Nitrile imines, nitrile oxides and nitrile ylides are widely used in 1,3‐dipolar cycloaddition reactions. They also undergo thermal and photochemical rearrangements to carbodiimides, isocyanates, and ketenimines, respectively. Calculations at DFT and CASPT2 levels of theory reveal novel, potential rearrangements, in which the aromatic 1,3‐dipoles mimic phenylcarbene and undergo ring expansion to cycloheptatetraene derivatives. These rearrangements can potentially take place in both the singlet ground states and the triplet excited states, and they are accelerated by m,m’‐bis(dimethylamino) substitution on the phenyl moieties. The new rearrangement becomes the energetically preferred path for m,m’‐bis(dimethylamino)benzonitrile oxide in the triplet state. In the m,m’‐bis(dimethylamino)benzo nitrile ylide, the cyclization to the 2‐phenyl‐1‐azirine is favored over the ring expansion to a cycloheptatetraene by ca. 5 kcal mol−1 in the singlet state. In the bent triplet states, 1,3‐hydrogen shifts interconverting nitrile ylides are potentially possible.

The denitrogenative rearrangements of several types of benzotriazoles were investigated by DFT (B3LYP/6-311G­(d,p)) and CASPT2­(10,10)­sp/6-311G­(d,p) calculations. The Graebe–Ullmann synthesis of carbazoles 18 by pyrolysis or photolysis of 1-arylbenzotriazoles 14 proceeds without the involvement of benzazirines and without Wolff-type ring contraction to fulvenimines. However, 1-aryltetrahydrobenzotriazoles undergo both cyclization to tetrahydrocarbazole and ring contraction. Triazoloquinones like 34 undergo predominant ring contraction to aminofulvenediones like 38 and also ring expansion to azepinediones like 40 and cyclization to N-arylbenzaziridinediones 39, whereas carbazolediones are not formed. Denitrogenation of 1-methylbenzotriazole 64 results in a facile 1,2-H shift with formation of N-phenylmethanimine 67. 1-Cyanobenzotriazole 71 undergoes destructive pyrolysis with charring, and the calculations predict the occurrence of several low-activation energy reaction pathways.