Hammett correlations in the photosensitized oxidation of 4-substituted thioanisoles

SM Bonesi, M Fagnoni, A Albini

Index: Bonesi, Sergio M.; Fagnoni, Maurizio; Albini, Angelo Journal of Organic Chemistry, 2004 , vol. 69, # 3 p. 928 - 935

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Citation Number: 25

Abstract

Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant kt= 7× 104 to 7× 106 M-1 s-1, close to the value observed for the myoglobin- catalyzed sulfoxidation of the same sulfides. Correlations with σ (ρ=-1.97) and with E ox (slope-3.9 V-1) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths ...