Communications: 16-Methylene and Δ15-16-Methyl Cortical Steroids
Communications: 16-Methylene and Δ15-16-Methyl Cortical Steroids
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通讯：16-亚甲基和 Δ15-16-甲基皮质类固醇
DOI：
10.1021/jo01082a034
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发表时间：
1960
影响因子：
3.6
通讯作者：
N. Wendler
中科院分区：
文献类型：
--
作者：
D. Taub;R. D. Hoffsommer;N. Wendler
(2) D. Taub, R. D. Hoffsommer, HL Slates, and NL Wendler, J. Am. Chem. Soc., 80, 4435 (1958);(b) EP Oliveto, R. Rausser, AL Nussbaum, W. Gebert, EB Hershberg, S. Tolksdorf, M. Eisler, P. L. Perlman, and. M. Pechet, J. Am. Chem. Soc., 80, 4428 (1958);(c) EP Oliveto, R. Rausser, HL Herzog, EB Hershberg, S. Tolksdorf, M. Eisler, P. L. Perlman, and. M. Pechet, J. Am. Chem. Soc., 80, 6627 (1958).(3) RD Hoffsommer, HL Slates, D. Taub, and NL Wendler, J. Org. Chem., 24, 1617 (1959).(4) G. Nominé, D. Bertin, and A. Pierdet, Tetrahedron, 8, 217 (1960). give 21-bromo-16-methylenepregnane-3a-17a-diol-11, 20-dione, mp 200-204;[a] gHC1’+ 34. Anal. Found: C, 60.31; H, 7.38. The 21-bromo compound on treatment with potassium iodide and potassium acetate in refluxing acetone was converted into 21-acetoxy-16-methylenepregnane-3a, 17 a-diol-l 1, 20-dione (II), mp 172-175;[a] gHC1’+ 44. Anal. Found: C, 68.47; H, 8.24. Oxidation of II at C-3 with sodium dichromate in acetic acid led to 21-acetoxy-16-methylenepregnane-17a-ol-3, 11, 20-trione, double mp 175-185, 205-215;[a] gHCl! 1+ 38. Anal. Found: C, 68.85; H, 7.72. Dibromina-tion of the latter followed by dehydrobromination in dimethylformamide-dimethylaniline led to 16-methyleneprednisone 21-acetate (VI), mp 214-217;"[a] gHCl1+ 123; Xg^ 011 238 m, u (14,100);™ 01" 2.74, 2.86-3.00, 5.73 sh., 5.76, 5.84, 6.00, 6.14, 6.20, 11.19 µ. Anal. Found: C, 69.96; H, 6.94. The 16-methylene hydrogens in VI as well as in other 16-methylene steroids exhibited a charac-teristic NMR doublet near 44 and 51 cps relative to benzene.The 16-methylene group was introduced into 16-unsubstituted cortical steroids by an alternate pro-cedure capable of general application. 9a-Fluoroprednisolone 21-acetate was converted by dehydra-tion of its 3, 20-disemicarbazone6 into 21-acetoxy-9a-fluoro-l, 4, 16-pregnatriene-11/3-ol-3, 20 dione (III), mp 220-223;[a] gHCh+ 148; Xg^ 0H 239
