Catalytic synthesis of ethanol from methyl formate

Article abstract of DOI:10.1016/0022-328X(94)80083-9

Ethanol can be synthesized from aqueous methyl formate under ruthenium catalysis in the presence of tri-n-butylphosphine and an onium salt.Hydrogen chloride promotes the reaction which takes place above 180 deg C and does not need initial pressurization.It is highly selective with respect to ethanol (80-90percent, methanol not being considered).Carbon monoxide and hydrogen are produced in situ with pressures high enough to induce homologation of the methyl group.The mechanism involves HRu3(CO)^-11 species.The role of the phosphine is to activate methyl formate assisted by the onium halide.Key words: Ruthenium; Methyl formate; Hydrocarbonylation; Ethanol; Phosphine; Onium salt