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Date
87 reactions in Reaxys
2017-10-08 12h:27m:28s (EST)
87 reactions in Reaxys
2017-10-08 12h:28m:45s (EST)
O
1. Query
O
HO
O
Search as: As drawn, No salts, No mixtures, No charges, No radicals 2. Query
(1. Query) AND NOT itemno in (8)
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O O O
O
HO
OH
O
Rx-ID: 152746 View in Reaxys 1/87 Yield
Conditions & References With sodium hydroxide, chloroform Graebe; Martz; Chemische Berichte; vol. 36; (1903); p. 1033 View in Reaxys Reaction Steps: 3 1: zinc chloride; urea; glacial acetic acid 2: durch aufeinanderfolgende Verseifung und Oxydation mit Kupfersulfat 3: dimethyl-p-toluidine With 2,3,4-trimethylaniline, acetic acid, urea, zinc(II) chloride Mauthner; Justus Liebigs Annalen der Chemie; vol. 395; (1913); p. 279 View in Reaxys Reaction Steps: 2 1: potassium carbonate With potassium carbonate Pauly; Strassberger; Chemische Berichte; vol. 62; (1929); p. 2279 View in Reaxys Reaction Steps: 2 1: potassium carbonate With potassium carbonate Pauly; Strassberger; Chemische Berichte; vol. 62; (1929); p. 2279 View in Reaxys Reaction Steps: 2 1: (i) aq. NaOH, (ii) /BRN= 1209228/, As2O3, aq. NaOH 2: O2, CuCl / dimethylsulfoxide With oxygen, copper(l) chloride in dimethyl sulfoxide Claus,P. et al.; Monatshefte fuer Chemie; vol. 103; (1972); p. 1178 - 1193 View in Reaxys
O O
O
O O
O
HO
O
O
Rx-ID: 296739 View in Reaxys 2/87 Yield
Conditions & References With chloroform, sodium methylate Freudenberg; Huebner; Chemische Berichte; vol. 85; (1952); p. 1181,1188 View in Reaxys O N N
O
O
O
N N
HO
OH
O
Rx-ID: 300739 View in Reaxys 3/87 Yield
Conditions & References With boric acid, glycerol, T= 150 - 160 °C , Erhitzen des Reaktionsgemisches mit wss.H2SO4
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Allen; Leubner; ; vol. IV; (1963); p. 866 View in Reaxys Manske; Ledingham; Holmes; Canadian Journal of Research, Section B: Chemical Sciences; vol. 23; (1945); p. 100,102 View in Reaxys With trifluoroacetic acid, Heating Diana, Guy D.; Cutcliffe, David; Oglesby, Richard C.; Otto, Michael J.; Mallamo, John P.; et al.; Journal of Medicinal Chemistry; vol. 32; nb. 2; (1989); p. 450 - 455 View in Reaxys I
O
HO O
O
O
HO
O
Rx-ID: 310191 View in Reaxys 4/87 Yield
Conditions & References With methanol, sodium methylate, copper, unter Druck Pearl; Journal of Organic Chemistry; vol. 22; (1957); p. 1229,1231 View in Reaxys Pepper; MacDonald; Canadian Journal of Chemistry; vol. 31; (1953); p. 476,483 View in Reaxys
O
O
O HO O
HO
O
Rx-ID: 322714 View in Reaxys 5/87 Yield
Conditions & References With sodium hydroxide, nitrobenzene Pearl; Journal of the American Chemical Society; vol. 70; (1948); p. 1746 View in Reaxys
O O
O
O O
O
HO
N
O
Rx-ID: 379907 View in Reaxys 6/87 Yield
Conditions & References With hydrogenchloride, diethyl ether, tin(ll) chloride, Reagens 4:Chloroform;Erwaermen des Reaktionsprodukts mit Wasser McCord; Journal of the American Chemical Society; vol. 53; (1931); p. 4181 View in Reaxys OH
Cl Cl
O
O
O
Cl OH O
HO
O
Rx-ID: 486656 View in Reaxys 7/87 Yield
Conditions & References Pauly; Strassberger; Chemische Berichte; vol. 62; (1929); p. 2279 View in Reaxys
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O HO
O
O
O
O
OH O
HO
O
Rx-ID: 487606 View in Reaxys 8/87 Yield
Conditions & References With 2,3,4-trimethylaniline Mauthner; Justus Liebigs Annalen der Chemie; vol. 395; (1913); p. 279 View in Reaxys
O O
O
O O
O
O
HO
O
O
Rx-ID: 493926 View in Reaxys 9/87 Yield
Conditions & References With sodium hydroxide, ethanol, hydrogen Mauthner; Journal fuer Praktische Chemie (Leipzig); vol. <2> 142; (1935); p. 26,31 View in Reaxys
O O
O
O O
O
O
HO
Cl
O
Rx-ID: 496776 View in Reaxys 10/87 Yield
Conditions & References With Pd-BaSO4, xylene, T= 150 - 160 °C , Hydrogenation Imaki et al.; Nippon Nogei Kagaku Kaishi; vol. 20; (1944); p. 289,292; ; (1949); p. 1743 View in Reaxys Reaction Steps: 2 1: palladium/BaSO4; xylene / Hydrogenation 2: CHCl3; methanol. sodium methylate With Pd-BaSO4, chloroform, sodium methylate, xylene Freudenberg; Huebner; Chemische Berichte; vol. 85; (1952); p. 1181,1188 View in Reaxys
O
O O
O O O
HO
O
Rx-ID: 590499 View in Reaxys 11/87 Yield 95 %
Conditions & References With aluminum (III) chloride in dichloromethane, Time= 12h, T= 20 °C , Inert atmosphere Shirali, Anupama; Sriram, Madhavi; Hall, John J.; Nguyen, Benson L.; Guddneppanavar, Rajsekhar; Hadimani, Mallinath B.; Ackley, J. Freeland; Siles, Rogelio; Jelinek, Christopher J.; Arthasery, Phyllis; Brown, Rodney C.; Murrell, Victor Leon; McMordie, Austin; Sharma, Suman; Chaplin, David J.; Pinney, Kevin G.; Journal of Natural Products; vol. 72; nb. 3; (2009); p. 414 - 421 View in Reaxys
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92 %
With N,N,N,N,N,N-hexamethylphosphoric triamide, sodium hydride, thiophenol in toluene, Heating Zou, Hong Bin; Dong, Sheng Yi; Zhou, Chang Xin; Hu, Li Hong; Wu, Yi Hang; Li, Hai Bo; Gong, Jing Xu; Sun, Lian Li; Wu, Xiu Mei; Bai, Hua; Fan, Bo Tao; Hao, Xiao Jiang; Stoeckigt, Joachim; Zhao, Yu; Bioorganic and Medicinal Chemistry; vol. 14; nb. 6; (2006); p. 2060 - 2071 View in Reaxys
92 %
With magnesium iodide, Time= 0.5h, T= 80 °C , neat (no solvent) Bao, Kai; Fan, Aixue; Dai, Yi; Zhang, Liang; Zhang, Weige; Cheng, Maosheng; Yao, Xinsheng; Organic and Biomolecular Chemistry; vol. 7; nb. 24; (2009); p. 5084 - 5090 View in Reaxys
80 %
With piperidine, water, Time= 48h, Heating Ren, Xinfeng; Chen, Xiaochuan; Peng, Kun; Xie, Xingang; Xia, Yamu; Pan, Xinfu; Tetrahedron Asymmetry; vol. 13; nb. 16; (2002); p. 1799 - 1804 View in Reaxys
80 %
With piperidine in water, Time= 48h, Heating Su, Ying; Ren, Xin-Feng; She, Xue-Gong; Pan, Xin-Fu; Journal of the Chinese Chemical Society; vol. 51; nb. 6; (2004); p. 1333 - 1337 View in Reaxys
78 %
Typical procedure for O-demethylation General procedure: A mixture of aryl methyl ether (1 mmol) and [FemMerBenz]Al2Cl7 (200 mg, 0.96 mol percent) in DMF (5 mL) was refluxed in an oil bath. After completion of the reaction as monitored by the TLC, the reaction mixture was cooled and filtered. The filtrate was poured into water (20 mL) and extracted with ethyl acetate (3 20 mL). The combined organic layers were dried over Na2SO4. Evaporation of the solvent followed by column chromatography over silica gel using ethyl acetate/ petroleum ether (1:4 v/v) afforded pure O-demethylated product, which was characterized by spectral methods. With 1-N-ferrocenylmethyl benzimidazole tagged polymer in N,N-dimethyl-formamide, Reflux Kurane, Rajanikant; Gaikwad, Vipul; Jadhav, Jagannath; Salunkhe, Rajashri; Rashinkar, Gajanan; Tetrahedron Letters; vol. 53; nb. 47; (2012); p. 6361 - 6366,6 View in Reaxys
74 %
With piperidine in water, Time= 48h, Reflux Pettit, George R.; Melody, Noeleen; Thornhill, Andrew; Knight, John C.; Groy, Thomas L.; Herald, Cherry L.; Journal of Natural Products; vol. 72; nb. 9; (2009); p. 1637 - 1642 View in Reaxys
72 %
3 :EXAMPLE 3A 100 ml glass autoclave is charged with 11.8 g (60.0 mmol) of 3,4,5-trimethoxybenzaldehyde and 47.2 g (420 mmol) of dimethylamine (40percent solution in water). The autoclave is closed and the biphasic reaction mixture is stirred at 140° C. (autogenous pressure 10 bar) for 18 h. Excess dimethylamine and water are removed under reduced pressure, methyl tert-butyl ether is added and the mixture is acidified with 30percent hydrochloric acid in water. After phase separation and removal of all volatile constituents of the organic phase, 4-hydroxy-3,5-dimethoxybenzaldehyde is obtained in a yield of 72percent. With dimethyl amine in water, Time= 18h, T= 140 °C , p= 7500.75Torr , Autoclave Patent; BASF SE; US2011/245544; (2011); (A1) English View in Reaxys
72 %
With piperidine, water, Time= 48h, Reflux Ding, Junwei; Qi, Rongwei; Zhou, Haitang; Jiao, Bin; Xia, Yamu; Journal of Chemical Research; vol. 35; nb. 9; (2011); p. 519 - 521 View in Reaxys
72 %
3 :In a 100 ml glass autoclave are 1 1, 8 g (60.0 mmol) of 3,4,5-trimethoxy and 47.2 g (420 mmol) dimethylamine (40percent solution in water) filled.The autoclave is closed and stirred at 140 ° C (self-pressure 10 bar), the biphasic reaction mixture for 18 h.Excess dimethylamine and water are removed under reduced pressure, methyl tert added
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and asked the mixture with 30percent hydrochloric acid in water.After phase separation and removal of all volatile components of the organic phase, 4-hydroxy-3,5-dimethoxybenzaldehyde in a yield of 72percent. With dimethyl amine in water, Time= 18h, T= 140 °C , p= 7500.75Torr , Autoclave Patent; BASF SE; EBEL, KLAUS; RUDENAUER, STEFAN; (12 pag.); JP5816260; (2015); (B2) Japanese View in Reaxys 65 %
With piperidine in water, Time= 20h, Heating Rizzacasa, Mark A.; Sargent, Melvyn V.; Australian Journal of Chemistry; vol. 40; nb. 10; (1987); p. 1737 - 1743 View in Reaxys With sulfuric acid, T= 40 °C Sharp; Journal of the Chemical Society; (1937); p. 852 View in Reaxys 1.1; 2.1 With sulfuric acid, Time= 8h, T= 40 °C Patent; MERCK PATENT GESELLSCHAFT MIT BESCHRAENKTER HAFTUNG; JP2005/522479; (2005); (A) Japanese View in Reaxys OH
O
HO
O
O
S
O
O
O
O
O HO
O
Rx-ID: 753924 View in Reaxys 12/87 Yield
Conditions & References With sodium hydroxide Kratzl; Billek; Holzforschung; vol. 7; (1953); p. 66,69 View in Reaxys Kratzl et al.; Monatshefte fuer Chemie; vol. 85; (1954); p. 1154,1160 View in Reaxys O
HO
O
O
O
N
O
OH O
HO
O
Rx-ID: 796047 View in Reaxys 13/87 Yield
Conditions & References Mauthner; Justus Liebigs Annalen der Chemie; vol. 395; (1913); p. 279 View in Reaxys OH
O
O O
HO
O
HO
O
Rx-ID: 1992884 View in Reaxys 14/87 Yield 96 %
Conditions & References With copper diacetate, ethylene glycol, Time= 8h, T= 50 °C , Green chemistry, chemoselective reaction Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
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90 %
General procedure: A mixture of alcohol (5.0 mmol), Cu(OAc)2 (9.1 mg, 0.05 mmol), and TEMPO (7.8 mg, 0.05 mmol) in CH3CN/H2O (5/10 mL) was stirred at room temperature for specified time. After completion of the reaction (monitored by TLC, eluents: petroleum ether/ethyl acetate = 4/1), dichloromethane (10 mL) was added to the resulting mixture. The dichloromethane phase was separated, and the aqueous phase was further extracted with dichloromethane (10 mL × 2). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography (eluents: petroleum ether/ethyl acetate = 10/1) to provide the desired product. With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, copper diacetate in water, acetonitrile, Time= 3h, T= 20 °C , Green chemistry Jiang, Jian-An; Du, Jia-Lei; Wang, Zhan-Guo; Zhang, Zhong-Nan; Xu, Xi; Zheng, Gan-Lin; Ji, Ya-Fei; Tetrahedron Letters; vol. 55; nb. 10; (2014); p. 1677 - 1681 View in Reaxys
86 %
With 2,3-dicyano-5,6-dichloro-p-benzoquinone in 1,4-dioxane, Time= 16h, Ambient temperature Becker, Hans-Dieter; Bjoerk, Anders; Adler, Erich; Journal of Organic Chemistry; vol. 45; nb. 9; (1980); p. 1596 1600 View in Reaxys
63 %
With nitric acid, sodium nitrite in acetonitrile Bozell, Joseph J.; Hoberg, John O.; Dimmel, Donald R.; Tetrahedron Letters; vol. 39; nb. 16; (1998); p. 2261 2264 View in Reaxys With oxygen, copper(l) chloride in dimethyl sulfoxide Claus,P. et al.; Monatshefte fuer Chemie; vol. 103; (1972); p. 1178 - 1193 View in Reaxys With pyridinium chlorochromate Kang, Tae-Souk; Jo, Hyang-Ok; Park, Woo-Kyu; Kim, Jong-Pyung; Konishi, Yasuo; Kong, Jae-Yang; Park, No-Sang; Jung, Young-Sik; Bioorganic and Medicinal Chemistry Letters; vol. 18; nb. 5; (2008); p. 1663 - 1667 View in Reaxys Br
O
HO O
O
O
–O
O
O
O
Na +
Na +
O
O– HO
O
Rx-ID: 2000481 View in Reaxys 15/87 Yield 99 %
Conditions & References With cupric(II) carbonate, copper (II) hydroxide in methanol, Time= 3h, T= 125 °C , var. time; also without CO2, other aromatic bromides, Mechanism, Product distribution Nobel, D.; Journal of the Chemical Society, Chemical Communications; nb. 4; (1993); p. 419 - 420 View in Reaxys
Br
O
O –O
HO
Na +
O HO
Br
O
Rx-ID: 2040581 View in Reaxys 16/87 Yield 98 %
Conditions & References Typical procedure for synthesis of 1 (Table 1) General procedure: A Teflon-lined autoclave (25 mL) was charged with MeONa (1.08 g, 20.0 mmol), MeOH (10 mL), CuCl (40 mg, 0.40 mmol), HCOOMe (0.25 mL, 0.97 g/mL, 4.0 mmol), and monohaloarene (10.0 mmol) then heated to 115 °C, with stirring, for 2 h. After completion of the reaction, the reactor was cooled to room temperature. The mixture was stirred for 0.5 h in the open, then concentrated to recover pure MeOH. Diethyl ether (15 mL) and dilute hydrochloric acid (1.6 M, 15 mL) were added to the residue. The mixture separated into two layers, and the aqueous
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phase was extracted with diethyl ether (15 mL x 3). The combined organic layers were dried over anhydrous Na2SO4 and concentrated to give a residue which was purified by column chromatography on silica gel (mobile phase: petroleum ether–ethyl acetate 15:1) to furnish 1 (conversion and selectivity were determined by GC–MS analysis). The purity of the recovered MeOH was measured as more than 99 percent by GC, and the water content of the recovered MeOH was measured as less than 0.12 percent by use of the Karl Fischer method. With methanol, Methyl formate, copper(l) chloride, Time= 2h, T= 115 °C , Autoclave, Green chemistry Guo, Ying; Ji, Si-Zhe; Chen, Cheng; Liu, Hong-Wei; Zhao, Jian-Hong; Zheng, Yu-Lin; Ji, Ya-Fei; Research on Chemical Intermediates; vol. 41; nb. 11; (2015); p. 8651 - 8664 View in Reaxys 92 %
With copper(I) bromide in DMFA Zabinski, Jerzy; Wolska, Irena; Maciejewska, Dorota; Journal of Molecular Structure; vol. 833; nb. 1-3; (2007); p. 74 - 81 View in Reaxys
88 %
With Cu2Cl2 in DMFA, Time= 2.5h, T= 97 °C Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys Br
O
HO
O
O
–O
Na +
O HO
O
Rx-ID: 2072939 View in Reaxys 17/87 Yield 99 %
Conditions & References With copper(II) carbonate, copper(II) hydroxide, carbon dioxide in methanol, Time= 3h, T= 125 °C Nobel, D.; Journal of the Chemical Society, Chemical Communications; nb. 4; (1993); p. 419 - 420 View in Reaxys
95 %
With ethyl acetate, copper(I) bromide in methanol, Time= 14h, Heating Capdevielle, Patrice; Maumy, Michel; Tetrahedron Letters; vol. 34; nb. 6; (1993); p. 1007 - 1010 View in Reaxys
91 %
With copper(I) chloride in N,N-dimethyl-formamide, Time= 2.5h, T= 97 °C Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys
90 %
With copper(l) chloride in N,N-dimethyl-formamide Li, Yan; Dai, Fang; Jin, Xiao-Ling; Ma, Meng-Meng; Wang, Yi-Hua; Ren, Xiao-Rong; Zhou, Bo; Food Chemistry; vol. 158; (2014); p. 41 - 47 View in Reaxys
83 %
With copper dichloride in methanol, N,N-dimethyl-formamide, Time= 1h, T= 100 °C Rao, Durvasula V.; Stuber, F. A.; Synthesis; nb. 4; (1983); p. 308 View in Reaxys
18 g
With copper dichloride in N,N-dimethyl-formamide, Time= 1h, T= 120 °C Puri, S. C.; Anand, S. M.; Atal, C. K.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 24; (1985); p. 294 - 295 View in Reaxys
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OH
O O O
HO
O
HO
O
O
O
O
O
O
O
O
O
HO
HO
HO
O
Rx-ID: 2432624 View in Reaxys 18/87 Yield
Conditions & References With aluminium(III) iodide, tetra-(n-butyl)ammonium iodide in cyclohexane, Time= 6h, other reaction time, other molar ratios of educt/AlI3 and educt/catalyst, Product distribution Andersson, Sven; Synthesis; nb. 4; (1985); p. 437 - 439 View in Reaxys O
OH
O
O
O
O
O HO
O
HO
O
O
Rx-ID: 4159178 View in Reaxys 19/87 Yield
Conditions & References
6% Spectr., 90 %
With oxygen, (pyridine)lt;bis(salicylidene)ethylenediaminegt;cobalt in methanol, p= 2585.7Torr , Ambient temperature Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys
19 %, 75 %
With C38H57CoN3O2, oxygen in methanol, T= 0 °C , Inert atmosphere, Reagent/catalyst, Concentration, Temperature Biannic, Berenger; Bozell, Joseph J.; Organic Letters; vol. 15; nb. 11; (2013); p. 2730 - 2733 View in Reaxys
67 %, 25 %
With C45H72CoN4O2, oxygen in methanol, Time= 16h, T= 20 °C , p= 2585.81Torr , Reagent/catalyst Biannic, Berenger; Bozell, Joseph J.; Elder, Thomas; Green Chemistry; vol. 16; nb. 7; (2014); p. 3635 - 3642 View in Reaxys
29 %, 11 % With C37H56CoN4O2, oxygen in methanol, T= 0 °C , Inert atmosphere, Concentration, Reagent/catalyst, Time Biannic, Berenger; Bozell, Joseph J.; Organic Letters; vol. 15; nb. 11; (2013); p. 2730 - 2733 View in Reaxys 28 %, 50 % Spectr.
With oxygen, cobalt-salen complex in methanol, p= 2585.7Torr , Ambient temperature Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys With Melanocarpus albomyces laccase, oxygen in 1,4-dioxane, Time= 24h, sodium succinate buffer Maarit, Lahtinen; Kristiina, Kruus; Petri, Heinonen; Jussi, Sipilae; Journal of Agricultural and Food Chemistry; vol. 57; nb. 18; (2009); p. 8357 - 8365 View in Reaxys
O O
O
O O
O HO O
O
HO
O
Rx-ID: 4160050 View in Reaxys 20/87
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Yield
Conditions & References
17 %, 10 % Spectr.
With oxygen, lt;bislt;(salicylideneamino)ethylgt;aminegt;cobalt in methanol, Time= 24h, p= 2585.7Torr , Ambient temperature, Title compound not separated from byproducts Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys
10 % Spectr., 17 %
With oxygen, lt;bislt;(salicylideneamino)ethylgt;aminegt;cobalt in methanol, Time= 24h, p= 2585.7Torr , Ambient temperature Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys O O
O O
O O
O OH
HO
O
O
Rx-ID: 4160457 View in Reaxys 21/87 Yield
Conditions & References
11 %, 44 % With oxygen, lt;bislt;(salicylideneamino)ethylgt;aminegt;cobalt in methanol, p= 2585.7Torr , Ambient temperature, TiSpectr. tle compound not separated from byproducts Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys 45 % Spectr., 11 %
With oxygen, lt;bislt;(salicylideneamino)ethylgt;aminegt;cobalt in methanol, Time= 24h, p= 2585.7Torr , Ambient temperature Bozell, Joseph J.; Hames, Bonnie R.; Dimmel, Donald R.; Journal of Organic Chemistry; vol. 60; nb. 8; (1995); p. 2398 - 2404 View in Reaxys O
Cl
S O
O
O
Cl HO
OH
O
Rx-ID: 4385830 View in Reaxys 22/87 Yield
Conditions & References (i) SnCl4, CH2Cl2, (ii) aq. HCl, HgCl2, Multistep reaction Kratzl,K.; Vierhapper,F.W.; Monatshefte fuer Chemie; vol. 102; (1971); p. 425 - 430 View in Reaxys
O
N
O
N O
HO O
HO
O
Rx-ID: 5292806 View in Reaxys 23/87 Yield 98 %
Conditions & References With chloro-trimethyl-silane, sodium iodide in water, acetonitrile, Time= 0.05h, deprotection Kamal, Ahmed; Ramana, K. Venkata; Arifuddin; Chemistry Letters; nb. 8; (1999); p. 827 - 828 View in Reaxys
92 %
With triethylene diamine nickel thiosulfate, water in chloroform, Time= 0.0833333h, T= 20 °C , Hydrolysis Kamal; Arifuddin; Rao; Synlett; nb. 10; (2000); p. 1482 - 1484
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View in Reaxys
O O O
O OH
HO
O
Rx-ID: 5322686 View in Reaxys 24/87 Yield 92 %
Conditions & References With copper diacetate, ethylene glycol, Time= 12h, T= 50 °C , p= 760.051Torr , Green chemistry, Reagent/catalyst, Temperature, Solvent, chemoselective reaction Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
91 %
With oxygen, diethylamine, copper(l) chloride in methanol, T= 20 °C Tripathi; Sama; Taneja; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 49; nb. 3; (2010); p. 379 - 381 View in Reaxys
91 %
General procedure General procedure: a mixture of substrate 1a(1 mmol), cobalt salt (n1molpercent) and NaOH (n2 equiv)in EG (5 mL) was stirred with O2 (1 atm) being bubbled, under 80 oCfor 8 h. Hydrochloric acid (10 mL, 2percent) and methyl tertbutyl ether (MTBE, 10 mL) were successively added to the reactionmixture. The organic layer was separated, and the aqueous phase was furtherextracted with MTBE(10 mL × 2). The combined organic phase was dried over anhydrous sodium sulfateand concentrated to give a residue, which was purified by column chromatographyon silica gel (eluents: petroleum ether/ethyl acetate, 10/1) to provide thedesired products 2a. With oxygen, cobalt(II) diacetate tetrahydrate, sodium hydroxide in ethylene glycol, Time= 4h, T= 80 °C , p= 760.051Torr Jiang, Jian-An; Du, Jia-Lei; Liao, Dao-Hua; Wang, Zhan-Guo; Ji, Ya-Fei; Tetrahedron Letters; vol. 55; nb. 8; (2014); p. 1406 - 1411 View in Reaxys
91 %
2.2. Typical procedure for the Co(OAc)2-catalyzed aerobic oxidation of 1 (Table 2 in the text) General procedure: Typical procedure: a mixture of substrate 1 (5.0 mmol), Co(OAc)2*4H2O (0.05 mmol, 12 mg) and NaOH (5.0 mmol, 0.2 g) in EG/H2O (5.0 mL/0.25 mL) was stirred with O2 (1.0 atm) being bubbled at 50 °C for 12 h. Hydrochloric acid (10.0 mL, 2 percent) and chloroform (10.0 mL) were successively added to the reaction mixture. The chloroform phase was separated, and the aqueous phase was further extracted with chloroform (10.0 mL × 2). The combined organic layer was dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography on silica gel (eluents: .petroleum ether/ethyl acetate, 5/1) to provide the desired products 2. With oxygen, cobalt(II) acetate, sodium hydroxide in water, ethylene glycol, Time= 12h, T= 50 °C , p= 760.051Torr , Green chemistry, chemoselective reaction Jiang, Jian-An; Du, Jia-Lei; Zhang, Zhong-Nan; Zhai, Jiao-Jiao; Ji, Ya-Fei; Synthetic Communications; vol. 44; nb. 10; (2014); p. 1430 - 1440 View in Reaxys
95 % Chromat.
With N-Bromosuccinimide in dimethyl sulfoxide, Time= 1h, T= 120 °C , Oxidation Baik, Woonphil; Lee, Hyun Joo; Jang, Jung Min; Koo, Sangho; Kim, Byeong Hyo; Journal of Organic Chemistry; vol. 65; nb. 1; (2000); p. 108 - 115 View in Reaxys Reaction Steps: 2 1: copper diacetate / 12 h / 50 °C / 760.05 Torr / |Inert atmosphere; |Green chemistry 2: ethylene glycol; copper diacetate / 8 h / 50 °C / |Green chemistry With copper diacetate, ethylene glycol
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Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys Reaction Steps: 2 1: copper diacetate / 4 h / 50 °C / |Green chemistry 2: ethylene glycol; copper diacetate / 8 h / 50 °C / |Green chemistry With copper diacetate, ethylene glycol Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
O
O OH HO
O
O
S OO
O O
HO
O
Rx-ID: 5701711 View in Reaxys 25/87 Yield
Conditions & References T= 40 °C Sharp; Journal of the Chemical Society; (1937); p. 852 View in Reaxys O O HO
O
Rx-ID: 6083842 View in Reaxys 26/87 Yield
Conditions & References Herstellung von 4-Hydroxy-3,5-dimethoxy-<α-14 C>benzaldehyd Kratzl; Billek; Monatshefte fuer Chemie; vol. 85; (1954); p. 845,854 View in Reaxys Ciaramitaro,D.; Steelink,C.; Phytochemistry (Elsevier); vol. 14; (1975); p. 543 - 552 View in Reaxys Hansson; Wickberg; Synthesis; (1976); p. 191 View in Reaxys Patent; Gulf Oil Corp., Pittsburgh, Pa (V. St. A.); DE2617585; (1976); ; vol. 86; nb. 55159 View in Reaxys Bu'lock; Walker; Journal of the Chemical Society [Section] C: Organic; (1967); p. 336 View in Reaxys 2 : Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde EXAMPLE 2 Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde Into a 2-l., 3-necked, round-bottomed flask equipped with a mechanical stirrer, thermometer, and a condenser was added 700 ml. of methanol. 68.0 G. of clean sodium was then added in small pieces and under nitrogen. After the reaction was complete, the methanol was removed in vacuo at 45°-50° and to the residue was added 312 ml. of dimethylformamide and 156 ml. of methanol. 5.85 G. of cuprous chloride was added followed, after 5 minutes, by 165 g. of 3,5-dibromo-4-hydroxybenzaldehyde, an exotherm resulted (25° to 50° during 5 minutes). The mixture was heated under reflux for 4 hours, the solvents were evaporated in vacuo (0.1 torr) at 55°, and the residue was treated with 440 ml. of 15percent brine. The mixture was stirred at room temperature for 30 minutes, again cooled to 0°, and filtered over 100 g. of celite. The filter cake was washed with three 250 ml. portions, a total of 750 ml. of cold (5°) water (that is, until neutral) followed, after discarding the aqueous washings, by three 500 ml. portions, a total of 1.5 l. of hot (60°) ethyl acetate.
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The ethyl acetate washings were added to a separatory funnel, excess water (about 10 ml.) was removed, and the ethyl acetate dried over magnesium sulfate and evaporated to give 95.0 g. (88.5percent) of 3,5-dimethoxy-4-hydroxybenzaldehyde as a yellow solid, mp 107°-109°. GLC indicated a purity of 99.7percent. Patent; Hoffmann-La Roche Inc.; US4218567; (1980); (A1) English View in Reaxys 4 : Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde EXAMPLE 4 Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde Into a 5-l., 3-necked, round-bottomed flask equipped with a mechanical stirrer, thermometer, and condenser was added 1.0 l. of methanol. 85.2 G. of clean sodium was then added in small pieces and under nitrogen. After the reaction was complete, the methanol was removed at 45°-50° and 450 ml. of dimethylformamide added to the residue. To the rapidly stirred slurry of sodium methoxide in dimethylformamide was added 10.7 g. of cuprous chloride to give a deep blue mixture which was stirred at 25° for 15 minutes. 214.4 G. of 3-methoxy-4-hydroxy-5-bromobenzaldehyde was added during 3 minutes, whereupon a slight exotherm ensued. The temperature of the reaction was increased to 97° during 15 minutes and the mixture was stirred at this temperature for 1.75 hours. The reaction was cooled to 60° and the dimethylformamide distilled off under high vacuum. 1.0 l. of 15percent brine was added to the residue, the mixture was stirred at 50° for 30 minutes, cooled to 0° and treated with 300 ml. of cold (0°) concentrated hydrochloric acid at such a rate that the temperature was kept below 15°. The mixture was stirred at room temperature for 1 hour, again cooled to 0° and filtered over 100 g. of celite. The filter cake was washed with four 400 ml. portions, a total of 1.6 l. of cold (5°) water, followed, after discarding the aqueous wash, by five 500 ml. portions, a total of 2.5 l. of hot (60°) ethyl acetate. The ethyl acetate washings were added to a separatory funnel, excess water (about 15 ml.) was ran off, and the ethyl acetate dried over magnesium sulfate and evaporated in vacuo to give 154.0 g. (91percent) of 3,5-dimethoxy-4-hydroxybenzaldehyde as yellow crystals, mp 109°-111°, purity of 99.72percent. Patent; Hoffmann-La Roche Inc.; US4218567; (1980); (A1) English View in Reaxys 8 : Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde EXAMPLE 8 Preparation of 3,5-dimethoxy-4-hydroxybenzaldehyde A 5-l., 3-necked, round-bottomed flask equipped with a mechanical stirrer, condenser capped with a drying tube, and a thermometer was charged with 1.2 l. of methanol. 109.5 G. of clean sodium was then added in small pieces and under nitrogen. When all the sodium had reacted, the methanol was removed in vacuo at 50° and a mixture of 500 ml. of dimethylformamide and 250 ml. of methanol added to the residue. To the vigorously stirred solution was added 9.45 g. of cuprous chloride followed, after 5 minutes, by 264.4 g. of 3,5dibromo-4-hydroxybenzaldehyde. An exotherm resulted in which the temperature rose from 23° to 50° over a period of 10 minutes. The mixture was stirred at 95° for 3.25 hours, during which time the color of the reaction changed from blue to greyish-green. The solvents were removed in vacuo at 45° and to the residue was added 700 ml. of 15percent brine. The mixture was stirred at 60° for 30 minutes, cooled to 0° and treated with 400 ml. of cold (0°) concentrated hydrochloric acid at such a rate that the temperature was kept below 30°. The mixture was stirred at room temperature for 30 minutes, then at 0° for another 30 minutes, and filtered over 100 g. of celite. The filter cake was washed with four 400 ml. portions, a total of 1.6 l. of cold (5°) water, followed, after removing the aqueous washings, by four 500 ml. portions, a total of 2.0 l. of hot (60°) ethyl acetate. The ethyl acetate washings were added to a separatory funnel, excess water (about 20 ml.) was removed, and the ethyl acetate dried over magnesium sulfate and evaporated to give 153.3 g. (88percent) of 3,5-dimethoxy-4-hydroxybenzaldehyde as a pale yellow solid, mp 105°-108°. Purity of 99.38percent. Patent; Hoffmann-La Roche Inc.; US4218567; (1980); (A1) English View in Reaxys
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O
3.5-dimethoxy-4-ethoxycarbonyloxy-benzaldehyde
O HO
O
Rx-ID: 6083843 View in Reaxys 27/87 Yield
Conditions & References With sodium hydroxide Spaeth; Monatshefte fuer Chemie; vol. 41; (1920); p. 278 View in Reaxys O
glucosyringaldehyde
O HO
O
Rx-ID: 6083844 View in Reaxys 28/87 Yield
Conditions & References With emulsin Koerner; Gazzetta Chimica Italiana; vol. 18; (1888); p. 215 View in Reaxys With sulfuric acid Koerner; Gazzetta Chimica Italiana; vol. 18; (1888); p. 215 View in Reaxys O
lignin-substances
O HO
O
Rx-ID: 6083845 View in Reaxys 29/87 Yield
Conditions & References With sodium hydrogensulfite, anschliessend Erwaermen mit wss.NaOH Leger; Hibbert; Journal of the American Chemical Society; vol. 60; (1938); p. 565 View in Reaxys Hibbert; Steeves; Journal of the American Chemical Society; vol. 59; (1937); p. 1768 View in Reaxys Bell et al.; Journal of the American Chemical Society; vol. 59; (1937); p. 598 View in Reaxys Hawkins; Wright; Hibbert; Journal of the American Chemical Society; vol. 59; (1937); p. 2447 View in Reaxys With sodium hydroxide, nitrobenzene, T= 160 °C Creighton; Hibbert; Journal of the American Chemical Society; vol. 66; (1944); p. 37 View in Reaxys Creighton; Gibbs; Hibbert; Journal of the American Chemical Society; vol. 66; (1944); p. 32,35 View in Reaxys Creighton; McCarthy; Hibbert; Journal of the American Chemical Society; vol. 63; (1941); p. 312,3049,3050 View in Reaxys With hydrogenchloride Kulka; Hibbert; Journal of the American Chemical Society; vol. 65; (1943); p. 1185 View in Reaxys Pyle; Brickman; Hibbert; Journal of the American Chemical Society; vol. 61; (1939); p. 2198 View in Reaxys MacInnes et al.; Journal of the American Chemical Society; vol. 62; (1940); p. 2803,2805 View in Reaxys West et al.; Journal of the American Chemical Society; vol. 61; (1939); p. 2556
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View in Reaxys O
OH
enzyme-substance from mushrooms
oxygen
O HO
O
O O
O
O
O
HO
O
Rx-ID: 7065063 View in Reaxys 30/87 Yield
Conditions & References in gepufferter wss. Loesung (pH 8) Richtzenhain; Chemische Berichte; vol. 77/79; (1944); p. 409,416 View in Reaxys
O
O
O
aqueous NaOH
N HO
O
O O
HO
O
Rx-ID: 7448653 View in Reaxys 31/87 Yield
Conditions & References Pearl; Journal of the American Chemical Society; vol. 70; (1948); p. 1746 View in Reaxys O
HO
aspen wood
O
O
O
HO
O
Rx-ID: 8509396 View in Reaxys 32/87 Yield
Conditions & References
61.5 %
With sodium hydroxide, nitrobenzene, PEG-400, 1,10-phenanthroline in water, Time= 3h, T= 170 °C , Oxidation Gogotov; Rybal'chenko; Makovskaya; Babkin; Russian Chemical Bulletin; vol. 45; nb. 12; (1996); p. 2854 - 2857 View in Reaxys O
HO
birch wood
O
O
O
HO
O
Rx-ID: 8509397 View in Reaxys 33/87 Yield
Conditions & References
52.2 %
With sodium hydroxide, nitrobenzene, 1,10-phenanthroline in water, Time= 3h, T= 170 °C , Oxidation Gogotov; Rybal'chenko; Makovskaya; Babkin; Russian Chemical Bulletin; vol. 45; nb. 12; (1996); p. 2854 - 2857 View in Reaxys
O
O
O
O Si
O O
HO
O
Rx-ID: 9261486 View in Reaxys 34/87 Yield 98 %
Conditions & References With N,N,N-triethylamine N-oxide in methanol, Time= 3h Zubaidha; Bhosale; Hashmi; Tetrahedron Letters; vol. 43; nb. 40; (2002); p. 7277 - 7279 View in Reaxys
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O
/PXGAB114--212/
OH O
O HO
O
Rx-ID: 11645842 View in Reaxys 35/87 Yield
Conditions & References Reaction Steps: 2 1: 97 percent / Br2 / methanol 2: 92 percent / CuBr / dimethylformamide With bromine, copper(I) bromide in methanol, N,N-dimethyl-formamide Zabinski, Jerzy; Wolska, Irena; Maciejewska, Dorota; Journal of Molecular Structure; vol. 833; nb. 1-3; (2007); p. 74 - 81 View in Reaxys
O
O O
O OH
HO
O
O
Rx-ID: 12099118 View in Reaxys 36/87 Yield
Conditions & References Reaction Steps: 2 1: 85 percent / pyridinium chlorochromate / CH2Cl2 / 20 °C 2: 92 percent / NaH; PhSH; HMPT / toluene / Heating With N,N,N,N,N,N-hexamethylphosphoric triamide, sodium hydride, thiophenol, pyridinium chlorochromate in dichloromethane, toluene Zou, Hong Bin; Dong, Sheng Yi; Zhou, Chang Xin; Hu, Li Hong; Wu, Yi Hang; Li, Hai Bo; Gong, Jing Xu; Sun, Lian Li; Wu, Xiu Mei; Bai, Hua; Fan, Bo Tao; Hao, Xiao Jiang; Stoeckigt, Joachim; Zhao, Yu; Bioorganic and Medicinal Chemistry; vol. 14; nb. 6; (2006); p. 2060 - 2071 View in Reaxys
O
O O
O
O O
HO
O
O
Rx-ID: 12099682 View in Reaxys 37/87 Yield
Conditions & References Reaction Steps: 3 1: 72 percent / LiAlH4 / tetrahydrofuran / Heating 2: 85 percent / pyridinium chlorochromate / CH2Cl2 / 20 °C 3: 92 percent / NaH; PhSH; HMPT / toluene / Heating With N,N,N,N,N,N-hexamethylphosphoric triamide, lithium aluminium tetrahydride, sodium hydride, thiophenol, pyridinium chlorochromate in tetrahydrofuran, dichloromethane, toluene Zou, Hong Bin; Dong, Sheng Yi; Zhou, Chang Xin; Hu, Li Hong; Wu, Yi Hang; Li, Hai Bo; Gong, Jing Xu; Sun, Lian Li; Wu, Xiu Mei; Bai, Hua; Fan, Bo Tao; Hao, Xiao Jiang; Stoeckigt, Joachim; Zhao, Yu; Bioorganic and Medicinal Chemistry; vol. 14; nb. 6; (2006); p. 2060 - 2071 View in Reaxys Br
O
HO
O
O
KOH-solution
O HO
O
Rx-ID: 16913830 View in Reaxys 38/87
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Yield
Conditions & References Reaction Steps: 2 1: 60 percent / NaOH, Cu / H2O / 25.5 h / 101 °C 2: Na2CO3 / acetone / 5 h / Heating With sodium hydroxide, copper, sodium carbonate in water, acetone Ellis, James E.; Lenger, Steven R.; Synthetic Communications; vol. 28; nb. 9; (1998); p. 1517 - 1524 View in Reaxys O
HO
O
alcoholic potash
O
O HO
O
Rx-ID: 19367461 View in Reaxys 39/87 Yield
Conditions & References Reaction Steps: 2 1: 48.5 g / Br2, AcOH 2: 18 g / CuCl2 / dimethylformamide / 1 h / 120 °C With bromine, acetic acid, copper dichloride in N,N-dimethyl-formamide Puri, S. C.; Anand, S. M.; Atal, C. K.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 24; (1985); p. 294 - 295 View in Reaxys O
HO
O
O
O HO
O
Rx-ID: 21269792 View in Reaxys 40/87 Yield
Conditions & References Reaction Steps: 2 1: 95 percent / Br2 / acetic acid / 1 h 2: 83 percent / CuCl2 / dimethylformamide; methanol / 1 h / 100 °C With bromine, copper dichloride in methanol, acetic acid, N,N-dimethyl-formamide Rao, Durvasula V.; Stuber, F. A.; Synthesis; nb. 4; (1983); p. 308 View in Reaxys Reaction Steps: 2 1: 95 percent / Br2 / methanol / 1 h / Ambient temperature 2: 91 percent / Cu2Cl2 / dimethylformamide / 2.5 h / 97 °C With copper(I) chloride, bromine in methanol, N,N-dimethyl-formamide Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys Reaction Steps: 2 1: bromine / methanol 2: copper(l) chloride / N,N-dimethyl-formamide With bromine, copper(l) chloride in methanol, N,N-dimethyl-formamide Li, Yan; Dai, Fang; Jin, Xiao-Ling; Ma, Meng-Meng; Wang, Yi-Hua; Ren, Xiao-Rong; Zhou, Bo; Food Chemistry; vol. 158; (2014); p. 41 - 47 View in Reaxys
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O O
HO
HO
O
Rx-ID: 21713992 View in Reaxys 41/87 Yield
Conditions & References Reaction Steps: 3 1: Br2 / chlorobenzene / 4.5 h / Heating 2: 0.1 N aq. HCl / methanol / 4.5 h / 5 °C 3: 88 percent / Cu2Cl2 / dimethylformamide / 2.5 h / 97 °C With Cu2Cl2, hydrogenchloride, bromine in methanol, N,N-dimethyl-formamide, chlorobenzene Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys Br
O
Br OH
O
Br HO
Br
O
Rx-ID: 21721941 View in Reaxys 42/87 Yield
Conditions & References Reaction Steps: 2 1: 0.1 N aq. HCl / methanol / 4.5 h / 5 °C 2: 88 percent / Cu2Cl2 / dimethylformamide / 2.5 h / 97 °C With Cu2Cl2, hydrogenchloride in methanol, N,N-dimethyl-formamide Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys O O
OH O
HO
O
Rx-ID: 21749848 View in Reaxys 43/87 Yield
Conditions & References Reaction Steps: 2 1: 95.5 percent / Br2 / methanol / 1 h / Ambient temperature 2: 88 percent / Cu2Cl2 / dimethylformamide / 2.5 h / 97 °C With Cu2Cl2, bromine in methanol, N,N-dimethyl-formamide Manchand, Percy S.; Belica, Peter S.; Wong, Harry S.; Synthetic Communications; vol. 20; nb. 17; (1990); p. 2659 - 2666 View in Reaxys
O
O
HO O
O
O OH
O
O
O HO
O
Rx-ID: 22058168 View in Reaxys 44/87 Yield
Conditions & References Reaction Steps: 2 1: durch aufeinanderfolgende Verseifung und Oxydation mit Kupfersulfat 2: dimethyl-p-toluidine With 2,3,4-trimethylaniline
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Mauthner; Justus Liebigs Annalen der Chemie; vol. 395; (1913); p. 279 View in Reaxys
O
O
O HO O
HO
O
Rx-ID: 22080862 View in Reaxys 45/87 Yield
Conditions & References Reaction Steps: 2 1: aqueous KOH; aniline / 180 °C 2: nitrobenzene; aq. NaOH solution With potassium hydroxide, sodium hydroxide, nitrobenzene, aniline Pearl; Journal of the American Chemical Society; vol. 70; (1948); p. 1746 View in Reaxys
O
O O
O
O O
O
O
HO
Cl
O
Rx-ID: 22103221 View in Reaxys 46/87 Yield
Conditions & References Reaction Steps: 2 1: toluene; palladium/barium sulfate / 110 °C / Hydrogenation 2: ethanol; aq. NaOH solution; hydrogen With sodium hydroxide, Pd-BaSO4, ethanol, hydrogen, toluene Mauthner; Journal fuer Praktische Chemie (Leipzig); vol. <2> 142; (1935); p. 26,31 View in Reaxys
O O
O
O O
O
O OH
HO
O
Rx-ID: 22395418 View in Reaxys 47/87 Yield
Conditions & References Reaction Steps: 3 1: pyridine; SOCl2 2: palladium/BaSO4; xylene / Hydrogenation 3: CHCl3; methanol. sodium methylate With pyridine, Pd-BaSO4, thionyl chloride, chloroform, sodium methylate, xylene Freudenberg; Huebner; Chemische Berichte; vol. 85; (1952); p. 1181,1188 View in Reaxys O
2-Ethylhexyl-alpha-aceto-3,5-dimethoxy-4-hydroxy cinnamate
O HO
O
Rx-ID: 25859063 View in Reaxys 48/87 Yield 92%
Conditions & References I : 2-Ethylhexyl-alpha-aceto-3,5-dimethoxy-4-hydroxy cinnamate Example I 2-Ethylhexyl-alpha-aceto-3,5-dimethoxy-4-hydroxy cinnamate
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Monodemethylation of 3,4,5-trimethoxy benzaldehyde using sulphuric acid at 40° C. for 8 hours yields 3,5-Dimethoxy-4-hydroxy benzaldehyde (Syringaldehyde). Condensation of syringaldehyde with 2-ethylhexyl acetoacetate in the presence of piperidine-acetic acid and benzene as the reaction medium at reflux temperature under continuous azeotropic water removal yields the title product. The reaction takes about 1.5 hours for completion. The yield obtained is typically 92percent. Patent; EMD CHEMICALS, INC.; US2004/247536; (2004); (A1) English View in Reaxys O
HO
lignin
OH
O
O
O
O
HO
O
Rx-ID: 28896028 View in Reaxys 49/87 Yield
Conditions & References
2.49 With water, oxygen, sodium hydroxide, T= 120 °C , p= 15001.5Torr %Chromat., 4.56 Zhang, Junhua; Deng, Haibo; Lin, Lu; Molecules; vol. 14; nb. 8; (2009); p. 2747 - 2757 View in Reaxys %Chromat., 11.51 %Chromat. With nitrobenzene, Autoclave, Alkaline conditions Yang, Xiao-Hui; Zhang, Ping-Hu; Zhou, Yong-Hong; Liu, Cheng-Guo; Lin, Xiao-Yu; Cui, Jing-Fang; Arkivoc; vol. 2011; nb. 10; (2011); p. 327 - 337 View in Reaxys
NH 2
O
OH
OH
HO O
O
H 2N
N
H O
S+
N
O
N
O
N
HO HO
O
OH
Rx-ID: 31162057 View in Reaxys 50/87 Yield
Conditions & References With sorgum caffeic acid O-methyltransferase (Bmr-12), sulfolobus S-adenosylhomocysteine hydrolase in water, N,N-dimethyl-formamide, T= 37 °C , pH= 7.5, aq. buffer, Enzymatic reaction, Kinetics Palmer, Nathan A.; Sattler, Scott E.; Saathoff, Aaron J.; Sarath, Gautam; Journal of Agricultural and Food Chemistry; vol. 58; nb. 9; (2010); p. 5220 - 5226 View in Reaxys
OH
O
O
O
HO
O O
O S
O
O
O
O O HO
HO
O
Rx-ID: 32612034 View in Reaxys 51/87 Yield 73 %
Conditions & References 5.2.7. 3-Hydroxy-4,5-dimethoxybenzaldehyde (15) A mixture of 14 (25 g, 148.8 mmol), (CH3)2SO4 (18.75 g, 148.8 mmol), and Na2CO3 (17.5 g, 165.1 mmol) was slurred into acetone and further reflux for 6 h. The resulting crude was further purified by column chromatography to obtain an oil and this was readily crystallized to give 15 (19.8 g, 73percent), m.p. 65-67 °C; IR (neat) νmax 3414, 2943, 2843, 1689, 1589, 1504, 1462, 1338, 1203, 1134, 995, 837, 752, 702 cm-1; 1HNMR (300 MHz, DMSO-d6) δ 9.78 (1H, s, CHO), 9.71 (1H, s, OH), 7.03 (2H, s), 3.83 (3H, s, OMe), 3.76 (3H, s, OMe); 13CNMR (75 MHz, DMSO-
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d6) δ 191.8, 153.5, 151.0, 141.8, 131.6, 111.0, 104.3, 59.9, 55.8; EIMS m/z (rel. int.): 182 [M]+ (100), 167 (35), 111 (26), 93 (11); HREIMS calcd for C9H10O4 [M]+ 182.0579, found 182.0576. With sodium carbonate in acetone, Time= 6h, Reflux Huang, Guan-Jhong; Bhaskar Reddy, M. Vijaya; Kuo, Ping-Chung; Huang, Chieh-Hung; Shih, Hung-Cheng; Lee, E.-Jian; Yang, Mei-Lin; Leu, Yann-Lii; Wu, Tian-Shung; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 371 - 378 View in Reaxys
Br
O
O
HO O
O
O
O O
HO
HO
O
Rx-ID: 32612041 View in Reaxys 52/87 Yield
Conditions & References Reaction Steps: 2 1.1: copper; sodium hydroxide / water / Reflux 1.2: Reflux 2.1: sodium carbonate / acetone / 6 h / Reflux With copper, sodium carbonate, sodium hydroxide in water, acetone Huang, Guan-Jhong; Bhaskar Reddy, M. Vijaya; Kuo, Ping-Chung; Huang, Chieh-Hung; Shih, Hung-Cheng; Lee, E.-Jian; Yang, Mei-Lin; Leu, Yann-Lii; Wu, Tian-Shung; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 371 - 378 View in Reaxys
O
O
HO O
O
O
O O HO
HO
O
Rx-ID: 32612066 View in Reaxys 53/87 Yield
Conditions & References Reaction Steps: 3 1.1: bromine; acetic acid / 1.5 h 2.1: copper; sodium hydroxide / water / Reflux 2.2: Reflux 3.1: sodium carbonate / acetone / 6 h / Reflux With bromine, copper, sodium carbonate, acetic acid, sodium hydroxide in water, acetone Huang, Guan-Jhong; Bhaskar Reddy, M. Vijaya; Kuo, Ping-Chung; Huang, Chieh-Hung; Shih, Hung-Cheng; Lee, E.-Jian; Yang, Mei-Lin; Leu, Yann-Lii; Wu, Tian-Shung; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 371 - 378 View in Reaxys
O
O O O
HO OH O
HO
O
Rx-ID: 34529951 View in Reaxys 54/87 Yield
Conditions & References With chromic acid in water, Kinetics, Mechanism, pH-value, Concentration, Temperature, Reagent/catalyst Kulkarni; Bongane; Gavali; Patel; Journal of the Indian Chemical Society; vol. 89; nb. 10; (2012); p. 1347 - 1350 View in Reaxys
Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.
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O
HO
liginin
OH
O
O
O
O
HO
O
Rx-ID: 35259189 View in Reaxys 55/87 Yield
Conditions & References
14.7 %, 8.8 %, 6.2 %
With oxygen, copper(II) sulfate, isobutyl methylketone, Time= 1.5h, T= 175 °C , p= 18751.9Torr , Ionic liquid, Concentration, Time, Temperature, Solvent Liu, Shiwei; Shi, Zhongliang; Li, Lu; Yu, Shitao; Xie, Congxia; Song, Zhanqian; RSC Advances; vol. 3; nb. 17; (2013); p. 5789 - 5793 View in Reaxys O
HO
liginin
O
O
O
HO
O
Rx-ID: 35259190 View in Reaxys 56/87 Yield
Conditions & References
10.5 %, 5.4 %
With oxygen, copper(II) sulfate, Time= 1.5h, T= 175 °C , p= 22502.3Torr , Ionic liquid Liu, Shiwei; Shi, Zhongliang; Li, Lu; Yu, Shitao; Xie, Congxia; Song, Zhanqian; RSC Advances; vol. 3; nb. 17; (2013); p. 5789 - 5793 View in Reaxys
O
OH
O O
O
OH
O
O
O HO
O O
O
O
O
HO
O
O
racemate
Rx-ID: 37061181 View in Reaxys 57/87 Yield
Conditions & References
9 %Spectr., 82 %Spectr., 6 %Spectr., 25 %Spectr.
With 2,6-dimethylpyridine, 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, (CuOTf)2*C6H5CH3, oxygen in toluene, Time= 36.0833h, T= 100 °C , Schlenk technique, Sealed tube, chemoselective reaction Sedai, Baburam; Diaz-Urrutia, Christian; Baker, R. Tom; Wu, Ruilian; Silks, L. A. Pete; Hanson, Susan K.; ACS Catalysis; vol. 3; nb. 12; (2013); p. 3111 - 3122 View in Reaxys
O
O
O
O HO O
HO
O
Rx-ID: 37471112 View in Reaxys 58/87 Yield 86 %
Conditions & References With copper diacetate, ethylene glycol, Time= 8h, T= 50 °C , Green chemistry, chemoselective reaction Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
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OH
O O
O HO O
O
O OH
Rx-ID: 37471113 View in Reaxys 59/87 Yield
Conditions & References
94 %
With copper diacetate, ethylene glycol, Time= 8h, T= 50 °C , Green chemistry, chemoselective reaction Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
92 %
With oxygen, cobalt(II) acetate, sodium hydroxide in water, ethylene glycol, Time= 12h, T= 50 °C , p= 760.051Torr , Green chemistry Jiang, Jian-An; Du, Jia-Lei; Zhang, Zhong-Nan; Zhai, Jiao-Jiao; Ji, Ya-Fei; Synthetic Communications; vol. 44; nb. 10; (2014); p. 1430 - 1440 View in Reaxys O
O
O OH
O HO O
HO
O
Rx-ID: 39163500 View in Reaxys 60/87 Yield
Conditions & References With peracetic acid, T= 50 °C , pH= 2 Popova; Beloglazova; Bogolitsyn; Tortseva; Verkholomova; Pokryshkin; Russian Journal of General Chemistry; vol. 84; nb. 11; (2014); p. 2092 - 2097; Zh. Obshch. Khim.; vol. 84; nb. 11; (2014); p. 1794 - 1799,6 View in Reaxys
H N
lignin
HO
O O
HO
OH
O
O
OH
O
O
O
HO
HO
O O
HO
OH
O
O
O HO
O
Rx-ID: 39373755 View in Reaxys 61/87 Yield
Conditions & References With anhydrous iron chloride in water, Time= 2h, T= 130 °C , Ionic liquid Yi, Fengping; Jiang, Xiaoyan; Niu, Jihua; Zhang, Lirong; Wang, Zhen; Asian Journal of Chemistry; vol. 27; nb. 3; (2015); p. 885 - 888 View in Reaxys OH O
O
O O
O
OH
OH O
HO
O
Rx-ID: 44160112 View in Reaxys 62/87
Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.
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Yield
Conditions & References
11 %
With sodium persulfate, Ir(2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine)2(4,4’-di-tert-butyl-2,2’-bipyridine)PF6, palladium diacetate in N,N-dimethyl-formamide, Time= 15h, T= 20 °C , Irradiation, chemoselective reaction Kärkäs, Markus D.; Bosque, Irene; Matsuura, Bryan S.; Stephenson, Corey R. J.; Organic Letters; vol. 18; nb. 19; (2016); p. 5166 - 5169 View in Reaxys
O O
O
O O
O
HO
O
O
Rx-ID: 45724436 View in Reaxys 63/87 Yield
Conditions & References
90 %
MOM Deprotection by pTSA General procedure: MOM ether (5 mmol) and pTSA.H2O (7.7 mmol) weretriturated well in a mortar for 5 min (in the case of entry 10trituration time was about 15 min), reaction mixture was leftat room temperature for another 30 min. After completion ofthe reaction (monitored by TLC), cold water (4oC) wasadded. The products were separated by centrifugation. Theyields of the products ranged from 85-98percent. The purities andthe identities of the products were established by direct comparisonwith known compounds (TLC, Mp and IR). See supplementaryinformation for further details. With toluene-4-sulfonic acid in neat (no solvent, solid phase), Time= 0.583333h, T= 20 °C , Green chemistry Pandurangan, Nanjan; Letters in Organic Chemistry; vol. 14; nb. 4; (2017); p. 231 - 235 View in Reaxys O
O 2H
2H
O HO
O
O
O OH
Rx-ID: 9030246 View in Reaxys 64/87 Yield
Conditions & References With nafion resin, water-d2, Time= 24h, T= 90 °C Tuck, Kellie L.; Hayball, Peter J.; Journal of Labelled Compounds and Radiopharmaceuticals; vol. 44; nb. 14; (2001); p. 1005 - 1012 View in Reaxys H 14C
O
O HO
O
Rx-ID: 7406770 View in Reaxys 65/87 Yield
Conditions & References Amid d. unmark. O-Benzyl-syringasaeure (mehrere Stufen) Freudenberg; Reichert; Naturwissenschaften; vol. 41; (1954); p. 229 View in Reaxys 4-Brom-2,6-dimethoxy-phenol, 1. Cu14CN, 2. Raney-Nickel, NaH2PO2, Reduktion Billek et al.; Journal of Labelled Compounds; vol. 5; (1969); p. 3,7 View in Reaxys
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NH 2
OH
N
HO
O
N
H 14 3 C
O N
–O
O
O
O
N
O S+
H 2N
HO
14CH
3
HO
O
OH
Rx-ID: 10399428 View in Reaxys 66/87 Yield
Conditions & References With 5-O-methyltransferase, caffeic acid, 3-(4,5-dihydroxy-3-methoxyphenyl)prop-2-enoic acid, Enzyme kinetics, Further Variations: Reagents Kota, Parvathi; Guo, Dianjing; Zubieta, Chloe; Noel, Joe; Dixon, Richard A.; Phytochemistry; vol. 65; nb. 7; (2004); p. 837 - 846 View in Reaxys O
HO –O
Na +
O
2H
O
2H
2H
O
O
OH
2H
2H
2H
Rx-ID: 11261464 View in Reaxys 67/87 Yield
Conditions & References Stage 1: With sodium hydroxide, iodine, potassium iodide in water, Time= 8h, T= 20 °C Stage 2: With copper, Time= 3h, T= 128 °C , Further stages. Sakakibara, Norikazu; Nakatsubo, Tomoyuki; Suzuki, Shiro; Shibata, Daisuke; Shimada, Mikio; Umezawa, Toshiaki; Organic and Biomolecular Chemistry; vol. 5; nb. 5; (2007); p. 802 - 815 View in Reaxys O N
N
2H
N
2H
O
2H
N
2H
2H
O
2H
2H 2H
OH
2H
O
2H
2H
O
2H
OH
Rx-ID: 9189517 View in Reaxys 68/87 Yield
Conditions & References
40.5 %
With sulfuric acid, boric acid in glycerol, Time= 1h, T= 110 °C Yamauchi, Kazuchika; Yasuda, Seiichi; Fukushima, Kazuhiko; Journal of agricultural and food chemistry; vol. 50; nb. 11; (2002); p. 3222 - 3227 View in Reaxys
HO
2H
2H
2H
O
2H
O
I
O
2H 2H
2H
2H
O
2
H
2
H
2
2H
O
2
H
O
H
OH
Rx-ID: 9388028 View in Reaxys 69/87 Yield
Conditions & References With sodium, Time= 3h, T= 128 °C Sakakibara, Norikazu; Suzuki, Shiro; Umezawa, Toshiaki; Shimada, Mikio; Organic and biomolecular chemistry; vol. 1; nb. 14; (2003); p. 2474 - 2485 View in Reaxys
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O
HO O
2H 2H
2H
2H
2H
O
2H
O
2H
2H
O
2H
OH
Rx-ID: 14046247 View in Reaxys 70/87 Yield
Conditions & References Reaction Steps: 2 1: I2; KI; aq. NaOH / 2 h / 20 °C 2: Na / 3 h / 128 °C With sodium hydroxide, iodine, sodium, potassium iodide Sakakibara, Norikazu; Suzuki, Shiro; Umezawa, Toshiaki; Shimada, Mikio; Organic and biomolecular chemistry; vol. 1; nb. 14; (2003); p. 2474 - 2485 View in Reaxys 2H
O
O
2H 2H
O
2H
2H
O
2H
2H
2H
O
2H
OH
O
Rx-ID: 14054186 View in Reaxys 71/87 Yield
Conditions & References Reaction Steps: 3 1: aq. HCl / acetic acid / 1 h / Heating 2: I2; KI; aq. NaOH / 2 h / 20 °C 3: Na / 3 h / 128 °C With hydrogenchloride, sodium hydroxide, iodine, sodium, potassium iodide in acetic acid Sakakibara, Norikazu; Suzuki, Shiro; Umezawa, Toshiaki; Shimada, Mikio; Organic and biomolecular chemistry; vol. 1; nb. 14; (2003); p. 2474 - 2485 View in Reaxys O
2H
Br
Br OH
2H
2H
O
2H
2H
O
2H
OH
Rx-ID: 14472923 View in Reaxys 72/87 Yield
Conditions & References Reaction Steps: 2 1: 67 percent / CuCl2 / dimethylformamide; tetradeuteriomethanol / 1 h / Heating 2: 40.5 percent / boric acid; aq. H2SO4 / glycerol / 1 h / 110 °C With sulfuric acid, boric acid, copper dichloride in d(4)-methanol, N,N-dimethyl-formamide, glycerol Yamauchi, Kazuchika; Yasuda, Seiichi; Fukushima, Kazuhiko; Journal of agricultural and food chemistry; vol. 50; nb. 11; (2002); p. 3222 - 3227 View in Reaxys forest plant material
O
O
HO
HO
E
O
O
Z O
O
HO O
HO
O
O
Rx-ID: 8603883 View in Reaxys 73/87 Yield
Conditions & References With air, Formation of xenobiotics, Oxidation, Further byproducts given
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Kjaellstrand, Jennica; Ramnaes, Olle; Petersson, Goeran; Chemosphere; vol. 41; nb. 5; (2000); p. 735 - 741 View in Reaxys
OH O
O S
O
O
O
O
O
O
HO
O
O
O
O
O
O
HO
O
HO
O
Rx-ID: 4892260 View in Reaxys 74/87 Yield
Conditions & References
70 %, 10 %
With sodium carbonate in acetone, Time= 5h, Heating Ellis, James E.; Lenger, Steven R.; Synthetic Communications; vol. 28; nb. 9; (1998); p. 1517 - 1524 View in Reaxys
O
bamboo lignine
HO
HO
O
O
O
O
HO O
O
O
HO
O
O
Rx-ID: 40788860 View in Reaxys 75/87 Yield
Conditions & References With oxygen, copper(II) sulfate, sodium hydroxide in water, T= 170 °C , p= 6375.64Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Overall yield = 9.5 percent Alunga, Kissa R.; Ye, Yue-Yuan; Li, Shui-Rong; Wang, Duo; Liu, Yun-Quan; Catalysis Science and Technology; vol. 5; nb. 7; (2015); p. 3746 - 3753 View in Reaxys
O O
E
OH
O
O O
OH
O
O
HO
HO
OH O
HO
O
HO
O
O
Rx-ID: 9315496 View in Reaxys 76/87 Yield 26 %, 13 %, 8 %
Conditions & References With Stichococcus bacillaris 155LTAP, Microbiological reaction DellaGreca, Marina; Pinto, Gabriele; Pollio, Antonino; Previtera, Lucio; Temussi, Fabio; Tetrahedron Letters; vol. 44; nb. 14; (2003); p. 2779 - 2780 View in Reaxys
O HO
lignin
O
O
O
OH
OH
O
O O
O
HO
O
O
O HO
O
Rx-ID: 29377398 View in Reaxys 77/87 Yield
Conditions & References 11 :Experiments 01-11 and Blank Sample (see Table 1):In a typical experiment, 9.13 g of the POM H3PMo12O40 were dissolved in 100 ml of water or a water/alcohol mixture, which corresponds formally to a 0.05 molar solution. This was then transferred into a 500 ml autoclave (Premex Reactor AG, Lengnau, Switzerland). Before the closure of the reactor, 1 g of pulverulent lignin was added. The reaction mixture was then contacted three times with 5 bar of oxygen or nitrogen and vented, in order to displace the air initially present. Finally, the reactor was filled with 5 bar of oxygen or 10 bar of nitrogen. The reaction mixture was heated to 170° C. at a rate of 8 K/min at a stirrer speed of 1200 rad/min. The mixture was kept at 170° C. for 20 minutes. The liquid phase was removed after 20 minutes. This was followed by the sampling through a water-cooled cooling coil. The sample was filtered once and then extracted
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three times with 10 ml of chloroform. 30 μl of n-decane were added to the organic phase as an internal standard for the GC-MS analysis (Fisons instruments GC8000/MD800; column from Restek Rtx-5MS 30 m.x.0.25 mm.x.0.25 μm).In experiments 03, 04, 08, 09, 10 and 11, free-radical scavengers (methanol, ethanol) were used.In experiment 02, a second liquid phase in the form of 30 ml of chloroform was added before the closure of the reactor.In experiment 05, 9.45 g of the POM Na3PMo12O40 were used. In the blank sample, no POM was used.Experiment 12 and Wu et al. (G. X. Wu, M. Heitz, E. Chornet, Ind. Eng. Chem. Res. 33, 718 (March, 1994)) (see table 1):The experimental method in experiment 12 is kept analogous to Wu et al. 10 g of lignin were dissolved in 100 ml of a 3 molar sodium hydroxide solution. The solution was added to a 500 ml autoclave, and the catalyst system consisting of 500 mg of copper sulfate and 50 mg of iron chloride was added. The reactor was closed and filled three times with oxygen at 10 bar and emptied, in order to displace the air originally present. Subsequently, the reaction vessel was placed under pressure with 13.2 bar of oxygen. The reaction mixture was heated to 170° C. at a rate of 8 K/min at a stirrer speed of 1200 rad/min. The mixture was kept at 170° C. for 20 minutes. The liquid phase was withdrawn after 20 minutes. The sampling was effected through a water-cooled cooling coil.In experiment 01, lignin was treated in a 0.05 molar aqueous H3PMo12O40 solution under inert gas. In the course of this, the color of the solution changed from yellowish to dark blue. This shows clearly that the polymolybdate used was reduced. By means of GC-MS analysis, 0.56 mg of lignin-based products (principally vanillin) was quantified.The yield of lignin-based products could be increased by approx. 30percent by in situ extraction (cf. experiment 01 with experiment O2). To this end, a second liquid phase (chloroform) was added to the reaction mixture. This has a higher solubility for the desired degradation products and can therefore withdraw any products formed from the actual reaction medium (aqueous POM solution) before possible further reactions destroy the products formed again.The degradation of lignin with 0.05 molar H3PMo12O40 solution under oxygen (experiment 06) likewise increased the yield compared to the degradation under inert gas (experiment 01). After the experiment under oxygen, in contrast to the experiment under inert gas, only slight discoloration of the solution to yellow-greenish was detected, i.e. the polyoxomolybdate was reduced only very slightly, if at all. This leads to the suspicion that the POM is reoxidizable under the conditions used and, in this case, oxygen is consumed by the POM during the degradation of lignin.Experiment 07 shows that various lignin types can be used and that the yield of chemicals here is within the same order of magnitude. According to the manufacturer, the lignin from Aldrich (batch No. 09724CE) is a softwood lignin (principally from spruce wood), which was obtained in the Kraft process. The lignin from the Granit.(R). process was, in contrast, obtained from plants utilized in agriculture and therefore has a different chemical structure.In experiment 05, the POM used was the sodium salt Na3PMo12O40 corresponding to H3PMo12O40. The yield of chemicals is noticeably higher in this experiment. It is therefore found that changes in the POM system used which are slight from a chemical point of view can affect the yield of desired products. The use of a very substantially optimal POM system is therefore of crucial significance for the attainment of high yields.The positive effect of the free-radical scavenger with regard to the yield of chemicals was demonstrated in experiments 03 and 04 compared to experiment 01 and the blank sample. In experiments 03 and 04, ethanol and methanol were used as free-radical scavengers. Using the free-radical scavengers, the yield was enhanced from 0.56 mg to 1.17 mg in the case of ethanol and to 2.38 mg in the case of methanol.In the case of the blank sample without POM, no lignin-based products were detectable.FIG. 1 shows the corresponding GC-MS chromatograms and illustrates that not only are the amounts of vanillin and 4-hydroxyacetyl-2-methoxyphenol produced greater when the free-radical scavengers are used, but novel components are also prepared in amounts comparable to vanillin.The formation of vanillic acid methyl ester in experiment 04 shows that methanol is incorporated into the product (see equation 11).Using ethanol as the free-radical scavenger, in contrast, vanillic acid ethyl ester is formed (see equation 12).In addition, experiments were carried out to verify the mechanism indicated in equations 11 and 12. With deuterated methanol CD3OD, it was possible to show clearly that a methanol radical is incorporated into the vanillic acid methyl ester product. The molecular weight of vanillic acid methyl ester produced in reactions of lignin in the presence of undeuterated methanol was determined by means of GC-MS analysis to be 182 g/mol. Using deuterated methanol, the molecular weight was determined to be 185 g/mol. In addition, it was checked whether the formation of the vanillic acid methyl ester is also possible from vanillin, for example via the reaction route of vanillin vanillic acid vanillic acid methyl ester. The treatment of vanillin in 0.05 molar H3PMo12O40 solution under nitrogen in the presence of methanol gave no products whatsoever. It can consequently be assumed that the acyl radical shown in equations 11 and 12 results from the scission of the Cα-Cβ bond in the lignin.The formation of the CH3O. radical from methanol was also considered in more detail. The homolytic scission of the O-H bond in methanol is thermodynamically improbable owing to the high bond energy of 104 kcal/mol. It was, however, found that methanol in aqueous H3PMo12O40 solution under nitrogen is converted partly to dimethyl ether. The homolytic scission of the C-O bond in dimethyl ether is possible owing to the relatively low bond energy of 84 kcal/mol. It is consequently possible that methanol can form free radicals via acid-catalyzed ether formation and is thus considered to be a freeradical scavenger in the context of this invention. The direct addition of dimethyl ether as a free-radical scavenger for conversion of lignin in aqueous H3PMo12O40 solution under nitrogen and in the absence of methanol results in the production of a small amount of vanillic acid methyl ester. It was thus shown that dimethyl ether is directly active as a free-radical scavenger, and the homolytic scission of dimethyl ether and the associated formation of vanillic acid methyl ester is possible. In order to be able to compare the results of the degradation of lignin by means of POM and
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free-radical scavengers with the prior art, the method used by Wu et al. (benchmark) was applied to the lignin from Aldrich used in our examples.A comparison of the results revealed that the yield of lignin-based chemicals using the softwood lignin is very much lower compared to Wu et al. (one factor of ten). The reason for this may be the use of a very different lignin type. The lignin from Sigma-Aldrich used in our study is, according to the manufacturer, a typical softwood lignin which was isolated from spruce wood by means of the Kraft process. Wu et al. used, in contrast, a self-produced lignin type produced from hardwood by means of steam digestion. It is known that hardwood lignin has a very much higher proportion of syringyl units (50percent). The comparatively high proportion of syringyl units is also reflected in the results of Wu et al. in the considerable amount of syringaldehyde produced (7.8percent by weight). Softwood lignin (from the spruce) possesses, in contrast, a very great proportion of guaiacyl units (90percent). This corresponds with our results, in which only traces of syringaldehyde were formed. It is additionally known that the degradation of hardwood lignin proceeds very much more easily and rapidly than the degradation of softwood lignin. In addition, the hardwood lignin produced by Wu et al. was not characterized fully. The composition of the acid-insoluble lignin is reported by Wu et al. as: Klason lignin=84.7percent; acid-soluble lignin=3.0percent and others (unknown)=12.3percent.An economically viable process requires a reliable and inexpensive lignin source. It therefore appears to be advisable to use softwood lignin, which is obtainable in large amounts, as a starting material for chemical production. As already indicated, softwood lignin is obtained as a waste product in papermaking (for example in the Kraft or sulfite process). The method of Wu et al. is therefore applied below to the lignin available to us as a benchmark.A comparison of experiment 10 in which lignin was converted under oxygen in the presence of POM and free-radical scavenger with the prior art method (experiment 12) shows that a higher product yield is achieved with the inventive method. The chemicals produced are principally vanillin (16.5 mg) and vanillic acid methyl ester (13.5 mg).In experiment 11, poplar lignin was used. The product yield is likewise in the region of 3.5percent by weight. The main products here are, however, vanillin (5.0 mg), vanillic acid methyl ester (6.2 mg), syringaldehyde (8.2 mg) and syringic acid methyl ester (12.2 mg), corresponding to the chemical structure of poplar lignin with a relatively high proportion of syringyl units.It should be noted that the examples adduced in this document represent the first test series. The achievement of the comparatively higher yields is therefore particularly promising, since the inventive method has not yet been optimized. In view of the numerous possible combinations of POM, free-radical scavengers and ultimately also lignin types, there is still a very large amount of room for improvement of the yields. In addition, some reaction technology solutions, for example in situ extraction, are still available. The potential becomes clear in a comparison of experiments 06 and 10, among others. Here, the yield of chemicals was increased by a factor of 30 solely through the use of an aqueous methanol solution. One advantage of the invention presented here also lies in the possibility of preparing different chemicals depending on the free-radical scavenger. For instance, vanillic acid methyl ester is formed in the case of use of methanol, and vanillic acid ethyl ester in the case of use of ethanol. It consequently appears possible, through suitable combinations of POM and free-radical scavenger, to be able to crucially influence not just the yield but also the selectivity for a target product. TABLE 1 Results for production of chemicals from lignin by means of POM and free-radical scavenger compared to conventional methods. Products Experi- Catalytic Lignin [mg] percent by ment system Medium Gas type GC-MSwt.*) 01H3PMo12O40 H2ON2 Aldrich 0.56 0.06 (9.13 g) (100 ml) (10 bar) (1 g) 02H3PMo12O40 H2ON2 Aldrich 0.74 0.08 (9.13 g) (100 ml) (10 bar) (1 g) CHCl3 (30 ml) 03H3PMo12O40 H2ON2 Aldrich 1.17 0.13 (9.13 g) (60 ml) (10 bar) (1 g) C2H5OH (40 ml) 04H3PMo12O40 H2ON2 Aldrich 2.38 0.26 (9.13 g) (60 ml) (10 bar) (1 g) CH3OH (40 ml) 05Na3PMo12O40 H2OO2 Aldrich 1.47 0.16 (9.45 g) (100 ml) (5.1 bar) (1 g) 06H3PMo12O40 H2OO2 Aldrich 0.97 0.11 (9.13 g) (100 ml) (5.1 bar) (1 g) 07H3PMo12O40 H2OO2 Granit 0.59 0.06 (9.13 g) (100 ml) (5.1 bar) (1 g) 08H3PMo12O40 H2OO2 Aldrich 9.5 1.04 (9.13 g) (60 ml) (5.1 bar) (1 g) CH3OH (40 ml) 09H3PMo12O40 H2OO2 Aldrich 25.63 2.79 (9.13 g) (40 ml) (5.1 bar) (1 g) CH3OH (60 ml) 10H3PMo12O40 H2OO2 Aldrich 32.73 3.57 (9.13 g) (20 ml) (5.1 bar) (1 g) CH3OH (80 ml) 11H3PMo12O40 H2OO2 Poplar 34.22 3.64 (9.13 g) (20 ml) (5.1 bar) (1 g) CH3OH (80 ml) 12CuSO4/FeCl3 H2OO2 Aldrich 145 1.58 (0.5 g/0.05 g) (100 ml) (13.2 bar) (10 g) NaOH (12 g) Wu et al.CuSO4/FeCl3 H2OO2 Hardwood 12.9 (0.5 g/0.05 g) (100 ml) (13.8 bar) (10 g) NaOH (14.7 g) Blank noneH2ON2 Aldrich 0 0 sample (60 ml) (10 bar) (1 g) C2H5OH (40 ml) *)Based on dry lignin With oxygen, 12-molybdophosphoric acid HPMo in water, T= 170 °C , p= 3825.38Torr Patent; ETH ZURICH; US2010/121110; (2010); (A1) English View in Reaxys
Organosolv-beech-lignin
O
O OH
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O
O O
O
O
HO OH
O
E
O
O
O
HO O
O
O
O
HO
OH
HO
O
Rx-ID: 32062737 View in Reaxys 78/87 Yield
Conditions & References With manganese(II) nitrate, T= 100 °C , p= 6000.6Torr , Ionic liquid, Autoclave Stärk, Kerstin; Taccardi, Nicola; Bösmann, Andreas; Wasserscheid, Peter; ChemSusChem; vol. 3; nb. 6; (2010); p. 719 - 723 View in Reaxys
O
O
O
O
O
O
O
aspen lignin
O
HO OH
OH
OH
O
O
O
O
HO
O
Rx-ID: 39573517 View in Reaxys 79/87 Yield
Conditions & References Stage 1: With oxygen Stage 2: With formic acid, sodium formate in water, Time= 24h, T= 110 °C Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.; Nature; vol. 515; nb. 7526; (2014); p. 249 252 View in Reaxys OH 18O
O HO
O
OH
O
O
OH
O OH
O
O OH
Rx-ID: 37471086 View in Reaxys 80/87 Yield
Conditions & References
83 %, 9 %
With copper diacetate, oxygen-18, Time= 8h, T= 50 °C , p= 760.051Torr , Green chemistry Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys OH
O O HO
O
O
OH
O
HO
OH
O
O
O OH
Rx-ID: 37471087 View in Reaxys 81/87 Yield 27 %, 69 %
Conditions & References With copper diacetate, Time= 4h, T= 50 °C , Green chemistry Jiang, Jian-An; Chen, Cheng; Huang, Jian-Gang; Liu, Hong-Wei; Cao, Song; Ji, Ya-Fei; Green Chemistry; vol. 16; nb. 3; (2014); p. 1248 - 1254 View in Reaxys
65 %, 26 %
2.3 Mechanistic studies (Scheme 2 in the text).
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General procedure: Procedure for Scheme 2(a): mixture of substrate 1 (5.0 mmol), Co(OAc)2*4H2O (0.05 mmol, 12 mg)and NaOH (5.0 mmol, 0.2 g) in EG/H2O (5.0 mL/0.25 mL) was stirred with O2 (1.0 atm) being bubbled at 50 °C for 3 h. Hydrochloric acid (10.0 mL, 2 percent) and chloroform (10.0 mL) were successively added to reaction mixture. The chloroform phase was separated, and the aqueous phase was further extracted with chloroform (10.0 mL × 2). The combined organic layer was dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography on silica gel (eluents:petroleum ether/ethyl acetate, 5/1) to provide the intermediates 3 and desired products 2. With oxygen, cobalt(II) acetate, sodium hydroxide in water, Time= 3h, T= 50 °C , p= 760.051Torr , Green chemistry, Mechanism, regioselective reaction Jiang, Jian-An; Du, Jia-Lei; Zhang, Zhong-Nan; Zhai, Jiao-Jiao; Ji, Ya-Fei; Synthetic Communications; vol. 44; nb. 10; (2014); p. 1430 - 1440 View in Reaxys O O
E
HO
O OH
O O
O HO
OH O
HO
O
O
Rx-ID: 9315497 View in Reaxys 82/87 Yield 75 %, 5 %
Conditions & References With Ankistrodesmus braunii C202.7a, Microbiological reaction DellaGreca, Marina; Pinto, Gabriele; Pollio, Antonino; Previtera, Lucio; Temussi, Fabio; Tetrahedron Letters; vol. 44; nb. 14; (2003); p. 2779 - 2780 View in Reaxys
O
O
O O
O O
HO
O
HO
OH
O
O
Rx-ID: 5317122 View in Reaxys 83/87 Yield 76 % Chromat., 4 % Chromat.
Conditions & References With N-bromosuccinmide, zinc(II) chloride in tetrachloromethane, Time= 3h, T= 120 °C , Arylation Baik, Woonphil; Lee, Hyun Joo; Jang, Jung Min; Koo, Sangho; Kim, Byeong Hyo; Journal of Organic Chemistry; vol. 65; nb. 1; (2000); p. 108 - 115 View in Reaxys
OH
HO
O
O OH
O
O
HO
O
O
O
O
OH HO
O
O
O
HO
O
Rx-ID: 9116148 View in Reaxys 84/87 Yield 47 % Chromat., 47 % Chromat., 3 % Chromat.
Conditions & References With oxygen, 4-methyl-4'-vinyl-2,2'-bipyridine in methanol, Time= 8h, T= 120 °C , p= 3040Torr Takaki, Ken; Shimasaki, Yohei; Shishido, Tetsuya; Takehira, Katsuomi; Bulletin of the Chemical Society of Japan; vol. 75; nb. 2; (2002); p. 311 - 317 View in Reaxys
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H
O
O
H
enzyme-substance from mushrooms
oxygen
O OH O
OH O
O
O
O
O
O
O HO
HO
O
OH O
O
O
HO
O
Rx-ID: 7448654 View in Reaxys 85/87 Yield
Conditions & References Richtzenhain; Chemische Berichte; vol. 77/79; (1944); p. 409,416 View in Reaxys
O O
O
E
O
O
O
O
OH
Z Z
HO
HO O
HO
O
O
O
O
Rx-ID: 9249165 View in Reaxys 86/87 Yield
Conditions & References With horseradish peroxidase II, dihydrogen peroxide in phosphate buffer, T= 30 °C , pH= 8, Kinetics, Product distribution, Further Variations: pH-values Fournand, David; Cathala, Bernard; Lapierre, Catherine; Phytochemistry; vol. 62; nb. 2; (2003); p. 139 - 146 View in Reaxys OH O
O O
E
HO
OH
O
O
OH
HO O
O
O
O
O
O HO
O
OH
Rx-ID: 5199857 View in Reaxys 87/87 Yield
Conditions & References in water, Time= 0.5h, T= 121 °C , p= 750.06Torr , Oxidation Cai; Arntfield; Charlton; JAOCS, Journal of the American Oil Chemists' Society; vol. 76; nb. 4; (1999); p. 433 - 441 View in Reaxys
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