The loss of nitrogen and rearrangement to benzophenone phenylimine of triphenylmethyl azide can be effected by photolysis in the presence of a variety of triplet sensitizers. The sensitizers definitely produced a reaction range in triplet energy from 67.6 kcal/mole (fluorene) to 48.7 kcal/mole (pyrene), so the triplet energy of triphenylmethyl azide must be less than 48.7 kcal/mole. Migration aptitudes in the photolysis sensitized by triphenylene of diphenyl(p-X-phenyl)methyl azides (X = NO2, Cl, CH3, OCH3, N(CH3)2) were all close to unity, as previously observed3 in the direct photolysis. It is concluded that both the direct and sensitized photolyses involve a triplet azide and probably a discrete triplet nitrene as intermediates.
ASJC Scopus subject areas
- Colloid and Surface Chemistry