Patent GB-997614-A (GB)
Title: Activated hydrogenation catalysts
IPC: C07B31/00
Filed: 1963-09-24
Abstract: Saturated and unsaturated aldehydes, alcohols, phenols, acetals, acids, esters, ethers, amides, ketones, nitro compounds, halogen compounds, imido compounds and nitriles are reduced in the presence of a catalyst made by contacting a compound of Rn, Rh, Pd, Os or Pt with compound containing Si-H grouping so that the oxidation state of Group VIII metal is lowered.  Compounds which may be reduced are 3-cyclohexenylmethanol, p-allylphenol, p-crotylphenol, dicrotylphenols, p-(2-cyclopentenyl)phenol, 3-penten-1-ol, 5-decen-1 - ol, 9 - octadecen - 1 - ol, 2 - ethyl - 2 - hexenol, 3 - cyclopentenol, 4 - cyclohexenol, diallylethers of diphenylolmethane and 2 : 2-diphenylolpropane, diallylether, butyl crotyl ether, 2-pentenyl butyl ether; 4-pentenyl butyl ether; 4-octenyl 3-pentenyl ether; orthoallylphenyl ethyl ether; butyl 3-dodecenyl ether; 2,4-diallylphenyl ethyl ether; 3-cyclohexenylmethyl alkyl ethers; 3-cyclohexenylmethyl aryl ethers; 4-decenyl 2-propenyl ether; 1,4-pentadienyl alkyl ether; and 1,4-alkadienyl alkenyl ether, acrylonitrile, propionitrile, pentanenitrile, decanentrile, 3-pentenenitrile, 4-pentenenitrile, 4-cyanocyclohexene, ortho-, meta-, and paravinylbenzonitrile, 3-pentenamide, 4-pentenamide, oleamide, ortho-, meta, and para-vinylbenzamide, 3-cyclohexene-1-carboxamide, N-crotylmaleimide, and N-allylphthalimide, acrolein, crotonaldehyde, 3-hexenal, 3-decanal, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, phenylacetaldehyde, succinaldehyde, glyceraldehyde, adipaldehyde, 2-hydroxyadipaldehyde, vinylacetic acid, oleic acid, cinnamic acid, soybean oil, linseed oil, linoleic acid, mesityl oxide, allyl acetate, allyl methacrylate, crotyl acrylate, a -phenyl-b -pentenyl a -benzylcrotonate, b -pentenyl a -ethyl-b -propyl-acrylate, octyl-b , d -pentadienoate, crotyl a -cyclohexyl-crotonate, 2-ethylhexyl oleate, 2-cyclopentenyl crotonate, glycol dioleate, vinyl a  - ethyl - b  - propyl - b  - butylacrylate, 4-decenoic acetone, methyl ethyl ketone, butyrene, methyl allyl ketone, methyl 2-pentenyl ketone, diallyl maleate, vinyl a -tolyl-b -ethylacrylate, 2-ethylhexyl a -methyl b -ethylacrylate, propyl 1-cyclohexenecarboxylate, butyl a ,g -diethyl-a , g -pentadienoate, methyl a -phenyl-a , g -hexadienoate, tolyl b -phenethyl-g -butyl a ,g -heptadienoate, phenyl 1-cyclopentenecarboxylate, tolyl 2 - methyl - 1 - cycloheptenecarboxylate, 2 - ethylhexyl 6 - methyl-3 - cyclohexenecarboxylate, butyl 2 - phenyl- 1 cyclohexenecarboxylate, allyl 2 - benzyl-2,3 - epoxyhexanoate, 3 - cyclohexenylmethyl acetate, 3 - cyclohexenylmethyl acrylate, 3-cyclohexenylmethyl acylates ethylene glycol bis-(2-butenoate), propylene glycol bis-(acrylate), 1,5 - pentanediol bis - (2 - butenoate), 1,3-butylene glycol crotonate, 2,3-epoxybutyrate, ethylene glycol methacrylate, 2-methyl-2,3-epoxypropionate; aryl, alkenyl, cycloalkyl, cycloalkenyl, alkaryl, alkyl, and aralkyl alkenoates; aryl, alkenyl, cycloalkyl, alkyl, cycloalkenyl, alkaryl, and aralkyl alkadienoates; aryl, alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkaryl, and aralkyl cycloolefin-1-carboxylates; alkylene glycol bis-(2-alkenoates); and alkylene glycol 2-alkenoate 2,3-epoxyalkanoates, 1,2,5,6-tetrahydrobenzaldehyde diethyl acetal, paravinylbenzaldehyde dibutyl acetal; the dialkyl acetals of alkenals, such as the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dihexyl, di-2-ethylhexyl, and didecyl acetals of unsaturated aliphatic aldehydes, for example, 2-, 3-, and 4-alkenals, allyl chloride, crotyl chloride, 1,4 - dichloro - 2 - butene, 3,4 - dichloro - 1-butene, 3 - chloro - 1 - butene, 2 - chloro - 3-pentene, 2 - ethyl - 2 - hexenyl chloride, methallyl chloride, crotyl fluoride, crotyl bromide, ortho-, meta-, and para-chlorostyrene, ortho-, meta-, and para-chloromethylstyrene, 1 - chloro - 3 - vinylcyclohexane, 4 - (trichloromethyl) - 1 - cyclohexene, tetra - (chloromethyl) ethylene, 1 - chloro - 4 - fluoro - 2 - butene, and parabromobenzylethylene, nitromethane, 1-nitropropane, 1 - nitrobutane, nitrobenzene, m - nitrobenzaldehyde, o - nitroanisole, p-nitroethylbenzene, p - nitrocinnamic acid, 2,4 - dinitroaniline, m - dinitrobenzene, 1,5-dinitronaphthalene, and 2,4-dinitrophenol.ALSO:Hydrocarbons are reduced in the presence of a catalyst made by contacting a compound of Rn, Rh, Pd, Os or Pt with compound containing Si-H grouping so that the oxidation state of Group VIII metal is lowered.  Compounds which may be reduced are ethylene, acetylene, vinylacetylene, 2-butyne, propene, butenes, pentenes, hexenes, heptenes, octenes, decenes, dodecenes, octadecenes, butadiene, isoprene, pentadienes, hexadienes, heptadienes, octadienes, decadienes, dodecadienes, octadecadienes, styrene, divinylbenzenes, dihydronaphthalenes, indene, stilbene, 1-phenyl-1-propene, 1,1-diphenylene, cyclopentenes, cyclohexenes, cyclopentadiene, dicyclopentadiene, vinylcyclohexenes, alkyl-substituted cycloalkenes, alkyl-substituted cycloalkadienes, aryl-substituted alkadienes, aryl-substituted cyclopentenes, and unsaturated macromolecules such as butadiene polymer and copolymers. Hydrogenation is preferably effected in the liquid phase at 0-300 DEG C. and 1-300 atmospheres; an inert diluent may be used.ALSO:In a process for producing an activated hydrogenation catalyst, a compound of Ru, Rh, Pd, Os, or Pt wherein the metal is in one of its oxidation states is contacted with an Si-H bonded compound which contains at least one hydrogen atom bonded to a silicon atom in a ratio of equivalents of silanic hydrogen atoms for the Si-H bonded compound per mol of the metal compound in excess of that required to reduce the metal component from its original oxidation state to its zero oxidation state, for a period of time sufficient to reduce at least a portion of the metal component from its original to a lower oxidation state.  Numerous examples of Group VIII metal compound are given, e.g. alkali metal haloplatinates, trialkyl-platinum halides and cyclopentadienyl rhodium cyclopentadiene.  Similarly numerous silicon compounds are given, e.g. R3SiH, HSi(OR1)3, HRSi(NR12)2, polysilylcarbanes and methyl hydrogen diethoxysilane.  If desired a support e.g. charcoal or g -Al2O3 may be incorporated in the catalyst.