Chlorination of amides: Kinetics and mechanisms of formation of N-chloramides and their reactions with phenolic compounds.

Amides are common constituents in natural organic matter and synthetic chemicals. In this study, we investigated kinetics and mechanisms of the reactions of chlorine with seven amides, including acetamide, N-methylformamide, N-methylacetamide, benzamide, N-methylbenzamide, N-propylbenzamide, and N-(benzoylglycyl)glycine amide. Apparent second-order rate constants for the reactions of the amides with chlorine at pH 8 are in the range of 5.8 × 10 - 1.8 Ms and activation energies in the range of 62-88 kJ/mol. The second-order rate constants for the reactions of chlorine with different amides decrease with increasing electron donor character of the substituents on the amide-N and N-carbonyl-C in the amide structures. Hypochlorite (OCl) dominates the reactions of chlorine with amides yielding N-chloramides with species-specific second-order rate constants in the range of 7.3 × 10 - 2.3 Ms. Kinetic model simulations suggest that N-chlorinated primary amides further react with HOCl with second-order rate constants in the order of 10 Ms. The chlorination products of amides, N-chloramides are reactive towards phenolic compounds, forming chlorinated phenols via electrophilic aromatic substitution (phenol and resorcinol) and quinone via electron transfer (hydroquinone). Meanwhile, N-chloramides were recycled to the parent amides. At neutral pH, apparent second-order rate constants for the reactions between phenols and N-chloramides are in the order of 10-0.1 Ms, comparable to those with chloramine. The findings of this study improve the understanding of the fate of amides and chlorine during chlorination processes.