Kinetics and mechanism of bromamine-T oxidation of some cyclic ketones in acidic media

Article abstract of DOI:10.1016/S0040-4020(01)96607-4

Kinetics of the oxidation cyclopentanone and cyclohexanone by bromamine-T(BAT) have been reported in perchloric acid media. A zero order dependence to BAT and first order dependence on both ketones and hydrogen ion concentrations have been observed. Observed stoichiometry, zero effects of ionic strength of the medium and p-toluenesulphonamide (TSA) and a negative dielectric effect point to a mechanism involving acid catalysed enolisation of ketones in the slow and rate determining step, followed by its subsequent fast interaction with BAT giving corresponding 1,2-diketones as final products. A solvent isotope effect (kD₂O/kH₂O = 2.0-2.2 (35°), 2.1-2.3 (40°) and 2.2-2.4 (35°), 2.3-2.5 (40°) for cyclopentanone and cyclohexanone, respectively) has been observed. Various thermodynamic parameters have been computed.