Russian Chemical Bulletin

, Volume 46, Issue 9, pp 1611–1614 | Cite as

Synthesis of 6α-methyl-16α,17α-cyclohexano-19-norprogesterone from a 19-methyl-6-desmethyl precursor

  • I. S. Levina
  • L. E. Kulikova
  • V. S. Bogdanov
Chemistry of Natural Compounds and Bioorganic Chemistry
  • 21 Downloads

Abstract

After prolonged refluxing of 19-tosyloxy-16α,17α-cyclohexanopregn-5-en-3β-ol-20-one (3) with NaI in 2-propanol, the initially formed 19-iodo derivative (4) undergoes supraface migration of the CH2I group from the C(10) atom to the C(6) atom, probably through involvement of a homoallyl cation. The resulting 6β-iodomethyl-16α,17α-cyclohexano-19-norpregn-5(10)-en-3β-ol (5) was transformed in three steps into 6α-methyl-16α,17α-cyclohexano-19-norprogesterone (6α-methyl-19-nor-D′ 6-pentarane,8). The transformation of compound5 into the target product8 also gave a side product, a pentarane with aromatic ringA (10), which was isolated and characterized by spectroscopic methods.

Key words

6-methyl-19-norpentaranes synthesis transformations homoallylic rearrangement 

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References

  1. 1.
    I. S. Levina and A. V. Kamernitskii,Khim. -farm. Zh. [Chem. -Pharm. J.], 1990,24, 31 (in Russian).Google Scholar
  2. 2.
    A. V. Kamernitskii and I. S. Levina,Khim. -farm. Zh. [Chem. -Pharm. J.], 1991,25, 4 (in Russian).Google Scholar
  3. 3.
    I. S. Levina, A. V. Kamernitskii, and L. E. Kulikova,Izv. Akad. Nauk SSSR, Ser. Khim., 1990, 1636 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990,39, 1486 (Engl. Transl.)].Google Scholar
  4. 4.
    I. S. Levina and L. E. Kulikova,Abstrs. IX Intern. Congr. Horm. Steroids (September 1994), Dallas (USA), C151.Google Scholar
  5. 5.
    J. Tadanoer,J. Org. Chem., 1966,31, 2124.Google Scholar
  6. 6.
    M. Maeda, M. Kojima, H. Ogawa, K. Nitta and T. Ito,Steroids, 1975,26, 241.CrossRefGoogle Scholar
  7. 7.
    M. Maeda, H. Komatsu, M. Kojima and H. Ogawa,Chem. Pharm. Bull., 1976,24, 1398.Google Scholar
  8. 8.
    H. Komatsu, M. Maeda, and M. Kojima,Synthesis, 1977, 36.Google Scholar
  9. 9.
    J. N. Wright, P. T. van Leersum, S. G. Chamberlin and M. Akhtar,J. Chem. Soc., Perkin Trans. 1, 1989, 1647.CrossRefGoogle Scholar
  10. 10.
    H. J. Ringold, E. Batres, and G. Rosenkranz,J. Org. Chem., 1957,22, 99.CrossRefGoogle Scholar

Copyright information

© Plenum Publishing Corporation 1997

Authors and Affiliations

  • I. S. Levina
    • 1
  • L. E. Kulikova
    • 1
  • V. S. Bogdanov
    • 1
  1. 1.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation

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