Abstract

The kinetics of oxidation of inositol (INOS) by permanganate ion in both perchloric and sulfuric acids solutions was studied using a spectrophotometric technique at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [INOS] were found to be less than unity. The effect of acids concentrations suggests that the reactions were acid-catalyzed with fractional-second order kinetics in [H+]. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of inositol were identified by spectral and chemical tools as the corresponding monoketone derivative, namely inosose. Under comparable experimental conditions, the oxidation rate in sulfuric acid was approximately three times higher than that in perchloric acid. Regarding to the second order rate constants of these reactions, the activation parameters have been evaluated and discussed.

Highlights

  • Oxidation reactions are very important in organic synthesis

  • It is evident that the Mn(VII) in permanganate is reduced to various oxidation states in acidic, neutral and alkaline media

  • Various sets of reaction mixtures containing various amounts of permanganate ion and inositol at constant [H+], ionic strength, and temperature were allowed to react for 24 h for completion of the oxidation reactions

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Summary

Introduction

Oxidation reactions are very important in organic synthesis. Among the important oxidizing agents, permanganate ion is widely used in the oxidation of many organic compounds in acidic, neutral and alkaline media [111]. The mechanism of oxidation reactions by permanganate ion is governed by pH of the medium [12]. It is evident that the Mn(VII) in permanganate is reduced to various oxidation states in acidic, neutral and alkaline media. Permanganate ion (MnO4-) can exist in several different forms, HMnO4, H2MnO4+, HMnO3, and Mn2O7. The oxidant has been assigned with an inner-sphere and an outer-sphere mechanism pathways in their redox reactions [13, 14]. Reduction of permanganate ion in acidic media goes to either MnIV or MnII, where the reduction potential of the

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