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Abstract

The oxidation of glycollic, lactic, malic and a few substituted mandelic acids by morpholinium chlorochromate (MCC) in dimethylsulfoxide (DMSO) leads to the corresponding oxoacids. The reaction is first order each in MCC and hydroxyacid. The reaction failed to induce the polymerisation of acrylonitrile. The oxidation of α–deuteriomandelic acid shows a primary kinetic isotope effect (k_H/k_D = 5.63 at 298 K) but does not exhibit a solvent isotope effect. The reaction is catalysed by hydrogen ions according to: k_obs = a + b[H⁺]. The oxidation of p-methyl mandelic acid has been studied in 19 different organic solvents and the solvent effect analysed using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed.

Keywords

correlation analysis hydroxyacid morpholinium chlorochromate oxidation solvent effect

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Kinetics and Mechanism of the Oxidation of Some α-Hydroxyacids by Morpholinium Chlorochromate

Abstract

Keywords

References