Abstract: The thermolysis of five tertiary alkyl azides leads to both carbon-nitrogen and nitrogen-nitrogen bond fission in roughly equivalent amounts. Strong evidence for the intermediacy of alkylnitrenes was obtained by the isolation of intramolecular aromatic substitution products, dihydrophenanthridines from 2-CsHsC6H4CR2N3 (R= Me and Ph). Other less ideally situated azides lead to no intramolecular aliphatic CH insertion or ...
