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Lipids

, 26:675 | Cite as

A facile chemical synthesis of cholest-4-en-3-one. Carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and cholest-5-en-3-one

  • Edward J. Parish
  • Hiroshi Honda
  • Sarawanee Chitrakorn
  • Peter Livant
Plant and Fungal Sterols: Biosynthesis, Metabolism and Function Papers Presented at a Symposium Held at the AOCS Annual Meeting. Baltimore, MD, April 1990 Communication

Abstract

This paper presents a simplified method for the chemical synthesis of cholest-4-en-3-one, which is a naturally occurring steroid and a salient intermediate in steroid chemistry. Pyridinium chlorochromate (PCC) in refluxing benzene has been found to be an effective and convenient reagent for the oxidation and concomitant isomerization of cholest-5-en-3β-ol (cholesterol) to cholest-4-en-3-one in high yield. Also described are the carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and of the isolated reaction intermediate cholest-5-en-3-one.

Keywords

Cholesterol Anhydrous Magnesium Sulfate Proton Chemical Shift Allylic Alcohol Pyridinium Chlorochromate 
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.

Abbreviations

COSY

correlation spectroscopy

DEPT

distortionless enhancement polarization transfer

GLC

gas-liquid chromatography

IR

infrared spectrometry

MS

mass spectrometry

NMR

nuclear magnetic resonance

PCC

pyridinium chlorochromate

SS

solvent system

TLC

thin-layer chromatography

UV

ultraviolet

References

  1. 1.
    Smith, L.L. (1981)Cholesterol Autoxidation, pp. 50–54, Plenum Press, New York.Google Scholar
  2. 2.
    Smith, L.L. (1987)Chem. Phys. Lipids 44, 87–125.PubMedCrossRefGoogle Scholar
  3. 3.
    Woodward, R.B., Patchett, A.A., Barton, D.H.R., Ives, D.A.J., and Kelly, R.B. (1957)J. Chem. Soc., 1131–1144.Google Scholar
  4. 4.
    Woodward, R.B., Patchett, A.A., Barton, D.H.R., Ives, D.A.J., and Kelly, R.B. (1954)J. Am. Chem. Soc. 76, 2852–2853.CrossRefGoogle Scholar
  5. 5.
    Gautschi, F., and Bloch, K. (1958)J. Biol. Chem. 233, 1343–1347.PubMedGoogle Scholar
  6. 6.
    Schroepfer, G.J., Jr., Parish, E.J., Tsuda, M., and Kandutsch, A. (1988)Chem. Phys. Lipids 47, 187–207.PubMedCrossRefGoogle Scholar
  7. 7.
    Holland, H.L., Daum, U., and Riemland E. (1981)Tetrahedron Letters 22, 5127–5131.CrossRefGoogle Scholar
  8. 8.
    Holland, H.L., Riemland, E., and Daum, U. (1982)Can. J. Chem. 60, 1919–1926.CrossRefGoogle Scholar
  9. 9.
    Fieser, L.F., and Fieser, M. (1959)Steroids, Reinhold Publishing Corp., New York.Google Scholar
  10. 10.
    Djerassi, C. (1963)Steroid Reactions, Holden-Day Inc., San Francisco.Google Scholar
  11. 11.
    Fieser, L.F., and Fieser, M. (1949)Natural Products Related to Phenanthrene, 3rd edn., Reinhold Publishing Corp., New York.Google Scholar
  12. 12.
    Fried, J., and Edwards, J.A. (1972)Organic Reactions in Steroid Chemistry, Vol. 1 and 2, Van Nostrand Reinhold Co., New York.Google Scholar
  13. 13.
    Parish, E.J., Wei, T.-Y., and Livant, P. (1987)Lipids 22, 760–763.PubMedCrossRefGoogle Scholar
  14. 14.
    Parish, E.J., Nanduri, V.B.B., Seikel, J.M., Kohl, H.H., and Nusbaum, K.E. (1986)Steroids 48, 407–418.PubMedCrossRefGoogle Scholar
  15. 15.
    Fieser, L.F. (1953)J. Am. Chem. Soc. 75, 5421–5425.CrossRefGoogle Scholar
  16. 16.
    Fieser, L.F. (1963)Org. Synth. 4 195–201.Google Scholar
  17. 17.
    Parish, E.J., and Chitrakorn, S. (1983)Org. Prep. Procd. Intern. 15, 365–367.CrossRefGoogle Scholar
  18. 18.
    Eastham, J.F., and Teranisha, R. (1963) inOrg. Synth. 4, 192–195.Google Scholar
  19. 19.
    Djerassi, C., Engle, R.R., and Bowers, A. (1956)J. Org. Chem. 21, 1547.CrossRefGoogle Scholar
  20. 20.
    Djerassi, C. (1951) inOrganic Reactions (Adams, R., ed.), Vol. 6, pp. 207–272, John Wiley and Sons, Inc., New York.Google Scholar
  21. 21.
    Hendrickson, J.B., and Schwartzman, S.M. (1975)Tetrahedron Lett., 273–276.Google Scholar
  22. 22.
    Huang, S.L., Omura, K., and Swern, D. (1978)Synthesis, 297–299.Google Scholar
  23. 23.
    Smith, A.G., and Brooks, J.W. (1976)J. Steroid Biochem. 7, 705–713.PubMedCrossRefGoogle Scholar
  24. 24.
    Parish, E.J., Chitrakorn, S., Taylor, F.R., and Saucier, S.E. (1984)Chem. Phys. Lipids 36, 179–186.PubMedCrossRefGoogle Scholar
  25. 25.
    Dehar, D.N., and Singh, A.K. (1977)Z. Naturforsch. 32b, 1476–1480.Google Scholar
  26. 26.
    Corey, E.J., and Sugg. J.W. (1974)Tetrahedron Lett., 2647–2651.Google Scholar
  27. 27.
    Piancatelli, G., Scettri, A., and D'Auria, M. (1982)Synthesis, 245–257.Google Scholar
  28. 28.
    Parish, E.J., and Schroepfer, F.J., Jr. (1980)Chem. Phys. Lipids 27, 281–286.CrossRefGoogle Scholar
  29. 29.
    Parish, E.J., Scott, A.D., Dickerson, J.R., and Dykes, W. (1984)Chem. Phys. Lipids 35, 315–320.CrossRefGoogle Scholar
  30. 30.
    Parish, E.J., Chitrakorn, S., and Lowery, S. (1984)Lipids 19, 550–552.CrossRefGoogle Scholar
  31. 31.
    Parish, E.J., and Scott, A.D. (1983)J. Org. Chem. 48, 4766–4768.CrossRefGoogle Scholar
  32. 32.
    Parish, E.J., and Chitrakorn, S. (1985)Synth. Commun. 15, 393–397.Google Scholar
  33. 33.
    Parish, E.J., Chitrakorn, S., and Wei, T.-Y. (1986)Synth. Commun. 16, 1371–1375.Google Scholar
  34. 34.
    Parish, E.J., and Wei, T.-Y. (1987)Synth. Commun. 17, 1227–1230.Google Scholar
  35. 35.
    Brown, H.C., Kulkarni, S.U., Rao, G.C., and Patil, V.D. (1986)Tetrahedron 42, 5515–5522.CrossRefGoogle Scholar
  36. 36.
    Parish, E.J., Honda, H., Chitrakorn, S., and Taylor, F.R. (1988)Chem. Phys. Lipids 48, 255–263.PubMedCrossRefGoogle Scholar
  37. 37.
    Stothers, J.B. (1972)Carbon-13 NMR Spectroscopy, pp. 439–447, Academic Press, New York.Google Scholar
  38. 38.
    Blunt, J.W., and Stothers, J.B. (1977)Org. Magn. Res. 9, 439–464.CrossRefGoogle Scholar
  39. 39.
    Parish, E.J., Tsuda, M., and Schroepfer, G.J., Jr. (1988)Chem. Phys. Lipids 49, 119–121.PubMedCrossRefGoogle Scholar
  40. 40.
    Abraham, R.J., Fisher, J., and Loftus, P. (1988)Introduction to NMR Spectroscopy, pp. 160–163, John Wiley and Sons Inc., New York.Google Scholar
  41. 41.
    Wehrli, F.W., Marchand, A.P., and Wehrli, S. (1988)Interpretation of Carbon-13 NMR Spectra, 2nd edn., pp. 161–163, John Wiley and Sons Inc., New York.Google Scholar

Copyright information

© American Oil Chemists’ Society 1991

Authors and Affiliations

  • Edward J. Parish
    • 1
  • Hiroshi Honda
    • 1
  • Sarawanee Chitrakorn
    • 1
  • Peter Livant
    • 1
  1. 1.Department of ChemistryAuburn UniversityAuburn

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