Effect of Alcohols on the Photooxidative Behavior of Diethyl Sulfide.
The reactions of singlet oxygen with diethyl sulfide (Et(2)S) in benzene alcohol mixtures have been examined. The salient discoveries include: (1) the rate constants of product formation, k(r), in benzene/methanol mixtures are a function of the concentration of methanol, (2) the ability of alcohols to supress physical quenching are a function of their pK(a)'s, and (3) trapping experiments with diphenyl sulfoxide are consistent with two distinct intermediates. A mechanism which involves formation of a persulfoxide followed by reaction with methanol to give a hydroperoxy-methoxy sulfurane is consistent with all of the results.
Clennan
Edward L.
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Department of Chemistry, University of Wyoming, Laramie, Wyoming 82071.
Greer
Alexander
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