Dihydro-1,3-diazepinones and diazabicyclo[3.2.0]heptenones from pyridyl azides

Abstract

2-Alkoxy-1H-1,3-diazepines 5 and 7, 2-dialkylamino-5H-1,3-diazepines 6, 2,3-dihydro-1H-1,3-diazepin-2-ones 8 and 2,4-diazabicyclo[3.2.0]hepten-3-ones 9 are obtained by photolysis of tetrazolo[1,5-a]pyridines or 2-azidopyridines 1/2, including the unsubstituted parent compounds; the relative stabilities of the 2-alkoxy- and 2-dialkylamino-1,3-diazepines 5 and 6 are in excellent agreement with ab initio energy calculations.

References

1. A. Reisinger and C. Wentrup, Chem. Commun., 1996, 813.
2. H. Sawanishi and T. Tsuchiya, J. Chem. Soc., Chem. Commun., 1990, 723.
3. For CF₃-substituted carbodiimides 4, nitrenes 3, and further references, see R. A. Evans, M. W. Wong and C. Wentrup, J. Am. Chem. Soc., 1996, 118, 4009.
4. W. J. Hehre, L. Radom, P. v. R. Schleyer and J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986; M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Peterson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. DeFrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, GAUSSIAN 94; Gaussian Inc., Pittsburgh PA, 1995.
5. G2(MP2,SVP) theory: L. A. Curtiss, P. C. Redfern, B. J. Smith and L. Radom, J. Chem. Phys., 1996, 104, 5148.