ORGN 235 |
| Mark G. Steinmetz and Chicheng Ma. Department of Chemistry, Marquette University, PO Box 1881, Milwaukee, WI 53201-1881 |
Phenolic leaving groups attached a to the keto carbonyl in a-keto amides are photochemically released in aqueous CH3CN via a heterolytic cleavage mechanism when the para substituent is an electron withdrawing group or hydrogen. The chemical yields of the phenols are essentially quantitative in most cases and quantum yields are 0.2-0.3. With para-electron donating groups the leaving group release becomes inefficient and 1,3-photorearrangement products strongly predominate. Laser flash photolyses suggest that the latter products result from photodissociation to radicals. |
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
8:00 AM-12:00 PM, Tuesday, March 30, 2004 Anaheim Convention Center -- 303A, Oral
Division of Organic Chemistry |
