Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium

Abstract

The oxidation of inositol by quinquevalent vandadium in acid medium is a first-order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one more of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1M-6M perchloric acid solutions the reaction has shown a variable order in H' , but in solutions of 2M-5M sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H+I2. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of -14 e.u. A suitable mechanism, consistent with the kinetics in 2M-5M acid solutions, is suggested and the values of various rate constants are evaluated.

Kinetic and Mechanistic Investigations of Oxidation of Myo-Inositol by Diperiodatocuprate(III) in Aqueous Alkaline Medium

“…Verification of rate law(11) for the oxidation of inositol by diperiodatocuprate(III) in aqueous alkaline medium at 301K.The effect of ionic strength and dielectric constant of the medium on the rate explains quantitatively the reaction between molecule and ion, as seen in Scheme 1. The moderate ∆H # and ∆S # values…”

“…Oxidation of myo-inositol was studied by different oxidants like alkaline potassium periodate 10 , alkaline hexacyano ferrate(III) ion in presence of Os VIII , V V in acid medium 11 in absence 12 and presence 13 of Cu II , periodic acid 14,15 . The literature survey reveals that there are no reports on the mechanistic studies of myo-inositol oxidation by DPC in alkaline medium.…”

Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium

“…Inositol and some of its derivatives used as the basis for some signaling and secondary messenger molecules [2,3] which are involved in insulin signal transduction, gene expression, breakdown of fats and reducing blood cholesterol [4]. Kinetics of oxidation of inositol was investigated by different oxidants like alkaline potassium periodate [5], alkaline diperiodatocuprate(III) [6], alkalinepermanganate [7], vanadium(V) in acid medium [8] and by chromic acid [9].…”

“…Although a number of investigations on the kinetics of oxidation of inositol by various oxidants has been performed [5][6][7][8][9], there is a lack of literature on the kinetics of oxidation of this polyol compound by cerium(IV) in acidic medium. This observation prompted us to investigate the title reaction.…”

Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions

“…These are involved in insulin signal transduction, gene expression, breakdown of fats and reducing blood cholesterol [19]. Oxidation of inositol was studied by different oxidants like alkaline potassium periodate [20], alkaline diperiodatocuprate(III) [21], alkalinepermanganate [22], V(V) in acid medium [23] and chromic acid [24].…”