Rates of Hydrolysis of N-Chlorinated Molecules

Abstract

Formation and hydrolysis rate constants were calculated for N-chlorosuccinimide, N-chloroquinuclidinium ion, and N-chloro-N-methylbenzenesulfonamide in water. The rates of hydrolysis of these compounds were much slower than the rates at which they are known to transfer their active chlorine to nitrogenous bases in water. Hence, the present results confurm an earlier suggestion that chlorine transfer between nitrogenous bases in water is not mediated by hydrolysis of the N-chloro compounds to hypochlorous acid but involves a direct reaction between the nitrogenous chlorine donor and acceptor molecules. The kinetic results are also consistent with a postulate that the rate-determining step in the reaction between nitrogenous compounds and hypochlorous acid involves reaction between the amide and imide anions and amine neutral molecules and neutral molecules of hypochlorous acid. The rate-determining step in the hydrolysis reactions appears to involve attack of hydroxide ion on the N-chloro compounds.