SELECTIVE HOMOGENEOUS PRODUCTION OF ALKYL FORMATE FROM CO AND ALCOHOL USING METAL-CARBONYL ALKOXIDE CATALYST SYSTEMS

The homogeneously catalyzed production of alkyl formates from alcohols and carbon monoxide by transition metal carbonyl complexes in the presence of alkali metal alkoxides is reported. The key intermediate in the proposed catalytic cycle is a short-lived metallo-ester derivative which at elevated temperatures ( greater than 100 degree C) is protonated by alcohol to afford the alkyl formate product. The reactivity of the metal carbonyl with alkali metal alkoxides is sharply affected by the solvent system employed, e. g. , tetrahydrofuran is much more effective than alcohols. Reactions of triruthenium dodecacarbonyl with alcohols in the presence of alkoxides and CO have led to the production of alkyl formates. In addition, a convenient route to **1**3CO-enriched Ru//3(CO)//1//2 is achieved in the presence of trace quantities of alkoxides. In the absence of CO, XRu//3(CO)//1//0Y (X equals H or OR; Y equals OR) derivatives are produced by direct reaction of Ru//3(CO)//1//2 with alcohols.