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The Cyclopropylcarbinyl Cation

  • Herbert C. Brown
Chapter

Abstract

The fascinating behavior of cyclopropylcarbinyl derivatives in solvolytic processes and other carbonium ion transformations1 was explored in detail by J. D. Roberts and his coworkers.2 The exceptionally fast rate of solvolysis and the facile interconversions of cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl derivatives led to the proposal that σ-bridged intermediates were involved. Indeed, the first use of the term “nonclassical ion,” appears to have been Roberts’ proposed tricyclobutonium structure 2 for the cyclopropylcarbinyl cation 1 3 (1).

Keywords

Cyclopropane Ring Methanol Acetic Acid Stereochemical Characteristic Cyclopropyl Group Allyl Cation 
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.
    H. G. Richey, Jr., Carbonium Ions, Vol. III, G. A. Olah and P. v. R. Schleyer, Eds., Wiley-Interscience, New York, 1972, Chapter 25Google Scholar
  2. K. B. Wiberg, B. A. Hess, Jr., and A. J. Ashe III, Carbonium Ions, Vol. III, G. A. Olah and P. v. R. Schleyer, Eds., Wiley-Interscience, New York, 1972, Chapter 26.Google Scholar
  3. 2.
    J. D. Roberts and R. H. Mazur, J. Amer. Chem. Soc., 73, 2509 (1951).CrossRefGoogle Scholar
  4. 3.
    J. D. Roberts and R. H. Mazur, J. Amer. Chem. Soc., 73, 3542 (1951).CrossRefGoogle Scholar
  5. 4.
    A. Streitwieser, Jr., Solvolytic Displacement Reactions, McGraw-Hill, New York, 1962.Google Scholar
  6. 5.
    C. G. Bergstrom and S. Siegel, J. Amer. Chem. Soc., 74, 145, 254 (1952).CrossRefGoogle Scholar
  7. 6.
    H. C. Brown and E. N. Peters, J. Amer. Chem. Soc., 95, 2400 (1973).CrossRefGoogle Scholar
  8. 7.
    H. Hart and P. A. Law, J. Amer. Chem. Soc., 86, 1957 (1964)CrossRefGoogle Scholar
  9. H. Hart and J. M. Sandri, J. Amer. Chem. Soc., 81, 320 (1959).CrossRefGoogle Scholar
  10. b.
    H. Marshall, J. Amer. Chem. Soc., 74,1120 (1952)CrossRefGoogle Scholar
  11. c.
    S. Winstein, E. Grunwald, and H. W. Jones, J. Amer. Chem. Soc., 73, 2700 (1951).CrossRefGoogle Scholar
  12. 9.
    H. C. Brown and M. Borkowski, J. Amer. Chem. Soc., 74, 1894 (1952).CrossRefGoogle Scholar
  13. 10.
    Z. Majerski, S. Borcić, and D. E. Sunko, Tetrahedron, 25, 301 (1969)CrossRefGoogle Scholar
  14. 11.
    R. H. Mazur, W. N. White, D. A. Semenov, C. C. Lee, M. S. Silver, and J. D. Roberts, J. A mer. Chem. Soc., 81, 4390 (1959).CrossRefGoogle Scholar
  15. 12.
    K. B. Wiberg and G. Szeimies, J. Amer. Chem. Soc., 92, 571 (1970).CrossRefGoogle Scholar
  16. 13.
    Z. Majerski and P. v. R. Schleyer, J. Amer. Chem. Soc., 93, 665 (1971).CrossRefGoogle Scholar
  17. 14.
    H. G. Richey, Jr., and N. C. Buckley, J. Amer. Chem. Soc., 85, 3057 (1963).CrossRefGoogle Scholar
  18. 15.
    H. C. Brown and E. N. Peters, J. Amer. Chem. Soc., 97, 1927 (1975).CrossRefGoogle Scholar
  19. 16.
    J. D. Roberts, W. Bennett, and R. Armstrong, J. Amer. Chem. Soc., 72, 3329 (1950).CrossRefGoogle Scholar
  20. 17.
    B. R. Ree and J. C. Martin, J. Amer. Chem. Soc., 92, 1660 (1970).CrossRefGoogle Scholar
  21. V. Buss, R. Gleiter, and P. v. R. Schleyer, ibid., 93, 3927 (1971).Google Scholar
  22. 18.
    R. C. Hahn, T. F. Corbin, and H. Shechter, J. Amer. Chem. Soc., 90, 3404 (1968).CrossRefGoogle Scholar
  23. 19.
    H. C. Brown and J. D. Cleveland, J. Amer. Chem. Soc., 88, 2051 (1966).CrossRefGoogle Scholar
  24. 20.
    G. A. Olah, C. L. Jeuell, D. P. Kelly, and R. D. Porter, J. Amer. Chem. Soc., 94, 146 (1972).CrossRefGoogle Scholar
  25. 21.
    D. S. Kabakoff and E. Namanworth, J. Amer. Chem. Soc., 92, 3234 (1970).CrossRefGoogle Scholar
  26. 22.
    M. Vogel and J. D. Roberts, J. Amer. Chem. Soc., 88, 2262 (1966).CrossRefGoogle Scholar
  27. 23.
    G. A. Olah, D. P. Kelly, C. L. Jeuell, and R. D. Porter, J. Amer. Chem. Soc., 92,2544 (1970).CrossRefGoogle Scholar
  28. 24.
    P. v. R. Schleyer and G. W. Van Dine, J. mer. Chem. Soc., 88, 2321 (1966).CrossRefGoogle Scholar
  29. 25.
    W. J. Hehre and P. C. Hiberty, J. Amer. Chem. Soc., 96, 302 (1974)CrossRefGoogle Scholar
  30. W. J. Hehre, Accounts, Chem. Res., 8, 369 (1975).CrossRefGoogle Scholar
  31. 26.
    C. D. Poulter and C. J. Spillner, J. Amer. Chem. Soc., 96,7591 (1974).CrossRefGoogle Scholar
  32. 27.
    L. Radom, P. C. Hariharan, J. A. Pople, and P. v. R. Schleyer, J. Amer. Chem. Soc., 95, 6531 (1973).CrossRefGoogle Scholar
  33. 28.
    L. Radom, J. A. Pople, and P. v. R. Schleyer, J. Amer. Chem. Soc., 94, 5935 (1972).CrossRefGoogle Scholar
  34. 29.
    Y. E. Rhodes and V. G. DiFate, J. Amer. Chem. Soc., 94, 7582 (1972).CrossRefGoogle Scholar
  35. 30.
    J. M. R. Stone and I. M. Mills, Mol. Phys., 18, 631 (1970).CrossRefGoogle Scholar
  36. 31.
    L. H. Scharpen and V. W. Laurie, J. Chem. Phys., 49, 221 (1968).CrossRefGoogle Scholar
  37. 32.
    G. A. Olah, R. J. Spear, P. C. Hiberty, and W. J. Hehre, J. A mer. Chem. Soc., 98, 7470 (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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