Kinetic Investigation of Oxidation of Aromatic Anils by Potassium Peroxymonosulfate in Aqueous Acidic Medium

The kinetics of oxidation of aromatic anils to benzaldehyde and azobenzene by potassium peroxymonosulfate has been studied in aqueous acetic acid medium. The low dielectric constant of the medium facilitates the reactivity. It has been found that the variation in the ionic strength of the reaction has a negligible effect on the rate. Similarly, polymerization was not observed when acrylonitrile was added to the reaction mixture. This observation rules out the formation of any free radical in the reaction. The added Mn(II) increases the rate of the reaction, which indicates the involvement of two‐electron transfer. Highly negative ?S^# values indicate a structured transition state. The deviation of the Hammett plot was noted, and a concave downward curve was obtained for the anils with substituents in the aniline moiety. The observed break in the log k_obs versus σ is attributed to the transition state whereas the concave upward curve was observed for the substituents in the benzaldehyde moiety and in the combination of aniline and benzaldehyde moieties, and a suitable mechanism was proposed.