Photochemical adventures with substituted thiophene-S-oxides

ORGN 80

Melanie J. Heying, melheyi@iastate.edu1, Mrinmoy Nag2, Stacey A. Stoffregen, sstoffre@macalester.edu1, and William S. Jenks, wsjenks@iastate.edu1. (1) Department of Chemistry, Iowa State University, Gilman Hall, Ames, IA 50011, (2) Department of Chemistry, Washington University in St. Louis, Campus Box 1134, One Brookings Drive, St. Louis, MO 63130-4899
Photochemical treatment of selected sulfoxides results in production of atomic oxygen O(3P). Previous studies have used dibenzothiophene-S-oxide (DBTO) and related compounds as substrates, and have relied on solvent effects and product studies for mechanistic support. Energetic considerations suggest the photochemically active state is the lowest singlet, rather than the lowest triplet, which contributes to a low quantum yield of O(3P). The lowest triplet state of thiophene-S-oxide (TO) has the potential to be higher than the S-O bond cleavage energy, which could increase the quantum yield of O(3P). Although experimental work with unsubstituted TO is not possible, substituted derivatives can be studied. The photochemistry of several of these substituted TOs has been investigated, leading to the observation of simple deoxygenation and also the formation of the corresponding furans. Trapping experiments have been carried out to compare with results from DBTO.
 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007