Premium
NATURE OF PEROXY INTERMEDIATES PRODUCER BY THE PHOTOSENSITIZED OXYGENATION OF DIETHYL SULFIDE AND PHENYLBENZOYL DIAZOMETHANE: KINETIC STUDIES BY CO‐OXIDATION WITH 4‐MONO SUBSTITUTED DIPHENYL SULFIDES
Author(s) -
Ando Wataru,
Kabe Yoshio,
Mivazaki Hajime
Publication year - 1980
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1980.tb03706.x
Subject(s) - diazomethane , chemistry , sulfide , diazo , oxidizing agent , photochemistry , medicinal chemistry , sulfur , electrophile , methanethiol , benzene , organic chemistry , catalysis
— Competitive oxidations of pairs of 4‐monosubstituted diphenyl sulfides by intermediates produced in the photosensitized oxygenation of diethyl sulfide and phenylbenzoyl diazomethane were carried out in methanol and benzene, respectively. Relative rates of oxidation correlate well with Ham‐mett's a, and p values of ‐0.61 (oxidation in the presence of diethyl sulfide) and ‐0.32 (oxidation in the presence of phenylbenzoyl diazomethane) show that the diphenyl sulfides oxidizing intermediates have electrophilic character. In the photosensitized oxygenation of sulfides and diazo compounds, peroxy intermediates (a persulfoxide and a carbonyl oxide, respectively) have been proposed as the most probable intermediates.