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Vol. 26 No. 9 (2014): Vol 26 Issue 9

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Oxidation of Organic Sulfides by Imidazolium Fluorochromate: A Kinetic and Mechanistic Approach

https://doi.org/10.14233/ajchem.2014.15753
Lokesh Mathur
Department of Chemistry, J.N.V. University, Jodhpur-342 005, India
A. Choudhary
Department of Chemistry, J.N.V. University, Jodhpur-342 005, India
Om Prakash
Department of Chemistry, J.N.V. University, Jodhpur-342 005, India
Pradeep K. Sharma
Department of Chemistry, J.N.V. University, Jodhpur-342 005, India

Corresponding Author(s) : Pradeep K. Sharma

drpkvs27@yahoo.com

Asian Journal of Chemistry, Vol. 26 No. 9 (2014): Vol 26 Issue 9

Abstract

The oxidation of organic sulfides by imidazolium fluorochromate resulted in the formation of the corresponding sulfoxides. The reaction is first order with respect to imidazolium fluorochromate. A Michaelis-Menten type kinetics was observed with respect to the reactants. The reaction is catalyzed by toluene-p-sulfonic acid. The oxidation was studied in nineteen different organic solvents. An analysis of the solvent effect by Swain's equation showed that the both cation- and anion-solvating powers of the solvents play important roles. The correlation analyses of the rate of oxidation of thirty four sulfides were performed in terms of various single and multiparametric equations. For the aryl methyl sulfides, the best correlation is obtained with Charton's LDR and LDRS equations. The oxidation of alkyl phenyl sulfides exhibited a 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.

Keywords

Correlation analysis Halochromate Kinetics Mechanism Oxidation
Mathur, L., Choudhary, A., Prakash, O., & K. Sharma, P. (2014). Oxidation of Organic Sulfides by Imidazolium Fluorochromate: A Kinetic and Mechanistic Approach. Asian Journal of Chemistry, 26(9), 2597–2603. https://doi.org/10.14233/ajchem.2014.15753
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