Kinetics and mechanism oxidation of aromatic amines by N-bromoacetamide

Abstract

Kinetic of oxidation of unsubstituted and substituted anilines by N-bromoacetamide (NEA) in methanol-water (50:50 v/v) mixture has been investigated in the presence of ercuric acetate and excess acetamide (AA). Electron-releasing substituents in the aromatic ring accelerate e reaction rates and electron-withdrawing substituents retard them. The value of the reaction constant (ρ) 303 K, obtained from the Hammett's plot (corr. coeff.= 0.998) is -0.785. The Bronsted plot is also linear with a β value of 0.186 at 303 K. A mechanism involving electrophilic attack of the oxidant on the amino group has been proposed to explain the observed results. Thermodynamic and activation parameters have also been evaluated.