Oxidation of organic sulfides by tetraethylammonium chlorochromate: a kinetic and mechanistic study

Abstract

The oxidation of organic sulfides by quinolinium chlorochromate (QCC) resulted the formation of the corresponding organic sulfoxides. These reactions are first order ones with respect to QCC. A Michaelis-Menten type kinetics was observed with respect to the reactants. The reaction is catalyzed by p-toluene sulfonic acid (TsOH). The oxidation was studied in nineteen different organic solvents. An analysis of the solvent effect on 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 done in terms of various single and multiparametric equations. In the reactions of aryl methyl sulfides, the best correlation could be obtained with Charton's LDR and LDRS equations. The oxidation reactions of alkyl phenyl sulfides exhibited an excellent correlation in terms of Pavelich-Taft equation. The negative values of polar reaction constants indicate an electron-deficient sulfur center in the rate-determining step. The proposed reaction mechanism involves the formation of a sulphenium cation intermediate in a slow step * Corresponding Authors Phone: +91 94144-10900 E-Mail: drpkvs27@yahoo.com [a]

Oxidation and Reduction

“…223 The Arrhenius expressions for the gas-phase reactions of 1-butene, isobutene, 2-methyl-1-butene, and 3-methyl-1-butene with O 3 were determined, and the reaction rate constant and activation energy agreed with those reported in the literature. 224 The Arrhenius expressions, rate constants, and atmospheric residence times for gas-phase reactions of α- (71) and β-farnesene (72), β-myrcene (73), and β-ocimene (74) with O 3 and • OH radicals using He as the diluent gas were reported. The reactions of αand β-farnesene with • OH radical had no significant temperature dependence.…”

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

“…Imidazolium fluorochromate (IFC) is also one of such compounds used for the oxidation of benzylic alcohols 2 . We have been interested in the kinetic and mechanistic aspects of the oxidation by complexed Cr(VI) species and several reports on halochromates have already reported from our laboratory [3][4][5][6] . It is, known that mode of oxidation depends upon the nature of counter-ion attached to the chromium anion.…”

Kinetics and Mechanism of the Oxidation of DL-Methionine by Tetrakis(Pyridine)silver Dichromate

“…One of such compounds is tetrakis(pyridine)silver dichromate reported by Firozabadi et al 2 . We have been interested in the kinetic and mechanistic aspects of the oxidation by complex salts of Cr(VI) and several studies have already been reported from our laboratory [3][4][5][6] . It is, known however, that mode of oxidation depends upon the nature of counter-ion attached to the chromium anion.…”