INTERMEDIATES IN DIRECT PHOTOLYSIS OF ALKYL AZIDES

The lack of selectivity shown in migration aptitudes in triarylmethyl azide photolysis, and the formation of triphenylmethylamine in photolysis of triphenylmethyl azide in the presence of efficient hydrogen donors support the existence of a discrete nitrene intermediate. While the occurrence of a triplet-sensitized decomposition shows that a triplet azide, and presumably a triplet nitrene, can be involved, efforts to detect triplet azide in the direct photolysis by quenching experiments failed. This failure, and the high quantum yields, indicate that part or all of the direct photolysis may occur via a singlet azide and a singlet nitrene. © 1968, American Chemical Society. All rights reserved.