Carbon-Nitrogen Cleavage in the Photolysis and Pyrolysis of Triphenylmethyl Azide

The formation of triphenylmethyl radical in the photolysis of triphenylmethyl azide is demonstrated by its esr spectrum. Photolysis of azide labeled in the terminal nitrogen with nitrogen-15 leads to isotope-position rearrangement, suggesting that recombination of triphenylmethyl and azide radicals occurs. Pyrolysis of the labeled azide results in extensive isotope-position rearrangement. No radicals can be detected in the pyrolysis products by esr measurement, however, so the rearrangement probably occuss by an intramolecular process or ion-pair recombination.