Oxidation of some α‐hydroxy acids by tetraethylammonium chlorochromate: A kinetic and mechanistic study

Abstract

The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by tetraethylammonium chlorochromate (TEACC) in dimethylsulfoxide leads to the formation of corresponding oxoacids. The reaction is first order each in TEACC and hydroxy acids. Reaction is failed to induce the polymerization of acrylonitrile. The oxidation of α-deuteriomandelic acid shows the presence of a primary kinetic isotope effect (k H /k D = 5.63 at 298 K). The reaction does not exhibit the solvent isotope effect. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the following form:Oxidation of p-methylmandelic acid has been studied in 19 different organic solvents. The solvent effect has been analyzed by using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed. C 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 50-55, 2010

Kinetic Studies on Tetrabutylammonium Bromochromate Oxidation of Some Mono- and Di-substituted Benzhydrols

“…The oxidation of 12 mono-and di-substituted benzhydrols such as p-H (S1), p-OCH 3 (Fig. 2), confirming the first-order dependence on [BH].…”

Comparative Studies on Tributylammonium Chlorochromate Oxidation of Pentaammine Cobalt(III) Complexes of a-Hydroxy Acids Catalyzed by Benzalkonium Chloride

“…It is proved that Cr(VI) reagents is the best for the oxidation of most organic functional groups [1][2][3]. In recent years, more achievement were made using new Cr(VI) reagents such as tripropylammonium fluorochromate [4], pyridinium fluorochromate [5], tetrabutylammonium chlorochromate [6] and tetraethyl ammonium chlorochromate [7] etc., have been attempted to determine the kinetic and mechanistic route of various organic compounds [8][9][10][11][12][13][14][15][16].…”

Oxidation of Some Methoxy Anilines by Tetrabutylammoniumbromochromate in Aqueous Acetic Acid Medium: A Kinetics Study

“…Corey in his novel attempt to establish pyridiniumchlorochromate [3] as a versatile oxidant, revisited Sarett's reagent and discovered it to be pyridinium dichromate [4]. Significant improvements are achieved in the development of new Cr(VI) based oxidizing agents, such as pyridiniumfluorochromate [5], benzimidazoliumfluorochromate [6], tetrahexylammoniumbromochromate [6], triethylammoniumchlorochromate [7], tetraethyl ammonium bromochromate [9], tetraethylammoniumchlorochromate [10] and tetrabutylammoniumbromochromate [11].…”