Pathways and kinetics of the hydrolysis of chlorantraniliprole and cyantraniliprole: a density functional theory investigation

Abstract

Chlorantraniliprole (CLAP) and cyantraniliprole (CNAP), two extensively used diamide insecticides, may be released into the environment during their manufacturing, transportation, storage, and disposal. A detailed computational study at the IEFPCM/B3LYP/6-311++G(d,p) level is conducted to investigate the possible pathways of alkaline and neutral hydrolysis, and the results are in good agreement with the corresponding experimental data. The computational results show that CLAP and CNAP undergo hydrolysis under base-catalyzed conditions but remain stable under neutral conditions. For both CLAP and CNAP, the cleavage of the amide bond between the benzene and pyrazole rings is a favorable hydrolysis pathway. The main hydrolysis products of CLAP are 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid and 2-amino-5-chloro-N,3-dimethylbenzamide anion under base-catalyzed conditions. The main hydrolysis products of CNAP are 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid and 2-amino-5-cyano-N,3-dimethylbenzamide anion at base-catalyzed conditions. This study conducted a theoretical investigation on the hydrolysis mechanisms of CLAP and CNAP, offering significant insights into the rapid assessment of the persistence and environmental fate of pollutants in aquatic environments.