Chemistry of Natural Compounds

, Volume 19, Issue 4, pp 437–440 | Cite as

Preparation of 16-substituted 3-hydroxyestra-1,3,5(10)-triene-17-ones starting with the bromination of estrone acetate

  • O. I. Fedorova
  • L. S. Morozova
  • L. M. Alekseeva
  • G. S. Grinenko


The bromination of estrone acetate (Ia) leads to a mixture of acetates of 16α-bromo-16β-bromo-, and 16,16-dibromoestrone (IIa, IIIa, and IVa) in a ratio of 63:28:9. On treatment with an aqueous methanolic solution of potash, depending on the conditions, a mixture of (IIa) and (IIIa) gives 3,16α-dihydroxyestra-1,3,5(10)-trien-17-one (V) or 3,17β-dihydroxyestra-1,3,5(10)-trien-16-one (VI). When 5 g of (Ia) was brominated with 2.8 g of Br2 in chloroform and the products were chromatographed on silica gel, 0.36 g of (IVa), C20H22Br2O3, mp 165–166°C (from ether) 0.37 g of (IIIa), mp 169–170.5°C, 4.6 g of a mixture of (IIa) and (IIIa), 30 mg of (Ia) and 0.2 g of a mixture of 16α- and 16β-bromoestrones was obtained. The action of potash on a mixture of (IIa) and (IIIa) in aqueous MeOH at 20°C led to the epimerization of the (IIa) into (IIIa) and then the conversion of the latter into (V) with mp 203.5–206°C; diacetate with mp 172–173°C (acetone-ethanol). Similarly, but with heating (98°C, 3 h), a mixture of (IIa) and (IIIa) was converted into (VI), with mp 234–236°C. Characteristics of the IR and PMR spectra of the compounds obtained are given.


Potash Estrone Bromo Aqueous Methanolic Solution Aqueous MeOH 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literature cited

  1. 1.
    G. P. Mueller, W. F. Johns, D. L. Cook, and R. A. Edgren, J. Am. Chem. Soc.,80, 1769 (1958).CrossRefGoogle Scholar
  2. 2.
    H. Tawikawa, Chem. Pharm. Bull.,25, 501 (1977).CrossRefGoogle Scholar
  3. 3.
    P. Genet, P. Henry, S. Vandel, B. Desfosses, and M. F. Jayle, Ann. Endocrinol. (Paris),23, 693 (1962).Google Scholar
  4. 4.
    C. H. Kuo, D. Taub, and N. L. Wendler, J. Org. Chem.,28, 1619 (1963).CrossRefGoogle Scholar
  5. 5.
    J. Fajkos, Collection Czech. Chem. Communs.,20, 312 (1955).CrossRefGoogle Scholar
  6. 6.
    W. S. Johnson and W. F. Johns, J. Am. Chem. Soc.,79, 2005 (1957).CrossRefGoogle Scholar
  7. 7.
    J. Fishman and W. R. Biggerstaff, J. Org. Chem.,23, 1190 (1958).CrossRefGoogle Scholar
  8. 8.
    G. P. Mueller and W. F. Johns, J. Org. Chem.,26, 2403 (1961).CrossRefGoogle Scholar
  9. 9.
    R. Gardi, C. Pedrali, and A. Ercoli, Gazzetta Chim. Ital.,93, 1028 (1963).Google Scholar
  10. 10.
    J. Fishman, J. Am. Chem. Soc.,82, 6143 (1960).CrossRefGoogle Scholar
  11. 11.
    G. F. Marrian, K. H. Loke, E. J. D. Watson, and M. Panattoni, Biochem. J.,66, 60 (1957).CrossRefGoogle Scholar

Copyright information

© Plenum Publishing Corporation 1984

Authors and Affiliations

  • O. I. Fedorova
  • L. S. Morozova
  • L. M. Alekseeva
  • G. S. Grinenko

There are no affiliations available

Personalised recommendations