Kinetics and mechanism of bromamine-T oxidation of some cyclic ketones in acidic media |
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Authors: | Bharat Singh Rajendra Chand |
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Affiliation: | Department of Chemistry, University of Allahabad, Allahabad-2 India |
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Abstract: | 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. |
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