MECHANISM OF OXIDATION OF SOME ALIPHATIC KETONES BY N-BROMOSUCCINIMIDE IN ACIDIC MEDIA

Article abstract of DOI:10.1016/0040-4020(82)85062-X

Kinetics of the oxidation of methyl n-propyl ketone and methyl isobutyl ketone by N-bromosuccinimide (NBS) have been studied in perchloric acid media in presence of mercuric acetate.A zero order dependence to N-bromosuccinimide and a first order dependence to both ketones and hydrogen ion concentrations have been observed.Sodium perchlorate, mercuric acetate and succinimide additions have negligible effect while methanol addition has a positive effect on the reaction rate.A solvent isotope effect (k₀D2O/K₀H2O=2.3-2.7 and 2.4-2.8 for MeCOn.pr and MeCOi-Bu, respectively) has been observed at 35 deg.Kinetic investigations have revealedthat the order of reactivity is methyl n-propyl ketone>methyl isobutyl ketone.Various thermodinamic parameters have been computed and corresponding 1,2-diketones were found to be the products.A suitable mechanism in conformity with the above observations has been proposed.