ORGN 415 |
| Keith B. Thomas and Alexander Greer. Department of Chemistry and The Graduate Center, The City University of New York (CUNY), Brooklyn College, Brooklyn, NY 11210 |
| An exciting recent observation was that a fused aromatic sulfoxide in the presence of low energy light can undergo photodeoxygenation to generate a highly reactive oxidant. In the presence of light of only 76 kcal in energy, 1,2-benzodiphenylene sulfoxide can react with alkanes to afford alcohols. We consider atomic oxygen [O(3P)] as the most likely candidate for the intermediate based on mechanistic studies with substrate acceptors to the oxidation. In an effort to devise methods to accomplish similar transformations we are developing a research topic (with H. Gafney, Queens College) aimed at a heterogeneous source of reactive oxygen species. We describe our recent progress on the sulfoxide photodeoxygenation reaction in solution and in porous glasses. Experiments are carried out with samples of porous glasses derived from the base catalyzed polymerization of tetramethoxysilane, ethanol, and water. The chemistry of atomic oxygen in solution is largely unknown which is an interesting commentary on the state of this topic since its gas phase chemistry has been examined so extensively. Experiments thus far show that gas-phase triplet oxygen atoms have the same characteristic as the intermediate in the condensed-phase sulfoxide photochemistry. The discussion will, among other steps, present our effort to examine the number of photogenerated oxygen atoms that diffuse from the porous glass into the surrounding medium. Measurements of the photoproducts in fluid solution and the porous glass can indicate the fraction of oxygen atoms which are synthetically available to gauge the feasibility for the delivery of oxygen atoms via an optical fiber. |
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Physical Organic, Materials, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Tuesday, September 9, 2003 Hilton New York -- Americas Hall 1, Poster
Sci-Mix
Division of Organic Chemistry |