Summary
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1.
Total syntheses of steroid diketones of the cis-cis series have been performed by the condensation of 3,4,4a,7,8,8a-hexahydro-4a-methyl-5-vinyl-2(1H)-naphthalenom (I) and of 3,4,4a,5,6,8a-hexahydro-8a-methyl-8-vinyl-2(1H)-naphthalenone (II) with 2,4-dimethyl-2-cycloperiten-1-one (III). In both cases a total yield of about 60% was obtained of a mixture of three or four isomeyic steroid diketones having the A and Brings and the C and D rings united in the cis-configuration.
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2.
It has been shown that, i-wespective of the presence and positions of substitutents in the A ring, all steroid diketones synthesized by the diene-condensation method have the so-called “inverted” structure, i.e. the D ring has an angular methyl group in the 14-position and a carbonyl group in the 15-position. For some compounds the difference between the isomers lies in the difference in relative spatial positions of the A and B rings and of the C and D rings; and for other compounds it lies in she difference in the spatial disposition of the hydrogen at C-8.
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3.
It has been shown that the 9(11) do,uble bond in tetracyclic steroid diketones migrates comparatively readily to the 8(9)-position under the action of hydrochloric acid,
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4.
It has been found that the keto group in the D ring is extremely stable under the conditions of Clemmensen reduction, tetracyclic steroid 2,15- and 3. 15 -diketones being converted into 15-monoketones.
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I. N. Nazarov and L. D. Bergelson, J. Gen. Chem., 20, 648 (1950).
I. N. Nazarov, I. V. Torgov, I. I. Zaretskaya, G. P. Verkholetova, S. N. Ananchenko, and V. M. Andreev, Bull. Acad, Sci, USSR, Div, Chem. Sci., No, 1, 73 (1953). * *
I. N. Nazarov, Bull. Acad. Sci. USSR, Div, Chem., Sci., No. 4, 726 (1953).* *
I. N. Huffmann and M. Lott, J. Am. Cbem. Soc., 73, 878 (1951).
D. Banerjee and P. Shafer, S. Am. Chem. Soc., 72, 1931 (1950).
L. Ruzicka et. al., Helv. chim. acta 16, 833 (1933).
S. Harper, G. Kon and F. Ruzicka, J. Chem. Soc., 124 (1934); A. Butenandt and L. Suranij, Ber. 75,., 597 (1942).
E. Bagmam and H. Hillemann, Ber, 66, 1302 (1933).
O. Diels et. al., Ann. 459, 15 (l927).
R. Haworth et, al., J. Chem. Soc., 460 (1934).
W. Bachmann and A. Seidly, J. Am. Chem. Soc. 72, 1323 (1950).
F. Schenk, K. Buchholz and 0. Wiese, Ber. 69, 2696 (1936).
F. Reindel, E. Waiter and H. Rauch, Ann. 452, 34 (1927); 460, 212 (1928), F. Laucht, Z. physiol. Chem, 237, 2:36 (1935), H. Stavely and N. Bollenback, J. Am. Chem. Soc. 65, 1285 (1943), D. Barton, j. Chem. Soc., 513 (1946).
H. Stavely and N. Bellenback, J. Am. Chem. Soc. 65, 1600 (1943); D. Barton, J. Chem. Soc., 813 (1945).
H. Wieland and L. C. Gornhardt, Ann. 557, 248 (1947).
D. Banes, I. Carol and E. Haenni, J. Biol. Chem. 187, 557 (1950).
G. Anner and K. Miescher, Helv. chim. acta 31, 219 (1948).
0. Wintersteiner and M. Moore, J. Am. Chem. Soc. 65, 1507 (1943).
T. Achtermann, Z. physiol. Chem. 225, 141 (1934); F. Laucht, op. cit., 237, 2,36 (19.85).
D. Barton, J. Chem. Soc, 813 (1945); 513 (1946).
I. N. Nazarov, L. D. Bergelson, I. V. Torgov, and S. N. Anancheako, Bull. Acad. Sci. USSR, Div., Chem. Sci. No. 5, 891 (1953).
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Nazarov, I.N., Torgov, I.V. Synthesis of steroid compounds and related substances Communication XVIII. Condensation of 3,4,4a,7,8,8a-hexahydro-4a-methyl-5-vinyl-2(1H)-naphthalenone and 3,4,4a,5,6,8a-hexahydro-8a-methyl-8-vinyl-2(1H)-naphthalenone with 2,4-dimethyl-2-cyclopenten-1-one. Russ Chem Bull 2, 799–816 (1953). https://doi.org/10.1007/BF01178859
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DOI: https://doi.org/10.1007/BF01178859