Kinetics and Mechanism of the Oxidation of Pyridine by Caro's Acid Catalyzed by Ketones

Article abstract of DOI:10.1021/jo00321a032

The kinetics of the oxidation of pyridine by peroxomonosulfate ion catalyzed by acetone and cyclohexanone has been investigated.The oxidation product was identified as pyridine 1-oxide, and the yield was found to be pH dependent.The rate law for the pyridine oxidation was shown to be .A mechanism involving a dioxirane intermediate which is consistent with the rate law has been postulated.Experiments leading to simplified forms of the rate law have been carried out.The ratios of rate constants k_b/k_a and k_a'/k_a were determined for both acetone and cyclohexanone.A side reaction, the Baeyer-Villiger process, is significant with cyclohexanone near pH 7.