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Kinetics and mechanism of oxidation of aliphatic ketoximes by thallium(III) acetate—part I
Author(s) -
Balakrishnan T.,
Santappa M.
Publication year - 1978
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.550100808
Subject(s) - chemistry , thallium , kinetics , reaction rate constant , ionic strength , inorganic chemistry , reaction mechanism , first order , medicinal chemistry , organic chemistry , catalysis , physics , quantum mechanics , mathematics , aqueous solution
The oxidative cleavage of some aliphatic ketoximes by thallium(III) acetate was studied in the temperature range of 20–40°C. The reactions were followed by determination of the rates of disappearance of thallium(III) acetate for variations in [substrate], [Tl(III)], [H + ], ionic strength, temperature, etc. The reactions were found to be totally second order–first order with respect to each reactant. The second‐order rate constants and thermodynamic parameters were evaluated and discussed. The mechanism proposed involves one‐electron oxidation to the iminoxy radical followed by an another one‐electron oxidation to the hydroxynitroso compound which dimerizes and decomposes to give the carbonyl compounds and hyponitrous acid.