Mechanism of chloramine-T oxidation of methyl vinyl ketone and isopropyl methyl ketone in aqueous alkaline media

The oxidation kinetics of methyl vinyl ketone and isopropyl ketone by chloramine-T in aqueous alkaline solutions show first-order dependence on chloramine-T, both substrates and alkali. No effect of p-toluenesulphonamide was evident. Observed stoichiometry, negligible effect of ionic strength and a positive dielectric effect point to a mechanism involving interaction of enolate anions with chloramine-T in the rate determining step. Activation parameters and the isolation of the product formaldehyde are in agreement with the proposed mechanism.