Kinetics and mechanism of the base-catalysed hydrolysis of some substituted phenyl chloroformates

Abstract

A study of kinetic isotope effects and activation parameters indicates that, in the hydrolysis of phenyl chloroformate, acetate ion and pyridine act as nucleophilic catalysts. Both the spontaneous and pyridine catalysed hydrolyses of substituted phenyl chloroformates fit a Hammett plot. The effect of solvent polarity and added salt indicates that there is little charge separation in the transition state for hydrolysis. The mechanism of reaction is discussed.