The chlorination of glycine and α-alanine at excess HOCl: Kinetics and mechanism

Abstract

The chlorination of the two simplest amino acids at HOCl excess was studied by stopped-flow, conventional spectrophotometric and time resolved 1H NMR kinetic methods at 25 °C. These reactions show distinct characteristics under neutral and alkaline conditions. At high pH, the common feature of the two systems is that the N-dichloroamino carboxylate ion does not form and the overall process is controlled by the initial decomposition of the N-monochloro derivative. Under such conditions, carbanions form in equilibrium acid – base processes and open alternative reaction paths, resulting in enhanced complexity of the corresponding mechanisms. In the case of α-alanine, the formation of acetonitrile and N-chloro acetamide as main products; acetate ion, acetaldehyde, chloroacetaldehyde, chloroform as byproducts; acetamide and N-chloro ethanimine as intermediates was confirmed. In the case of glycine, the final products are formamide and OCN−. Under neutral conditions, monochloroamino acid forms immediately upon mixing the reactants, and subsequently it is converted into dichloroamino acid by Cl2O in a fast process. In considerably slower further reaction steps, acetonitrile and acetate ion form as final products in the α-alanine system, while the chlorination of glycine proceeds to full mineralization. The detailed mechanisms suggested for these reactions postulate the formation of various imines and N-chloro imines which are involved in decarboxylation, dechlorination, hydration and hydrolytic reaction steps.