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【结 构 式】 
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【分子编号】21885 【品名】(10S,13R)-17-(1,5-dimethyl-4-oxohexyl)-10,13-dimethyl-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-3-one 【CA登记号】 |
【 分 子 式 】C27H38O2 【 分 子 量 】394.59752 【元素组成】C 82.18% H 9.71% O 8.11% |
合成路线1
该中间体在本合成路线中的序号：(III)The dehydrogenation of 3beta-hydroxycholest-5-en-24-one with dichlorodicyanobenzoquinone in refluxing dioxane, or of cholest-4-ene-3,24-dione (II) with chloranil in refluxing tert-butyl alcohol gives cholesta-1,4,6-triene-3,24-dione (III), which is epoxidized with 30% H2O2 and NaOH in methanol-dioxane-THF yielding 1 alpha,2alpha-epoxycholesta-4,6-diene-3,24-dione (IV). The reduction of (IV) with Li in liquid NH3 affords 1alpha,3beta,24-trihydroxycholest-5-ene (V), which is benzoylated with benzoyl chloride in pyridine and submitted to column chromatography on silica gel to give 1alpha,3beta,24R-tribenzoyloxycholest-5-ene (VI). The dehydrogenation of (VI) with dibromodimethylhydantoin of N-bromosuccinimide yields lalpha,3beta,24R-trihydroxy-cholesta-5,7-diene (VII), which is finally submitted to irradiation with a medium-pressure Hg lamp in ether.
| 【1】 Ikekawa, N.; Koizumi, N.; Morisaki, M.; Synthesis of active forms of vitamin D. Part IX. S. J Chem Soc - Perkins Trans I 1975, 1421. |
| 【2】 Takeshita, T.; Hashimoto, Y.; Kawashima, H.; Ishimoto, S.; Ikekawa, N.; Morisaki, M. (Teijin Ltd.); 1alpha,24-Dihydroxycholecalciferol derivs. and pro. DE 2526981; US 4022891 . |
| 【3】 Castaner, J.; Prous, J.; TV-02. Drugs Fut 1988, 13, 2, 133. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (A) | 21890 | 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; 4,5-dichloro-3,6-dioxo-1,4-cyclohexadiene-1,2-dicarbonitrile | 84-58-2 | C8Cl2N2O2 | 详情 | 详情 |
| (B) | 21891 | 2,3,5,6-Tetrachloro-1,4-benzoquinone; 2,3,5,6-Tetrachlorobenzo-1,4-quinone; p-Chloranil | 118-75-2 | C6Cl4O2 | 详情 | 详情 |
| (I) | 21883 | 6-[(3S,10R,13R)-3-hydroxy-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]-2-methyl-3-heptanone | C27H44O2 | 详情 | 详情 | |
| (II) | 21884 | (10R,13R)-17-(1,5-dimethyl-4-oxohexyl)-10,13-dimethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one | C27H42O2 | 详情 | 详情 | |
| (III) | 21885 | (10S,13R)-17-(1,5-dimethyl-4-oxohexyl)-10,13-dimethyl-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-3-one | C27H38O2 | 详情 | 详情 | |
| (IV) | 21886 | (2aR,3aR,3bR,5aR)-6-(1,5-dimethyl-4-oxohexyl)-3b,5a-dimethyl-2a,3a,3b,3c,4,5,5a,6,7,8,8a,8b-dodecahydro-2H-cyclopenta[7,8]phenanthro[3,4-b]oxiren-2-one | C27H38O3 | 详情 | 详情 | |
| (V) | 21887 | (1S,3R,10R,13R)-17-(4-hydroxy-1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-1,3-diol | C27H46O3 | 详情 | 详情 | |
| (VI) | 21888 | (1S,3R,10R,13R)-1-(benzoyloxy)-17-[(4R)-4-(benzoyloxy)-1,5-dimethylhexyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl benzoate | C48H58O6 | 详情 | 详情 | |
| (VII) | 21889 | (1S,3R,10R,13R)-17-[(4R)-4-hydroxy-1,5-dimethylhexyl]-10,13-dimethyl-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene-1,3-diol | C27H44O3 | 详情 | 详情 | |
| (C) | 10463 | Benzoyl chloride | 98-88-4 | C7H5ClO | 详情 | 详情 |