Abstract
In an attempt for developing new oxochromium(VI) reagents for effective and selective oxidation of organic substrates under mild conditions we report in the present paper the kinetic and mechanistic study of the oxidation of D-fructose by tetraethylammonium chlorochromate (C 2 H 5 ) 4 NCrO 3 Cl. The reaction has been carried out in aqueous acetic acid 50% (v/v) medium in presence of perchloric acid at constant ionic strength. The reaction has been found to be first-order with respect to each of the oxidant and substrate under pseudo first-order conditions. The reaction is catalysed by acid and follows a first-order dependence on H + ion concentration. The ionic strength variation has no effect on the reaction rate. The decrease in dielectric constant of the medium increases the rate of reaction. A 1: 1 stoichiometry is observed in the oxidation and the reaction rate is not retarded by the addition of radical trapping agent acrylonitrile. Effect of temperature on the rate of oxidation has been studied to show the validity of Arrhenius equation and various activation parameters have been computed. The products of oxidation are identified to be D-erythrose and glycollic acid. On the observed facts a hydride ion transfer mechanism is proposed.
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