Applications of Homogeneous Water-gas Shift Reaction. IV. Hydrocarbonylation and Dimerization of Methyl Acrylate with CO and H2O

Abstract

Abstract Hydrocarbonylation of methyl acrylate with CO and H2O forms dimethyl 4-oxopimelate in 94% yield based on H2O, the Co2(CO)8-1,2-bis(diphenylphosphino)ethane (diphos) catalyst system being used as in the case of ethylene or propylene. Increasing temperature tends to promote the dimerization and/or hydrodimerization of methyl acrylate to give 1,3-bis(methoxycarbonyl)-1-butene and/or dimethyl 2-methylglutarate. Effects of CO pressure and H2O concentration on the hydrocarbonylation and dimerization were examined at 135 and 165 °C. Catalytically active intermediates for the hydrocarbonylation take part in the dimerization of methyl acrylate.