HOMOLOGATION WITH CO+H2 OF ETHYL ORTHOFORMATE IN THE PRESENCE OF RUTHENIUM CATALYSTS: A STEPWISE HYDROGENATION AND CARBONYLATION REACTION

Article abstract of DOI:10.1016/0022-328X(85)88032-3

The reaction of ethyl orthoformate with CO+H2 (P 10-15 MPa) in the presence of ruthenium carbonyl iodide catalysts at temperatures of 130-200 deg C has been studied.Products of hydrogenation, carbonylation and homologation of the CH, Et and EtO moieties of the ester are formed, indicating that the catalyst can activate the substrate in three ways.Diethoxymethane was the main product at lower temperatures, whereas methyl ethyl ether, methanol, and ethyl propionate predominate at higher temperatures.The formation of significant amounts of diethyl carbonate and diethoxyethane indicates the intermediate formation of EtO-Ru derivatives.Results of experiments with CO+D2 suggest a step-wise process of hydrogenation and carbonylation of the substrate, and shed new light on the mechanism of activation of esters by ruthenium carbonyl iodide catalysts.