Acyl Iodides in Organic Synthesis: V. Reactions with Carboxylic Acid Esters

Abstract

Acyl iodides react with alkyl, alkenyl, and aralkyl esters derived from saturated, unsaturated, and aromatic mono- and dicarboxylic acids in the absence of a catalyst. The reaction involves cleavage of the OR bond and formation of organic iodide RI (including CH2=CHI) and one or two symmetric carboxylic acid anhydrides. Phenyl acetate reacts with benzoyl iodide to give acetyl iodide and phenyl benzoate as a result of cleavage of the (O=)C–O bond. The reaction of diethyl fumarate with acetyl iodide is accompanied by cis– trans isomerization to afford maleic anhydride. In the reactions of acetyl iodide with diethyl oxalate and diethyl malonate, CO and CO2 and CO2 and polyketene are formed, respectively, in addition to ethyl iodide and acetic anhydride. Ethyl esters of strong organic acids, e.g., ethyl trihaloacetates, failed to react with acyl iodides under analogous conditions.