Patent GB-1017604-A (GB)
Title: Preparation of ethylenically unsaturated compounds
IPC: C07C209/02
Filed: 1961-12-20
Abstract: Ethylenically unsaturated compounds are prepared by reacting a hydrocarbon olefinic compound, e.g. high molecular weight olefine polymers containing ethylenic unsaturation such as polybutadiene and polyisoprene, in the vapour phase and under substantially anhydrous conditions with a nucleophilic compound which yields a monovalent anion in the presence of an organic salt of a Group VIII metal (with an A.N. of at least 44) namely palladium, platinum, ruthenium, iridium, rhodium, and osmium or mixtures thereof.  An acid acceptor which does not water upon reaction with the acid may be present and is essential in a modification in which the reaction is in the liquid phase in an organic diluent. The nucleophilic reactant H.A. includes inorganic and organic compounds in which the anion may be alkoxy, aryloxy, carboxylate, halogen, cyano, amino, amido, cyanate, isocyanate, carbanions of organometallic compounds, thiocyanate, mercapto and sulphydryl, and many compounds are specified.  The acid acceptors may be alkali metal or alkaline earth metal phosphates or hydrogen phosphates. The reaction incorporates reactive sites to the polymers, e.g. reaction with amines introduces dye-reactor sites, and with carboxylic acid introduces ester radicals.ALSO:Ethylenically unsaturated compounds are prepared by reacting a hydrocarbon olefinic compound in the vapour phase and under substantially anhydrous conditions with a nucleophilic compound which yields a monovalent organic anion in the presence of a salt of a Group VIII metal (with an atomic number at least 44), namely palladium, platinum, ruthenium, iridium, rhodium, and osmium or mixtures thereof.  An acid acceptor, which does not form water upon reaction with the acid, may be present and is essential in a modification in which the reaction is in the liquid phase in an organic liquid diluent.  Ethylenically unsaturated compounds include substituted and unsubstituted aliphatic acyclic and alicyclic compounds (2-200 or more C atoms per molecule), or by a bond with methylene groups, carbocyclic, and examples mentioned are ethylene, propylene, butene, pentene, hexene, heptene, decene, dodecene, isobutene, isopentene, iso-octene, butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene-1,4, cyclopentyl ethylene, cyclopentene, cyclohexene, cyclopentadiene, styrene, a -methyl styrene, p-ethylstyrene, 2,4-dimethyl styrene, vinyl acetylene, divinyl acetylene, vinyl diacetylene, allyl chloride, 3,4 - dichlorostyrene, 1 - chloro - 3 - butene methyl and propyl vinyl ether and vinyl acetate.  The nucleophilic reactant H-A includes inorganic and organic compounds in which the anion may be alkoxy, aryloxy, carboxylate, halogen, cyano, amino, amido, cyanate, isocyanate, carbanions of organometallic compounds, thiocyanate, mercapto, and sulphydryl and many compounds are exemplified.  The acid acceptors may be alkali metal or alkaline earth metal phosphates or hydrogen phosphates, and the diluents may be saturated hydrocarbons, aromatics, ethers, tetrahydrofuran, dioxane and dimethylformamide.  The regeneration of the Group VIII metal salt by reaction of the metal with hydrogen halide and oxygen, or with salts of polyvalent metals which are reduced, and which may be carried out simultaneously with at least two reactors is described. Examples describe the preparation of vinyl acetate, vinyl isopropyl ether, butadiene monoacetate, isopropenyl acetate, N-vinyl carbazole and N-vinyl pyrrolidone and many other products are listed.