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Oxidation of thioanisole by hydrogen peroxide: activation by nitriles
Author(s) -
Gillitt Nicholas D.,
Domingos Josiel,
Bunton Clifford A.
Publication year - 2003
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.646
Subject(s) - chemistry , thioanisole , acetonitrile , propionitrile , hydrogen peroxide , medicinal chemistry , amide , photochemistry , decomposition , catalysis , organic chemistry
The oxidation of thioanisole (PhSMe) by H 2 O 2 is activated by acetonitrile (MeCN) and propionitrile (EtCN) and involves the formation of a transient peroxyimidate, 1 , by reaction of $\rm{HO}_2^-$ and RCN, and 1 can be rapidly trapped by PhSMe. The rate of oxidation of PhSMe is then independent of the concentrations of PhSMe and of H 2 O 2 , but varies linearly with $\rm{HO}_2^-$ and [RCN]. In very dilute PhSMe it and H 2 O 2 compete in reacting with 1 , and the rate then depends on [PhSMe]. The initial reaction gives PhSOMe, and subsequent formation of PhSO 2 Me is slow. The rates of oxidation are slightly higher than that expected from the MeCN‐activated decomposition of H 2 O 2 , which involves a second molecule of H 2 O 2 in conversion of the peroxyimidate into amide and oxygen. Copyright © 2003 John Wiley & Sons, Ltd.