Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 86, Issue 23, Pages 16992-17001Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.1c02131
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- Queensland Cyber Infrastructure Foundation (QCIF) at The University of Queensland [g01]
- Mesocentre de Calcul Intensif Aquitain of the Universite de Bordeaux
- Universite de Pau et des Pays de l'Adour
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The denitrogenative rearrangements of various benzotriazoles were studied using DFT and CASPT2 calculations, showing different reaction pathways for different types of benzotriazoles during pyrolysis or photolysis.
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.
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