Kinetics and mechanisms of the neutral and acid-catalysed hydrolyses of chloro-substituted alkyl acetates in aqueous solutions of constant ionic strength

Abstract

The simultaneous neutral and acid-catalysed hydrolyses of different chloro-substituted alkyl acetates in water and in aqueous acetone solutions have been studied using electrolyte solutions of constant ionic strength. The mechanism of the acid-catalysed hydrolyses of monochloroesters is A_AC2. When an ester has two chloro-substituents the acid-catalysed hydrolysis takes place simultaneously by the A_AC2 and A–B_AC3 mechanisms and in the case of trihalogenated esters the mechanism is A–B_AC3, a mechanism with an unsymmetrically catalysed partition of the intermediate formed from the water-catalysed addition of water to the carbonyl group of the ester. Structural and solvent effects of these reactions are discussed.