ORGN 841 |
| Azidoarylketones 1 undergo intramolecular H-atom abstraction to form azido ketyl radicals 2 that rearrange efficiently into ketyl imine radicals 3. Laser flash photolysis of azides 1 show that imine radicals 3 formed, have a lifetime of a few microseconds and that they are efficiently trapped by molecular oxygen. Product studies demonstrate that imine radicals 3 decay by intramolecular reactivity. In comparison, azides 4 undergo intermolecular energy transfer to form triplet alkyl nitrene intermediates 5. Laser flash photolysis of azides 4 demonstrated that the triplet alkyl nitrene are highly unreactive and have a lifetime of several milliseconds. Product studies indicate that they decay through bimolecular reactivity. The triplet alkyl nitrene are also efficiently trapped with oxygen. We have used molecular modeling to explain the different reactivity of azides 1 and 4
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Total Synthesis, Materials, Molecular Recognition, Process R&D, and Physical Organic Chemistry
8:00 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster
Sci-Mix
Division of Organic Chemistry |
