KINETICS AND MECHANISM OF THE OXIDATION OF SOME ALIPHATIC KETONES BY N-BROMOACETAMIDE IN ACIDIC MEDIA

Article abstract of DOI:10.1016/0040-4020(84)85017-6

Kinetics of the oxidation of methyl ethyl ketone (MEK) and diethyl ketone (DEK) by N-bromoacetamide (NBA) have been studied in perchloric acid media in the presence of mercuric acetate.A zero order dependence to NBA and a first-order dependence to both ketones and H(1+) have been observed.Acetamide, mercuric acetate and sodium perchlorate additions have negligible effect while addition of acetic acid has a positive effect on the reaction rate.A solvent isotope effect (K₀D2O/k₀H2O=2.1-2.4 and 2.2-2.5 for MEK and DEK, respectively) has been obsvered at 40 deg C.Kinetic investigations have revealed that the order of reactivity is MEK > DEK.The rates were determined at four different temperatures and the activation parameters were evaluated.The main product of the oxidation is the corresponding 1,2-diketone.A suitable mechanizm consistent with the above observations has been proposed.