ORGN 86 |
| We have previously shown that dibenzothiophene-S-oxide (DBTO) undergoes deoxygenation upon photolysis. We hope to extend this chemistry to the generation of reactive intermediates such as carbenes and nitrenes through the photochemical scission of the S-C and S-N bonds of sulfonium ylides and sulfilimines. Dimethyl malonate ylides of thioanisole, thiophene, benzothiophene, and dibenzothiophene have been prepared. Chemical trapping studies with cyclohexene and methanol are suggestive of a carbene intermediate. The quantum yields of sulfide formation upon photolysis from the thiophene, benzothiophene, and dibenzothiophene ylides are all greater than that of DBTO. Further product studies and time-resolved IR studies will be used to unambiguously establish the presence and multiplicity of the intermediate carbenes generated. |
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
1:00 PM-5:20 PM, Sunday, 10 September 2006 Moscone Center -- Room 133, Oral
Division of Organic Chemistry |