Kinetics and mechanism of oxidation of anisole and substituted anisoles by acid bromate in acetic acid-water mixture

Abstract

Oxidation of anisoles by acid bromate has been studied in acetic acid-water system in the presence of sulphuric acid. The reaction is first order each in [anisole] and [Br(V)]. The rate of reaction increased with increase in [H+] and percentage of acetic acid. The products of oxidation have been identified as ortho and para hydroxyanisoles. From the effect of [H+] and [acetic acid] on rate, H2+ BrO3 has been established as the reactive species. Anisoles having electron-donating substituents in the benzene ring accelerate the rates and vice versa with a Hammett ρ value of −0.6. A mechanism involving the attack of H2+ BrO3 on ortho/para position of the anisole in the rate-determining step has been proposed.