Advertisement

Carbon — Bridged Cations

  • Herbert C. Brown
Chapter
  • 109 Downloads

Abstract

In the last chapter, the evidence for π-, aryl-, and σ-participation in representative systems was examined. Unambiguous evidence for both π- and aryl participation was found, but no unambiguous evidence for σ-participation was uncovered in symmetrical systems not undergoing rearrangement to more stable structures. However, detailed consideration of 2-norbornyl and cyclopropylcarbinyl, considered at one time to be the best examples for such σ-participation, was deferred until later (Chapters 5 and 6).

Keywords

Center Bond Methyl Cation Ethyl Cation Vinyl Cation Tertiary Carbocations 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    G. S. Hammond, J. Amer. Chern. Soc., 77, 334 (1955).CrossRefGoogle Scholar
  2. 2.
    S. Winstein, J. Amer. Chern. Soc., 87,381 (1965).CrossRefGoogle Scholar
  3. 3.
    J. D. Roberts and R. H. Mazur, J. Amer. Chem. Soc., 73, 3542 (1951).CrossRefGoogle Scholar
  4. 4.
    S. Winstein and D. Trifan, J. Amer. Chem. Soc., 74, 1147, 1154 (1952).CrossRefGoogle Scholar
  5. 5.
    J. D. Roberts and J. A. Yancy, J. Amer. Chem. Soc., 74, 5943 (1952).CrossRefGoogle Scholar
  6. 6.
    P. D. Bartlett, Nonclassical Ions, Benjamin, New York, 1965.Google Scholar
  7. 7.
    G. D. Sargent, Carbonium Ions, Vol. III, G. A. Olah and P. v. R. Schleyer, Eds., Wiley- Interscience, New York, 1972, Chapter 24.Google Scholar
  8. 8.
    H. C. Brown, H. W. Pearsall, L. P. Eddy, W. J. Wallace, M. Grayson, and K. L. Nelson, Ind. Eng. Chem., 45, 1462 (1953).CrossRefGoogle Scholar
  9. 9.
    W. v. E. Doering, M. Saunders, H. G. Boyton, H. W. Earhart, E. F. Wadley, W. R. Edwards, and G. Laber, Tetrahedron, 4, 178 (1958).CrossRefGoogle Scholar
  10. 10.
    F. Brown, E. D. Hughes, C. K. Ingold, and J. F. Smith, Nature, 168, 65 (1951).CrossRefGoogle Scholar
  11. 11.
    L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, N.Y., 1960.Google Scholar
  12. 12.
    A. E. Remick, Electronic Interpretations of Organic Chemistry, Wiley, New York, 1943.Google Scholar
  13. 13.
    C. K. Ingold, Structure and Mechanism in Organic Chemistry, 2nd ed., Cornell University Press, Ithaca, N.Y., 1969, pp. 766–787.Google Scholar
  14. 14.
    F. K. Fong, J. Amer. Chem. Soc., 96, 7638 (1974).CrossRefGoogle Scholar
  15. 15.
    F. K. Fong, Theory of Molecular Relaxation, Wiley-Interscience, New York, 1975, Chapter 8.Google Scholar
  16. 16.
    F. H. Field and M. S. B. Munson, J Amer. Chem. Soc., 87, 3289 (1965).CrossRefGoogle Scholar
  17. 17.
    F. H. Field, Mass Spectroscopy, Vol. V, A. Maccoll, Ed., Butterworths, London, 1972.Google Scholar
  18. 18.
    V. Dyczmons and W. Kutzelnigg, Theor. Chim. Acta, 33, 239 (1974).CrossRefGoogle Scholar
  19. 19.
    S. Chong and J. L. Franklin, J Amer. Chem. Soc., 94, 6347 (1972).CrossRefGoogle Scholar
  20. 20.
    L. Radom, J. A. Pople, V. Buss, and P. v. R. Schleyer, J. Amer. Chem. Soc., 94, 311 (1972); P.CrossRefGoogle Scholar
  21. C. Hariharan, L. Radom, J. A. Pople, and P. v. R. Schleyer, ibid., 96, 599 (1974).Google Scholar
  22. 21.
    M. Saunders, P. Vogel, E. L. Hägen, and J. Rosenfeld, Accounts Chem. Res., 6,53 (1973).CrossRefGoogle Scholar
  23. 22.
    H. C. Brown, “The Transition State,” Chem. Soc. (London) Spec. Publ, 16, 140–158, 174–178 (1962)Google Scholar
  24. W. L. Jorgensen, J. Amer. Chem. Soc., 99, 280 (1977).CrossRefGoogle Scholar
  25. 23.
    G. A. Olah, J. Shen, and R. H. Schlosberg, J. Amer. Chem. Soc., 95, 4957 (1973).CrossRefGoogle Scholar
  26. 24.
    G. A. Olah, G. Klopman, and R. H. Schlosberg, J. Amer. Chem. Soc., 91, 3261 (1969).CrossRefGoogle Scholar
  27. 25.
    J. D. Roberts and M. Halmann, J. Amer. Chem. Soc., 75, 5759 (1953).CrossRefGoogle Scholar
  28. 26.
    O. A. Reutov and T. N. Shatkina, Tetrahedron, 18, 327 (1962).Google Scholar
  29. 27.
    J. D. Roberts, W. Bennett, R. E. McMahon, and E. W. Holroyd, Jr., J Amer. Chem. Soc., 74, 4283 (1952).CrossRefGoogle Scholar
  30. 28.
    J. D. Roberts and J. A. Yancey, J Amer. Chem. Soc., 77, 5558 (1955).CrossRefGoogle Scholar
  31. 29.
    H. C. Brown and C. J. Kim, J. Amer. Chern. Soc., 90, 2082 (1968)CrossRefGoogle Scholar
  32. 30.
    W. J. le Noble, Highlights of Organic Chemistry, M. Dekker, New York, 1974.Google Scholar
  33. 31.
    S. Winstein, F. Gadient, E. T. Stafford, and P. E. Klinedinst, Jr., J. Amer. Chem. Soc., 80, 5895 (1958).CrossRefGoogle Scholar
  34. 32.
    P. G. Gassman and J. M. Hornback, J. Amer. Chem. Soc., 89, 2487 (1967).CrossRefGoogle Scholar
  35. 33.
    F. B. Miles, J. Amer. Chem. Soc., 89, 2488 (1967); ibid., 90, 1265 (1968).CrossRefGoogle Scholar
  36. 34.
    M. J. S. Dewar and W. W. Schoeller, Tetrahedron, 27, 4401 (1973).CrossRefGoogle Scholar
  37. 35.
    P. v. R. Schleyer, J. Amer. Chem. Soc., 86, 1856 (1964).CrossRefGoogle Scholar
  38. 36.
    R. A. Sneen, Accounts Chem. Res., 6, 46 (1973).CrossRefGoogle Scholar
  39. 37.
    D. J. Raber, J. M. Harris, and P. v. R. Schleyer, Ions and Ion Pairs in Organic Reactions, Vol. II, M. Szwarc, Ed., Wiley, New York, 1974.Google Scholar
  40. 38.
    H. C. Brown, K. L. Morgan, and F. J. Chloupek, J Amer. Chem. Soc., 87, 2137 (1965).CrossRefGoogle Scholar
  41. 40.
    H. C. Brown, F. J. Chloupek, and M.-H. Rei, J. Amer. Chern. Soc., 86, 1246 (1964).CrossRefGoogle Scholar
  42. 41.
    D. G. Farnum and G. Mehta, J. Amer. Chern. Soc., 91, 3256 (1969).CrossRefGoogle Scholar
  43. 42.
    S. Winstein, M. Shatavsky, C. Norton, and R. B. Woodward, J. Amer. Chem. Soc., 77,4183 (1955).CrossRefGoogle Scholar
  44. 43.
    S. Winstein and C. Ordronneau, J. Amer. Chem. Soc., 82, 2084 (1960).CrossRefGoogle Scholar
  45. 24.
    H. C. Brown and H. M. Bell, J. Amer. Chem. Soc., 85, 2324 (1963).CrossRefGoogle Scholar
  46. 25.
    H. Tanida, T. Tsuji, and T. Irie, J. Amer. Chem. Soc., 88, 864 (1966).CrossRefGoogle Scholar
  47. 46.
    A. Diaz, M. Brookhart, and S. Winstein, J. Amer. Chem. Soc., 88, 3133 (1966).CrossRefGoogle Scholar
  48. 47.
    J. J. Tufariello and R. J. Lorence, J. Amer. Chem. Soc., 91, 1546 (1969).CrossRefGoogle Scholar
  49. 48.
    P. G. Gassman and D. S. Patton, J. Amer. Chem. Soc., 91, 2160 (1969).CrossRefGoogle Scholar
  50. 49.
    P. D. Bartlett and G. D. Sargent, J. Amer. Chem. Soc., 87, 1297 (1965).CrossRefGoogle Scholar
  51. 50.
    H. Goering and K. Humski, J. Amer. Chem. Soc., 90, 6213 (1968).CrossRefGoogle Scholar
  52. 51.
    H. Tanida, Accounts Chem. Res., 1, 239 (1968).CrossRefGoogle Scholar
  53. 52.
    C. J. Lancelot, D. J. Cram, and P. v. R. Schleyer, Carbonium Ions, Vol. III, G. A. Olah and P. v. R. Schleyer, Eds., Wiley-Interscience, New York, 1972, Chapter 27.Google Scholar
  54. d.
    S. Winstein and E. T. Stafford, J. Amer. Chern. Soc., 79, 505 (1957).CrossRefGoogle Scholar
  55. j.
    H. Tanida, Y. Hata, S. Ikegami, and Y. Ishitobi, J. A mer. Chern. Soc., 89, 2928 (1967)CrossRefGoogle Scholar
  56. l.
    H. Tanida, T. Tsuji, and H. Ishitobi, J. Amer. Chern. Soc., 86, 4904 (1964)CrossRefGoogle Scholar
  57. 53.
    D. J. Cram, J. Amer. Chem. Soc., 71, 3863 (1949).CrossRefGoogle Scholar
  58. 54.
    S. Winstein and B. K. Morse, J. Amer. Chem. Soc., 74, 1133 (1952).CrossRefGoogle Scholar
  59. 55.
    P. v. R. Schleyer et al., J. Amer. Chem. Soc., 92, 2538, 2540, 2542 (1970).CrossRefGoogle Scholar
  60. 56.
    H. C. Brown and C. J. Kim, J. Amer. Chem. Soc., 93, 5765 (1971).CrossRefGoogle Scholar
  61. 57.
    B. Zurawski, R. Ahlrichs, and W. Kutzelnigg, Chem. Phys. Lett., 21,309 (1973);CrossRefGoogle Scholar
  62. 59.
    J. Weber and A. D. McLean, J Amer. Chem. Soc 98, 875 (1976)CrossRefGoogle Scholar
  63. J. Weber, M. Yoshimine, and A. D. McLean, J. Chem. Phys., 64, 4159 (1976).CrossRefGoogle Scholar
  64. 60.
    H. G. Richey, Jr., J. D. Nichols, P. G. Gassman, A. F. Fentiman, Jr., S. Winstein, M. Brookhart, and R. K. Lustgarten, J. Amer.Chern. Soc.,92, 3783 (1970).CrossRefGoogle Scholar
  65. 61.
    G. A. Olah and G. Liang, J. Amer. Chern. Soc., 97, 6803 (1975).CrossRefGoogle Scholar
  66. 62.
    B. Capon and S. P. McManus, Neighboring Group Participation, Vol. 1, Plenum Press, New York, 1976Google Scholar

Copyright information

© Plenum Press, New York 1977

Authors and Affiliations

  • Herbert C. Brown
    • 1
  1. 1.Purdue UniversityWest LafayatteUSA

Personalised recommendations