View PDF Version
 
DOI: 10.1039/A604719J (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 411-418

Nitrogen inversion and N–O bond rotation in some hydroxylamine and isoxazolidine derivatives

(Note: The full text of this document is currently only available in the PDF Version )

Azfar Hassan, Mohamed I. M. Wazeer, Herman P. Perzanowski and Sk. Asrof Ali

Abstract

A series of trisubstituted hydroxylamine derivatives, both cyclic and acyclic, has been prepared. The energy barriers in these hydroxylamines are found to be dominated either by nitrogen inversion or N–O bond rotation depending on the nature of the substituents attached to the nitrogen. In several series of compounds, having XC6H4CH2 substituents attached to nitrogen, Hammett free energy correlations are obtained with positive ρ values, indicating increased electron density at the transition state for the inversion process. Isoxazolidines with C(5) ethoxy substituents demonstrate a strong anomeric effect.

References

  1. F. G. Riddell, Tetrahedron, 1981, 37, 849 CrossRef CAS.
  2. D. L. Griffith and J. D. Roberts, J. Am. Chem. Soc., 1965, 87, 4089 CrossRef CAS.
  3. (a) J. R. Fletcher and I. O. Sutherland, Chem. Commun., 1970, 687 RSC; (b) D. L. Griffith, B. L. Olson and J. D. Roberts, J. Am. Chem. Soc., 1971, 93, 1648 CrossRef CAS.
  4. J. E. Anderson and J. E. T. Corrie, J. Chem. Soc., Perkin Trans. 2, 1992, 1027 RSC.
  5. (a) C. L. Perrin, J. D. Thoburn and S. Elsheimer, J. Org. Chem., 1991, 56, 7034 CrossRef CAS; (b) A. D. Walsh, Discuss. Faraday Soc., 1947, 2, 18 RSC; (c) H. A. Bent, Chem. Rev., 1961, 61, 275 CrossRef CAS; (d) C. C. Levin, J. Am. Chem. Soc., 1975, 97, 5649 CrossRef CAS.
  6. J. Sandstrom, Dynamic NMR Spectroscopy, 1982, Academic Press, London Search PubMed.
  7. M. Raban and D. Kost, Tetrahedron, 1984, 40, 3345 CrossRef CAS.
  8. F. Bernardi, I. G. Csizmadia, A. Mangini, H. B. Schelgel, M. H. Whangbo and S. Wolfe, J. Am. Chem. Soc., 1975, 97, 2209 CrossRef CAS.
  9. J. March, Advanced Organic Chemistry, 3rd edn., John Wiley, New York, 1985, p. 244 Search PubMed.
  10. Sk. A. Ali, A. Hassan and M. I. M. Wazeer, Spectrochim. Acta, 1995, 51A, 2279 Search PubMed.
  11. (a) P. Deshong, C. M. Dicken, R. R. Staib, A. J. Freyer and S. M. Weinreb, J. Org. Chem., 1982, 47, 4397 CrossRef CAS; (b) A. T. Bottini and J. D. Roberts, J. Am. Chem. Soc., 1958, 80, 5203 CrossRef CAS; (c) E. Juaristi and G. Cuevas, Recent Studies of the Anomeric Effect, Tetrahedron Report No. 315; Tetrahedron, 1992, 48, 5019 Search PubMed.
  12. M. I. M. Wazeer and Sk. A. Ali, Can. J. Appl. Spect., 1995, 40, 53 Search PubMed.
  13. The NMR Program Library, Science and Engineering Research Council, 1975, Daresbury, UK.
  14. Sk. A. Ali, A. Hassan and M. I. M. Wazeer, J. Chem. Soc., Perkin Trans. 2, 1996, 1479 RSC.
  15. M. I. M. Wazeer, H. A. Muallem, S. Fayyaz and Sk. A. Ali, Can. J. Appl. Spec., 1995, 40, 27 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.