The nickel-catalyzed hydroesterification of acetylene with methyl formate to methyl acrylate Original Research Article

The catalytic synthesis of methyl acrylate by hydroesterification of acetylene with methyl formate was studied under various conditions. Mixtures of nickel acetate tetrahydrate, copper sulfate pentahydrate and sodium iodide dihydrate were used as catalysts, and N,N-dimethylformamide as solvent. The experimental results concerning the effects of the reaction condition on selectivity to methyl acrylate, methanol and methyl propionate suggested the synthesis of methyl acrylate through the carbonylation reaction of acetylene. When the reaction was carried out under the total initial pressure of 6.0 MPa and the CO initial partial pressure of 3.0 MPa at the temperature of 180°C with the catalyst composition of 0.040 M Ni(OAc)2·4H2O and 0.054 M NaI·2H2O, 86% selectivity to methyl acrylate and 64% conversion of methyl formate were achieved.