Comparative Study of Kinetics of Oxidation of Aliphatic Primary Amines by N-Bromosuccinimide in Acidic and Basic Solutions

Department of Chemistry, S. N. V. M. V. College, Hyderabad-500 001

Manuscript received 12 May 1989, revised 3 April 1990, accepted 24 September 1990

The title reaction studied in the presence of mercuric acetate and sulphuric acid is first order each In (NBS) and amine. Increase In [H⁺] increased the rate marginally. The rate of reaction Increased with decrease in dielectric constant of the medium. The observed order of reactivity of different amines towards oxidation was : methyl < ethyl < n-propyl < n-butyl isobutyl < isopropyl amine. The oxidation of these amines by NBS in basic solution was also first order each in (NBS] and [amine]. Increase in (OH^-) increased the rate of reaction while added succinimide decreased the rate of oxidation. The rate of reaction decreased with decrease in dielectric constant of the medium. The order of reactivity of different amines towards oxidation was found to be Just the reverse of that observed in acid solution. Appli-cabllity of Taft's equation was tested in both the reactions. The rate constants (\(\mathscr{k}\)') and activation parameters have been evaluated and suitable mechanisms In conformity with the experimental observations have been suggested.