DECOMPOSITION OF PHENYL AZIDE ADDUCT OF NORBORNYLENE

The pyrolysis of the triazoline adduct formed upon the reaction of phenyl azide with bicyclo (2.2.1) heptene results in the elimination of nitrogen and the formation of at least five products. The major products of pyrolysis in decalin were 3-azatricyclo (3.2.1.02,4exo) octane (19) and N-phenylbicyclo (2.2.1) hept-2-imine (20). Also formed in substantial amounts were syn-7-N-phenylaminobicyclo (2.2.1) hept-2-ene (22), 3-N-phenylaminotricyclo (2.2.1.02,6) heptane (23), and 3-azatricyclo(3.2.1.02,4endo) octane (21). The mechanism of decomposition of the triazoline adduct is considered to proceed via a multistep mechanism involving initial heterolytic cleavage of the NN single bond to give a diazonium betaine (16) which undergoes CC bond cleavage to give a diazoimine (17) prior to loss of nitrogen. Both kinetic and chemical evidence is offered to support the proposed mechanism. © 1969.