Zusammenfassung
Eine Anzahl am D-Ring substituierter Derivate von Reichsteins Verbindung S wurde als Modellverbindungen in der Synthese neuer Corticosteroide hergestellt. Die beschriebenen Strukturtypen schliessen Dehydroverbindungen, Epoxyde, Halogenhydrine und ein Glykol ein.
References
J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953);76, 1455 (1954);77, 1068 (1955);77, 4181 (1955).
A. Nobile et al., J. Amer. chem. Soc.77, 4184 (1955).
R. F. Hirschmann, R. Miller, R. E. Beyler, L. H. Sarett, andM. Tishler, J. Amer. chem. Soc.77, 3166 (1955).
J. A. Hogg et al., J. Amer. chem. Soc.77, 4438 (1955).
E. Vischer, Ch. Meystre, andA. Wettstein, Helv. chim. Acta38, 835 (1955).
E. J. Agnello, B. M. Bloom, andG. D. Laubach, J. Amer. chem. Soc.77, 4684 (1955); Abstracts of 128th Meeting, Amer. Chem. Soc., Minneapolis, Minn., September 11–16, 1955, p. 50.
H. C. Murray andD. H. Peterson, U.S. 2,602,769, July 8, 1952; U.S. 2,673,866, March 30, 1954.
P. D. Meister et al., Abstracts of Papers, 123rd Amer. Chem. Soc. Meeting, Los Angeles, Calif., March 15–19, 1953, p. 5C.
A. F. St. André, H. B. MacPhillamy, J. A. Nelson, A. C. Shabica, andC. R. Scholz, J. Amer. chem. Soc.74, 5506 (1952).
Activated 14α-hydroxyl functions are known to dehydrate readily toward C(15) under mild acidic conditions.Cf. G. D. Laubach, E. C. Schreiber, E. J. Agnello, E. N. Lightfoot, andK. J. Brunings, J. Amer. chem. Soc.75, 1514 (1953).
N. L. McNiven, J. Amer. chem. Soc.76, 1725 (1954).
A. Zürcher, H. Heusser, O. Jeger, andP. Geistlich, Helv. chim. Acta37, 1562 (1954).
Private communication from Dr.Howard Ringold of Syntex, S.A.
E. J. Corey, J. Amer. chem. Soc.76, 175 (1954).
H. M. E. Cardwell andS. Smith, J. chem. Soc.1954, 2012.
C. J. W. Brooks andJ. K. Norymberski, Biochem. J.55, 371 (1953).
A. F. St. André, H. B. MacPhillamy, J. A. Nelson, A. C. Shabica, andC. R. Scholz, J. Amer. chem. Soc.74, 5506 (1952).
The formation of identical epoxidation products from highly substituted olefins using either peracids or chromate oxidizing agents has been observed frequently [cf. H. Reich andA. Lardon, Helv. chim. Acta30, 329 (1947).
C. W. Shoppee, Helv. chim. Acta30, 766 (1947)]. A recent example in the terpene series is cited byJ. D. Johnston andF. S. Spring, J. chem. Soc.1954, 1556.
Preferential α-face attack by bulky reagents in the steroid series is thoroughly documented.Cf. L. F. Fieser, Exper.6, 312 (1950).
Pl. A. Plattner et al., Helv. chim. Acta29, 2023 (1946).
T. F. Gallagher andT. H. Kritchevsky, J. Amer. chem. Soc.72, 882 (1950).
G. H. Alt andD. H. R. Barton, J. chem. Soc.1954, 1356.
P. Bladon, J. chem. Soc.1954, 736.
Unsuccessful attempts were made to cleave the epoxide linkage in VII with boiling acetic acid [J. Pataki, G. Rosenkranz, andC. Djerassi, J. Amer. chem. Soc.73, 5375 (1951).
A. Forst andPl. A. Plattner, Helv. chim. Acta32, 275 (1949)], thiocyanic acid [E. E. van Tamelen, J. Amer. chem. Soc.73, 3444 (1951)], pyridine hydrobromide [P. N. Chakravorty andR. H. Levin, J. Amer. Chem. Soc.64, 2317 (1942)], thiourea andp-toluenesulfonic acid [L. C. King andJ. A. Campell, J. Amer. chem. Soc.71, 3556 (1949)], magnesium bromide etherate [W. E. Bachmann, J. P. Horwitz, andR. J. Warzynski, J. Amer. chem. Soc.75, 3268 (1953).
R. B. Turner, J. Amer. chem. Soc.75, 3484 (1953)], and trichloroacetic acid in benzene [A. Forst andR. Scotoni, Jr., Helv. chim. Acta36, 1410 (1953)].
Inter al.,S. A. Julia andH. Heusser, Helv. chim. Acta35, 2080 (1952).
More vigorous reaction conditions resulted in the formation of III as the predominant product. The reduction of steroid epoxides to the parent olefins by hydriodic acid has been previously observed. [J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953);
P. L. Julian et al., J. Amer. chem. Soc.72, 5145 (1950).
L. B. Barkley, M. W. Farrar, W. S. Knowles, andH. Raffelson, J. Amer. Chem. Soc.76, 5017 (1953).
J. Schmidlin andA. Wettstein, Helv. chim. Acta36, 1241 (1953).
G. P. Mueller, R. E. Stobaugh, andR. S. Winniford, J. Amer. chem. Soc.75, 4888 (1953).
J. W. Cornforth, J. M. Osbond, andG. H. Phillips, J. chem. Soc.1954, 907.
L. F. Fieser andX. A. Dominguez, J. Amer. chem. Soc.75, 1704 (1953).
J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953).
J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953).
G. H. Ott andT. Reichstein, Helv. chim. Acta26, 1799 (1943).
G. I. Poos, G. E. Arth, R. E. Beyler, andL. H. Sarett, J. Amer. chem. Soc.75, 422 (1953).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bloom, B.M., Agnello, E.J. & Laubach, G.D. C(14)-substituted corticosteroids. some D ring transformations in the compound S series. Experientia 12, 27–30 (1956). https://doi.org/10.1007/BF02156992
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF02156992