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  • Chem Sci Trans., 2014, 3(3),  pp 1051-1063  

    DOI:10.7598/cst2014.807

    Research Article

    Kinetics and Mechanism of ZnCl2 Catalyzed Oxidation of Organic Sulfides by Permanganate in Non-Aqueous Medium

  • K. P. SRIVASTAVA* and SANJAY KUMAR RAI
  • P.G. Department of Chemistry, Ganga Singh College, Jai Prakash University, Chapra-841 301, Bihar, India
  • Abstract

    The rates of zinc chloride (Lewis acid) catalysed oxidation of thioanisole and several para-substituted thioanisoles by permanganate have been studied in anhydrous acetone solutions. The kinetic rate law obtained indicates that a complex between permanganate and the Lewis acid (ZnCl2) is formed before oxidation of the sulfur-containing compounds occurs. The function of the zinc chloride is to enhance the reactivity of permanganate. A Hammett ρ value of -1.09 ±0.05 is obtained for the oxidation of sulfides at 23.0 oC. A negative ? value means that the sulfur is electron deficient in the transition state. Values for the HOMO energies of sulfides and the LUMO energies for permanganate ion and the permanganate-zinc chloride complex have been calculated. The results indicate that electron donating substituents on the ring increase the rate of the reaction and electron withdrawing groups slow down the reaction.

    Keywords

    Thioanisoles, Permanganate, Acid catalysedoxidation, LUMO, HOMO

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