The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison.

The initial degradation mechanisms of ⁱOH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and ⁱOH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for ⁱOH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that ⁱOH abstracting H-atom from -CH(3) group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH(2) group is slightly easier to be abstracted than that in -CH(3) group. For ⁱOH addition reactions, the addition of ⁱOH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.