Pradeep K Sharma
Articles written in Journal of Chemical Sciences
Volume 107 Issue 2 April 1995 pp 133-141 Physical and Theoretical
Kinetics of oxidation of five vicinal, four non-vicinal diols, and one of thier monoethers by pyridinium hydrobromide perbromide (PHPB) have been studied. The vicinal diols yield products arising out of the glycol bond fission while the other diols yield hydroxycarbonyl compounds. The reaction is first order with respect to PHPB. Michaelis-Menten type kinetics are observed with respect to the diol. There is no effect of added pyridinium bromide on the reaction. The oxidation of [1,1,2,2-2H4]ethanediol shows the absence of a primary kinetic isotope effect. The values of solvent isotope effect,
Volume 108 Issue 4 August 1996 pp 421-430 Physical And Theoretical
Kinetics of oxidation of five vicinal, four non-vicinal diols, and one of their monoethers by
Volume 110 Issue 1 February 1998 pp 65-73 Physical And Theoretical
Kinetics of oxidation of five vicinal diols, four non-vicinal diols, and two of their monoethers by bromine in strong acid solutions have been studied. The vicinal diols yielded the products arising out of glycol bond fission while the other diols yielded the hydroxycarbonyl compounds. The reaction is first order with respect to both bromine and the diol. The rate decreases with an increase in the acidity. The oxidation of [1,1,2,2-2H4] ethanediol showed the absence of a primary kinetic isotope effect. The value of solvent isotope effect, k(H2O)/k(D2O), at 303 K for the oxidation of ethanediol, propane-1,3-diol and 3-methoxybutane-1-ol are 4.71, 1.04 and 1.07 respectively. A mechanism involving a glycol bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidised by a hydride-transfer mechanism as are monohydric alcohols.
Volume 111 Issue 6 December 1999 pp 741-746 Physical And Theoretical
The oxidation of glycollic, lactic, malic and a few substituted mandelic acids by benzyltrimethylammonium chlorobromate (BTMACB) in acetic acid-water (1:1) leads to the formation of the corresponding oxoacids. The reaction is of first order in BTMACB as well as the hydroxy acid. Addition of benzyltrimethylammonium chloride or bromide ion does not affect the rate indicating that BTMACB itself is the reactive oxidizing species. The oxidation of
Volume 113 Issue 2 April 2001 pp 139-146
Oxidation of nine primary aliphatic alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the polymerization of acrylonitrile. Tetrabutylammonium chloride has no effect on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The oxidation of [1,1-2H2]ethanol exhibits a substantial kinetic isotope effect. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The reaction is susceptible to both polar and steric effects of substituents. A mechanism involving transfer of a hydride ion in the rate-determining step has been proposed.
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