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Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II)

Research Authors
Basim H. Asghar, Ahmed Fawzy
Research Abstract

The kinetics of permanganate oxidation of two substituted azinylformamidines (AznFs), namely N,N-dimethyl-N0 -(pyridin-2-yl)formamidine (Py) and N,N-dimethyl-N0 -(pyrimidin-2- yl)formamidine (Pym), in sulfuric acid were investigated using conventional spectrophotometry. Kinetic evidence for the formation of 1:1 intermediate complexes between the oxidant and substrates was obtained. The reactions of both substrates with permanganate showed similar kinetics, i.e. first order in [MnO4 ]0 and fractional-first-order with respect to both [Azn-F]0 and [H+]. The initial product, Mn2+, was found to autocatalyze the oxidation process. Changes in the ionic strength and dielectric constant of the medium had no significant effect on the rate. The final oxidation products of Py and Pym were identified as 2-aminopyridine and 2-aminopyrimidine, respectively, in addition to dimethylamine and carbon dioxide. A plausible reaction mechanism is suggested and the reaction constants involved in the mechanism were evaluated

Research Date
Research File
Research Journal
Journal of Saudi Chemical Society
Research Member
Research Publisher
Elsevier
Research Rank
1
Research Vol
20
Research Year
2016
Research Pages
561–569