Catalytic hydrocyanation process

摘要

1,146,330. Hydrocyanation of unsaturated organic compounds. E. I. DU PONT DE NEMOURS & CO. 23 June, 1967 [24 June, 1966], No. 29134/67. Heading C2C. Unsaturated organic compounds having at least one non-conjugated ethylenic carboncarbon double bond and containing from 2 to 20 carbon atoms are catalytically hydrocyanated by reaction with hydrogen cyanide in the presence of a zero valent nickel complex at a temperature of -25‹ to 200‹ C. in the presence of a promoter which is a compound having a zinc, cadmium, beryllium, aluminium, gallium, indium, silver, titanium, zirconium, hafnium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, erbium, iron or cobalt cation or any mixture of two or more of such compounds, the promoter being present in a molar ratio of from 1 : 16 to 50 : 1 based on the nickel complex. The anion of the promoter is preferably a fluoride, chloride, bromide or iodide, an anion of a lower fatty acid of from 2-7 carbons, HPO 3 2-, H 2 PO 2 -, CF 3 COO-, OSO 2 C 7 F 15 - or SO 4 2- but organometallic compounds, e.g. (C 2 H 5 ) 3 Al 2 Cl 3 and C 2 H 5 AlCl 2 may also be used, the reaction may be effected in an inert solvent, e.g. a hydrocarbon or a nitrile, and certain ethers, which may act as solvents, may also be added. The catalysts may be either preformed or prepared in situ and a part of the promoter may be added during the course of the reaction. The neutral ligand in the zero valent nickel complex may be an alkyl or aryl group containing up to 18 carbon atoms, a phosphine, an arsine, a stibine, a phosphite, an arsenite, a stibite or a mixture thereof, preferred nickel compounds having the formula where A 1 , A 2 , A 3 and A 4 are neutral ligands which may be the same or different and have the formula P(XYZ) wherein X and Y are R or OR and Z has the formula OR, wherein the radical R may be the same or different and represents an alkyl or aryl group containing up to 18 carbons. An excess of the neutral ligand may be present in the reaction mixture when it may act as a solvent and a preferred group of nickel complexes are those which cause the isomerization of 3-pentenenitrile to 4-pentenenitrile in the presence of acid.