Intramolecularity of the Thermal Rearrangement of Allyloxytetrazoles to N-Allyltetrazolones†

Abstract

The intramolecularity of the thermal rearrangement of 1-aryl-5-allyloxy-1H-tetrazoles 1 to 1-aryl-4-allyl-1,4-dihydrotetrazol-5-ones 2 has been investigated through cross-over studies: the results support the hypothesis for a concerted sigmatropic rearrangement occurring through a highly polar transition state, in which a partially positively charged allyl group migrates from oxygen to nitrogen, without leaving the solvent cage.

References

1. M. L. S. Cristiano, R. A. W. Johnstone and P. J. Price, J. Chem. Soc., Perkin Trans. 1, 1996, 1453.
2. M. L. S. Cristiano and R. A. W. Johnstone, J. Chem. Soc., Perkin Trans. 1, 1996, in press; M. L. S. Cristiano, PhD Thesis, University of Liverpool, 1994.
3. P. A. Evans, A. B. Holmes and K. Russel, J. Chem. Soc., Perkin Trans. 1, 1994, 3397; K. M. Mattia and B. Ganem, J. Org. Chem., 1994, 59, 720; S. Blechert, Synthesis, 1989, 71; M. Lounasmaa, P. Hanhinan and R. Jokela, Tetrahedron, 1995, 51, 8623; P. J. Parsons, C. S. Penkett and A. J. Shell, Chem. Rev., 1996, 96, 195; P. A. Evans, A. B. Holmes, R. P. McGeary, A. Nadim, K. Russel, P. J. Ohanlon and N. D. Pearson, J. Chem. Soc., Perkin Trans 1, 1996, 123.
4. C. J. Moody, Adv. Heterocycl. Chem., 1987, 42, 203; G. B. Bennett, Synthesis, 1977, 589; F. E. Ziegler, Acc. Chem. Res., 1977, 10, 227.
5. F. E. Ziegler, Chem. Rev., 1988, 88, 1423.
6. J. F. Bunnett, in Techniques in Chemistry, Vol. VI: Investigation of Rates and Mechanisms of Reactions, part 1, ed. E. S. Lewis, Wiley, New York, 3rd edn., 1974, pp. 129–209; R. G. Pearson, J. Chem. Phys., 1955, 20, 1478.
7. J. C. Kawer and W. A. Sheppard, J. Org Chem., 1967, 32, 3580.
8. J. K. Elwood and J. W. Gates, J. Org. Chem., 1967, 32, 2956.