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 OH 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 OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH 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 OH abstracting H-atom from –CH3 group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in –CH2 group is slightly easier to be abstracted than that in –CH3 group. For OH addition reactions, the addition of OH 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.

Highlight
► We investigate the degradation mechanism of OH and MCPA including two forms.
► Two type reactions of H-atom abstraction and OH addition are considered.
► Reaction mechanism for anionic MCPA is different from that for molecular MCPA.
► Addition of OH to the C1 site is the initial step for molecular MCPA.
► The C4 site is the most reactive site for anionic MCPA.