Patent GB-410148-A (GB)
Title: Hydrogenation of organic compounds
IPC: C07B31/00
Filed: 1932-08-12
Abstract: Organic compounds are hydrogenated in the liquid phase in the presence of catalysts comprising copper oxide, chromium oxide and an oxide of an alkali metal and/or an alkaline earth.  In an example, the catalyst is prepared by mixing aqueous solutions of the nitrates of barium, copper and chromium, adding a solution of ammonium carbonate, and decomposing the resulting precipitate. Before use it is suspended in aqueous acetic acid, filtered, washed and dried.  The following reduction processes are mentioned : acetone to isopropyl alcohol, pinacolone to methyl tert. butylcarbinol, acetophenone to methylphenylcarbinol, benzaldehyde to benzyl alcohol, furfural to furfuryl alcohol, acetoacetic ester to b -hydroxybutyric ester, a -methyl-b -ketovaleric to a -methyl-b -hydroxyvaleric ester, diacetone alcohol to 2-methylpentanediol-2 : 4, isobutylmethylketone to 2-methylpentanol-4, benzoin to diphenylethyleneglycol, cyclohexene to cyclohexane, cinnamic to b -phenylpropionic acid, benzalacetone to 4-phenylbutanol-2, mesityloxide to isobutylmethylketone, nitrobenzene to aniline, m-dinitrobenzene to m-phenylenediamine, N-benzylaniline to phenylbenzylamine, N-caproylpiperidine to N-hexylpiperidine, pyridine to piperidine, quinoline to tetrahydroquinoline, benzylalcohol to toluene, diphenylcarbinol to diphenylmethane, methylphenylcarbinol to methylphenylmethane, diphenylethyleneglycol to diphenylethane, furfurylalcohol to pentanediols, ethyl-b -piperidinepropionate to piperidine and ethylpropionate, triphenylmethylketone to triphenylmethane, methylsalicylate to 2-methylcyclohexanol, acetoaceticester to ethyl alcohol.  Either a bomb or a flow system may be employed for the hydrogenation, pressures of 200--350 atmospheres being the most effective. Specification 356,731 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the hydrogenation of organic compounds in the presence of a catalyst comprising an oxide of a hydrogenating metal, an oxide of an acid forming metal with or without oxides of alkalies and alkaline earths.  In further examples: (1) a catalyst is prepared by adding copper oxide to the mixture of oxides obtained by heating barium and ammonium chromates; (2) copper nitrate, barium nitrate, ammonium dichromate and ammonium hydroxide are mixed in aqueous solution and the resulting precipitate decomposed to form the oxides; the barium may be replaced by magnesium or calcium; (3) sodium bicarbonate, and the nitrates of copper, chromium, cadmium and barium are mixed in aqueous solution, and a mixture of oxides prepared by decomposition of the resulting precipitate; (4) ammonium hydroxide and dichromate are mixed in aqueous solution with nitrates of copper, silver and barium and a catalyst prepared from the precipitate; (5) ammonium molybdate and copper nitrate are used in the preparation of a catalyst.  Catalysts comprising oxides of zinc, vanadium, iron potassium and molybdenum are mentioned.  The following reactions are specified: a  - a -diethylacetoacetic ester to a -diethyl-b -hydroxybutyric ester, glucose to sorbitol, phenylethylene to ethylbenzene, 1 : 2-diphenylethylene to 1 : 2-diphenylethane, triphenyl-ethylene to triphenylethane, tetrophenyl-ethylene to tetraphenylethane, cinnamic ester to b -phenylpropionic ester, b -phenylethyl-alcohol to ethylbenzene, b -hydroxypropionic ester to propionic ester and alcohol, 4-methyl-2 : 6-dihydroxymethylphenol to 2 : 4 : 6-trimethylphenol, cyclohexanediol-1 : 5 to cyclohexanol, diphenyl-2-phenoxyethane to phenol and diphenylethane, tetraphenylethane to diphenylmethane, pentaphenylethane to di- and tri-phenylethanes, 2-methylpentanediol to isopropyl alcohol, ethylvalerate to n-amyl alcohol, ethyl trimethylacetate to tert : butylcarbinol, ethyl caproate to n-hexyl alcohol, ethyl caprylate to n-octylalcohol, ethyl laurate to dodecyl alcohol, ethylmyristate to tetradecylalcohol, butyl stearate to octadecyl alcohol, cetylpalmitate to cetyl alcohol, ethyl hexahydrobenzoate to cyclohexyl carbinol, ethyl b -phenyl-propionate to b -phenylpropylalcohol, ethylglutarate to pentamethylene glycol, ethylsebacate to decamethyleneglycol, ethyl lactate to propanediol, valerolacetone to pentanediol, ethyl - a  - phenylbutyrate to 2 - phenylbutanol, ethylsuccinate to tetramethylene glycol, dimethylphenylsuccinate to 2-phenylbutanediol and 3-phenylbutanol, diethyl ester of ethylmalonic ester to 2-methylbutanol, ethyl-N-ethylnicotinate to 1-ethyl-3-methylpiperidine, a  : a -dimethylacetoacetic ester to ethyl and isobutyl alcohols, benzylacetoacetic ester to ethyl alcohol and 3-phenylpropanol-1. This subject-matter does not appear in the Specification as accepted.ALSO:Organic compounds are hydrogenated in the liquid phase in the presence of catalysts comprising copper oxide, chromium oxide, and an oxide of an alkali metal and/or an alkaline earth.  In an example, the catalysts is prepared by mixing aqueous solutions of the nitrates of barium, copper and chromium, adding a solution of ammonium carbonate, and decomposing the resulting precipitate. Before use it is suspended in aqueous acetic acid, filtered, washed and dried.  The following reduction processes are mentioned: acetone to isopropyl alcohol, pinacolone to methyl tert: butylcarbinol, acetophenone to methylphenylcarbinol, benzaldehyde to benzyl alcohol, furfural to furfuryl alcohol, acetoacetic ester to b -hydroxybutyric ester, a -methyl-b -ketovaleric to a -methyl-b -hydroxyvaleric ester, diacetone alcohol to 2 - methylpentanediol - 2 : 4, isobutylmethylketone to 2 - methylpentanol - 4, benzoin to diphenylethyleneglycol, cyclohexene to cyclohexane, cinnamic to b -phenylpropionic acid, benzalacetone to 4-phenylbutanol-2, mesityloxide to isobutylmethylketone, nitrobenzene to aniline, m-dinitrobenzene to m-phenylenediamine, N-benzylaniline to phenylbenzylamine, N-caproylpiperidine to N-hexylpiperidine, pyridine to piperidine, quinoline to tetrahydroquinoline, benzylalcohol to toluene, diphenylcarbinol to diphenylmethane, methylphenylcarbinol to methylphenylmethane, diphenylethyleneglycol to diphenylethane, furfurylalcohol to pentanediols, ethyl-b -piperidinepropionate to piperidine and ethylpropionate, triphenylmethylketone to triphenylmethane, methylsalicylate to 2 - methylcyclohexanol, acetoaceticester to ethyl alcohol.  Either a bomb or a flow system may be employed for the hydrogenation, pressures of 200--350 atmospheres being the most effective.  Specification 356,731 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the hydrogenation of organic compounds in the presence of a catalyst comprising an oxide of a hydrogenating metal, an oxide of an acid forming metal with or without oxides of alkalies and alkaline earths.  In further examples: (1) a catalyst is prepared by adding copper oxide to the mixture of oxides obtained by heating barium and ammonium chromates; (2) copper nitrate, barium nitrate, ammonium dichromate and ammonium hydroxide are mixed in aqueous solution and the resulting precipitate decomposed to form the oxides; the barium may be replaced by magnesium or calcium; (3) sodium bicarbonate, and the nitrates of copper, chromium, cadmium and barium are mixed in aqueous solution, and a mixture of oxides prepared by decomposition of the resulting precipitate; (4) ammonium hydroxide and dichromate are mixed in aqueous solution with nitrates of copper, silver and barium and a catalyst prepared from the precipitate; (5) ammonium molybdate and copper nitrate are used in the preparation of a catalyst.  Catalysts comprising oxides of zinc, vanadium, iron, potassium and molybdenum are mentioned.  The following reactions are specified: a  : a -diethylacetoacetic ester to a -diethyl-b -hydroxybutyric ester, glucose to sorbitol, phenylethylene to ethylbenzene, 1 : 2-diphenylethylene to 1 : 2-diphenylethane, triphenylethylene to triphenylethane, tetraphenylethylene to tetraphenylethane, cinnamic ester to b -phenylpropionic ester, b -phenylethylalcohol to ethylbenzene, b -hydroxypropionic ester to propionic ester and alcohol, 4-methyl-2 : 6 - dihydroxymethylphenol to 2 : 4 : 6 trimethylphenol, cyclohexanediol-1 : 5 to cyclohexanol, diphenyl-2-phenoxyethane to phenol and diphenylethane, tetraphenylethane to diphenylmethane, pentaphenylethane to di-and tri-phenylethanes, 2-methylpentanediol to isopropyl alcohol, ethylvalerate to n-amyl alcohol, ethyl trimethylacetate to tert: butyl-carbinol, ethyl caproate to n-hexyl alcohol, ethyl caprylate to n-octylalcohol, ethyl laurate to dodecyl alcohol, ethylmyristate to tetradecylalcohol, butyl stearate to octodecyl alcohol cetylpalmitate to cetyl alcohol, ethyl hexahydrobenzoate to cyclohexyl carbinol, ethyl b -phenylpropionate to b -phenylpropylalcohol, ethylglutarate to pentamethylene glycol, ethylsebacate to decamethyleneglycol, ethyl lactate to propanediol, valerolactone to pentanediol, ethyl-a -phenylbutyrate to 2-phenylbutanol, ethylsuccinate to tetramethylene glycol, dimethylphenylsuccinate to 2-phenylbutanediol and 3-phenylbutanol, diethyl ester of ethylmalonic ester to 2-methylbutanol, ethyl-N-ethylnicotinate to 1-ethyl-3-methyl-piperidine, a  : a -dimethylacetoacetic ester to ethyl and isobutyl alcohols, benzylacetoacetic ester to ethyl alcohol and 3-phenylpropanol-1.  This subject-matter does not appear in the Specification as accepted.