ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Photochemistry of Acylazides. I. Photo- and Thermochemistry of 5-Azidocarbonyldibenz[b,f]azepine and its DimerThe reactions of the title compounds, two new carbamoylazides, by photoexcitation and in the ground state, respectively, were investigated. The photochemistry of compounds 1 und 2 differs from that of other heterocycles of the same type and is determined by the azido group. They exhibit the three known kinds of reactions of carbamoylazides via singlet and triplet nitrene, respectively, and the Curtius-rearrangement forming an intramolecular insertion product 6, dibenz-[b,f]azepine 4 and the isocyanate. Products from triplet nitrenes are lacking in the photoreaction of the dimeric azide 2.The decomposition of the azide 1 can be sensitized by triplet energy transfer. Surprisingly, the isocyanate is also formed by triplet sensitization.Photoexcited pyrene reacts with 1 via electron transfer yielding rearrangement and triplet products, respectively. In contrast to diphenylcarbamoylazide, the reaction pathway of the thermally excited compounds leads to nitrene products mainly.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19883300317
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