Mechanistic studies on the oxidation of some organic sulphides with quinolinium fluorochromate in nonaqueous medium

• Autorzy: Meenakshisundaram S. , Sathiyendiran V.
• Języki publikacji: EN

Abstrakty

EN

The oxidation kinetics of diphenyl, dialkyl and methyl phenyl sulphides has been investigated under pseudo-first-order conditions with quinolinium fluorochromate (QFC), a newly developed Cr(VI) reagent in acetonitrile medium. p- Toluene sulphonic acid (TsOH) is used for catalyzing the reaction. Initial-rate methods are used for determining the orders with respect to reactants in dialkyl sulphides. The oxidation is first-order with respect to [QFC] and second-order dependence is observed on [TsOH]. [Sulphide] has no effect on the reaction rate. Diphenyl sulphide (DPS) oxidation follows the rate law, v = k2Rrl [S][Ox][TsOH]. Acrylonitrile retards the rate of oxidation significantly in diphenyl sulphides indicating the involvement of free radical cation sulphur intermediate in the rate-limiting step. The Michaelis-Menten dependence each on [sulphide] and [TsOH] can be well explained by a two-pathway mechanism in methyl phenyl sulphide oxidation. The derived rate law, v = k1[Ox][TsOH] -+ k3[OX][S] is consistent with experimental observations.

Słowa kluczowe

EN

oxidation; kinetic; quinolinium fluorochromate; sulpides

• Wydawca: Centrum Upowszechniania Nauki PAN
• Czasopismo: Bulletin of the Polish Academy of Sciences. Chemistry
• Rocznik: 1999
• Tom: Vol. 47, No. 2
• Strony: 167--174
• Opis fizyczny: Bibliogr. 23 poz.

Twórcy

autor

Meenakshisundaram S.

autor

Sathiyendiran V.

• Department of Chemistry, Annamali University, Annamalainagar - 608 002, India