Selenium dioxide catalysed acetic acid hydrazide oxidation by bromate was studied in hydrochloric acid medium. The order in oxidant concentration, substrate and catalyst were found to be unity. Increasing hydrogen ion concentration increases the rate of the reaction due to protonation equilibria of the oxidant. The mechanism of the reaction involves prior complex formation between the catalyst and substrate, hydrazide, followed by its oxidation by diprotonated bromate in a slow step. Acetic acid was found to be the oxidation product. Other kinetic data like effect of solvent polarity and ionic strength on the reaction support the proposed mechanism.
The oxidation of isoniazid by bromate was investigated
kinetically under pseudo-first-order conditions in acid medium. The
reaction was accelerated by the hydrogen ion due to the various protonation
equilibria of both the reactants. The mechanism involves diprotonated
isoniazid as the active species which forms two complexes with the
diprotonated and unprotonated oxidant. The complex formed between
the diprotonated oxidant and the protonated −NH2 group of hydrazide moiety of isoniazid decomposes into isonicotinic
acid. Formation of another stable ion pair complex decreases the rate
of reaction. The UV–vis examination of the solutions support
the formation of both protonated isoniazid and the complexes. A probable
mechanism on the basis of kinetic results involving formation of an
acyl diimide of the isoniazid was proposed.
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