Structure and reactivity in steroids
An analysis was made of a previously proposed mechanism of the oxidation of secondary alcohols by CrO3 in CH3COOH; a formula was derived for the rate of this conversion under equilibrium conditions, and it was shown that the reactivity of the substrates can be characterized by two constants: thermodynamic and kinetic.
The kinetics of the oxidation of the 17β-OH group of derivatives of 3,17β-estradiol, D-3,17αβ-homoestradiol was studied, and it was shown that the experimental data satisfy the equation obtained.
A relationship was established between the reactivity of the 17β- and 17αβ-OH groups of estrogens as a function of the size of the D ring, the coupling of the B and C rings, and the electronic character of the substituent at C3.
KeywordsOxidation Alcohol Experimental Data Steroid Estrogen
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- 1.L. Vellus, J. Valls, and G. Nomine, Angew. Chemie,77, 185 (1965).Google Scholar
- 2.D. H. R. Barton, A. J. Head, J. Chem. Soc., 932 (1956); D. H. R. Barton, A. J. Head, and P. J. May, J. Chem. Soc., 935 (1957).Google Scholar
- 3.D. H. R. Barton, Experientia,6, 316 (1960).Google Scholar
- 4.D. H. R. Barton, F. Mc. Capra, P. J. May, and F. Thudium, J. Chem. Soc., 1297 (1960).Google Scholar
- 5.O. H. Wheeler and J. L. Mateos, Canad. J. Chem.,36, 712 (1958);36, 1735 (1958).Google Scholar
- 6.R. Bucourt, Bull. Soc. Chim. France, 2081 (1964).Google Scholar
- 7.M. J. T. Robinson and W. B. Whalley, Tetrahedron,19, 2123 (1963).Google Scholar
- 8.V. Schwarz, S. Hermanek, and J. Trojanek, Chem. Industr., 1212 (1960).Google Scholar
- 9.V. Schwarz, S. Hermanek, and J. Trojanek, Coll. Czechosl. Chem. Comm.,27, 2778 (1962).Google Scholar
- 10.V. Schwarz and S. Hermanek, Tetrahedron Letters, 809 (1962); Coll. Czechosl. Chem. Comm.,29, 2360 (1964).Google Scholar
- 11.P. E. Peterson, Tetrahedron Letters, 181 (1963).Google Scholar
- 12.J. Mathieu, M. Legrand, and J. Valls, Bull. Soc. Chim. France, 549 (1960).Google Scholar
- 13.M. Legrand, V. Delaroff, and J. Mathieu, Bull. Soc. Chim. France, 1346 (1961).Google Scholar
- 15.V. V. Egorova, S. N. Ananchenko, A. V. Zakharychev, and I. V. Torgov, Izv. Akad. Nauk SSSR, Ser. Khim., 943 (1969).Google Scholar
- 16.K. B. Wiberg, Oxidation in Organic Chemistry,5A, Ch. 11, Academic Press, New York-London (1965), p. 69.Google Scholar
- 17.K. B. Wiberg and H. Schafer, J. Amer. Chem. Soc.,89, 455 (1967);91, 927 (1969);91, 933 (1969).Google Scholar
- 18.J. Schreiber and A. Eschenmoser, Helv. Chim. Acta,38, 1529 (1955).Google Scholar
- 19.L. M. Batuner and M. E. Pozin, Mathematical Methods in Chemical Technology [in Russian], Goskhimizdat, Leningrad (1963).Google Scholar
- 20.D. G. Lee, W. L. Downey, and R. M. Maass, Canad. J. Chem.,46, 441 (1968).Google Scholar
- 21.L. Fieser and M. Fieser, Steroids [Russian translation], IL (1964), p. 476.Google Scholar
- 22.T. Miki, K. Higaro, and T. Asako, Chemical Pharm. Bull.,13, 1285 (1965).Google Scholar
- 23.V. E. Limanov, S. N. Ananchenko, and I. V. Torgov, Izv. Akad. Nauk SSSR, Ser. Khim., 1814 (1964).Google Scholar
- 24.K. K. Koshoev, S. N. Ananchenko, and I. V. Torgov, Khimiya Prirodn. Soed.,3, 172 (1965).Google Scholar
- 25.V. M. Rzheznikov, S. N. Ananchenko, and I. V. Torgov, Khimiya Prirodn. Soed.,2, 90 (1965).Google Scholar