1H-1,3-Diazepines and Ketenimines from Cyanotetrazolopyridines*

Chris Addicott; Curt Wentrup

doi:10.1071/CH08252

RESEARCH ARTICLE

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1H-1,3-Diazepines and Ketenimines from Cyanotetrazolopyridines*

Chris Addicott ^A and Curt Wentrup ^A ^B

+ Author Affiliations

- Author Affiliations

^A Chemistry Building, School of Molecular and Microbial Sciences, University of Queensland, Brisbane, QLD 4072, Australia.

^B Corresponding author. Email: wentrup@uq.edu.au

Australian Journal of Chemistry 61(8) 592-599 https://doi.org/10.1071/CH08252
Submitted: 11 June 2008 Accepted: 7 July 2008 Published: 15 August 2008

Abstract

Cyano-substituted tetrazolo[1,5-a]pyridines/2-azidopyridines 8T and 15T undergo thermal ring opening to the azides 8A and 15A. Solution photolysis causes nitrogen elimination and ring expansion to 1,3-diazacyclohepta-1,2,4,6-tetraenes 10 and 17, which react with alcohols to afford 2-alkoxy-1H-1,3-diazepines, with secondary amines to 2-dialkylamino-5H-1,3-diazepines, and with water to 1,3-diazepin-2-ones (12–14, 19, 21). Argon matrix photolysis of the azides affords the diazacycloheptatetraenes 10 and 17 as principal products together with ring-opened dicyanovinylketenimines 11 and 18. The matrix-isolated species were identified on the basis of comparison of the infrared spectra with those calculated at the B3LYP/6–31+G* level.

Acknowledgements

The present research was supported by the Australian Research Council. We are indebted to the Centre for Computational Molecular Science at the University of Queensland for access to supercomputing facilities.

References

^* This paper is Diazepines Part IV. For Part III, see A. Reisinger, R. Koch, P. V. Bernhardt, C. Wentrup, Org. Biomol. Chem. 2004, 2, 1227. doi:10.1039/B317099C

1H-1,3-Diazepines and Ketenimines from Cyanotetrazolopyridines*

Abstract

Acknowledgements

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