Kinetics of the hydrolysis of acyl chlorides in pure water

Abstract

The activation parameters ΔH≠, ΔS≠, and ΔCP≠ for the hydrolyses of a series of alkyl chloroformates and dimethylcarbamyl chloride in water have been determined. The results indicate that, with increasing electron donation to the chlorocarbonyl group, the mechanism changes from bimolecular to unimolecular (SN1) displacement at this position. For isopropyl chloroformate, some concurrent alkyl–oxygen bond fission is also indicated. The bimolecular mechanism involves reversible addition of water to the carbonyl group followed by ionization of the carbon–chlorine bond.