Insights into C–C Bond Cleavage Mechanisms in Dichloroacetonitrile Formation during Chlorination of Long-Chain Primary Amines, Amino Acids, and Dipeptides

Abstract

Dichloroacetonitrile (DCAN) as one of the potentially prioritized regulated DBPs has drawn great attention; however, understanding its formation, especially the C–C bond cleavage mechanisms, is limited. In this study, DCAN formation mechanisms from long-chain primary amines, amino acids, and dipeptides during chlorination were investigated by a combined computational and experimental approach. The results indicate that nitriles initially generate for all of the above precursors, then they undergo β-C-hydroxylation or/and α-C-chlorination processes, and finally, DCAN is produced through the Cα–Cβ bond cleavage. For the first time, the underlying mechanism of the C–C bond cleavage was unraveled to be electron transfer from the O– anion into its attached C atom in the chlorinated nitriles, leading to the strongly polarized Cα–Cβ bond heterocleavage and DCAN– formation. Moreover, DCAN molar yields of precursors studied in the present work were found to be determined by their groups at the γ-site of the amino group, where the carbonyl group including −CO2 –, −COR, and −CONHR, the aromatic group, and the −OH group can all dramatically facilitate DCAN formation by skipping over or promoting the time-consuming β-C-hydroxylation process and featuring relatively lower activation free energies in the C–C bond cleavage. Importantly, 4-amino-2-hydroxybutyric acid was revealed to possess the highest DCAN yield among all the known aliphatic long-chain precursors to date during chlorination. Additionally, enonitriles, (chloro-)isocyanates, and nitriles can be generated during DCAN formation and should be of concern due to their high toxicities.