PHOTOCHEMISTRY OF PHENYL AZIDE: CHEMICAL PROPERTIES OF THE TRANSIENT INTERMEDIATES.

Article abstract of DOI:10.1021/ja00330a032

The photochemistry of phenyl azide was examined by laser-flash photolysis in inert and reactive (nucleophilic) solvents. Direct irradiation and triplet sensitization give triplet phenylnitrene (PhN**3). The products of the reaction of PhN**3 depend dramatically on the concentration of the azide and on the power of the light source. In the direct irradiation, a relatively long-lived precursor to PhN**3 is formed. This singlet-state intermediate reacts with the nucleophilic solvents. The structure of this species and the rates of its reaction with secondary amines are discussed.