Journal of Organic Chemistry 2001-06-29

Electrophilic oxidant produced in the photodeoxygenation of 1,2-benzodiphenylene sulfoxide.

E Lucien, A Greer

Index: J. Org. Chem. 66(13) , 4576-9, (2001)

Full Text: HTML

Abstract

We report that the photodeoxygenation of 1,2-benzodiphenylene sulfoxide, 1, generates an intermediate capable of oxidizing the solvent benzene to phenol. The reactivity of the intermediate was probed with various substrates (2-methylbutane, chloride ion, and para-substituted aryl sulfides). The intermediate produced in the sulfoxide photodeoxygenation displays an electrophilic oxidation chemistry. Our data on 1 contrast with the behavior of hydroxyl radical but resemble the chemistry observed for gas-phase atomic oxygen [O((3)P)] and for solution-phase photodeoxygenations of dibenzothiophene sulfoxide, 3, and pyridine N-oxide, 5. Correlations are made between the ionization potential of the acceptor molecules and the logarithm of the relative rate constants in order to advance the idea that the oxidizing agent of the title reaction may be solution-phase O((3)P).