Kinetics and mechanism of the acetate catalysed hydrolysis of 4-methoxyphenyl chloroformate and 4-methoxyphenyl fluoroformate in aqueous dioxan. Evidence for rate-determining attack of acetate ions on an intermediate mixed anhydride

Abstract

Esters of fluoroformic acid hydrolyse more rapidly than the corresponding chloroformate esters, suggesting that carbon–halogen bond breaking is not greatly advanced in the rate-determining step. The rate of reaction of 4-methoxyphenyl fluoroformate with aqueous dioxan is markedly decreased in the presence of acetate ions whereas the rate of reaction of 4-methoxyphenyl chloroformate is increased. The rate curves for the latter reaction are sigmoid in shape. The results are interpreted in terms of the formation of an intermediate mixed anhydride for both reactions, which then undergoes nucleophilic attack by acetate ions to yield acetic anhydride and the phenol. This step is rate determining in the case of the fluoroformate.