Journal of Organic Chemistry, volume 85, issue 12, pages 7952-7958
Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles
1
CNRS/Université de Pau et des Pays de l’Adour/E2S UPPA, Institut des Sciences Analytiques et de Physicochimie pour l’Environnement et les Matériaux, UMR5254, Pau 64000, France
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Publication type: Journal Article
Publication date: 2020-05-20
Journal:
Journal of Organic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 3.6
ISSN: 00223263, 15206904
Organic Chemistry
Abstract
Both photolysis and flash vacuum pyrolysis (FVP) of tetrazoles (1/5) are known to generate nitrile imines (13, 19, and 38), which rearrange to 1H-diazirines, imidoylnitrenes, and carbodiimides. Moreover, FVP of 5-aryltetrazoles is a convenient source of aryldiazo compounds (30/47) and arylcarbenes, including pyridylcarbenes. The factors that determine which path is followed are poorly understood. Calculations at the density functional theory and CASPT2 levels now examine cyclization of N-phenylnitrile imine 13 to indazole 17. A corresponding cyclization of C-phenylnitrile imine 19 can also lead to indazole, but this reaction, which passes through a carbenic nitrile imine, requires a much higher activation energy and is therefore not competitive with the known rearrangements to phenyldiazirines, ring expansion to diazenylcycloheptatetraene, or a new, potential rearrangement to cyanoazepine. C-(2-Pyridyl)nitrile imine 38 is predicted to undergo a new rearrangement to cyanopyridine N-imide 40 with an activation energy of 43 kcal/mol. The experimental observation that 2-pyridyldiazomethane 47 is actually formed requires a reaction with an energy barrier below 43 kcal/mol. This is found in the H-transfer from the tetrazole ring in 5-(2-pyridyl)tetrazole to the pyridine ring with a subsequent formation of 1H-2-(diazomethylene)pyridine and elimination of N2 with a barrier of ca. 26 kcal/mol. This new, facile mechanism has not previously been considered.
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- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Bégué D., Dargelos A., Wentrup C. Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles // Journal of Organic Chemistry. 2020. Vol. 85. No. 12. pp. 7952-7958.
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Bégué D., Dargelos A., Wentrup C. Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles // Journal of Organic Chemistry. 2020. Vol. 85. No. 12. pp. 7952-7958.
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TY - JOUR
DO - 10.1021/acs.joc.0c00773
UR - https://doi.org/10.1021/acs.joc.0c00773
TI - Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles
T2 - Journal of Organic Chemistry
AU - Dargelos, Alain
AU - Bégué, Didier
AU - Wentrup, Curt
PY - 2020
DA - 2020/05/20 00:00:00
PB - American Chemical Society (ACS)
SP - 7952-7958
IS - 12
VL - 85
SN - 0022-3263
SN - 1520-6904
ER -
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@article{2020_Bégué,
author = {Alain Dargelos and Didier Bégué and Curt Wentrup},
title = {Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles},
journal = {Journal of Organic Chemistry},
year = {2020},
volume = {85},
publisher = {American Chemical Society (ACS)},
month = {may},
url = {https://doi.org/10.1021/acs.joc.0c00773},
number = {12},
pages = {7952--7958},
doi = {10.1021/acs.joc.0c00773}
}
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Bégué, Didier, et al. “Aryl Nitrile Imines and Diazo Compounds. Formation of Indazole, Pyridine N-Imine, and 2-Pyridyldiazomethane from Tetrazoles.” Journal of Organic Chemistry, vol. 85, no. 12, May. 2020, pp. 7952-7958. https://doi.org/10.1021/acs.joc.0c00773.