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13C NMR Studies of some Bicyclo[2.2.2]Octanones.a Characterization of the Isomeric 1,5,5,8-Tetramethylbicyclo[2.2.2]Octan-2-Ones

  • K. R. Stephens
  • J. B. Stothers
  • C. T. Tan
Chapter
Part of the Environmental Science Research book series (ESRH, volume 4)

Abstract

The 13C nmr spectra of a series of sixteen bicyclo[2.2.2]octenones and octanones have been determined to examine the variation of 13C shieldings with methyl substitution. The well-defined effects arising from 1,4-nonbonded interactions are apparent and are useful for stereochemical assignments. Evidence is presented to show that closely neighboring ´ carbons experience deshielding effects, in sharp contrast to the influence of steric crowding on y carbons. The 13C shieldings observed for 1,5,8,8-tetramethylbicyclo[2.2.2]oct-5-en-2-one and the isomeric saturated bicyclooctanones obtained therefrom establish their structures.

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References

  1. 1.
    D.K. Dalling and D.M. Grant. J. Am. Chem. Soc. 89, 6612 (1967); 94. 5318 (1972).CrossRefGoogle Scholar
  2. 2.
    (a) J.B. Grutzner, M. Jautelat, J.B. Dence, R.A. Smith and J.D. Roberts. J. Am. Chem. Soc. 92, 7107 (1970).(b) E. Lippmaa, T. Pehk, J. Paasivirta, N. Belikova and A. Plate. Org. Mag. Res. 2, 581 (1970).Google Scholar
  3. 3.
    J.B. Stothers, C.T. Tan and K.C. Teo. Can. J. Chem. 00t 0000 (0000).Google Scholar
  4. 4.
    For general discussions see (a) G.C. Levy and G.L. Nelson. 13C Nuclear Magnetic Resonance for Organic Chemists. Wiley-Interscience. New York, 1972; (b) J.B. Stothers. Carbon-13 NMR Spectroscopy. Academic Press. New York, 1972; (c) N.K. Wilson and J.B. Stothers in Topics in Stereochemistry. Vol. 8. edited by E.L. Eliel and N.L. Allinger. Wiley-Interscience, New York. 1973. Chap. 1.Google Scholar
  5. 5.
    J.I. Kroschwitz, M. Winokur, H.J. Reich and J.D. Roberts. J. Am. Chem. Soc. 91, 5927 (1969).CrossRefGoogle Scholar
  6. 6.
    S.H. Grover, J.P. Guthrie, J.B. Stothers and C.T. Tan. J. Mag. Res. 00, 0000 (0000).Google Scholar
  7. 7.
    C.M. Cimarusti and J. Wolinsky. J. Am. Chem. Soc. 90, 113 (1968).CrossRefGoogle Scholar
  8. 8.
    Gurudata and J.B. Stothers. Can. J. Chem. 47, 3515 (1969).CrossRefGoogle Scholar
  9. 9.
    G. vanBinst and D. Tourwe. Org. Mag. Res. 4, 625 (1972).CrossRefGoogle Scholar
  10. 10.
    J.B. Stothers, C.T. Tan., A. Nickon, F. Huang, R. Sridhar and R. Weglein. J. Am. Chem. Soc. 94, 8581 (1972).CrossRefGoogle Scholar
  11. 11.
    Gurudata and J.B. Stothers. Can. J. Chem. 47, 3601 91969).CrossRefGoogle Scholar
  12. 12.
    J.D. Roberts, F.J. Weigert, J.I. Kroschwitz and H.J. Reich. J. Am. Chem. Soc. 92, 1338 (1970).CrossRefGoogle Scholar
  13. 13.
    E.J. Corey, R. Hartmann and R.A. Vatakencherry. J. Am. Chem. Soc. 84, 2611 (1962).CrossRefGoogle Scholar
  14. 14.
    A. Orahovats, M. Tichy and J. Sicher. Call. Czech. Chem. Comm. 35, 838 (1970).CrossRefGoogle Scholar
  15. 15.
    R.M. Nowak. J. Org. Chem. 28, 1182 (1963).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1974

Authors and Affiliations

  • K. R. Stephens
    • 1
  • J. B. Stothers
    • 1
  • C. T. Tan
    • 1
  1. 1.Department of ChemistryUniversity of Western OntarioLondonCanada

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