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DOI: 10.1039/A608095B (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 881-886

Proton chemical shifts in NMR. Part 9.1 Steric and electric field effects in chlorine substituent chemical shifts (SCS)

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Raymond J. Abraham, Mark A. Warne and Lee Griffiths

Abstract

A model for the prediction of the proton chemical shifts of chloroalkanes is given and applied to a variety of chloro compounds. These include chloro- and 1,1-dichloro-cyclohexane for which the proton spectra have been obtained and the individual proton chemical shifts assigned at -80 °C where the ring inversion is slowed sufficiently to give the spectra of the individual conformers. The proton spectra of 1-chloro- and 2-chloro-adamantane are also reported and completely assigned.The chlorine SCS are shown to be multifunctional. The short range effects (three bonds or less) are calculated from the partial atomic charges obtained from the CHARGE scheme. The long range (>three bonds) effects are shown to be due to the electric field of the C–Cl bond plus the steric effect of the chlorine atom.This model (CHARGE4) predicts the proton chemical shifts of a variety of chloroalkanes over 70 data points spanning ca. 6.2 ppm with an rms error of 0.15 ppm. These compounds include chloroethanes, propanes, cyclohexanes, bornanes, norbornanes, adamantanes and steroids.Analysis of the chlorine steric term shows that the quadratic term in the Buckingham equation is much too small to account for the observed steric effects which are considered to arise from van der Waal’s interactions.

References

  1. Part 8. R. J. Abraham, L. Griffiths and M. A. Warne, J. Chem. Soc., Perkin Trans. 2, 1997, 203 Search PubMed.
  2. R. F. Zürcher, Prog. Nucl. Magn. Reson. Spectrosc., 1967, 2, 205 CrossRef.
  3. A. K. Davis, D. W. Mathieson and P. D. Nicklin, Tetrahedron Lett., 1973, 6, 413 CrossRef.
  4. W. Gschwendtner and H. J. Schneider, J. Org. Chem., 1980, 45, 3507 CrossRef CAS.
  5. H.-J. Schneider, U. Buchneit, N. Becker, G. Schmidt and U. Siehl, J. Am. Chem. Soc., 1985, 107, 7027 CrossRef CAS.
  6. H.-J. Schneider and M. Jung, Magn. Reson. Chem., 1988, 26, 679 CAS.
  7. R. J. Abraham, A. P. Barlow and A. E. Rowan, Magn. Reson. Chem., 1989, 27, 1074 CAS.
  8. C. R. Kaiser, R. Rittner and E. A. Basso, Magn. Reson. Chem., 1994, 32, 503 CAS.
  9. R. J. Abraham, M. Edgar, R. P. Glover, L. Griffiths and M. A. Warne, J. Chem. Soc., Perkin Trans. 2, 1996, 333 RSC.
  10. Part 7. R. J. Abraham, L. Griffiths and M. A. Warne, J. Chem. Soc., Perkin Trans. 2, 1997, 31 Search PubMed.
  11. (a) A. Y. Meyer, N. L. Allinger and Y. Yuh, Isr. J. Chem., 1980, 20, 57 CAS; (b) PCMODEL (4.0), Serena Software, PO Box 3076, Bloomington, IN, USA, 1986.
  12. B. S. Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell, Vogel's Textbook of Practical Organic Chemistry, Longman, London, 5th edn., 1991, pp. 558–559 Search PubMed.
  13. W. Kwestroo, F. A. Meijer and E. Havinga, Recl. Trav. Chim. Pays-Bas, 1954, 73, 717 CAS.
  14. GAUSSIAN 92, Gaussian Inc., Pittsburgh PA, 1992: M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart and J. A. Pople.
  15. Landolt-Börnstein, Structure Data of Free Polycyclic Molecules, Series II, vol. 7 and 15, Springer-Verlag, Berlin, 1976 and 1987 Search PubMed.
  16. S. D. Morley, R. J. Abraham, I. S. Haworth, D. E. Jackson, M. R. Saunders and J. G. Vinter, J. Comput.-Aided Mol. Des., 1991, 5, 475 Search PubMed.
  17. D. Höffner, S. A. Lesko and G. Binsch, Org. Magn. Reson., 1978, 11, 179 Search PubMed.
  18. G. Schrumpf, W. Sanweld and R. Machinek, Magn. Reson. Chem., 1987, 25, 11 CAS.
  19. H.-E. Mons, K. Bergander and H. Gunther, Magn. Reson. Chem., 1993, 31, 509 CAS.
  20. R. C. Fort Jun. and P. v. R. Schleyer, J. Org. Chem., 1965, 30, 789 CrossRef.
  21. R. J. Abraham and J. Fisher, Magn. Reson. Chem., 1985, 23, 863.
  22. F. W. van Deursen and P. K. Korver, Tetrahedron Lett., 1967, 3923 CrossRef CAS.
  23. J. Emsley, J. Feeney and H. Sutcliffe, High Resolution NMR Spectroscopy, 2, App. B, Pergamon Press, Oxford, 1966 Search PubMed.
  24. C. Altona, J. H. Ippel, A. J. A. W. Hoekzema, C. Erkelens, M. Groesbeek and L. A. Donders, Magn. Reson. Chem., 1989, 27, 564 CAS.
  25. J. Gaasteiger and M. Marsili, Org. Magn. Reson., 1981, 15, 353 Search PubMed.
  26. C. K. Fay, J. B. Grutzner, L. F. Johnson, S. Sternhall and P. W. Westerman, 1973, 38, 3122.
  27. R. J. Abraham and J. Fisher, Magn. Reson. Chem., 1985, 23, 856 CAS.
  28. F. W. van Deursen and A. C. Udding, Recl. Trav. Chim. Pays-Bas, 1968, 87, 1243 CAS.
  29. A. D. Buckingham, Can. J. Chem., 1960, 38, 300 CAS.
  30. M. Grayson and W. T. Raynes, Magn. Reson. Chem., 1995, 33, 138 CAS.
  31. R. J. Abraham and J. S. E. Holker, J. Chem. Soc., 1963, 806 RSC.
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