A kinetic and mechanistic study on oxidation of Isoniazid drug by alkaline diperiodatocuprate(III) - A free radical intervention

The kinetics of oxidation of isoniazid (INH) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.05 mol dm^-3 has been studied spectrophotometrically. The reaction showed first order kinetics both in [DPC] and [INH] and negative less than unit order, both in alkali and periodate concentrations under the experimental conditions. Intervention of free radicals was observed in the reaction. Products of the reaction, isonicotinic acid and copper(II) have no effect on the rate of reaction. Ionic strength and dielectric constant did not affect the rate of reaction. Based on the observed orders and experimental evidences, a mechanism involving the monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. The main products were identified by I.R, N.M.R. and GC-MS spectral studies. The reaction constants involved in the mechanism were evaluated. Investigations at different temperatures allowed the determination of the activation parameters with respect to the slow step of proposed mechanism. The mechanism proposed and the derived rate laws are consistent with the observed kinetics.