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【结 构 式】 
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【分子编号】16815 【品名】(3S,8R,9S,10R,13S,14S)-17-[(E)-2-(aminocarbonyl)hydrazono]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate 【CA登记号】 |
【 分 子 式 】C22H33N3O3 【 分 子 量 】387.52244 【元素组成】C 68.19% H 8.58% N 10.84% O 12.39% |
合成路线1
该中间体在本合成路线中的序号：(IV)Prasterone can be obtained by two related ways: 1) The acetylation of cholesterol (I) with refluxing acetic anhydride gives the corresponding acetate (II), which is brominated with Br2 in acetic acid to the dibromide (III). The oxidation of (III) with CrO3 in acetic acid followed by debromination with Zn in the same solvent and treatment with semicarbazide and sodium acetate in ethanol/water affords 3beta-acetoxyandrost-5-en-17-one semicarbazone (IV), which is finally hydrolyzed with 5N H2SO4 in refluxing ethanol. 2) The partial silylation of androst-5-ene-3beta,17beta-diol (V) with tert-butyldimethylsilyl chloride and imidazole in DMF yields the 3beta-silyloxy derivative (VI), which is oxidized with CrO3-pyridine complex in pyridine affording 3-(tert-butyldimethylsilyloxy)androst-5-en-17-one (VII). Finally, this compound is deprotected with hot acetic acid/water/THF or with tetrabutylammonium fluoride in THF.
| 【1】 Fernholz, E.; Wallis, E.S.; The preparation of dehydroandrosterone from cholesterol. J Am Chem Soc 1935, 57, 1504-6. |
| 【2】 Castañer, J.; Mealy, N.; Rabasseda, X.; Prasterone. Drugs Fut 1995, 20, 6, 575. |
| 【3】 Ruzicka, L.; Wettstein, A.; Sexual hormones: Synthetic preparation of the male sexual hormones trans-dehydroandrosterone and androstene-3,17-dione. Helv Chim Acta 1935, 18, 986-95. |
| 【4】 Fernholz, E.; Wallis, E.S.; The constitution of dehydro-androsterone and its preparation from cholesterol. J Am Chem Soc 1935, 57, 1379-80. |
| 【5】 Hosoda, H.; Fishman, J.; Fukushima, D.K.; Convenient, high yield conversion of androst-5-ene-3beta,17beta-diol to dehydroisoandrosterone. J Org Chem 1973, 38, 24, 4209-11. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 32057 | tert-butyl(chloro)dimethylsilane | 18162-48-6 | C6H15ClSi | 详情 | 详情 | |
| (I) | 16812 | (+)-Cholesterol; (+)-(3S,8S,9S,10R,13R,14S,17R)-17-[(1R)-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-ol | 14868-17-8 | C27H46O | 详情 | 详情 |
| (II) | 16813 | (3S,8S,9S,10R,13R,14S,17R)-17-[(1R)-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 acetate | 604-35-3 | C29H48O2 | 详情 | 详情 |
| (III) | 16814 | (3S,8S,9S,10R,13R,14S,17R)-5,6-dibromo-17-[(1R)-1,5-dimethylhexyl]-10,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C29H48Br2O2 | 详情 | 详情 | |
| (IV) | 16815 | (3S,8R,9S,10R,13S,14S)-17-[(E)-2-(aminocarbonyl)hydrazono]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C22H33N3O3 | 详情 | 详情 | |
| (V) | 16816 | (3S,8R,9S,10R,13S,14S,17S)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-3,17-diol; 3beta,17beta-Dihydroxyandrost-5-ene; 5-Androstene-3beta,17beta-diol | 521-17-5 | C19H30O2 | 详情 | 详情 |
| (VI) | 16817 | (3S,8R,9S,10R,13S,14S,17S)-3-[[tert-butyl(dimethyl)silyl]oxy]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-ol | C25H44O2Si | 详情 | 详情 | |
| (VII) | 16818 | (3S,8R,9S,10R,13S,14S)-3-[[tert-butyl(dimethyl)silyl]oxy]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | C25H42O2Si | 详情 | 详情 |