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Kinetics and mechanism of the oxidation of aliphatic aldehydes by tetrabutylammonium tribromide
Author(s) -
Baghmar Manju,
Sharma Pradeep K.
Publication year - 2001
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.1033
Subject(s) - chemistry , reaction rate constant , acetaldehyde , kinetic isotope effect , tribromide , aldehyde , inorganic chemistry , oxidizing agent , kinetics , acetic acid , hydride , aqueous solution , chloride , rate determining step , catalysis , medicinal chemistry , organic chemistry , deuterium , hydrogen , physics , quantum mechanics , ethanol
Abstract The oxidation of six aliphatic aldehydes by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid resulted in the formation of corresponding carboxylic acids. The reaction is first order with respect to TBATB and the aldehydes. The oxidation of deuteriated acetaldehyde (MeCDO) showed the presence of substantial kinetic isotope effect ( k H / k D = 5.92 at 298 K). Addition of tetrabutylammonium chloride has no effect on the reaction rate. Tribromide ion has been proposed as the reactive oxidizing species. The rate constants correlate well with Taft's σ* values, the reaction constant being negative. A mechanism involving a hydride‐ion transfer from the aldehyde hydrate to the oxidant in the rate‐determining step has been suggested. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 390–395, 2001