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Kinetics and mechanism of the oxidation of some α‐hydroxy acids by 2,2′‐bipyridinium chlorochromate
Author(s) -
Kumbhat Vinita,
Sharma Pradeep K.,
Banerji Kalyan K.
Publication year - 2002
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.10036
Subject(s) - chemistry , kinetic isotope effect , mandelic acid , hydride , solvent , medicinal chemistry , catalysis , kinetics , glycolic acid , ion , organic chemistry , hydrogen , inorganic chemistry , photochemistry , lactic acid , deuterium , biology , bacteria , genetics , physics , quantum mechanics
The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by 2,2′‐bipyridinium chlorochromate (BPCC) in dimethylsulphoxide leads to the formation of corresponding oxoacids. The reaction is first order each in BPCC and the hydroxy acids. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the form: k obs = a + b [H + ]. The oxidation of α‐deuteriomandelic acid exhibited a substantial primary kinetic isotope effect ( k H / k d = 5.29 at 303 K). Oxidation of p ‐methylmandelic acid was 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. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 248–254, 2002