas to that of the internal standard and is reported as the percent remaining relative to the initial analysis at time zero. Figure 1 presents the loss of each benzyl ether. This graph shows that the volatiles are released progressively over a period of 2 to 14 days. GC-MS analyses of these extracts also revealed the formation of volatile compounds. The most abundant volatile compounds formed by the decomposition of each benzyl ether is indicated in Table 5.

With oxygen, Sealed tube, UV-irradiation Patent; FIRMENICH SA; INDRADAS, Brenda; VIRTUCIO, Gilbert; WOMACK, Gary; WO2014/180782; (2014); (A1) English View in Reaxys

Br

O

O

O

O O

O

Rx-ID: 39989062 View in Reaxys 18/181 Yield

Conditions & References

59 %

With triethylsilane, dichloro bis(acetonitrile) palladium(II), sodium carbonate, 1,4-di(diphenylphosphino)-butane in N,N-dimethyl-formamide, Time= 20h, T= 20 - 100 °C , p= 15001.5Torr , Inert atmosphere, Autoclave Natte, Kishore; Dumrath, Andreas; Neumann, Helfried; Beller, Matthias; Angewandte Chemie - International Edition; vol. 53; nb. 38; (2014); p. 10090 - 10094; Angew. Chem.; vol. 126; nb. 38; (2015); p. 10254 - 10258,5 View in Reaxys

E

O

O

O

O O

Rx-ID: 3824783 View in Reaxys 19/181 Yield 78 %

Conditions & References With sodium periodate, osmium(VIII) oxide, N-benzyl-N,N,N-triethylammonium chloride in tetrahydrofuran, water, Microwave irradiation

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Sharma, Upendra K.; Sood, Swati; Sharma, Nandini; Rahi, Praveen; Kumar, Rakesh; Sinha, Arun K.; Gulati, Arvind; Medicinal Chemistry Research; vol. 22; nb. 11; (2013); p. 5129 - 5140 View in Reaxys 77 %

1.2 :(2) Synthesis of Piperonal A solution of isoafrole (2 g, 12.1 mmol) in acetic acid (10 ml) was saturated with ozone at 0° C., until the formation of a slight blue color.

After removal of the excess of ozone by bubbling N2 through for some time, the ozonide was decomposed by stirring in the presence of zinc (Zn)(Zn) (5 g, 0.076 atg) at 0° C. for 2 h.

After filtration, ethyl acetate was added, the reaction mixture was washed with water, and the solvent was evaporated, following which it was dried over anhydrous sodium sulfate, affording 1.42 g (77percent) of piperonal, as a white solid, m.p. 36-37° C. Stage 1: With ozone, acetic acid, T= 0 °C Stage 2: With zinc, Time= 2h, T= 0 °C Patent; University of Maryland; US7091238; (2006); (B1) English View in Reaxys

48.9 %

With [Ru(2,2':6':2''-terpyridine)(2,2'-bipyridine)O](2+) in water, tert-butyl alcohol, Ambient temperature, electrolysis in phosphate buffer (pH 6.8) Madurro, Joao Marcos; Chiericato, Glaico Jr.; Giovani, Wagner F.De; Romero, Jose Ricardo; Tetrahedron Letters; vol. 29; nb. 7; (1988); p. 765 - 768 View in Reaxys

HO

N

O

O

O

O O

Rx-ID: 5069479 View in Reaxys 20/181 Yield 96 %

Conditions & References With water, dihydrogen peroxide, iodine in acetonitrile, Time= 4h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasis; Barik, Sujoy Kumar; Synthetic Communications; vol. 39; nb. 22; (2009); p.

4053 - 4061 View in Reaxys

95 %

With 2-iodoxybenzoic acid, β-cyclodextrin in water, acetone, Time= 12h, T= 20 °C Krishnaveni, N. Srilakshmi; Surendra; Nageswar; Rao, K. Rama; Synthesis; nb. 13; (2003); p. 1968 - 1970 View in Reaxys

95 %

With perchloric acid, dihydrogen peroxide, potassium bromide, hexaammonium heptamolybdate tetrahydrate in water, Time= 3h, T= 20 °C Ganguly, Nemai C.; Barik, Sujoy Kumar; Synthesis; nb. 3; (2008); p. 425 - 428 View in Reaxys

94 %

With tungsten hexachloride, zinc in acetonitrile, Time= 0.25h, T= 20 °C Firouzabadi, Habib; Jamalian, Arezu; Karimi, Babak; Bulletin of the Chemical Society of Japan; vol. 75; nb. 8; (2002); p. 1761 - 1764 View in Reaxys

94 %

With tert.-butylhydroperoxide, pyridinium chlorochromate, Time= 1h Ganguly, Nemai C.; Datta, Mrityunjoy; De, Prithwiraj; Journal of the Indian Chemical Society; vol. 81; nb. 4; (2004); p. 308 - 312 View in Reaxys

94 %

With CuCl2·2H2O, water in acetonitrile, Time= 2h, T= 75 °C Quan, Na; Shi, Xiao-Xin; Nie, Liang-Deng; Dong, Jing; Zhu, Rui-Heng; Synlett; nb. 7; (2011); p. 1028 - 1032 View in Reaxys

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92 %

With 1,4-dibenzyl-1,4-diazoniabicyclo[2.2.2]octane chlorochromate in acetonitrile, Time= 0.333333h, Heating xxx; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 39; nb. 11; (2000); p. 863 - 866 View in Reaxys

92 %

With formyl formic acid in water, Time= 1h, T= 20 °C Chavan, Subhash P.; Soni, Priti; Tetrahedron Letters; vol. 45; nb. 15; (2004); p. 3161 - 3162 View in Reaxys

91 %

With iodobenzene, β-cyclodextrin, potassium bromide in water, acetone, Time= 12h, T= 20 °C Narender; Somi Reddy; Srilakshmi Krishnaveni; Surendra; Nageswar; Rama Rao; Synthetic Communications; vol. 36; nb. 10; (2006); p. 1463 - 1470 View in Reaxys

90 %

With aluminum oxide, PFC in dichloromethane, Time= 0.25h Ganguly, Nemai C.; De, Prithwiraj; Sukai, Arun K.; De, Sripada; Synthetic Communications; vol. 32; nb. 1; (2002); p. 1 - 7 View in Reaxys

90 %

With CuCl2*2H2O, Time= 0.0133333h, microwave irradiation Karchaudhuri, Nilay; De, Aparna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 81; nb. 1; (2004); p. 79 - 81 View in Reaxys

88 %

With dihydrogen peroxide, H3[PW12O40] in various solvent(s), Time= 4h, T= 20 °C , Product distribution, Further Variations: Catalysts Jain, Nidhi; Kumar, Anil; Chauhan, Shive M.S.; Tetrahedron Letters; vol. 46; nb. 15; (2005); p. 2599 - 2602 View in Reaxys

88 %

With (NH4)6[Mo7O24]*4H2O, dihydrogen peroxide in water, acetic acid, Time= 4h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasish; Barik, Sujoy Kumar; Dutta, Sanjoy; Journal of the Indian Chemical Society; vol. 85; nb. 7; (2008); p. 711 - 716 View in Reaxys

86 %

With aluminium trichloride, BTPPD in chloroform, Time= 0.5h, Heating, Oxidation Baltork, I. Mohammadpoor; Sadeghi, M. M.; Mahmoodi, N.; Kharamesh, B.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 36; nb. 5; (1997); p. 438 - 441 View in Reaxys

85 %

With hydrogenchloride, iron in methanol, water, Time= 0.5h, Heating Pradhan, Prasun K.; Dey, Sumit; Jaisankar, Parasuraman; Giri, Venkatachalam S.; Synthetic Communications; vol. 35; nb. 7; (2005); p. 913 - 922 View in Reaxys

80 %

With dihydrogen peroxide, PFC in acetone, Time= 0.25h, T= -10 °C Ganguly; Sukai; De; Synthetic Communications; vol. 31; nb. 10; (2001); p. 1607 - 1612 View in Reaxys

80 %

With SnCl2·2H2O in acetonitrile, Time= 0.5h, Reflux Ganguly, Nemai C.; Nayek, Subhasis; Chandra, Sumanta; Journal of the Indian Chemical Society; vol. 90; nb.

10; (2013); p. 1695 - 1702 View in Reaxys

79 %

With water, phosphorus pentoxide, Time= 0.0111111h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 80; nb. 3; (2003); p. 184 - 186

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View in Reaxys 79 %

With Pi, Time= 0.0111111h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 44; nb. 9; (2005); p. 1876 - 1879 View in Reaxys

78 %

With benzyltriphenylphosphonium peroxodisulfate in acetonitrile, Time= 1h, Heating, Oxidation Mohammadpoor-Baltork, Iraj; Hajipour, Abdol Reza; Mohammadi, Hasan; Bulletin of the Chemical Society of Japan; vol. 71; nb. 7; (1998); p. 1649 - 1653 View in Reaxys

78 %

With (NH4)2S2O8, Montmorillonite K10, silver nitrate in hexane, Time= 2.5h, T= 60 °C Hirano; Kojima; Yakabe; Morimoto; Journal of Chemical Research - Part S; nb. 7; (2001); p. 277 - 279 View in Reaxys

15 %

With iodine in acetonitrile, Time= 5h, Reflux, Beckmann rearrangement Ganguly, Nemai C.; Mondal, Pallab; Synthesis; nb. 21; (2010); p. 3705 - 3709; Art.No: Z16110SS View in Reaxys

HO

O

O O

HO

O

Rx-ID: 24270820 View in Reaxys 21/181 Yield

Conditions & References 6 : EXAMPLE 6 EXAMPLE 6 The same procedure is carried out as in example 1, charging 3,4-dihydroxybenzaldehyde in a solution of NMP instead of catechol.

At the end of the reaction after separation by distillation under vacuum (residue of 10 mmHg) 141.6 g of pure 3,4methylenedioxybenzaldehyde are obtained.

Patent; Borregaard Italia S.p.A.; US5936103; (1999); (A1) English View in Reaxys Reaction Steps: 4 1: potassium carbonate / acetonitrile / 24 h / |Reflux 2: potassium hydroxide / ethanol; water / 20 °C 3: potassium hydroxide / ethanol / 12 h / |Reflux 4: potassium carbonate / ethanol / 8 h / 80 °C With potassium carbonate, potassium hydroxide in ethanol, water, acetonitrile Wang, Hai-Hong; Qiu, Ke-Ming; Cui, Hong-En; Yang, Yu-Shun; Yin-Luo; Xing, Man; Qiu, Xiao-Yang; Bai, LiFei; Zhu, Hai-Liang; Bioorganic and Medicinal Chemistry; vol. 21; nb. 2; (2013); p. 448 - 455 View in Reaxys NH 2

HO

N

O

O

O

O

O

O

O O

Rx-ID: 32649540 View in Reaxys 22/181 Yield 82 %, 8 %

Conditions & References With SnCl2·2H2O, 1,8-diazabicyclo[5.4.0]undec-7-ene in toluene, Time= 3h, Reflux Ganguly, Nemai C.; Nayek, Subhasis; Chandra, Sumanta; Journal of the Indian Chemical Society; vol. 90; nb.

10; (2013); p. 1695 - 1702 View in Reaxys

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70 %, 30 %

With pyridine, SnCl2·2H2O in toluene, Time= 3h, Reflux, Reagent/catalyst Ganguly, Nemai C.; Nayek, Subhasis; Chandra, Sumanta; Journal of the Indian Chemical Society; vol. 90; nb.

10; (2013); p. 1695 - 1702 View in Reaxys

36 %, 40 %

With CuSO4‵5H2O, Time= 2h, T= 110 °C , Neat (no solvent) Ganguly, Nemai C.; Roy, Sushmita; Mondal, Pallab; Tetrahedron Letters; vol. 53; nb. 11; (2012); p. 1413 - 1416 View in Reaxys

O

O

O

O

O

O

Rx-ID: 34651663 View in Reaxys 23/181 Yield

Conditions & References Reaction Steps: 3 1: potassium hydroxide / ethanol; water / 20 °C 2: potassium hydroxide / ethanol / 12 h / |Reflux 3: potassium carbonate / ethanol / 8 h / 80 °C With potassium carbonate, potassium hydroxide in ethanol, water Wang, Hai-Hong; Qiu, Ke-Ming; Cui, Hong-En; Yang, Yu-Shun; Yin-Luo; Xing, Man; Qiu, Xiao-Yang; Bai, LiFei; Zhu, Hai-Liang; Bioorganic and Medicinal Chemistry; vol. 21; nb. 2; (2013); p. 448 - 455 View in Reaxys

O O

O

O

Br N

O

O

Br

N

O

NH 2 S

Rx-ID: 34651763 View in Reaxys 24/181 Yield

Conditions & References

78 %

20 : 4.2.4. General synthetic procedure of benzodioxole thiazolylpyrazoline derivatives (C1–C20) General procedure: A mixture of compound B (1 mmol) and substituted 2-bromoacetophenone (1 mmol) was dissolved in ethanol (20 mL) and kept stirring in 80 °C for 8 h. After cooling, the solution was poured into mass of icewater and stirred for a few minutes. The precipitate was filtered and crystallized from methylene dichloride/ethanol = 1:1.

With potassium carbonate in ethanol, Time= 8h, T= 80 °C Wang, Hai-Hong; Qiu, Ke-Ming; Cui, Hong-En; Yang, Yu-Shun; Yin-Luo; Xing, Man; Qiu, Xiao-Yang; Bai, LiFei; Zhu, Hai-Liang; Bioorganic and Medicinal Chemistry; vol. 21; nb. 2; (2013); p. 448 - 455 View in Reaxys

O S

O

O

O O

S

Rx-ID: 36328206 View in Reaxys 25/181 Yield 91 %

Conditions & References 4.3.1 Representative procedure for deprotection of 1,3-dithianes (Table 2, entry 3) General procedure: A mixture of 2-(2-methoxyphenyl)-1,3-dithiane (1c) (0.11 g, 0.50mmol), 1,4-benzoquinone (64.8 mg, 0.60 mmol), and NaI (0.70 mg, 0.005 mmol) in MeCN (2mL) and H2O (0.2mL) was stirred at 100°C for 24 h. The reaction mixture was filtered through a pad of Celite and the filtrate was concentrated in vacuo. The residue was purified by flash column chromatography (eluent: hexane/AcOEt=15/1) to give 2-methoxybenzaldehyde (2c, 66.5mg, 98percent) as colorless oil.

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With p-benozquinone, sodium iodide in water, acetonitrile, Time= 24h, T= 100 °C Inamoto, Kiyofumi; Yamada, Tetsuya; Kato, Sei-Ichi; Kikkawa, Shoko; Kondo, Yoshinori; Tetrahedron; vol. 69; nb. 44; (2013); p. 9192 - 9199 View in Reaxys

O

O

O

O

O

O

Rx-ID: 37027905 View in Reaxys 26/181 Yield

Conditions & References With alkene cleaving enzyme AlkCE from Trametes hirsuta FCC047, oxygen, manganese triacetate in aq. buffer, T= 21 °C , pH= 6, Enzymatic reaction Rajagopalan, Aashrita; Schober, Markus; Emmerstorfer, Anita; Hammerer, Lucas; Migglautsch, Anna; Seisser, Birgit; Glueck, Silvia. M.; Niehaus, Frank; Eck, Juergen; Pichler, Harald; Gruber, Karl; Kroutil, Wolfgang; ChemBioChem; vol. 14; nb. 18; (2013); p. 2427 - 2430 View in Reaxys

O

OH

O

O

O

O

O

OH

O

Rx-ID: 3871379 View in Reaxys 27/181 Yield 70 %

Conditions & References With silica gel, periodic acid, Time= 0.25h, T= 20 °C , Neat (no solvent) Dakdouki, Saada C.; Villemin, Didier; Bar, Nathalie; European Journal of Organic Chemistry; nb. 4; (2012); p. 780 - 784 View in Reaxys

65 %

With aluminum oxide, potassium meta-periodate, Time= 0.166667h, Microwave irradiation Dakdouki, Saada C.; Villemin, Didier; Bar, Nathalie; European Journal of Organic Chemistry; nb. 23; (2011); p.

4448 - 4454 View in Reaxys

99 % Chromat.

With NSC26899, oxygen, 5,10,15,20-tetrakisphenylporphyrinatoiron(III) chloride in dichloromethane, Time= 12h, Ambient temperature, Irradiation Okamoto; Sasaki; Oka; Journal of the American Chemical Society; vol. 110; nb. 4; (1988); p. 1187 - 1196 View in Reaxys

O

O

O

O O

Rx-ID: 34867767 View in Reaxys 28/181 Yield

Conditions & References 1.C; 2.C :To a stirred mixture of 3.8 grams of 5-(2-methyl-l-propen-l-yl)-l,3- benzodioxole, 18.0 grams of sulfuric acid and 1.0 gram of ammonium sulfate was added portion wise, 6.0 grams of potassium chromate, while maintaining a reaction temperature of less than 60°C. Upon complete addition, the mixture was stirred at 45 °C for one hour and 1.0 gram of potassium chromate was added. The mixture was stirred at 45 °C for forty minutes, cooled and diluted with 100 rriL of water. The mixture was extracted with 50 rriL of methylene chloride. The organic extract was washed with water then was concentrated under reduced pressure to yield 0.5 gram of oil. Gas chromatography analysis of the oil indicated 65percent by weight heliotropin and 15percent by weight 5-(2-methyl-l-propen-l-yl)-l,3-benzodioxole.

Analysis by GC- MS and the main peak analysis result shows EI-MS( (M-l) 149, 121, 91, 63) which is identical to heliotropin standard graph. Other impurity peak shows EI -MS (M 176) which is 5-(2-methyl-l-propen-l-yl)-l,3-benzodioxole.

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With ammonium sulfate, K2CrO4 in sulfuric acid, Time= 1.66667h, T= 45 - 60 °C Patent; FMC CORPORATION; MCMULLEN, Leonard, A.; JI, Junan; LIU, Luwei; RAGHAVAN, Krishna; WO2012/173842; (2012); (A2) English View in Reaxys

HO

O

O

O

HO

Rx-ID: 34867768 View in Reaxys 29/181 Yield

Conditions & References Reaction Steps: 4 1.1: potassium carbonate / water; isobutyl methylketone / 2 h / 130 °C / sealed autoclave reactor 1.2: 0.5 h / 70 °C / pH 3 - 4 1.3: 180 °C / sealed autoclave reactor 2.1: potassium hydroxide / water; dimethyl sulfoxide / 3 h / 95 °C 3.1: potassium hydroxide / polyethylene glycol (PEG 300) / 3.5 h / 120 °C 4.1: K2CrO4; ammonium sulfate / sulfuric acid / 1.67 h / 45 - 60 °C With ammonium sulfate, K2CrO4, potassium carbonate, potassium hydroxide, polyethylene glycol (PEG 300) in sulfuric acid, water, dimethyl sulfoxide, isobutyl methylketone Patent; FMC CORPORATION; MCMULLEN, Leonard, A.; JI, Junan; LIU, Luwei; RAGHAVAN, Krishna; WO2012/173842; (2012); (A2) English View in Reaxys Reaction Steps: 3 1.1: sodium hydroxide; aluminum oxide / water / 0.08 h 1.2: 24 h / 60 °C 2.1: CuCl2·2H2O / ethyl acetate; water / 5 h / 60 °C / |Inert atmosphere 3.1: sodium hydroxide; tetrabutylammomium bromide With aluminum oxide, CuCl2·2H2O, tetrabutylammomium bromide, sodium hydroxide in water, ethyl acetate Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco; Organic Process Research and Development; vol. 4; nb. 6; (2000); p. 534 - 543 View in Reaxys

O

O

O

O O

Rx-ID: 34867773 View in Reaxys 30/181 Yield

Conditions & References Reaction Steps: 2 1: potassium hydroxide / polyethylene glycol (PEG 300) / 3.5 h / 120 °C 2: K2CrO4; ammonium sulfate / sulfuric acid / 1.67 h / 45 - 60 °C With ammonium sulfate, K2CrO4, potassium hydroxide, polyethylene glycol (PEG 300) in sulfuric acid Patent; FMC CORPORATION; MCMULLEN, Leonard, A.; JI, Junan; LIU, Luwei; RAGHAVAN, Krishna; WO2012/173842; (2012); (A2) English View in Reaxys OH OH

O

O O

Rx-ID: 34867778 View in Reaxys 31/181

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Yield

Conditions & References Reaction Steps: 3 1: potassium hydroxide / water; dimethyl sulfoxide / 3 h / 95 °C 2: potassium hydroxide / polyethylene glycol (PEG 300) / 3.5 h / 120 °C 3: K2CrO4; ammonium sulfate / sulfuric acid / 1.67 h / 45 - 60 °C With ammonium sulfate, K2CrO4, potassium hydroxide, polyethylene glycol (PEG 300) in sulfuric acid, water, dimethyl sulfoxide Patent; FMC CORPORATION; MCMULLEN, Leonard, A.; JI, Junan; LIU, Luwei; RAGHAVAN, Krishna; WO2012/173842; (2012); (A2) English View in Reaxys

S S

O

O

O O

O

Rx-ID: 4470017 View in Reaxys 32/181 Yield 98 %

Conditions & References With periodic acid in tetrahydrofuran, diethyl ether, Time= 0.0833333h, Ambient temperature Shi, Xiao-Xin; Khanapure, Subhash P.; Rokach, Joshua; Tetrahedron Letters; vol. 37; nb. 25; (1996); p. 4331 4334 View in Reaxys

98 %

With NH4I, dihydrogen peroxide, sodium lauryl sulfate in water, Time= 0.25h, T= 20 °C , micellar medium Ganguly, Nemai C.; Mondal, Pallab; Synthetic Communications; vol. 41; nb. 16; (2011); p. 2374 - 2384 View in Reaxys

95 %

With nitric acid, As2O3 in dichloromethane, T= 0 - 5 °C Mehta, Goverdhan; Uma; Tetrahedron Letters; vol. 37; nb. 11; (1996); p. 1897 - 1898 View in Reaxys

95 %

With dihydrogen peroxide, iodine, sodium lauryl sulfate in water, Time= 0.5h, T= 20 °C , Micellar solution Ganguly, Nemai C.; Barik, Sujoy Kumar; Synthesis; nb. 8; (2009); p. 1393 - 1399; Art.No: Z26708SS View in Reaxys

90 %

With (NH4)2S2O8, Montmorillonite K-10 clay, Time= 0.0166667h, microwave irradiation Ganguly, Nemai C.; Datta, Mrityunjoy; Synlett; nb. 4; (2004); p. 659 - 662 View in Reaxys

90 %

With Amberlyst A (trifluoroacetoxy)iodate(I) form in water, acetonitrile, Time= 0.5h, T= 20 °C Luiken, Silke; Kirschning, Andreas; Journal of Organic Chemistry; vol. 73; nb. 5; (2008); p. 2018 - 2020 View in Reaxys

84 %

Stage 1: With 1-benzenesulfinyl piperidine, trifluoromethylsulfonic anhydride in dichloromethane, Time= 0.333333h, T= -60 °C Stage 2: With water in tetrahydrofuran, dichloromethane, T= -60 - 20 °C Crich, David; Picione, John; Synlett; nb. 9 SPEC. ISS.; (2003); p. 1257 - 1258 View in Reaxys

80 %

With 2,4,4,6-tetrabromo-2,5-cyclohexadien-1-one, dihydrogen peroxide in water, acetonitrile, Time= 1h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasis; Barik, Sujoy Kumar; Journal of the Indian Chemical Society; vol. 88; nb. 2; (2011); p. 251 - 256 View in Reaxys

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S O

O

O

S

O

O

Rx-ID: 9947635 View in Reaxys 33/181 Yield

Conditions & References

98 %

With 2,4,4,6-tetrabromo-2,5-cyclohexadien-1-one, dihydrogen peroxide in water, acetonitrile, Time= 1.5h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasis; Barik, Sujoy Kumar; Journal of the Indian Chemical Society; vol. 88; nb. 2; (2011); p. 251 - 256 View in Reaxys

96 %

With hydrogen bromide, dihydrogen peroxide in acetonitrile, Time= 0.2h, T= 25 °C Ganguly, Nemai C.; Datta, Mrityunjoy; Journal of Chemical Research; nb. 4; (2005); p. 218 - 221 View in Reaxys

Si

O

O

O

O O

O

Rx-ID: 9981625 View in Reaxys 34/181 Yield

Conditions & References

78 %

Stage 1: With bismuth trifluoromethanesulphonate, water in acetonitrile, Time= 1h Stage 2: With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, iodosylbenzene in acetonitrile, Time= 1h, T= 20 °C Barnych, Bogdan; Vatele, Jean-Michel; Synlett; nb. 14; (2011); p. 2048 - 2052; Art.No: D10511ST View in Reaxys

69 %

With N-bromosuccinmide, β-cyclodextrin in acetone, Time= 9h, T= 20 °C Reddy, M. Somi; Narender; Nageswar; Rao, K. Rama; Synthesis; nb. 5; (2005); p. 714 - 716; Art.No: Z20704SS View in Reaxys

O

S S

O

O O

O

Rx-ID: 28922515 View in Reaxys 35/181 Yield 95 %

Conditions & References With dihydrogen peroxide, iodine, sodium lauryl sulfate in water, Time= 0.333333h, T= 20 °C , Micellar solution Ganguly, Nemai C.; Barik, Sujoy Kumar; Synthesis; nb. 8; (2009); p. 1393 - 1399; Art.No: Z26708SS View in Reaxys

94 %

With NH4I, dihydrogen peroxide, sodium lauryl sulfate in water, Time= 1.5h, T= 20 °C , micellar medium Ganguly, Nemai C.; Mondal, Pallab; Synthetic Communications; vol. 41; nb. 16; (2011); p. 2374 - 2384 View in Reaxys

92 %

With 2,4,4,6-tetrabromo-2,5-cyclohexadien-1-one, dihydrogen peroxide in water, acetonitrile, Time= 0.75h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasis; Barik, Sujoy Kumar; Journal of the Indian Chemical Society; vol. 88; nb. 2; (2011); p. 251 - 256 View in Reaxys

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I

HO

I

O

O O

HO

O

Rx-ID: 28946821 View in Reaxys 36/181 Yield

Conditions & References

80 %

With potassium carbonate in N,N-dimethyl-formamide, Time= 5h, Reflux, Inert atmosphere Shingala, Shailesh D.; Venkateswar Reddy; Sateesh Chandra Kumar; Ashok Yadav; Suresh Babu; Journal of Asian Natural Products Research; vol. 13; nb. 2; (2011); p. 128 - 135 View in Reaxys 1.1 :To 4-dihydroxybenzaldehyde (5 g) in DMF (50 ml); K2CO3 (7.5 g), diiodomethane(12.5 g) were added and the reaction mixture was refluxed for 2 hrs at temperature 110°C. Progress of the reaction was monitored by TLC. When the reaction was complete the mixture was cooled to room temperature, filtered through a Celite bed and washed with DCM. Water - (100 ml) was added to the filtrate and the compound was extracted with DCM (3x200 ml). Combined extracts were washed with water, dried over Na2SO4 and concentrated under reduced pressure. The crude compound was purified by column chromatography (silica gel, 10percent EtOAc/hexane) to yield intermediate L With potassium carbonate in N,N-dimethyl-formamide, Time= 2h, T= 110 °C Patent; SPEAR THERAPEUTICS LIMITED DE MONTFORT UNIVERSITY; WO2009/146910; (2009); (A1) English View in Reaxys 1.1 :Step-1; To 4-dihydroxybenzaldehyde (5 g) in DMF (50 ml); K2CO3 (7.5 g), diiodomethane (12.5 g) were added and the reaction mixture was refluxed for 2 hrs at temperature 110° C. Progress of the reaction was monitored by TLC. When the reaction was complete the mixture was cooled to room temperature, filtered through a Celite bed and washed with DCM. Water (100 ml) was added to the filtrate and the compound was extracted with DCM (3.x.200 ml).

Combined extracts were washed with water, dried over Na2SO4 and concentrated under reduced pressure. The crude compound was purified by column chromatography (silica gel, 10percent EtOAc/hexane) to yield intermediate 1.

With potassium carbonate in N,N-dimethyl-formamide, Time= 2h, T= 110 °C , Reflux Patent; Potter, Gerard Andrew; Huxley, Philip; US2010/168180; (2010); (A1) English View in Reaxys

O S

Br

Br

Br

O

S

O

O HO

Br

O O

Br

Br

Br

Rx-ID: 32541561 View in Reaxys 37/181 Yield 98 %, 80 %

Conditions & References With dihydrogen peroxide in water, acetonitrile, Time= 0.25h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasis; Barik, Sujoy Kumar; Journal of the Indian Chemical Society; vol. 88; nb. 2; (2011); p. 251 - 256 View in Reaxys

Br

O

O

O

O O

Rx-ID: 33232079 View in Reaxys 38/181 Yield 80 %

Conditions & References With sodium periodate in dichloromethane, T= 40 - 50 °C , Ionic liquid Hullio, Ahmed Ali; Mastoi; Khan, Khalid; Asian Journal of Chemistry; vol. 23; nb. 12; (2011); p. 5411 - 5418 View in Reaxys

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O O O O

O

O

O O

O

Rx-ID: 4676793 View in Reaxys 39/181 Yield 99 %

Conditions & References With iron(II) sulfate in dichloromethane, Time= 0.166667h, Heating Jin; Ma; Zhang; Li; Organic Preparations and Procedures International; vol. 30; nb. 4; (1998); p. 463 - 466 View in Reaxys

98 %

With Montmorillonite K10 in dichloromethane, Time= 0.333333h, Heating Li, Tong-Shuang; Zhang, Zhan-Hui; Fu, Cheng-Guang; Tetrahedron Letters; vol. 38; nb. 18; (1997); p. 3285 3288 View in Reaxys

98 %

With carbon in dichloromethane, Time= 0.25h, Heating Jin, Tong-Shou; Ma, Yan-Ran; Zhang, Zhan-Hui; Li, Tong-Shuang; Synthetic Communications; vol. 27; nb. 19; (1997); p. 3379 - 3383 View in Reaxys

98 %

With water, anhydrous sulphate, Titanium(IV) oxide in benzene, Time= 0.116667h, Heating, Deacetylation Jin, Tong-Shou; Sun, Xu; Li, Tong-Shuang; Journal of Chemical Research - Part S; nb. 3; (2000); p. 128 - 129 View in Reaxys

98 %

With aminosulfonic acid in benzene, Time= 0.166667h, Heating Jin, Tong-Shou; Sun, Guang; Li, Yan-Wei; Li, Tong-Shuang; Journal of Chemical Research - Part S; nb. 1; (2003); p. 30 - 32 View in Reaxys

98 %

With Fe2(S0 4)3 in 1,2-dichloro-ethane, Time= 0.25h, Heating Li, Lingjun; Zhang, Xinying; Zhang, Guisheng; Qu, Guirong; Journal of Chemical Research; nb. 1; (2004); p. 39 40 View in Reaxys

98 %

With peroxymonosulfuric acid, silica gel in dichloromethane, Time= 0.0333333h, Heating Lakouraj; Tajbakhsh; Khojasteh; Gholami; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 179; nb. 12; (2004); p. 2645 - 2651 View in Reaxys

96 %

With sodium hydrogen sulphate, PEG-2000, Time= 0.266667h, T= 70 °C Zhang, Zhan-Hui; Monatshefte fur Chemie; vol. 136; nb. 7; (2005); p. 1191 - 1195 View in Reaxys

95 %

With indium tribromide in water, Time= 0.5h, Heating Zhang, Zhan-Hui; Yin, Liang; Li, Yi; Wang, Yong-Mei; Tetrahedron Letters; vol. 46; nb. 5; (2005); p. 889 - 893 View in Reaxys

95 %

With indium tribromide, 1-n-butyl-3-methylimidazolium hexafluorophosphate, Time= 0.25h, T= 20 °C Zhang, Zhan-Hui; Journal of Chemical Research; nb. 11; (2004); p. 753 - 755 View in Reaxys

92 %

With β-cyclodextrin in methanol, water, Time= 7h, T= 60 °C , Product distribution Arjun Reddy; Rajender Reddy; Bhanumathi; Rama Rao; Synthetic Communications; vol. 32; nb. 2; (2002); p.

273 - 277

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View in Reaxys 92 %

With water, TiF4, Time= 4h, T= 60 °C , screw-capped vial Jung, Misuk; Yoon, Jieun; Kim, Hak Sung; Ryu, Jae-Sang; Synthesis; nb. 16; (2010); p. 2713 - 2720; Art.No: F04310SS View in Reaxys

90 %

With ammonium cerium(IV) nitrate in acetonitrile, Time= 4.5h, T= 70 °C Roy, Subhas Chandra; Banerjee, Biplab; Synlett; nb. 10; (2002); p. 1677 - 1678 View in Reaxys

90 %

With silica phosphoric acid in methanol, Time= 0.75h, T= 20 °C Zhang, Fuyi; Liu, Hong; Zhang, Qing-Ju; Zhao, Yu-Fen; Yang, Feng-Ling; Synthetic Communications; vol. 40; nb. 21; (2010); p. 3240 - 3250 View in Reaxys

89 %

With carbon tetrabromide in acetonitrile, Time= 4h, Heating Ramalingam; Srinivas; Subba Reddy; Yadav; Synthetic Communications; vol. 31; nb. 7; (2001); p. 1091 - 1095 View in Reaxys

89 %

With zirconium tetrachloride in methanol, Time= 0.1h, T= 20 °C Smitha; Reddy, Ch. Sanjeeva; Tetrahedron; vol. 59; nb. 48; (2003); p. 9571 - 9576 View in Reaxys

88 %

With ammonium acetate, Time= 0.00805556h, microwave irradiation Mitra, Alok Kumar; Karchaudhuri, Nilay; De, Aparna; Journal of Chemical Research; nb. 3; (2004); p. 237 - 239 View in Reaxys With indium(III) chloride in water, T= 20 °C Yadav; Subba Reddy; Srinivas, Ch.; Synthetic Communications; vol. 32; nb. 8; (2002); p. 1175 - 1180 View in Reaxys 2H

S

O 2H

O

O

O S

O

Rx-ID: 29325859 View in Reaxys 40/181 Yield

Conditions & References

93 %

With periodic acid in tetrahydrofuran, Time= 0.166667h, T= 20 °C Xiao, Sen; Shi, Xiao-Xin; Ni, Feng; Xing, Jing; Yan, Jing-Jing; Liu, Shi-Ling; European Journal of Organic Chemistry; nb. 9; (2010); p. 1711 - 1716 View in Reaxys

O

H

OH O

O

O

O

O

H

O

OH O

O

O

racemate

Rx-ID: 29496038 View in Reaxys 41/181 Yield 41 %

Conditions & References With (1R,2R)-2-(diethylamino)cyclohexanaminium trifluoromethanesulfonate in dichloromethane, Time= 9h, T= 20 °C , Resolution of racemate, Retroaldol reaction, optical yield given as percent ee, enantioselective reaction Luo, Sanzhong; Zhou, Pengxin; Li, Jiuyuan; Cheng, Jin-Pei; Chemistry - A European Journal; vol. 16; nb. 15; (2010); p. 4457 - 4461 View in Reaxys

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O

O

O O

O

O O

O

Rx-ID: 29657997 View in Reaxys 42/181 Yield

Conditions & References With oxygen, bornyl acetate, palladium dichloride in isobutyramide, water, Time= 7h, T= 60 °C , p= 7600.51Torr Parreira, Luciana A.; Menini, Luciano; Da Cruz Santos, Joyce C.; Gusevskaya, Elena V.; Advanced Synthesis and Catalysis; vol. 352; nb. 9; (2010); p. 1533 - 1538 View in Reaxys

O

O

O

O O

Rx-ID: 809018 View in Reaxys 43/181 Yield 100 %

Conditions & References With [bis(acetoxy)iodo]benzene, Time= 0.5h, T= 84 °C , p= 1913.5Torr , Microwave irradiation, Reagent/catalyst, Time, Temperature Alvarez, Heiddy Marquez; Barbosa, Dayse P.; Fricks, Alini Tinoco; Aranda, Donato A. G.; Valdes, Ricardo H.; Antunes; Organic Process Research and Development; vol. 10; nb. 5; (2006); p. 941 - 943 View in Reaxys

93 %

Stage 1: With ozone, acetic acid, Time= 1h, T= 0 °C Stage 2: With acetic acid, zinc Kuemmerle, Arthur E.; Raimundo, Juliana M.; Leal, Carla M.; da Silva, Givanildo S.; Balliano, Tatiane L.; Pereira, Mariano A.; de Simone, Carlos A.; Sudo, Roberto T.; Zapata-Sudo, Gisele; Fraga, Carlos A.M.; Barreiro, Eliezer J.; European Journal of Medicinal Chemistry; vol. 44; nb. 10; (2009); p. 4004 - 4009 View in Reaxys With disodium hydrogenphosphate, phosphoric acid, acetic acid, Reagens 4: wss. Chromsaeure-Loesung Patent; Farinacci; US2794813; (1953) View in Reaxys With acetic acid, T= 100 °C , bei der Ozonisation Patent; Otto; Verley; DE97620 View in Reaxys Otto; Annales de Chimie (Cachan, France); vol. <7> 13; (1898); p. 123 View in Reaxys With Catalyst M-Chromium oxide, sulfuric acid Eijkman; Chemische Berichte; vol. 23; (1890); p. 862 View in Reaxys With Catalyst M-Chromium oxide, sulfuric acid Ciamician; Silber; Gazzetta Chimica Italiana; vol. 20; (1890); p. 571; Chemische Berichte; vol. 23; (1890); p. 1160 View in Reaxys With mineral acid, chromic acid, Reagens 4: Sulfanilsaeure Patent; Fritzsche and Co., Verona Chemical Co.; DE207702 View in Reaxys With chromic acid, acetic acid, Reagens 4: Sulfanilsaeure Patent; Fritzsche and Co., Verona Chemical Co.; DE207702 View in Reaxys With potassium dichromate, sulfuric acid, water

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Ciamician; Silber; Gazzetta Chimica Italiana; vol. 20; (1890); p. 571; Chemische Berichte; vol. 23; (1890); p. 1160 View in Reaxys With tetrachloromethane, ozone, Petroleum ether, Zersetzung des Ozonids mit NaHSO3 Nagai; ; vol. 13; p. 185; Chem. Zentralbl.; vol. 94; nb. III; (1923); p. 750 View in Reaxys With chloroform, ozone, weiteres Reagens: Petrolaether; Zersetzung des Ozonids mit NaHSO3 Nagai; ; vol. 13; p. 185; Chem. Zentralbl.; vol. 94; nb. III; (1923); p. 750 View in Reaxys With ozone, tetrachloroethane, 1,1,2,2-, weiteres Reagens: Petrolaether; Zersetzung des Ozonids mit NaHSO3 Nagai; ; vol. 13; p. 185; Chem. Zentralbl.; vol. 94; nb. III; (1923); p. 750 View in Reaxys With tetrachloromethane, ozone, Zersetzung des Ozonids mit NaHSO3 Briner; v. Tscharner; Paillard; Helvetica Chimica Acta; vol. 8; (1925); p. 407 View in Reaxys With Catalyst M-Chromium oxide, sulfuric acid Wagner; ; (1926); p. 65; Chem. Zentralbl.; vol. 97; nb. II; (1926); p. 1209 View in Reaxys Schwyzer,J.; View in Reaxys Wagner,A.; View in Reaxys With 1,1-dimethylpropan-1-ol, dihydrogen peroxide, Reagens 4: Vanadium(V)-oxid Milas; Journal of the American Chemical Society; vol. 59; (1937); p. 2342 View in Reaxys With Catalyst M-Chromium oxide, sulfuric acid Wagner,A.; Burger; Elze; View in Reaxys Knoll,R.; Wagner,A.; View in Reaxys With dihydrogen peroxide, tert-butyl alcohol, Reagens 4: Vanadium(V)-oxid Milas; Journal of the American Chemical Society; vol. 59; (1937); p. 2342 View in Reaxys With oxygen, Time= 24h, T= 25 °C , p= 1500.15Torr , pH= 6, aq. buffer, Enzymatic reaction, chemoselective reaction Lara, Miguel; Mutti, Francesco G.; Glueck, Silvia M.; Kroutil, Wolfgang; European Journal of Organic Chemistry; nb. 21; (2008); p. 3668 - 3672 View in Reaxys 77 %Chromat.

With potassium permanganate, CuSO4‵5H2O, Time= 1h, T= 95 °C , Neat (no solvent) Luu, Thi Xuan Thi; Lam, Trinh To; Le, Thach Ngoc; Duus, Fritz; Molecules; vol. 14; nb. 9; (2009); p. 3411 - 3424 View in Reaxys

O

O O

O

O O

Rx-ID: 28203993 View in Reaxys 44/181

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Yield

Conditions & References

85 %

With sodium dihydroperiodate, sulfuric acid in water, Time= 0.333333h, T= 20 °C Telvekar, Vikas N.; Patel, Dharmeshkumar J.; Mishra, Sanket J.; Synthetic Communications; vol. 39; nb. 2; (2009); p. 311 - 315 View in Reaxys

O

O

O

O

O

Rx-ID: 28704553 View in Reaxys 45/181 Yield

Conditions & References

87 %

With sodium dihydroperiodate, sulfuric acid in water, Time= 4h, T= 70 °C Telvekar, Vikas N.; Mishra, Sanket J.; Patel, Dharmeshkumar J.; Synthetic Communications; vol. 39; nb. 12; (2009); p. 2146 - 2150 View in Reaxys

O

O

O

O

O

O

O

Rx-ID: 28954909 View in Reaxys 46/181 Yield

Conditions & References

65 %Chromat.

With Candida antarctica lipase B immobilized, urea hydrogen peroxide addition compound in water, Time= 8h, T= 60 °C , Ionic liquid, Enzymatic reaction, chemoselective reaction Sharma, Upendra K.; Sharma, Nandini; Kumar, Rakesh; Kumar, Rajesh; Sinha, Arun K.; Organic Letters; vol.

11; nb. 21; (2009); p. 4846 - 4848 View in Reaxys

O

O

O

OO

O

O

O

O

O

O

O O

O O

O O

OO

O

O

O

O O

O

Rx-ID: 29045675 View in Reaxys 47/181 Yield

Conditions & References

48 %, 36 %

With AlCl3, aluminium chloride in dichloromethane, Time= 0.0333333h, Inert atmosphere Sanders, Shanina D.; Ruiz-Olalla, Andrea; Johnson, Jeffrey S.; Chemical Communications; nb. 34; (2009); p.

5135 - 5137 View in Reaxys

H N

N

O

O

O

O O

Rx-ID: 9393986 View in Reaxys 48/181 Yield 93 %

Conditions & References With Montmorillonite K-10 clay, pyridinium chlorochromate, Time= 0.0666667h, microwave irradiation Ganguly, Nemai C.; Datta, Mrityunjoy; De, Prithwiraj; Journal of the Indian Chemical Society; vol. 81; nb. 4; (2004); p. 308 - 312 View in Reaxys

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86 %

With (NH4)6[Mo7O24]*4H2O, dihydrogen peroxide in water, acetic acid, Time= 3h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasish; Barik, Sujoy Kumar; Dutta, Sanjoy; Journal of the Indian Chemical Society; vol. 85; nb. 7; (2008); p. 711 - 716 View in Reaxys

82 %

With phosphoric acid, Time= 0.0111111h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Patra, Amarendra; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 45; nb. 2; (2006); p. 537 - 539 View in Reaxys

80 %

With water, phosphorus pentoxide, Time= 0.0111111h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 80; nb. 3; (2003); p. 184 - 186 View in Reaxys

H N

O

O

N

NH 2

O

O

O

O

Rx-ID: 9417786 View in Reaxys 49/181 Yield 95 %

Conditions & References With (NH4)6[Mo7O24]*4H2O, dihydrogen peroxide in water, acetic acid, Time= 1.5h, T= 20 °C Ganguly, Nemai C.; Nayek, Subhasish; Barik, Sujoy Kumar; Dutta, Sanjoy; Journal of the Indian Chemical Society; vol. 85; nb. 7; (2008); p. 711 - 716 View in Reaxys

86 %

With CuCl2*2H2O, Time= 0.0138889h, microwave irradiation Karchaudhuri, Nilay; De, Aparna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 81; nb. 1; (2004); p. 79 - 81 View in Reaxys

80 %

With phosphoric acid, Time= 0.00555556h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Patra, Amarendra; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 45; nb. 2; (2006); p. 537 - 539 View in Reaxys

79 %

With water, phosphorus pentoxide, Time= 0.00555556h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 80; nb. 3; (2003); p. 184 - 186 View in Reaxys O

HO

O

O

O

O

HO

O

O O

Rx-ID: 11100434 View in Reaxys 50/181 Yield 59 %, 13 %

Conditions & References With 2,9-dimethyl-1,10-phenanthroline, oxygen, sodium hydrogencarbonate, gold(I) chloride in water, Time= 24h, T= 100 °C , p= 38002.6Torr Li, Huanrong; Guan, Bingtao; Wang, Wenjin; Xing, Dong; Fang, Zhao; Wan, Xiaobing; Yang, Liping; Shi, Zhangjie; Tetrahedron; vol. 63; nb. 35; (2007); p. 8430 - 8434 View in Reaxys

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Br

HO

Br 2H

O 2H

O

HO

O

O

Rx-ID: 25667604 View in Reaxys 51/181 Yield

Conditions & References 20 :EXAMPLE 20 2-deuterobenzo[d][1,3]dioxole-5-carbaldehyde (Formula XII wherein X1 is D and X2 is H). A solution of 3,4-dihydroxybenzaldehyde (20 mmol) in 60 mL of dimethylformamide (DMF) is treated under argon with 60 mmol of the product of example 1 and 70 mmol of CsF. The mixture is heated in a 140° C. oil bath for 3 h with vigorous stirring. The mixture is then filtered, concentrated in vacuo, and the residue is purified by silica gel flash chromatography (ether/hexanes eluant), yielding the title product.

With cesium fluoride in N,N-dimethyl-formamide, Time= 3h, T= 140 °C Patent; Tung, Roger; US2007/37815; (2007); (A1) English View in Reaxys 2 :Example 2: 2-deuterobenzo[d][l,3]dioxole-5-carbaldehyde (Formula V wherein Y = H and R = formyl).; A solution of 3,4-dihydroxybenzaldehyde (20 mmol) in 60 mL of dimethylformamide (DMF) is treated under argon with 60 mmol of the product of example 1 and 70 mmol of CsF. The mixture is heated in a 140 °C oil bath for 3 h with vigorous stirring. The mixture is then filtered, concentrated in vacuo, and the residue is purified by silica gel flash chromatography (ether/hexanes eluant), yielding the title product.

With cesium fluoride in N,N-dimethyl-formamide, Time= 3h, T= 140 °C Patent; CONCERT PHARMACEUTICALS INC.; WO2007/16431; (2007); (A2) English View in Reaxys

O O

O

O

S

O

O

Rx-ID: 9309023 View in Reaxys 52/181 Yield

Conditions & References

90 %

With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione, β-cyclodextrin in water, acetone, Time= 0.3h, T= 20 °C Somi Reddy; Narender; Mahesh; Nageswar; Rama Rao; Synthetic Communications; vol. 36; nb. 24; (2006); p.

3771 - 3775 View in Reaxys

76 %

Stage 1: With 1-benzenesulfinyl piperidine, trifluoromethylsulfonic anhydride in dichloromethane, Time= 0.333333h, T= -60 °C Stage 2: With water in tetrahydrofuran, dichloromethane, T= -60 - 20 °C Crich, David; Picione, John; Synlett; nb. 9 SPEC. ISS.; (2003); p. 1257 - 1258 View in Reaxys

S O

H N O

O N

O

O

O O

Rx-ID: 9418677 View in Reaxys 53/181 Yield 70 %

Conditions & References With phosphoric acid, Time= 0.00277778h, microwave irradiation Banerjee, Krishna; Mitra, Alok Kumar; Patra, Amarendra; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 45; nb. 2; (2006); p. 537 - 539 View in Reaxys

69 %

With water, phosphorus pentoxide, Time= 0.00555556h, microwave irradiation

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Banerjee, Krishna; Mitra, Alok Kumar; Journal of the Indian Chemical Society; vol. 80; nb. 3; (2003); p. 184 - 186 View in Reaxys H

N 13 C

O

O

13C

O

O

O

Rx-ID: 10078175 View in Reaxys 54/181 Yield

Conditions & References

86 %

With diisobutylaluminium hydride in diethyl ether, Time= 7h, T= -78 °C Haajanen, Kati; Botting, Nigel P.; Steroids; vol. 71; nb. 3; (2006); p. 231 - 239 View in Reaxys

N

O

O

O

O

O

O O

Rx-ID: 10162782 View in Reaxys 55/181 Yield

Conditions & References

83 %

With triethylsilane, triphenylphosphine, palladium diacetate in N,N-dimethyl-formamide, Time= 12h, T= 60 °C Nakanishi, Jun; Tatamidani, Hiroto; Fukumoto, Yoshiya; Chatani, Naoto; Synlett; nb. 6; (2006); p. 869 - 872 View in Reaxys O

O

N

NH

O

N HN

O

O

O

O O

O

Rx-ID: 10549730 View in Reaxys 56/181 Yield 42 %, 32 %

Conditions & References With sodium hydroxide, disodium ethylenediaminetetraacetate dihydrate, mercury(II) oxide in water, Time= 1h, pH= 9, Heating Moehrle; Azodi; Pharmazie; vol. 61; nb. 10; (2006); p. 815 - 822 View in Reaxys

O Cl

O

O

O

O O

isooxyurea

Rx-ID: 12454386 View in Reaxys 57/181 Yield

Conditions & References Reaction Steps: 2 1: K2CO3 / CH2Cl2 / 20 °C 2: 83 percent / triethylsilane; PPh3 / Pd(OAc)2 / dimethylformamide / 12 h / 60 °C With triethylsilane, potassium carbonate, triphenylphosphine, palladium diacetate in dichloromethane, N,N-dimethylformamide Nakanishi, Jun; Tatamidani, Hiroto; Fukumoto, Yoshiya; Chatani, Naoto; Synlett; nb. 6; (2006); p. 869 - 872 View in Reaxys

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O O

O

O

O

O

O

O

Rx-ID: 36572377 View in Reaxys 58/181 Yield

Conditions & References

91 %, 9 %

With NaY-supported PhI(OAc)2, Time= 0.0833333h, T= 130 °C , Microwave irradiation, Solvent, Concentration, Temperature, Time Alvarez, Heiddy Marquez; Barbosa, Dayse P.; Fricks, Alini Tinoco; Aranda, Donato A. G.; Valdes, Ricardo H.; Antunes; Organic Process Research and Development; vol. 10; nb. 5; (2006); p. 941 - 943 View in Reaxys O O

O

O

O

O

O

O

O

O

O

Rx-ID: 36572378 View in Reaxys 59/181 Yield

Conditions & References

29 %, 15 %, 55 %

With [bis(acetoxy)iodo]benzene in dichloromethane, Time= 0.0833333h, T= 50 °C , Microwave irradiation, Time, Temperature, Solvent Alvarez, Heiddy Marquez; Barbosa, Dayse P.; Fricks, Alini Tinoco; Aranda, Donato A. G.; Valdes, Ricardo H.; Antunes; Organic Process Research and Development; vol. 10; nb. 5; (2006); p. 941 - 943 View in Reaxys O O

O

O

O

HO

O

O

O

O

O

O

Rx-ID: 36572379 View in Reaxys 60/181 Yield

Conditions & References

57 %, 12 %, 31 %

With PhI(OAc)2/Al2O3, Time= 0.5h, T= 140 °C , Microwave irradiation Alvarez, Heiddy Marquez; Barbosa, Dayse P.; Fricks, Alini Tinoco; Aranda, Donato A. G.; Valdes, Ricardo H.; Antunes; Organic Process Research and Development; vol. 10; nb. 5; (2006); p. 941 - 943 View in Reaxys O O

O

O

O

O

HO

O

O

Rx-ID: 36572380 View in Reaxys 61/181 Yield

Conditions & References

69 %, 26 %

With PhI(OAc)2/Al2O3, Time= 0.0833333h, T= 110 °C , Microwave irradiation Alvarez, Heiddy Marquez; Barbosa, Dayse P.; Fricks, Alini Tinoco; Aranda, Donato A. G.; Valdes, Ricardo H.; Antunes; Organic Process Research and Development; vol. 10; nb. 5; (2006); p. 941 - 943 View in Reaxys

OH HO

O

O

O

O O

Rx-ID: 3828511 View in Reaxys 62/181 Yield 99 %

Conditions & References With sodium periodate, Ca(OCl)2, ammonium cerium(IV) nitrate in methanol, acetic acid, Time= 0.5h, Electrochemical and Chemical Oxidations

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Torii, Sigeru; Uneyama, Kenji; Ueda, Kyoji; Journal of Organic Chemistry; vol. 49; nb. 10; (1984); p. 1830 - 1832 View in Reaxys 99 %

in sodium hydroxide, hexane, Time= 3h, T= 65 °C , electrolysis or oxidation with NaIO4, ceric ammonium nitrate, Ca(ClO)2 Torii, Sigeru; Uneyama, Kenji; Ueda, Kyoji; Journal of Organic Chemistry; vol. 49; nb. 10; (1984); p. 1830 - 1832 View in Reaxys

91 %

4 :Into a 100 mL four-neck flask equipped with a stirrer and a reflux condenser, 0.10 g of 1,2-(methylenedioxy)-4(propane-1,2-diol)benzene (content:91 wtpercent), 10 mL of acetonitrile (water content 3 wtpercent), 0.05 g of succinimide, 0.05 g of triphenylbismuth and 2.7 g of potassium carbonate were charged. 10 mL of acetonitrile (water content 3 wtpercent) solution in which 0.88 g of 1,2-(methylenedioxy)-4-(propane-1,2-diol)benzene (content:91 wtpercent) was dissolved, and 10 mL of acetonitrile (water content 3 wtpercent) solution in which 0.94 g of bromine was dissolved were added dropwise thereto through parallel at an inner temperature of 55 C over 3 hrs and 3.8 hrs, respectively. The reaction mixture was stirred for 30 minutes to effect reaction at the same temperature and then insoluble matter was removed from the reaction mixture by filtration, and the removed insoluble matter was washed with about 15 mL of acetonitrile, and 34.1 g of an organic phase containing heliotropin was obtained. Content of heliotropin:1.8 wtpercent. Yield:91 percent.

With bromine, potassium carbonate, pyrrolidin-1-yl-2,5-dione, triphenylbismuthine in water, acetonitrile, Time= 7.3h, T= 55 °C Patent; Sumitomo Chemical Company, Limited; EP1609776; (2005); (A1) English View in Reaxys

O

O

O

O

O

O O

Rx-ID: 9894571 View in Reaxys 63/181 Yield

Conditions & References

90 %

With β-cyclodextrin, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in water, acetone, Time= 1.33333h, T= 20 °C Narender; Reddy, M. Somi; Kumar, V. Pavan; Nageswar; Rao, K. Rama; Tetrahedron Letters; vol. 46; nb. 12; (2005); p. 1971 - 1973 View in Reaxys OH

O

O

Cl

O

O

N

O

O

O

O

O

N

O

O

Rx-ID: 9940997 View in Reaxys 64/181 Yield

Conditions & References

46 %

With tetrabutyl ammonium fluoride in tetrahydrofuran, Hass-Bender/Henry reaction Klein, Thomas A.; Schkeryantz, Jeffrey M.; Tetrahedron Letters; vol. 46; nb. 27; (2005); p. 4535 - 4538 View in Reaxys

OH

N

N

N

OH O O

N

N

N

OH O N

N

N

O

O O

O

O O

Rx-ID: 10079356 View in Reaxys 65/181 Yield

Conditions & References With Pd[(-)-sparteine](OAc)2 in toluene, Time= 36h, Heating Sayyed, Iliyas Ali; Kumar, N.S.C. Ramesh; Sudalai; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 44; nb. 7; (2005); p. 1533 - 1535

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View in Reaxys O O

S

O– O

HO

O

O

Na +

O O

Rx-ID: 5212370 View in Reaxys 66/181 Yield

Conditions & References

92 %

With Montmorillonite KSF clay, Time= 0.00277778h, microwave irradiation, Elimination Mitra, Alok Kumar; De, Aparna; Karchaudhuri, Nilay; Journal of Chemical Research - Part S; nb. 9; (1999); p.

560 - 561 View in Reaxys

85 %

With ammonium acetate, Time= 0.0111111h, microwave irradiation Mitra, Alok Kumar; Karchaudhuri, Nilay; De, Aparna; Journal of Chemical Research; nb. 3; (2004); p. 237 - 239 View in Reaxys

O

O

O

O

O

O

Rx-ID: 9715287 View in Reaxys 67/181 Yield

Conditions & References

63 %

With sulfuric acid, 2,3-dicyano-5,6-dichloro-p-benzoquinone in acetonitrile, Time= 5h, T= 80 °C Branytska, Oiena; Neumann, Ronny; Synlett; nb. 9; (2004); p. 1575 - 1576 View in Reaxys

N

Z

O O

O

O O

Rx-ID: 10082031 View in Reaxys 68/181 Yield

Conditions & References With VOF3, trifluoroacetic acid in dichloromethane, ethyl acetate, Time= 1h, T= 0 - 20 °C Liepa, Andris J.; Nearn, Roland N.; Wright, Denis M.J.; Australian Journal of Chemistry; vol. 57; nb. 5; (2004); p.

473 - 482 View in Reaxys

S S

O

O

O

O O

Rx-ID: 3126714 View in Reaxys 69/181 Yield 90 %

Conditions & References With β-cyclodextrin, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in acetone, Time= 2h, T= 20 °C Krishnaveni, N. Srilakshmi; Surendra, K.; Nageswar, Y. V. D.; Rao, K. Rama; Synthesis; nb. 15; (2003); p. 2295 2297 View in Reaxys With triphenylmethyl methyl ether, sodium hydrogencarbonate, Cl(3)HO4, 1.) CH2Cl2, -45 deg C, 7 h, Yield given.

Multistep reaction

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Ohshima, Masahiro; Murakami, Masahiro; Mukaiyama, Teruaki; Chemistry Letters; (1986); p. 1593 - 1596 View in Reaxys

Cl

HO

Br

O

HO

O

O

O

O O

O

O

O

O

Rx-ID: 9342586 View in Reaxys 70/181 Yield

Conditions & References

88 %, 10 %

With caesium carbonate in N,N-dimethyl-formamide, T= 20 - 110 °C Cabiddu, Maria Grazia; Cadoni, Enzo; De Montis, Stefania; Fattuoni, Claudia; Melis, Stefana; Usai, Michele; Tetrahedron; vol. 59; nb. 24; (2003); p. 4383 - 4387 View in Reaxys

O

N

N

O

N

O

O

O

O

O

O

O

O

O

O

O

O

N H

O

Rx-ID: 9476830 View in Reaxys 71/181 Yield

Conditions & References

30 %, 7 %, in toluene, Photolysis 19 % Singh, Pradeep N. D.; Mandel, Sarah M.; Robinson, Rachel M.; Zhu, Zhendong; Franz, Roberto; Ault, Bruce S.; Gudmundsdottir, Anna D.; Journal of Organic Chemistry; vol. 68; nb. 21; (2003); p. 7951 - 7960 View in Reaxys

Z

O

O

O

O O

Rx-ID: 9548204 View in Reaxys 72/181 Yield 78 %

Conditions & References With sodium periodate, osmium(VIII) oxide, N-benzyl-N,N,N-triethylammonium chloride in tetrahydrofuran, water, Time= 0.025h, microwave irradiation Sinha, Arun K.; Joshi, Bhupendra P.; Acharya, Ruchi; Chemistry Letters; vol. 32; nb. 8; (2003); p. 780 - 781 View in Reaxys With oxygen, ozone, acetic acid, zinc in methanol Gonzalez-Serratos, Hugo; Chang, Ruzhang; Pereira, Edna F. R.; Castro, Newton G.; Aracava, Yasco; Melo, Paulo A.; Lima, Patricia C.; Fraga, Carlos A. M.; Barreiro, Eliezer J.; Albuquerque, Edson X.; Journal of Pharmacology and Experimental Therapeutics; vol. 299; nb. 2; (2001); p. 558 - 566 View in Reaxys

O O

pentacarbonyl(1-[N-(2-(ethenyl)phenyl)amino]-1-(1,3-benzodioxol-5-yl)methylidene)chromium

O

O N

O

Rx-ID: 9575346 View in Reaxys 73/181 Yield 51 %, 9 %

Conditions & References in acetonitrile, Time= 0.75h, T= 90 °C Soederberg, Bjoern C. G.; Shriver, James A.; Cooper, Seth H.; Shrout, Timothy L.; Helton, E. Scott; Austin, Lucinda R.; Odens, Herman H.; Hearn, Brian R.; Jones, Paula C.; Kouadio, Tiara N.; Ngi, Tan H.; Baswell, Rachel; Caprara, H. John; Meritt, Mark D.; Mai, Than T.; Tetrahedron; vol. 59; nb. 44; (2003); p. 8775 - 8791

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View in Reaxys O Br

O

O

O

glycocoll ester O

O

Rx-ID: 13948757 View in Reaxys 74/181 Yield

Conditions & References Reaction Steps: 2 1: NaN3 / ethanol; acetic acid; H2O / cooling 2: 19 percent / toluene / Photolysis With sodium azide in ethanol, water, acetic acid, toluene Singh, Pradeep N. D.; Mandel, Sarah M.; Robinson, Rachel M.; Zhu, Zhendong; Franz, Roberto; Ault, Bruce S.; Gudmundsdottir, Anna D.; Journal of Organic Chemistry; vol. 68; nb. 21; (2003); p. 7951 - 7960 View in Reaxys

O

O

O

HO

O

O

Rx-ID: 23858892 View in Reaxys 75/181 Yield

Conditions & References

86%

R.7.c : c c Title Compound To a mixture of 1.18 mL (13.50 mmol) of oxalyl chloride and 17.2 mL of CH2Cl2, cooled to -78° C., a mixture of 2.1 mL of DMSO and 3.9 mL of CH2Cl2 was added dropwise and under argon, and the resulting mixture was stirred for 5 min.

Next, 1.88 g (12.36 mmol) of 3,4-(methylenedioxy)phenylmethanol (obtained in the preceding section) dissolved in a mixture of 1.6 mL of DMSO and 1.6 mL of CH2Cl2 was added dropwise and the mixture was stirred for 30 min at -78° C. Then, 14.7 mL (106 mmol) of Et3N was added, the mixture was stirred for 10 min at the same temperature and was then allowed to warm up to room temperature.

It was poured into a mixture of ice and H2O, extracted with CH2Cl2 and the combined organic phases were dried over MgSO4 and concentrated, yielding 1.6 g of the title compound of the example as an oil (86percent yield).

1H-NMR

(300 MHz, CDCl3 δ TMS): 6.08 (s, 2H), 6.93 (d, J=7.8 Hz, 1H), 7.34 (s, 1H), 7.42 (d, J=7.8 Hz, 1H), 9.81 (s,

1H).

Patent; Rosales, Carmen Almansa; Gonzalez Gonzalez, Concepcion; Torres Barreda, Maria Carmen; US2003/176481; (2003); (A1) English View in Reaxys OH O

O

OH

O O

O

O

O

H

O

O

O

O

O

O O

O O

O

O

O

racemate

Rx-ID: 8998838 View in Reaxys 76/181 Yield 26 %, 21 %, 20 %, 17 %

Conditions & References With acetoxytrimethylsilane, boron trifluoride diethyl etherate in cyclohexane, Time= 4h, Prins cyclisation Crosby, Stuart R.; Harding, John R.; King, Clare D.; Parker, Gregory D.; Willis, Christine L.; Organic Letters; vol. 4; nb. 4; (2002); p. 577 - 580

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View in Reaxys

HO O

HO

O

O

methylene dihalide

O

Rx-ID: 9117524 View in Reaxys 77/181 Yield

Conditions & References With caesium carbonate in N,N-dimethyl-formamide Guay, Daniel; Hamel, Pierre; Blouin, Marc; Brideau, Christine; Chan, Chi Chung; Chauret, Nathalie; Ducharme, Yves; Huang, Zheng; Girard, Mario; Jones, Tom R; Laliberte, France; Masson, Paul; McAuliffe, Malia; Piechuta, Hanna; Silva, Jose; Young, Robert N; Girard, Yves; Bioorganic and medicinal chemistry letters; vol.

12; nb. 11; (2002); p. 1457 - 1461 View in Reaxys OH O

O

OH

O

O

O

O O

O

O

O

O O

O

O O

O

O

O

O

Rx-ID: 9943386 View in Reaxys 78/181 Yield

Conditions & References

24 %, 16 With acetoxytrimethylsilane, boron trifluoride diethyl etherate in cyclohexane, Time= 3h %, 8 %, 34 Crosby, Stuart R; Harding, John R; King, Clare D; Parker, Gregory D; Willis, Christine L; Organic letters; vol. 4; % nb. 20; (2002); p. 3407 - 3410 View in Reaxys O HO

O

O

O

O

O

Rx-ID: 8935605 View in Reaxys 79/181 Yield 84 % Spectr.

Conditions & References With hydrogen, trimethylacetic anhydride, tetrakis(triphenylphosphine) palladium(0) in tetrahydrofuran, Time= 24h, T= 80 °C , p= 22501.8Torr Nagayama; Shimizu; Yamamoto; Bulletin of the Chemical Society of Japan; vol. 74; nb. 10; (2001); p. 1803 - 1815 View in Reaxys

O

O

O

O

isooxyurea O

Rx-ID: 11908336 View in Reaxys 80/181 Yield

Conditions & References Reaction Steps: 2 1: KOH / butan-1-ol 2: O2-O3; Zn; AcOH / methanol With potassium hydroxide, oxygen, ozone, acetic acid, zinc in methanol, butan-1-ol

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Gonzalez-Serratos, Hugo; Chang, Ruzhang; Pereira, Edna F. R.; Castro, Newton G.; Aracava, Yasco; Melo, Paulo A.; Lima, Patricia C.; Fraga, Carlos A. M.; Barreiro, Eliezer J.; Albuquerque, Edson X.; Journal of Pharmacology and Experimental Therapeutics; vol. 299; nb. 2; (2001); p. 558 - 566 View in Reaxys OH HO

O O

O

O

O

O

Rx-ID: 320020 View in Reaxys 81/181 Yield

Conditions & References With silver benzoate-iodo, benzene Raman; Current Science; vol. 27; (1958); p. 22 View in Reaxys

96 %Chromat.

With sodium peroxodisulphate, silver nitrate in dichloromethane, water, Time= 5h, Reflux, Reagent/catalyst Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco; Organic Process Research and Development; vol. 4; nb. 6; (2000); p. 534 - 543 View in Reaxys

OH O

Si

O

O

O

O

Rx-ID: 8519395 View in Reaxys 82/181 Yield

Conditions & References

75 %

Stage 1: With tert.-butylnitrite in benzene, Nitrosation Stage 2: in benzene, T= 0 °C , Photolysis, Elimination, Further stages.

Paredes; Alonso; Journal of Organic Chemistry; vol. 65; nb. 8; (2000); p. 2292 - 2304 View in Reaxys

O

OH O

Pb

O

O O

O

O

Si

O

O

O

O

O

O

O O O

O

O

Rx-ID: 11012168 View in Reaxys 83/181 Yield

Conditions & References

37 %, 58 %

in benzene, Heating, Acetoxylation, elimination Paredes; Alonso; Journal of Organic Chemistry; vol. 65; nb. 8; (2000); p. 2292 - 2304 View in Reaxys

OH HO

OH O

O

OH

O O

Rx-ID: 36657759 View in Reaxys 84/181 Yield

Conditions & References Reaction Steps: 2 1: CuCl2·2H2O / ethyl acetate; water / 5 h / 60 °C / |Inert atmosphere 2: sodium hydroxide; tetrabutylammomium bromide With CuCl2·2H2O, tetrabutylammomium bromide, sodium hydroxide in water, ethyl acetate Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco; Organic Process Research and Development; vol. 4; nb. 6; (2000); p. 534 - 543

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View in Reaxys OH –

O

O

4

Si

OH O

Pb4+

O

O

O

O

O

O

O O

Rx-ID: 8526411 View in Reaxys 85/181 Yield

Conditions & References

58 %, 37 %

Stage 1: in benzene, Heating, Oxidation Stage 2: With silica gel, Decomposition Paredes, Maria Dolores; Alonso, Ricardo; Tetrahedron Letters; vol. 40; nb. 20; (1999); p. 3973 - 3976 View in Reaxys

O

O O

Rx-ID: 5432371 View in Reaxys 86/181 Yield

Conditions & References Holum; Journal of Organic Chemistry; vol. 26; (1961); p. 4814,4815 View in Reaxys Feugeas; Bulletin de la Societe Chimique de France; (1964); p. 1892 View in Reaxys Indo; Nippon Kagaku Zasshi; vol. 81; (1960); p. 1106,1107-1109; ; nb. 373; (1962) View in Reaxys Fujita; Ueda; Nippon Kagaku Zasshi; vol. 82; (1961); p. 400,402; ; vol. 56; nb. 13027; (1962) View in Reaxys By following the procedures of Example 1A and substituting for 3-nitrobenzaldehyde with the following: ...

3-methoxycarbonyl-4-methyl-benzaldehyde; 4-carboxybenzaldehyde; 4-carbamoylbenzaldehyde; 4-N,N-dimethylcarbamoylbenzaldehyde; and 3,4-methylenedioxybenzaldehyde; Patent; Syntex U.S.A. Inc.; US5716954; (1998); (A1) English View in Reaxys By following the procedures of Example 10A and substituting 3-chlorobenzaldehyde with the following: ...

3-methoxycarbonyl-4-methyl-benzaldehyde; 4-carboxybenzaldehyde; 4-carbamoylbenzaldehyde; 4-N,N-dimethylcarbamoylbenzaldehyde; and 3,4-methylenedioxybenzaldehyde; Patent; Syntex U.S.A. Inc.; US5716954; (1998); (A1) English View in Reaxys 3.v : EXAMPLE 3 (v) 22.26 g (220 mmol) of triethylamine (31 ml), i.e., a concentration of 3.49 moles/1.

2 bar of carbon monoxide followed by 7 bar of hydrogen were then introduced.

The contents of the reactor, agitated by a reciprocating shaking system, were heated to 170° C. and then connected to a reservoir containing a 1/1 mixture of carbon monoxide/hydrogen, the pressure drop in which made it possible to monitor the progress of the reaction.

The pressure in the autoclave was maintained at 15 bar during the period of the experiment.

These conditions were maintained for 4 hours.

The contents of the autoclave were degassed.

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The initial rate of absorption of the CO/H2 mixture rose to 47 mmoles.h-1.

7.56 g of piperonal were formed and the conversion rate of bromomethylenedioxybenzene rose to 56percent.

Patent; Rhone-Poulenc Chimie; US4978801; (1990); (A1) English View in Reaxys The following list of compounds exemplifies aromatic and heterocyclic aldehydes useful in carrying out the first step of the processes of this invention leading to the compounds of Formula I. Benzaldehyde, ...

4-Pyridinecarboxaldehyde, Pyrrole-2-carboxaldehyde, 2-Thiophenecarboxaldehyde, N-Ethyl-3-carbazolecarboxaldehyde, Piperonal, 2-Methyl-1-n-octylindole-3-carboxaldehyde, 1-n-Butyl-2-phenylindole-3-carboxaldehyde, 4-(N-Ethylbenzylamino)benzaldehyde, ...

Patent; The Hilton-Davis Chemical Co.; US4595768; (1986); (A1) English View in Reaxys A few illustrative examples of preferred aldehydes include ...

2-naphthaldehyde pentafluorobenzaldehyde phenanthrene-9-carboxaldehyde o-phthalicdicarboxaldehyde piperonal 1-pyrenecarboxaldehyde salicylaldehyde terephthaldicarboxaldehyde Patent; Ethyl Corporation; US4837327; (1989); (A1) English View in Reaxys Following essentially the same procedure as above but using an equivalent amount of ... c. 3,4-dimethoxybenzaldehyde; d. 3-trifluoromethylbenzaldehyde; e. 3,4-methylenedioxybenzaldehyde; f. 2-thiophenealdehyde; ...

Patent; Sandoz, Inc.; US3932430; (1976); (A1) English View in Reaxys IV : EXAMPLE IV EXAMPLE IV 152 Mg of 3,4-methylenedioxy-benzyl alcohol, 500 mg of silver silicate and 30 ml of benzene were added to the flask described in Example II and the mixture was refluxed for 45 minutes and was then filtered to obtain 139 mg of 3,4methylenedioxy-benzaldehyde melting at 36.8°C. Patent; Roussel-UCLAF; US3941811; (1976); (A1) English View in Reaxys Substitution of the following aldehydes: ... (b) Naphthalene-2-carboxaldehyde (c) 2,3-Dihydro-1,4-benzodioxin-6-carboxaldehyde (d) 1,3-Benzodioxole-5-carboxaldehyde (e) 3-Methylbenzaldehyde ...

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Patent; Smith Kline and French Laboratories Limited; US4185103; (1980); (A1) English View in Reaxys

O

HO

O

O

N

O

HO

O

Rx-ID: 25393909 View in Reaxys 87/181 Yield

Conditions & References 6 : EXAMPLE 6 EXAMPLE 6 The same procedure is carried out as in example 1, charging 3,4-dihydroxybenzaldehyde in a solution of NMP instead of catechol.

At the end of the reaction after separation by distillation under vacuum (residue of 10 mmHg) 141.6 g of pure 3,4methylenedioxybenzaldehyde are obtained.

Patent; Borregaard Italia S.p.A.; EP877023; (1998); (A1) English View in Reaxys

O

H 2N

O

O

O

O

N

O

N O

O

O

O

O

Rx-ID: 4763030 View in Reaxys 88/181 Yield 95 %

Conditions & References With sodium hypochlorite in ethanol, Time= 0.25h, Ambient temperature Yamazaki, Shigekazu; Synthetic Communications; vol. 27; nb. 20; (1997); p. 3559 - 3564 View in Reaxys

N

Z

OH

O O

O

O O

Rx-ID: 3826375 View in Reaxys 89/181 Yield 90 %

Conditions & References With [Ag(py)2MnO4] in dichloromethane, Time= 0.0333333h, Ambient temperature Firouzabadi, H.; Sardarian, A.; Synthetic Communications; vol. 13; nb. 10; (1983); p. 863 - 866 View in Reaxys

86 %

With CPCC in dichloromethane, Time= 2h, Heating Baltork; Pouranshirvani; Synthetic Communications; vol. 26; nb. 1; (1996); p. 1 - 7 View in Reaxys

75 %

With dicyclohexyl-carbodiimide, pyridinium chlorochromate in chloroform, ethyl acetate, Time= 0.5h, T= 30 °C Bhat, Neelima Balkrishen; Bhaduri, A. P.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 24; (1985); p. 1286 - 1287 View in Reaxys

70 %

With bis(2,2'-bipyridyl) copper(II) permanganate in dichloromethane, Time= 0.15h Firouzabadi, H.; Sardarian, A. R.; Naderi, M.; Vessal, B.; Tetrahedron; vol. 40; nb. 23; (1984); p. 5001 - 5004 View in Reaxys

70 %

With Zn(BiO3)2 in toluene, Time= 1.5h, Heating Firouzabadi; Mohammadpoor-Baltork; Synthetic Communications; vol. 24; nb. 4; (1994); p. 489 - 494 View in Reaxys

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62 %

With lt;(Py)2Aggt;2Cr2O7 in benzene, Time= 5h, Heating Firouzabadi, H.; Seddighi, M.; Ahmadi, Z. Arab; Sardarian, A. R.; Synthetic Communications; vol. 19; nb. 19; (1989); p. 3385 - 3396 View in Reaxys

60 %

With barium permanganate in acetonitrile, Time= 7h, Heating Firouzabadi, H.; Mottaghineiad, E.; Seddighi, M.; Synthetic Communications; vol. 19; nb. 20; (1989); p. 3469 3476 View in Reaxys

30 %

With lt;Ce(NO3)3gt;2CrO4 in benzene, Time= 8h, Heating Firouzabadi, H.; Iranpoor, N.; Parham, H.; Tootan, J.; Synthetic Communications; vol. 14; nb. 7; (1984); p. 631 638 View in Reaxys H

H

HO

14C 2

O

O

14C

O

O

O

Rx-ID: 4443849 View in Reaxys 90/181 Yield

Conditions & References

83.7 %

With pyridine, chromium(VI) oxide, Time= 2.5h, T= 0 - 20 °C Kurosawa; Kanamaru; Nishioka; Journal of Labelled Compounds and Radiopharmaceuticals; vol. 38; nb. 3; (1996); p. 285 - 297 View in Reaxys F

C

F

F

O

S O

O

O

O

O

O

O

O

Rx-ID: 4469110 View in Reaxys 91/181 Yield

Conditions & References

67 %

With palladium diacetate, (C8H17)3SiH, 1,3-bis-(diphenylphosphino)propane, triethylamine in N,N-dimethyl-formamide, Time= 8h, T= 70 °C Kotsuki, Hiyoshizo; Datta, Probal Kanti; Suenaga, Hitoshi; Synthesis; nb. 4; (1996); p. 470 - 472 View in Reaxys

O

O

O

O

S

O O

Rx-ID: 4641449 View in Reaxys 92/181 Yield 98 %

Conditions & References With periodic acid in tetrahydrofuran, diethyl ether, Time= 0.0833333h, Ambient temperature Shi, Xiao-Xin; Khanapure, Subhash P.; Rokach, Joshua; Tetrahedron Letters; vol. 37; nb. 25; (1996); p. 4331 4334 View in Reaxys O

N

Z

OH

O O

O

O

HO

O

O O

Rx-ID: 3826376 View in Reaxys 93/181

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Yield

Conditions & References

15.5 %, 65 %

With sodium hypochlorite in acetonitrile, Time= 0.5h, Ambient temperature Khurana, Jitender Mohan; Ray, Abhijit; Sahoo, Prabhat Kumar; Bulletin of the Chemical Society of Japan; vol.

67; nb. 4; (1994); p. 1091 - 1093 View in Reaxys

E

O O

O O

O

O

O

O

O

HO

O

O

O

O

O

O

O

O

O O racemate

Rx-ID: 3824787 View in Reaxys 94/181 Yield

Conditions & References

15 %, 14 With chromium(VI) oxide, perchloric acid, acetonitrile, Time= 3h, T= 0 - 5 °C , Further byproducts given %, 10 %, 4 Kuo; Lin; Chemical and Pharmaceutical Bulletin; vol. 41; nb. 9; (1993); p. 1507 - 1512 % View in Reaxys

E

O O

O

O O

O

O

O

O

O

O

O

O

O

O

O

O

O

O O racemate

racemate

Rx-ID: 3824788 View in Reaxys 95/181 Yield

Conditions & References

15 %, 14 With chromium(VI) oxide, perchloric acid, acetonitrile, Time= 3h, T= 0 - 5 °C , Further byproducts given %, 6 %, 10 Kuo; Lin; Chemical and Pharmaceutical Bulletin; vol. 41; nb. 9; (1993); p. 1507 - 1512 % View in Reaxys 14 %, 10 With chromium(VI) oxide, perchloric acid, acetonitrile, Time= 3h, T= 0 - 5 °C , Further byproducts given %, 6 %, 15 Kuo; Lin; Chemical and Pharmaceutical Bulletin; vol. 41; nb. 9; (1993); p. 1507 - 1512 % View in Reaxys 15 %, 10 With chromium(VI) oxide, perchloric acid, acetonitrile, Time= 3h, T= 0 - 5 °C , Further byproducts given %, 6 %, 14 Kuo; Lin; Chemical and Pharmaceutical Bulletin; vol. 41; nb. 9; (1993); p. 1507 - 1512 % View in Reaxys

HO

O O

O

O O

O

Rx-ID: 1760410 View in Reaxys 96/181

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Yield

Conditions & References With lt;Ru(OH)2lt;IO5(OH)gt;2gt;(6-), Aliquatreg; 336 in potassium hydroxide, 1,2-dichloro-ethane, Time= 3h, Ambient temperature, Yield given. Yields of byproduct given 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); nb. 24; (1992); p. 3489 - 3496 View in Reaxys

S

O

O

O

S

HS

SH

O

O

Rx-ID: 2045732 View in Reaxys 97/181 Yield 91 %

Conditions & References With anhydrous magnesium perchlorate, water, methylene green in acetonitrile, Irradiation Epling, Gary A.; Wang, Qingxi; Tetrahedron Letters; vol. 33; nb. 40; (1992); p. 5909 - 5912 View in Reaxys

NH 2 O

O

O

O

O O

Rx-ID: 2330943 View in Reaxys 98/181 Yield 99 %

Conditions & References With samarium diiodide, phosphoric acid in tetrahydrofuran, Time= 0.000833333h, Ambient temperature Kamochi; Kudo; Tetrahedron; vol. 48; nb. 21; (1992); p. 4301 - 4312 View in Reaxys OH HO

trichloro-1,1,1-ethane

O O

O

O

O O

Rx-ID: 24969250 View in Reaxys 99/181 Yield 79%

Conditions & References EXAMPLE EXAMPLE The following are mixed together under agitation at ambient temperature: 294.23 g (1.5 mole) of 3,4-methylenedioxy mandelic acid; 562 g of water; 258.75 g of 37percent hydrochloric acid being 2.625 moles; 2.1 g of 69percent nitric acid being 23 mmoles.

The suspension obtained is heated under agitation at 43°+-2° C., then 103.5 mg (1.5 mmole) of sodium nitrite dissolved in 4 g of water is introduced rapidly at this temperature, then 107.5 g of 69percent nitric acid, being 1.177 mole, is introduced slowly, over about three hours, in such a way so that the temperature of the reaction medium is maintained at between 40° and 50° C. without using external heating or cooling.

At the end of the introduction, the reaction medium is left for one our under agitation at 43°+-2° C., then it is cooled down to ambient temperature and finally extraction takes place three times with 600 g of trichloro-1,1,1-ethane.

The re-united organic phases are then washed successively, once with water, three times with a saturated aqueous solution of sodium hydrogen carbonate and finally once with water before being concentrated under reduced pressure.

Thus 220 g (1.46 mole) of crude piperonal is isolated which is purified by distillation under reduced pressure.

Thus 178 g (1.186 mole) of pure piperonal is isolated distilling at 106° C. under a vacuum of 2.4 mbars and having a melting point of 37°+1° C. The yield is established at 79percent of the theoretically calculated value relative to the 3,4-methylenedioxy mandelic acid used.

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With hydrogenchloride, anhydrous sodium hydrogen carbonate, nitric acid, sodium nitrite in water Patent; Societe Francaise Hoechst; US5095128; (1992); (A1) English View in Reaxys

Cl

Br

HO

HO

O

O O

O

Rx-ID: 3799196 View in Reaxys 100/181 Yield 89 %

Conditions & References With caesium carbonate in N,N-dimethyl-formamide, Time= 2h, T= 110 °C , or in MeCN, 8h, reflux Zelle; McClellan; Tetrahedron Letters; vol. 32; nb. 22; (1991); p. 2461 - 2464 View in Reaxys

H 2N

O

O

OH

O

O

N H

O

O

O

O

O

O

N H

O

O

Rx-ID: 1772015 View in Reaxys 101/181 Yield

Conditions & References

52 %, 7 %, With oxygen, copper in acetonitrile, Time= 24h, T= 60 °C 3% Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Tetrahedron; vol. 46; nb. 8; (1990); p. 2835 - 2844 View in Reaxys O H 2N

O

HO

O

O

O

N H

O

O

O

N H

O

O

O O

Rx-ID: 1772016 View in Reaxys 102/181 Yield

Conditions & References

48 %, 7 %, With oxygen, copper in acetonitrile, Time= 24h, T= 60 °C 3% Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Tetrahedron; vol. 46; nb. 8; (1990); p. 2835 - 2844 View in Reaxys

H 2N

O

O

N H

O

O

O

O

O

O

O

N H

O O

Rx-ID: 1772029 View in Reaxys 103/181 Yield

Conditions & References

52 %, 3 %, With oxygen, acetic acid, copper in acetonitrile, Time= 24h, T= 60 °C 7% Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Tetrahedron; vol. 46; nb. 8; (1990); p. 2835 - 2844 View in Reaxys 7 %, 3 %, 52 %

With oxygen, acetic acid, copper in acetonitrile, Time= 24h, T= 60 °C Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Tetrahedron; vol. 46; nb. 8; (1990); p. 2835 - 2844 View in Reaxys

52 %, 7 %, With oxygen, acetic acid, copper in acetonitrile, Time= 24h, T= 60 °C , other amines, kinetic isotope effect, Mecha3% nism Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Tetrahedron; vol. 46; nb. 8; (1990); p. 2835 - 2844 View in Reaxys

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O

O

O

OH

O

Rx-ID: 2061810 View in Reaxys 104/181 Yield

Conditions & References With tert.-butylhydroperoxide, titanium(IV) isopropylate Krohn, Karsten; Khanbabaee, Karamali; Rieger, Hagen; Chemische Berichte; vol. 123; nb. 6; (1990); p. 1357 1364 View in Reaxys

O

O O

N

O

O

O

O

Rx-ID: 2222922 View in Reaxys 105/181 Yield

Conditions & References Yield given. Multistep reaction Urpi, Feelix; Vilarrasa, Jaume; Tetrahedron Letters; vol. 31; nb. 51; (1990); p. 7499 - 7500 View in Reaxys

O O S S

O

O

OH

O O

O

O

O

O O

O

O O

racemate

Rx-ID: 2633622 View in Reaxys 106/181 Yield

Conditions & References

26 mg, 30 %

With mercury(II) trifluoroacetate in tetrahydrofuran, Time= 48h, Ambient temperature Pelter, Andrew; Ward, Robert S.; Pritchard, Martyn C.; Kay, I. Trevor; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1988); p. 1603 - 1614 View in Reaxys

OH N+

O N

O

O

I–

N I–

O

O

N+

Rx-ID: 2634300 View in Reaxys 107/181 Yield

Conditions & References With potassium carbonate in benzene, Yield given Ohta, Shunsaku; Hayakawa, Satoshi; Nishimura, Kazuko; Okamoto, Masao; Chemical and Pharmaceutical Bulletin; vol. 35; nb. 3; (1987); p. 1058 - 1069 View in Reaxys OH

N

O N

O

O

O O

alkali

Rx-ID: 20097877 View in Reaxys 108/181 Yield

Conditions & References Reaction Steps: 2 1: ethyl acetate / Heating

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2: 10 percent potassium carbonate / benzene With potassium carbonate in ethyl acetate, benzene Ohta, Shunsaku; Hayakawa, Satoshi; Nishimura, Kazuko; Okamoto, Masao; Chemical and Pharmaceutical Bulletin; vol. 35; nb. 3; (1987); p. 1058 - 1069 View in Reaxys O HN

O

O

N

O O

O

O

O

O

O

O

Rx-ID: 2331496 View in Reaxys 109/181 Yield

Conditions & References

47 %, 23 %

in dichloromethane, Time= 12h, Ambient temperature El-Din, Ahmed Moukhtar Nour; Mourad, Aboul-Fetouh El-Said; Mekamer, Ramadan; Heterocycles; vol. 23; nb.

5; (1985); p. 1155 - 1160 View in Reaxys

23 %, 47 %

in dichloromethane, Time= 12h, Ambient temperature El-Din, Ahmed Moukhtar Nour; Mourad, Aboul-Fetouh El-Said; Mekamer, Ramadan; Heterocycles; vol. 23; nb.

5; (1985); p. 1155 - 1160 View in Reaxys

OH N+

O N

O

O

I–

O

O

Rx-ID: 2634299 View in Reaxys 110/181 Yield

Conditions & References

92.8 % Chromat.

With potassium carbonate in benzene, Time= 2h, T= 60 °C Ohta, Shunsaku; Hayakawa, Satoshi; Nishimura, Kazuko; Okamoto, Masao; Tetrahedron Letters; vol. 25; nb.

30; (1984); p. 3251 - 3254 View in Reaxys

OH N

O N

O

O

O

O

Rx-ID: 21454032 View in Reaxys 111/181 Yield

Conditions & References Reaction Steps: 2 1: ethyl acetate / 2 h / Heating 2: 92.8 percent Chromat. / K2CO3 / benzene / 2 h / 60 °C With potassium carbonate in ethyl acetate, benzene Ohta, Shunsaku; Hayakawa, Satoshi; Nishimura, Kazuko; Okamoto, Masao; Tetrahedron Letters; vol. 25; nb.

30; (1984); p. 3251 - 3254 View in Reaxys

O

O

O

O

O

O

O

O

O

Br

OH

Rx-ID: 1799464 View in Reaxys 112/181

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Yield

Conditions & References With n-butyllithium, nitrobenzene, 1.) THF, hexane, -75 deg C, 50 min.; 2.) -75 deg C, 4h, -> room temp., Yield given. Multistep reaction Sinhababu, Achintya K.; Borchardt, Ronald T.; Journal of Organic Chemistry; vol. 48; nb. 12; (1983); p. 1941 1944 View in Reaxys

HO

O

N H

O

O

O

O

Rx-ID: 2548875 View in Reaxys 113/181 Yield

Conditions & References With aluminum oxide, N-chloro-succinimide, 1.) methylene chloride, room temp., 6h; 2.) 0.33h, Yield given. Multistep reaction Meyers, A. I.; Himmelsbach, Richard J.; Reuman, Michael; Journal of Organic Chemistry; vol. 48; nb. 22; (1983); p. 4053 - 4058 View in Reaxys

Cl Cl

O Cl O

Cl

O

O

O

N

O

Cl

O

Cl

O

O

O

N

O

O

O

O

O

O

HO

Rx-ID: 2626984 View in Reaxys 114/181 Yield

Conditions & References

13 %

With bis-(trifluoroacetoxy)-iodo-benzene, methyloxirane in dichloromethane, Time= 0.5h, T= -10 °C , Yields of byproduct given White, James D.; Chong, Wesley K. M.; Thirring, Klaus; Journal of Organic Chemistry; vol. 48; nb. 13; (1983); p.

2300 - 2302 View in Reaxys

HO O

O

O

HO

O

Br

Rx-ID: 21115039 View in Reaxys 115/181 Yield

Conditions & References Reaction Steps: 2 1: 85 percent / KF / dimethylformamide / 2 h / 105 °C 2: 1.) n-BuLi; 2.) nitrobenzene / 1.) THF, hexane, -75 deg C, 50 min.; 2.) -75 deg C, 4h, -> room temp.

With potassium fluoride, n-butyllithium, nitrobenzene in N,N-dimethyl-formamide Sinhababu, Achintya K.; Borchardt, Ronald T.; Journal of Organic Chemistry; vol. 48; nb. 12; (1983); p. 1941 1944 View in Reaxys

O N

O O

O

O O

Rx-ID: 21125800 View in Reaxys 116/181

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Yield

Conditions & References Reaction Steps: 2 1: 92 percent / DIBAL / diethyl ether / 3.5 h / Ambient temperature 2: 1.) NCS; 2.) alumina / 1.) methylene chloride, room temp., 6h; 2.) 0.33h With aluminum oxide, N-chloro-succinimide, diisobutylaluminium hydride in diethyl ether Meyers, A. I.; Himmelsbach, Richard J.; Reuman, Michael; Journal of Organic Chemistry; vol. 48; nb. 22; (1983); p. 4053 - 4058 View in Reaxys

Cl

Cl Cl

O N+ O

O

O

Cl –

O

HO

O

O O

Rx-ID: 21128626 View in Reaxys 117/181 Yield

Conditions & References Reaction Steps: 2 1: CHCl3 / 12 h / 25 °C 2: <bis(trifluoroacetoxy)iodo>benzene, propylene oxide / CH2Cl2 / 0.5 h / -10 °C With bis-(trifluoroacetoxy)-iodo-benzene, methyloxirane in dichloromethane, chloroform White, James D.; Chong, Wesley K. M.; Thirring, Klaus; Journal of Organic Chemistry; vol. 48; nb. 13; (1983); p.

2300 - 2302 View in Reaxys

O I

O

O O

O O

Br

O O

O O O

O O

O

O

O

O

O

O

O

O

O

O

O O

O

O

O

O O O

O O

O O

Rx-ID: 2331094 View in Reaxys 118/181 Yield

Conditions & References

59 %

With copper, Time= 0.583333h, T= 225 °C , Further byproducts given Brown, Eric; Robin, Jean-Pierre; Dhal, Robert; Tetrahedron; vol. 38; nb. 16; (1982); p. 2569 - 2580 View in Reaxys

O O Br

O

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O O O

O O

O

O

O

O

O

O

O

O

O

O

O O

O

O

O

O O O

O O

O O

Rx-ID: 2331152 View in Reaxys 119/181 Yield

Conditions & References

59 %

With (iodo-2 trimethoxy-3,4,5 benzyl)-3-butanolide-4, copper, Time= 0.583333h, T= 225 °C , Further byproducts given Brown, Eric; Robin, Jean-Pierre; Dhal, Robert; Tetrahedron; vol. 38; nb. 16; (1982); p. 2569 - 2580 View in Reaxys

O

O

N

O

O

Na +

O–

O

O

Rx-ID: 3177704 View in Reaxys 120/181 Yield

Conditions & References

100 %

With hydrogenchloride, Time= 0.0416667h, Ambient temperature, pH = 4-6, regeneration of aldehyde, Product distribution Ohta, Shunsaku; Okamoto, Masao; Chemical & Pharmaceutical Bulletin; vol. 28; nb. 6; (1980); p. 1917 - 1919 View in Reaxys

2H

O

O

O

O

O

O

O

O

O

Rx-ID: 591639 View in Reaxys 121/181 Yield

Conditions & References With lithium aluminium deuteride, diethyl ether, anschliessend mit Blei(IV)-acetat Wiberg; Stewart; Journal of the American Chemical Society; vol. 77; (1955); p. 1786,1788 View in Reaxys

O O

N

O

N

O O

O O

O

sodium-salt of/the/ chloromagnesio-phenyl-acetic acid

NH 2

O

O

O HO

O

O

Rx-ID: 5532214 View in Reaxys 122/181 Yield

Conditions & References anschliessend mit wss. Salzsaeure

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Marecoff; Doklady Bolgarskoi Akademii Nauk; vol. 6; nb. 3; (1953); p. 29; ; (1955); p. 8304 View in Reaxys O O

Cl

O

O

O

O

Rx-ID: 150332 View in Reaxys 123/181 Yield

Conditions & References With Pd-BaSO4, N,N-dimethyl-aniline, acetone, Hydrogenation Kondo et al.; Itsuu Kenkyusho Nempo; nb. 2; (1951); p. 11; dtsch. Ref. S. 48; ; (1953); p. 7519 View in Reaxys

O -1 O

O

O

CdCl 2

O

O

-1 CdCl 2

Rx-ID: 26581451 View in Reaxys 124/181 Yield

Conditions & References in ethanol, mixing rather concd. alcoholic soln. of CdCl2 with piperonal Marini-Bettolo, G.; Baroni, G.; Ric. Sci. Ricostr.; vol. 17; (1947); p. 435 - 436 ; (from Gmelin) View in Reaxys in ethanol, mixing rather concd. alcoholic soln. of CdCl2 with piperonal vol. Cd: SVol.; 20.1, page 781 - 787 ; (from Gmelin) View in Reaxys

O -1 O

O

O

CdCl 2

O O

-1 CdCl 2

Rx-ID: 26607267 View in Reaxys 125/181 Yield

Conditions & References in water, decompn. in hot water Marini-Bettolo, G.; Baroni, G.; Ric. Sci. Ricostr.; vol. 17; (1947); p. 435 - 436 ; (from Gmelin) View in Reaxys in water, decompn. in hot water vol. Cd: SVol.; 20.1, page 781 - 787 ; (from Gmelin) View in Reaxys

O

O

O

O O

O Cl 2Hg

Rx-ID: 26511108 View in Reaxys 126/181 Yield

Conditions & References With mercury dichloride in water Marini-Bettolo, G. B.; Paoloni, L.; Gazzetta Chimica Italiana; vol. 75; (1945); p. 78 - 86 View in Reaxys

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vol. Hg: MVol.B2; 81, page 566 - 568 ; (from Gmelin) View in Reaxys

HO

1,2-bis<2-(-p-toluenesulfonyloxy)ethoxy>amine

O

O O

HO

Rx-ID: 22404383 View in Reaxys 127/181 Yield

Conditions & References Reaction Steps: 3 1: aq.-ethanolic NaOH-solution / 110 °C 2: petroleum ether; zinc chloride; water; hydrochloric acid 3: hexamethylenetetramine; aqueous ethanol With hydrogenchloride, sodium hydroxide, ethanol, 1,3,5,7-tetra-azatricyclo[5.1.1.13,5]decane, water, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p.

2178 View in Reaxys Reaction Steps: 3 1: aq.-ethanolic NaOH-solution / 110 °C 2: paraformaldehyde; zinc chloride; petroleum ether / Reagens 4: Chlorwasserstoff 3: hexamethylenetetramine; aqueous ethanol With sodium hydroxide, formaldehyd, ethanol, 1,3,5,7-tetra-azatricyclo[5.1.1.13,5]decane, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p.

2178 View in Reaxys

S O

H N O

O

O

O O

N H

O O

Rx-ID: 416821 View in Reaxys 128/181 Yield

Conditions & References With sodium carbonate, ethylene glycol, T= 155 °C McFadyen; Stevens; Journal of the Chemical Society; (1936); p. 584 View in Reaxys

S O

H N O

O N H

O

HO

OH

sodium carbonate

O

O O

O

Rx-ID: 5432385 View in Reaxys 129/181 Yield

Conditions & References T= 155 °C McFadyen; Stevens; Journal of the Chemical Society; (1936); p. 584 View in Reaxys

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O O

O

O

O

O

O

Rx-ID: 22363180 View in Reaxys 130/181 Yield

Conditions & References Reaction Steps: 3 1: aqueous ethanol; hydrazine hydrate 2: pyridine 3: sodium carbonate; ethylene glycol / 155 °C With pyridine, ethanol, sodium carbonate, hydrazine hydrate, ethylene glycol McFadyen; Stevens; Journal of the Chemical Society; (1936); p. 584 View in Reaxys O

H 2N

O

N H

O

O

O

O

Rx-ID: 22363788 View in Reaxys 131/181 Yield

Conditions & References Reaction Steps: 2 1: pyridine 2: sodium carbonate; ethylene glycol / 155 °C With pyridine, sodium carbonate, ethylene glycol McFadyen; Stevens; Journal of the Chemical Society; (1936); p. 584 View in Reaxys

H N

OH

HO

OH O

N H

O

O

O

O

S

O

O

O

S

NH NH 2

HO

O

Rx-ID: 493794 View in Reaxys 132/181 Yield

Conditions & References allmaehliche Zersetzung Biltz; Chemische Berichte; vol. 68; (1935); p. 221,225 View in Reaxys

H N HO

OH O

N H

OH

O

O

O

O

O

O

S O

O

S

NH NH 2

HO

O

Rx-ID: 493795 View in Reaxys 133/181 Yield

Conditions & References schnelle Zersetzung Biltz; Chemische Berichte; vol. 68; (1935); p. 221,225 View in Reaxys

H N HO

O

H

O

H

O

O

O

O

O

O

S O

OH N H

S

HO

NH NH 2

O

Rx-ID: 5679552 View in Reaxys 134/181

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Yield

Conditions & References allmaehliche Zersetzung Biltz; Chemische Berichte; vol. 68; (1935); p. 221,225 View in Reaxys

H N HO

OH O

N H

O

O

O

O

S

O

O

O

hot water

S

NH NH 2

HO

O

Rx-ID: 5679553 View in Reaxys 135/181 Yield

Conditions & References schnelle Zersetzung Biltz; Chemische Berichte; vol. 68; (1935); p. 221,225 View in Reaxys

H N HO

OH O

N H

O

O

O

O

S

O

O

O

mineral acid

S

NH NH 2

HO

O

Rx-ID: 5679554 View in Reaxys 136/181 Yield

Conditions & References schnelle Zersetzung Biltz; Chemische Berichte; vol. 68; (1935); p. 221,225 View in Reaxys O

HO

O O

O

O

O

O

Rx-ID: 260445 View in Reaxys 137/181 Yield

Conditions & References With 4-(N,N-diethylamino)-toluene, T= 160 °C Ruschtschinskii; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 7; (1934); p. 1113; Chem.

Zentralbl.; vol. 107; nb. II; (1936); p. 2901 View in Reaxys

N

OH

N

O O

O

O

HO

E N

O

S

O N

N

O

Cl

O

Rx-ID: 436159 View in Reaxys 138/181 Yield

Conditions & References Buck; Ide; Journal of the American Chemical Society; vol. 54; (1932); p. 3302,3308; Journal of the American Chemical Society; vol. 53; (1931); p. 1912,1914 View in Reaxys O

N

Z

OH

O O

O

O O

O

N

N O

O O O

Rx-ID: 810545 View in Reaxys 139/181

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Yield

Conditions & References With nitric acid, acetic acid Charlton et al.; Journal of the Chemical Society; (1932); p. 30,39 View in Reaxys O

H O

O

N

HO

OH

OH

N

E

O

O

O

O

O

O

O

N

O O

N O

O

Rx-ID: 5500267 View in Reaxys 140/181 Yield

Conditions & References Charlton et al.; Journal of the Chemical Society; (1932); p. 30,39 View in Reaxys

N

Cl

H

O

Z

O

O

N

O

O

O

4-nitro-benzylhydroxylamine hydrochloride

O

O

Rx-ID: 5676617 View in Reaxys 141/181 Yield

Conditions & References Brady; Klein; Journal of the Chemical Society; (1927); p. 882 View in Reaxys

OH

O

O

S

O

E

permanganate

O

O

O

HO

O

O

O

OH

O

O

Rx-ID: 5678433 View in Reaxys 142/181 Yield

Conditions & References Chattaway; Morris; Journal of the Chemical Society; (1927); p. 2017 View in Reaxys

O

N

O

N

O

O

O

O

O N N

O

Rx-ID: 549921 View in Reaxys 143/181 Yield

Conditions & References T= 20 °C , im Dunkeln Alessandri; Gazzetta Chimica Italiana; vol. 54; (1924); p. 434 View in Reaxys

N-phenyl-piperonal isoxime

N O

O

O O

O N N

Rx-ID: 6048587 View in Reaxys 144/181 Yield

Conditions & References Alessandri; Gazzetta Chimica Italiana; vol. 54; (1924); p. 434

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View in Reaxys

Cl

H

N

E

O

O

O

H 2N

O O

Rx-ID: 5678902 View in Reaxys 145/181 Yield

Conditions & References Hamilton; Robinson; Journal of the Chemical Society; vol. 109; (1916); p. 1037 View in Reaxys

O

O

N O

O

O O

Rx-ID: 809009 View in Reaxys 146/181 Yield

Conditions & References Alessandri; Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti; vol. <5> 24 I; (1915); p. 63; Gazzetta Chimica Italiana; vol. 51 II; (1921); p. 135 View in Reaxys

O

N

E

N

O

O

diluted mineral acid

N

N

N

O

O

H 2N

O

O

Rx-ID: 5469275 View in Reaxys 147/181 Yield

Conditions & References Tiffeneau; Chem. Zentralbl.; vol. 85; nb. I; (1914); p. 1368 View in Reaxys

O OH

H N

O

O

N H

O

O

yellow mercury oxide

O O

Rx-ID: 5432386 View in Reaxys 148/181 Yield

Conditions & References bei Siedetemperatur Curtius; Journal fuer Praktische Chemie (Leipzig); vol. <2> 85; (1912); p. 468 View in Reaxys O

O N H

E

O

O

permanganate

O

O O

O

HO

O O

Rx-ID: 5446403 View in Reaxys 149/181 Yield

Conditions & References Thoms; Thuemen; Chemische Berichte; vol. 44; (1911); p. 3727 View in Reaxys

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HO

O O O

OH

potassium permanganate

O

O

natrium carbonate containing solution

O

O

HO

O

HO

O

O

O

O

O

OH

OH

Rx-ID: 5678506 View in Reaxys 150/181 Yield

Conditions & References δ-methyl-α-<3.4-methylenedioxy-phenyl>-α.γ-pentadiene-β.γ-dicarboxylic acid Stobbe; Justus Liebigs Annalen der Chemie; vol. 380; (1911); p. 31 View in Reaxys

HO

O O

O

OH

O

O

potassium permanganate

O

O

O

Rx-ID: 5687865 View in Reaxys 151/181 Yield

Conditions & References higher-melting α-methyl-α-phenyl-δ-<3.4-methylenedioxy-phenyl>-fulgenic acid Stobbe; Gademann; Rose; Justus Liebigs Annalen der Chemie; vol. 380; (1911); p. 91 View in Reaxys

HO

O O

O

OH

potassium permanganate

O

natrium carbonate containing solution

O

O

O

O

Rx-ID: 5687866 View in Reaxys 152/181 Yield

Conditions & References lower-melting α-methyl-α-phenyl-δ-<3.4-methylenedioxy-phenyl>-fulgenic acid Stobbe; Gademann; Rose; Justus Liebigs Annalen der Chemie; vol. 380; (1911); p. 90 View in Reaxys

O

O OH

O

OH

potassium permanganate

O

O O

natrium carbonate containing solution

O

O

O

HO

Rx-ID: 5690720 View in Reaxys 153/181

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Yield

Conditions & References α.α-diphenyl-δ-<3.4-methylenedioxy-phenyl>-α.γ-butadiene-β.γ-dicarboxylic acid Stobbe; Justus Liebigs Annalen der Chemie; vol. 380; (1911); p. 109 View in Reaxys Cl

O

OH

O

Cl

H

O

O

O

O

Rx-ID: 150826 View in Reaxys 154/181 Yield

Conditions & References Barger; Journal of the Chemical Society; vol. 93; (1908); p. 565; Chemische Berichte; vol. 42; (1909); p. 763 View in Reaxys O O

O N

O

O

N

N

Z

O

OH

O

O

O

O O

O

N O

N

O O O

Rx-ID: 5500266 View in Reaxys 155/181 Yield

Conditions & References lower-melting piperonal oxime Ponzio; Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti; vol. <5> 15 II; (1906); p. 127; Gazzetta Chimica Italiana; vol. 36 II; (1906); p. 597 View in Reaxys

O

O

O

O O

Rx-ID: 132173 View in Reaxys 156/181 Yield

Conditions & References With ozone, acetic acid, T= 50 °C Patent; Otto; Verley; DE97620; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 4; p. 1281 View in Reaxys With Catalyst M-Chromium oxide, sulfuric acid Power; Lees; Journal of the Chemical Society; vol. 85; (1904); p. 638 View in Reaxys Reaction Steps: 2 1: alcoholic KOH-solution 2: Cr2O3-H2SO4 With Catalyst M-Chromium oxide, potassium hydroxide, sulfuric acid Eijkman; Chemische Berichte; vol. 23; (1890); p. 862 View in Reaxys Reaction Steps: 2 1: alcoholic KOH-solution 2: potassium dichromate; sulfuric acid; water With potassium dichromate, potassium hydroxide, sulfuric acid, water Ciamician; Silber; Gazzetta Chimica Italiana; vol. 20; (1890); p. 571; Chemische Berichte; vol. 23; (1890); p. 1160 View in Reaxys

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O

OH

O

S OO

HO

O

O

potassium dichromate

O

Rx-ID: 5432383 View in Reaxys 157/181 Yield

Conditions & References Power; Lees; Journal of the Chemical Society; vol. 85; (1904); p. 638 View in Reaxys

O

potassium permanganate O

O

O

O

HO

O

O

O

O

12.13-dioxy-3.4-methylene-dioxy-1-propyl-benzene

O

HO

O

Rx-ID: 5466661 View in Reaxys 158/181 Yield

Conditions & References Miller; Archiv der Pharmazie (Weinheim, Germany); vol. 240; (1902); p. 377 View in Reaxys Wagner; Bouschmakin; Chemische Berichte; vol. 24; (1891); p. 3489 View in Reaxys Tiemann; Chemische Berichte; vol. 24; (1891); p. 2881 View in Reaxys Poleck; Chemische Berichte; vol. 19; (1886); p. 1094; Chemische Berichte; vol. 22; (1889); p. 2862 View in Reaxys Eijkman; Recueil des Travaux Chimiques des Pays-Bas; vol. 4; (1885); p. 39 View in Reaxys Wagner; Chemische Berichte; vol. 21; (1888); p. 3351 View in Reaxys

3

O

O

concentrated sulfuric acid

O

2

O

O

O

O S

HO

OH

O

Rx-ID: 8422768 View in Reaxys 159/181 Yield

Conditions & References Hoogewerff; van Dorp; Recueil des Travaux Chimiques des Pays-Bas; vol. 21; (1902); p. 356 View in Reaxys

O

(v4)

O

O

O

OH

O

O

O

O

O

Rx-ID: 5432374 View in Reaxys 160/181 Yield

Conditions & References T= 100 °C Patent; Otto; Verley; DE97620 View in Reaxys Otto; Annales de Chimie (Cachan, France); vol. <7> 13; (1898); p. 123 View in Reaxys

I

I

HO

HO

O

methanolic KOH-solution

O

O O

Rx-ID: 5802121 View in Reaxys 161/181

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Yield

Conditions & References T= 135 - 140 °C Wegscheider; Monatshefte fuer Chemie; vol. 14; (1893); p. 383 Anm. 1 View in Reaxys O O

O

O

O

O

HO

O

HO

O

O

Rx-ID: 247930 View in Reaxys 162/181 Yield

Conditions & References bei der Oxydation Tiemann; Chemische Berichte; vol. 24; (1891); p. 2881 View in Reaxys

O

HO

potassium permanganate

OH

O

O

O

O

O

HO

O

O

O

O

O

HO

Rx-ID: 5466660 View in Reaxys 163/181 Yield

Conditions & References Tiemann; Chemische Berichte; vol. 24; (1891); p. 2881 View in Reaxys

O O

O

O

Cr2O3-H2SO4

O

Rx-ID: 5432376 View in Reaxys 164/181 Yield

Conditions & References Eijkman; Chemische Berichte; vol. 23; (1890); p. 862 View in Reaxys Ciamician; Silber; Gazzetta Chimica Italiana; vol. 20; (1890); p. 571; Chemische Berichte; vol. 23; (1890); p. 1160 View in Reaxys

O HO

E

E

O

potassium permanganate

alkali

O

HO

O

O

O

O O

HO

O O

HO

H

H

HO

O

OH

O

O

OH

OH

racemate

Rx-ID: 5589115 View in Reaxys 165/181 Yield

Conditions & References T= 3 °C Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys Doebner; Chemische Berichte; vol. 23; (1890); p. 2378; Chemische Berichte; vol. 24; (1891); p. 1746

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View in Reaxys

O

O N O

O

O

O O

E

O

O

O

O

O

Rx-ID: 550266 View in Reaxys 166/181 Yield

Conditions & References bei laengerem Kochen Pomeranz; Monatshefte fuer Chemie; vol. 10; (1889); p. 786,787; Monatshefte fuer Chemie; vol. 9; (1888); p. 864 View in Reaxys

O

O

E

O

O

O

KOH-solution

O

O

O

Rx-ID: 5432379 View in Reaxys 167/181 Yield

Conditions & References bei laengerem Kochen Pomeranz; Monatshefte fuer Chemie; vol. 10; (1889); p. 786,787; Monatshefte fuer Chemie; vol. 9; (1888); p. 864 View in Reaxys

O

O

O O

HO

alkaline potassium-permanganate solution

O

O

O

O

HO

O

O

Rx-ID: 5446401 View in Reaxys 168/181 Yield

Conditions & References T= 50 °C , β-methoxy-γ-<3.4-methylenedioxy-cinnamal>-crotonic acid Pomeranz; Monatshefte fuer Chemie; vol. 9; (1888); p. 864; Monatshefte fuer Chemie; vol. 10; (1889); p. 786 View in Reaxys O O

O

O

O

O

HO

O

O

Rx-ID: 132174 View in Reaxys 169/181 Yield

Conditions & References With potassium permanganate Poleck; Chemische Berichte; vol. 19; (1886); p. 1094; Chemische Berichte; vol. 22; (1889); p. 2862 View in Reaxys OH

O O

Br O

N O

O

O

O

O

O

O

O

Rx-ID: 402382 View in Reaxys 170/181 Yield

Conditions & References Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 154; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 53

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View in Reaxys O

Br

Br O

HO Br

Br

O

O

alkali

O

O

Rx-ID: 5432375 View in Reaxys 171/181 Yield

Conditions & References Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 154; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 53 View in Reaxys OH O O

O

O

natrium carbonate

Br

O

O

O

Rx-ID: 5432380 View in Reaxys 172/181 Yield

Conditions & References Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 154; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 53 View in Reaxys

Cl O

Cl

H

O

O

O

H

O

O

Rx-ID: 5432372 View in Reaxys 173/181 Yield

Conditions & References Fittig; Remsen; Justus Liebigs Annalen der Chemie; vol. 159; (1871); p. 145 View in Reaxys Br O

Br O

KOH-solution

O

O

O

O

O

Rx-ID: 5432378 View in Reaxys 174/181 Yield

Conditions & References Ansaeuern der Loesung Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys Br O

Br O

O

natrium carbonate

O O

O

O

Rx-ID: 5432381 View in Reaxys 175/181 Yield

Conditions & References Ansaeuern der Loesung Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys

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O

O

piperinate potassium

O

Rx-ID: 5432382 View in Reaxys 176/181 Yield

Conditions & References With potassium permanganate, water Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys O O

OH

O

O

sodium amalgam

O

O

Br

Rx-ID: 5432384 View in Reaxys 177/181 Yield

Conditions & References Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys

O E

HO

O

O

O

alkaline potassium permanganate solution

O

O

Rx-ID: 8469591 View in Reaxys 178/181 Yield

Conditions & References Fittig; Mielck; Justus Liebigs Annalen der Chemie; vol. 152; (1869); p. 52,54; Justus Liebigs Annalen der Chemie; vol. 172; (1874); p. 140,152 View in Reaxys

O

O

O

O

(v4)

O

OH

O

O

O

O

Rx-ID: 5432373 View in Reaxys 179/181 Yield

Conditions & References Patent; Otto; Verley; DE97620; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 4; p. 1281 View in Reaxys

O

O

O O

S

NH 2

O

O

Cr2O3-H2SO4

O

HO

Rx-ID: 5432377 View in Reaxys 180/181 Yield

Conditions & References Patent; Fritzsche and Co., Verona Chemical Co.; DE207702 View in Reaxys

O HO

O

O Z

E

O

O

permanganate

O

HO

O

O

O O

Rx-ID: 5446402 View in Reaxys 181/181 Yield

Conditions & References Goebel; Berichte der Deutschen Pharmazeutischen Gesellschaft; vol. 32; p. 117

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View in Reaxys

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