Ruthenium catalysed ethylene—methyl formate reactions. Synthesis of propanol and ketones

Abstract

Ethylene can be reacted with methyl formate under ruthenium catalysis and phosphine promotion. In the presence of water, hydrocarbonylation to n-propanol and hydroesterification to methyl propionate takes place. When water is omitted, methyl ethyl ketone (MEK) and diethyl ketone are the dominant products. Addition of a Pd cocatalyst and use of N-methylpyrrolidone as solvent favour formation of MEK. The mechanism makes allowance for methyl formate participation as source of carbon monoxide and substrate for formation of MEK and considers methyl ruthenium hydride as a possible intermediate.