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Effects of Steric Strain on the Preparation, Stability and Reactions of Aryl Anions and Amines

  • Shelton Bank

Abstract

Steric effects as important contributors to the behavior of organic compounds were first identified by Kehrmann less than 100 years ago.1 The subsequent major developments were outlined by Brown in 1956.2 Since that time steric effects have become an important part of the fabric of organic chemistry and recent advances are highlighted in chapters in advanced textbooks.3,4 Steric effects have not always occupied a position of high regard, and the classic work since 1940 has altered indelibly the then prevailing view. The present-day organic chemist values and utilizes steric factors along with polar and resonance factors to account for chemical effects.

Keywords

Lone Pair Steric Effect Methyl Iodide Proton Nuclear Magnetic Resonance Proton Chemical Shift 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    F. Kehrmann, J. prakt. Chem., 40, 257 (1889).CrossRefGoogle Scholar
  2. 2.
    H. C. Brown, J. Chem. Soc., 1956, 1248.Google Scholar
  3. 3.
    W. J. le Noble, “Highlights of Organic Chemistry,” Marcel Dekker, Inc., New York, 1974, Chap. 7.Google Scholar
  4. 4.
    F. A. Carey and R. J. Sundberg, “Advanced Organic Chemistry,” Plenum Press, New York, 1977, Chap. 3.Google Scholar
  5. 5.
    H. C. Brown, G. K. Barbaras, H. L. Berneis, W. H. Bonner, R. B. Johnanneson, M. Grayson and K. LeRoi Nelson, J. Am. Chem. Soc., 75, 1, (1953).CrossRefGoogle Scholar
  6. 6.
    H. C. Brown, J. Chem. Educ., 36, 427 (1959).Google Scholar
  7. 7.
    J. Packer, J. Vaughan and E. Wong, J. Am. Chem. Soc., 80, 905 (1958).CrossRefGoogle Scholar
  8. 8.
    M. S. Newman and W. H. Powell, J. Org. Chem., 26, 812 (1961).CrossRefGoogle Scholar
  9. 9.
    Y. Okamoto and K. I. Lee, J. Am. Chem. Soc., 97, 4015 (1975).CrossRefGoogle Scholar
  10. 10.
    E. L. Eliel in M. S. Newman, Editor “Steric Effects in Organic Chemistry,” John Wiley and Son, Inc., New York, 1956, p. 161.Google Scholar
  11. 11.
    D. J. Cram, “Fundamentals of Carbanion Chemistry,” Academic Press, New York, 1965.Google Scholar
  12. 12.
    A. Streitwieser, Jr., J. R. Murdoch, G. Häfelinger and C. J. Chang, J. Am. Chem. Soc., 95, 4248 (1973).CrossRefGoogle Scholar
  13. 13.
    N. S. Frumina and E. G. Tregub, Zh. Analiticheskol Khim., 26, 669 (1971).Google Scholar
  14. 14.
    N. F. Hall, M. R. Sprinkle, J. Am. Chem. Soc., 54, 3469 (1932); D. D. Perrinn, “Dissociation Constants of Organic Bases in Aqueous Solution” Butterworths, London, 1965.Google Scholar
  15. 15.
    B. V. Cheney, J. Am. Chem. Soc., 90, 5386 (1968).CrossRefGoogle Scholar
  16. 16.
    V. R. Sandel and H. H. Freedman, J. Am. Chem. Soc., 85, 2328 (1963).CrossRefGoogle Scholar
  17. 17.
    S. Bank and J. S. Sturges, J. Ovganometal. Chem., in press (1978).Google Scholar
  18. 18.
    C. H. Bushweller, J. S. Sturges, M. Cipullo, S. Hoogasian, M. W. Gabriel and S. Bank, Tetrahedron Lett., 1359 (1978).Google Scholar
  19. 19.
    S. Bank and J. S. Sturges, research in progress.Google Scholar
  20. 20.
    R. B. Bates, L. M. Kiroposki and D. E. Potter, J. Org. Chem., 37, 560 (1972).CrossRefGoogle Scholar
  21. 21.
    R. Breslow and R. Goodin, J. Am. Chem. Soc., 98, 6076 (1976).CrossRefGoogle Scholar
  22. 22.
    P. West and R. Waack, J. Am. Chem. Soc., 89, 4395 (1967), R. A. H. Casling, A. G. Evans and N. H. Rees, J. Chem. Soc., B, 1966, 519.CrossRefGoogle Scholar
  23. H. C. Brown and A. Cahn, J. Am. Chem. Soc., 77, 1715 (1955).CrossRefGoogle Scholar
  24. 23.
    H. C. Brown and A. Cahn, J. Am. Chem. Soc., 77, 1715 (1955).CrossRefGoogle Scholar
  25. 24.
    B. M. Wepster in W. Klyne and de la Mare, Editors, “Progress in Stereochemistry,” Butterworths, London, 1958, p. 150.Google Scholar
  26. 25.
    C. Zener, Vhys. Rev., 36, 51 (1930). The reduction potentials were measured in DMSO with TBAP electrolyte using SCE as reference at 21°. The oxidation potentials are computed from the frequencies of the charge transfer complexes of DDQ and 1-substituted naphthalenes in methylene chloride (Reference 26) and the relationship between ionization potentials and charge transfer frequencies (Reference 27).Google Scholar
  27. 26.
    S, Bank and M. Platz, manuscript in preparation.Google Scholar
  28. 27.
    R. Foster, “Organic Charge-Transfer Complexes.” Academic Press, New York, 1969, pp. 60–62.Google Scholar
  29. 28.
    F. Gobert, S. Combrisson and M. Platzer, Tetrahedron, 30, 2919 (1974).CrossRefGoogle Scholar
  30. 29.
    P. R. Wells, D. P. Arnold and D. Doddrell, J. Chem. Soc., Perkin II, 1974, 1745.Google Scholar
  31. 30.
    R. Zahradnik, A. Kröhn, J. Pancis and J. Shobl., Coll. Czech. ehem. Comm., 34, 2553 (1969).Google Scholar
  32. 31.
    a) M. Daney, R. Lapouyade, M. Mary, and H. Bouas-Laurent, J. Ovganometal. Chem., 92, 267 (1975);CrossRefGoogle Scholar
  33. 31.
    b) C. Fahre, M. H. A. Salem, J. P. Mazaleyrat, A. Tchapla, and Z. Welvart, ibid. 87, 9 (1975);Google Scholar
  34. 31.
    c) P. P. Fu, R. G. Harvey, J. W. Paschal, and P. W. Rahideau, J. Am. Chem. Soc., 97, 1145 (1975);CrossRefGoogle Scholar
  35. 31.
    d) H. E. Zieger and L. T. Gelhaum, J. Org. Chem., 37, 1012 (1972).CrossRefGoogle Scholar
  36. 32.
    S. Bank, J. Bank, M. Daney, B. Lahrande, and H. Bouas-Laurent, J. Org. chem., 42, 4058 (1977).CrossRefGoogle Scholar
  37. 33.
    A. Streitwieser, “Solvolytic Displacement Reactions,” McGraw-Hill, New York, 1962, pp. 30–31.Google Scholar

Copyright information

© Plenum Press, New York 1978

Authors and Affiliations

  • Shelton Bank
    • 1
  1. 1.Department of ChemistryState University of New York at AlbanyAlbanyUSA

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