Patent GB-995459-A (GB)
Title: Process for the conversion of olefinic compounds
IPC: C07C51/56
Filed: 1962-08-23
Abstract: Olefinic hydrocarbons are reacted to form addition compounds at elevated temperature with carbon monoxide and a reactant having active hydrogen and an acid dissociation constant of 10-3 or less in the presence of a catalyst consisting essentially of a complex of carbon monoxide, one of the metals cobalt, ruthenium, rhodium and iridium, and an organic molecule containing a trivalent phosphorus, arsenic or bismuth atom.  A suitable complex is one of the formula [(R1zA)x-L-Ry]p M(CO)n in which M is a cobalt, ruthenium, rhodium or iridium atom,L is a phosphorus, arsenic or bismuth atom, R and R1 are each an alkyl, aryl, aralkyl or alkaryl group, A is an oxygen, nitrogen or sulphur atom, x and y are integers such that x+y = 3, p and n are integers such that p+n is equal to the co-ordination number of M, p is at least 1 and z is 1 or 2 and equal to the valency of A minus 1.  The process is preferably carried out at a temperature of 75-200 DEG  C. and a pressure of 800-3000 p.s.i. of carbon monoxide. The olefines may be reacted with, for example, an alcohol to give an ester and a ketone, water to give an acid, ammonia or an amine to give an acid amide, a thiol to give a thioester or an acid to give an acid anhydride.  The olefins used as starting materials preferably contain 2-12 carbon atoms and may be acyclic or alicyclic or aryl derivatives thereof and contain more than one double bond. The catalyst may be prepared by combining an organic acid salt of the desired metal with the selected trivalent phosphorus, arsenic or bismuth compound in the presence of carbon monoxide or by heating the metal carbonyl with the trivalent compound.  The preferred trivalent compounds in the catalyst are those of phosphorus and include trivalent phosphorus compounds having aliphatic, cycloaliphatic, heterocyclic or aromatic radicals satisfying the valencies.  These radicals may contain functional groups such as carbonyl, carboxyl, nitro, amino and hydroxyl groups.  Other suitable phosphorus compounds are those which contain several phosphorus atoms linked by hydrocarbon groups.  The preferred phosphorus compounds include esters, thioesters and amides of trivalent phosphorus such as phosphites, thiophosphites and amidophosphites and also phosphorus compounds in which the phosphorus is directly bonded to hydrocarbon groups such as tributyl and triphenyl phosphines. Suitable complexes are, for example, carbon monoxide-containing complexes of cobalt and triphenyl thiophosphite, rhodium and triethyl phosphite, cobalt and triphenyl phosphine, rhodium and triethyl arsenite, rhodium and triethyl bismuthite, cobalt and dibutylamidodiethylphosphinite, cobalt and dipropyl amidodimethyl arsenite, rhodium and tris-(dimethylamido) bismuthine, iridium and tripropyl arsenite, iridium and triethyl arsine, ruthenium and triphenyl bismuthine, ruthenium and trimethyl phosphite and ruthenium and O,o-dimethylphenyl phosphonite.  Examples are given of the reaction of ethylene and ethanol to give a mixture of diethyl ketone and ethyl propionate; (b) ethylene and diethanylamine to give diethyl propionamide; (c) ethylene and propionic anhydride, and (d) ethylene and water to give propionic acid.  The catalyst used in the examples are complexes of (a) dicobalt octacarbonyl and tri-n-butyl phosphine; (b) dicobalt octacarbonyl and tri-n-butyl arsine; (c) iridinium carbonyl and tri-n-butyl phosphine; (e) rhodium carbonyl and tri-n-butyl phosphine; and (f) iridium carbonyl and tri-n-butylphosphine. Specification 988,941 is referred to.