Kinetic and mechanistic investigations on the oxidation of N′-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium

Kinetic studies on the oxidation of two substituted azinyl formamidines (Azn-Fs), namely N,N-dimethyl-N'-(pyrimidin-2-yl) formamidine (Pym-F) and N,N-dimethyl-N'-(pyridin-2-yl) formamidine (Py-F), by alkaline permanganate have been performed by spectrophotometry. The spectroscopic and kinetic evidence reveals the formation of 1:1 intermediate complexes between the oxidant and substrates. The influence of pH on the oxidation rates indicated that the reactions are base-catalyzed. The reactions show identical kinetics, being first order each in [MnO4 (-)](0) and [Azn-F](0), but with a fractional first-order dependence on [OH-]. The effect of temperature on the reaction rate has been studied. Increasing ionic strength has no significant effect on the rate. The final oxidation products of Pym-F and Py-F were identified as 2-aminopyrimidine and 2-aminopyridine, respectively, in addition to dimethyl amine and carbon dioxide. Under comparable experimental conditions, the oxidation rate of Py-F is higher than that of Pym-F. A reaction mechanism adequately describing the observed kinetic behavior is proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-limiting step of the reactions, along with thermodynamic quantities, are presented and discussed.