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Department of Chemistry, RGPM, Kolar Road, Bhopal-462 042, Madhya Pradesh, India faculty of Science, National Law University, Mandore, Jodhpur-342 304, Rajasthan, lndta chemical Research Center, Hungarian Academy of Sciences, H-1025, Pusztaszeri u. 59-67, Budapest, Hungary Department of Chemistry, J. N. V. University, Jodhpur-342 011, Rajasthan, India E-mail : drpkvs27@yahoo.com Manuscript received 12 October 2011, accepted 17 October 2011 The oxidation of organic sulfides by bis(pyridine)silver permanganate (BPSP) resulted in the formation of the corresponding sulfoxides. The reaction is first order with respect to both BPSP and sulfides. The reaction is catalysed by hydrogen ions. The rate of reaction increases with an increase in the amount of acetic acid in the solvent. The correlation analyses of the rate of oxidation of thirty four sulfides were performed in terms of various single and multiparametric equations. The rate of oxidation of meta- and para-substituted phenyl methyl sulfides showed excellent correlation with Charton's LDR. The rates of ortho-compounds showed excellent correlation with LDRS equation. The oxidation of ortho- and para-compounds is more susceptible to the delocalization effect. The meta-compounds exhibited a greater dependence on the field effect. The oxidation of alkyl phenyl sulfides exhibited a very good correlation In terms of Pavelich-Taft equation. The polar reaction constants are negative indicating an electron-deficient sulfur centre in the rate-determining step. A mechanism involving formation of a sulphenium cation intermediate in the slow step has been proposed. |
