Equilibrating Tertiary 2-Norbornyl Cations

  • Herbert C. Brown

Abstract

The 1,2-di-p-anisyl-2-norbornyl cation is a particularly fascinating species with special historic interest. It is the first 2-norbornyl cation to be clearly characterized as a classical ion. It is also the first member to be investigated of a highly informative group of tertiary 2-norbornyl cations capable of existing either as a symmetrical σ-bridged nonclassical ion or as a pair of rapidly equilibrating classical ions. The experimental results clearly established the 1,2-di-p-anisyl-2-norbornyl cation to be the latter. The discovery was made by the individual who is still one of the leading exponents of σ-bridged cations. It must have been a heart-rending experience.

Keywords

Canonical Structure Classical Cation Resonance Hybrid Endo Isomer Bridgehead Proton 
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.
    S. Winstein and D. Trifan, J. Amer. Chem. Soc., 74, 1147, 1154 (1952).CrossRefGoogle Scholar
  2. 2.
    P. v. R. Schleyer, M. M. Donaldson, and W. E. Watts, J. Amer. Chem. SOC., 87, 375 (1965).CrossRefGoogle Scholar
  3. 3.
    R. Hasaline, E. Huang, K. Ranganayakulu, T. S. Sorensen, and N. Wong, Can. J. Chem., 53, 1876 (1975)CrossRefGoogle Scholar
  4. T. S. Sorensen, Accounts Chem. Res., 9, 257 (1976).CrossRefGoogle Scholar
  5. 4.
    C. A. Bunton, Nucleophilic Substitution at a Saturated Carbon Atom, Elsevier, New York, 1963.Google Scholar
  6. 6.
    G. S. Hammond, J. Amer. Chem. Soc., 77, 334 (1955).CrossRefGoogle Scholar
  7. 7.
    H. C. Brown and K. Takeuchi, J. Amer. Chem. Soc., 90, 2691 (1968).CrossRefGoogle Scholar
  8. 8.
    P. v. R. Schleyer, D. C. Kleinfelter, and H. G. Richey, Jr., J. Amer. Chem. Soc., 85, 479 (1963).CrossRefGoogle Scholar
  9. 9.
    P. D. Bartlett, E. R. Webster, C. E. Dills, and H. G. Richey, Jr., Ann., 623, 217 (1959)Google Scholar
  10. P. D. Bartlett, C. E. Dills, and H. G. Richey, Jr., J. Amer. Chem. Soc., 82, 5414 (1960).CrossRefGoogle Scholar
  11. 10.
    P. D. Bartlett, Nonclassical Ions, Benjamin, New York, 1965, p. 474.Google Scholar
  12. 11.
    G D. Sargent, Carbonium Ions, Vol. III, G. A. Olah and P. v. R. Schleyer, Eds., Wiley-Interscience, New York, 1972, pp. 1132–1136.Google Scholar
  13. l2.
    N. C. Deno and A. Schriesheim, J. Amer. Chem. Soc., 77, 3051 (1955).CrossRefGoogle Scholar
  14. 14.
    G. A. Olah and G. Liang, J. Amer. Chem. Soc., 96, 195 (1974).CrossRefGoogle Scholar
  15. 15.
    H. C. Brown and M.-H. Rei, J. Amer. Chem. Soc., 90, 6216 (1968).CrossRefGoogle Scholar
  16. 17.
    H. Goering and K. Humski, J. Amer. Chem. Soc., 90, 6213 (1968).CrossRefGoogle Scholar
  17. 18.
    S. Ikegami, D. L. Vander Jagt, and H. C. Brown, J. Amer. Chem. Soc., 90, 7124 (1968).CrossRefGoogle Scholar
  18. 19.
    H. L. Goering and J. V. Clevenger, J. Amer. Chem. Soc., 94, 1010 (1972).CrossRefGoogle Scholar
  19. 20.
    G. A. Olah, J. R. De Member, C. Y. Lui, and R. D. Porter, J. Amer. Chem. Soc., 93, 1442 (1971).CrossRefGoogle Scholar
  20. 21.
    L. Radom, J. A. Pople, V. Buss, and P. v. R. Schleyer, J. Amer. Chem. Soc., 94, 311 (1972).CrossRefGoogle Scholar
  21. 23.
    G.A. Olah and G. Liang, J. Amer. Chem. Soc., 95, 3792 (1973).CrossRefGoogle Scholar
  22. 24.
    E. W. Bittner, E. M. Arnett, and M. Saunders, J. Amer. Chem. Soc., 98, 3734 (1976).CrossRefGoogle Scholar
  23. 25.
    J. J. Solomon and F. H. Field, J. Amer. Chem. Soc., 98, 1567 (1976)CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1977

Authors and Affiliations

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

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