Abstract

Methyl formate can be selectively converted into acetic acid in quantitative yield by use of cobalt catalysts. Essential requirements include the presence of a tertiary amide as solvent, of an ionic iodide as promoter, a sufficiently high CO pressure (above 100 bar), and a reaction temperature between 160° and 180°C. Other alkyl formates are not transformed into acids. The reaction probably invovles, as the key step, the reduction of the cobalt(II) catalyst to a cobaltate species, which is then transformed into alkyl and acylcobalt species. The latter reacts with lithium formate, formed in situ, to afford a mixed anhydride, decarbonylation of which yields acetic acid with regeneration of CO.

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