Photodeoxygenation of Dibenzothiophene Sulfoxide: Evidence for a Unimolecular S-O Cleavage Mechanism
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- 作者：Daniel D. Gregory ; Zehong Wan ; and William S. Jenks
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：January 8, 1997
- 年：1997
- 卷：119
- 期：1
- 页码：94 - 102
- 全文大小：314K
- 年卷期：v.119,no.1(January 8, 1997)
- ISSN：1520-5126
文摘
Photolysis of dibenzothiophene sulfoxide results in the formationof dibenzothiophene and oxidized solvent.Though quantum yields are low, chemical yields of the sulfide arequite high. Yields of the oxidized solvents canalso be high. Typical products are phenol from benzene,cyclohexanol, and cyclohexene from cyclohexane and2-cyclohexenol and epoxycyclohexane from cyclohexene. A number ofexperiments designed to elucidate themechanism of the hydroxylation were carried out, including measurementsof quantum yields as a function ofconcentration, solvent, quenchers, and excitation wavelength.These data are inconsistent with a mechanisminvolvinga sulfoxide dimer, which also does not properly account for the solventoxidations. It is suggested that the activeoxidizing agent may be atomic oxygen O(3P) or a closelyrelated noncovalent complex, based on the nature of theoxidation chemistry, comparison to known rate constants forO(3P) reactivity, and the quantum yield data.