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Kinetics and mechanism of oxidation of some aliphatic esters by sodium N ‐bromo‐ p ‐toluenesulfonamide
Author(s) -
Rangappa K. S.,
Mythily C. K.,
Mahadevappa D. S.,
Gowda N. M. Made
Publication year - 1993
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.550250205
Subject(s) - chemistry , moiety , isopropyl , kinetics , enthalpy , aldehyde , acetic acid , medicinal chemistry , aqueous solution , sodium , organic chemistry , catalysis , thermodynamics , physics , quantum mechanics
The kinetics of oxidation of methyl, ethyl, n ‐propyl, isopropyl, and n ‐butyl acetates to acetic acid and the corresponding aldehyde by the title oxidant in aqueous HCl medium at 40°C has been studied. The reaction shows first‐order with respect to [oxidant] and fractional orders in [H + ] and [ester]. An isokinetic relationship was observed with β = 374 K indicating enthalpy as the rate controlling factor. Attempts have been made to arrive at a linear free energy relationship through the Taft treatment. Electron releasing groups in the ester moiety increase the rate with ρ* = −9.88. A two‐pathway mechanism, consistent with the observed kinetic data, has been proposed. © 1993 John Wiley & Sons, Inc.