Theoretical studies on degradation mechanism for OH-initiated reactions with diuron in water system

Diuron, a chlorine-substituted dimethyl herbicide, is widely used in agriculture. Though the degradation of diuron in water has been studied much with experiments, little is known about the detailed degradation mechanism from the molecular level. In this work, the degradation mechanisms for OH-induced reactions of diuron in water phase are investigated at the MPWB1K/6–311+G(3df,2p)//MPWB1K/6–31+G(d,p) level with polarizable continuum model (PCM) calculation. Three reaction types including H-atom abstraction, addition, and substitution are identified. For H-atom abstraction reactions, the calculation results show that the reaction abstracting H atom from the methyl group has the lowest energy barrier; the potential barrier of ortho- H (H1’) abstraction is higher than the meta- H abstraction, and the reason is possibly that part of the potential energy is to overcome the side chain torsion for the H1’ abstraction reaction. For addition pathways, the ortho- site (C (2) atom) is the most favorable site that OH may first attack; the potential barriers for OH additions to the ortho- sites (pathways R7 and R8) and the chloro-substituted para- site (R10) are lower than other sites, indicating the ortho- and para- sites are more favorable to be attacked, matching well with the -NHCO- group as an ortho-para directing group.