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【结 构 式】 
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【分子编号】29702 【品名】(7S,8R,9S,10R,13S,14S,15S)-3,7,15-trihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one 【CA登记号】 |
【 分 子 式 】C19H28O4 【 分 子 量 】320.42892 【元素组成】C 71.22% H 8.81% O 19.97% |
合成路线1
该中间体在本合成路线中的序号：(XVIII)3beta-Hydroxy-5-androsten-17-one (XVII) is dihydroxylated microbiologically by means of Colletotrichum lini to 3beta,7alpha,15alpha-trihydroxy-5-androsten-17-one (XVIII), which is treated with acetone and boron trifluoride etherate yielding the acetonide (XIX). Hydrolysis of (XIX) with HCl in methanol affords the 3beta,7beta,15alpha-isomer (XX), which is also obtained from (XVIII) by isomerization with perchloric acid in methylisobutylketone. Selective acylation of (XX) with pivaloyl chloride affords the 3beta,15alpha-dipivaloyloxy compound (XXI), which is submitted to cyclopropanation with trimethylsulfoxonium iodide and NaOH as before yielding (IX).
| 【1】 Losert, W.; Bittler, D.; Vasals-Stenzel, J.; Wiechert, R.; Kerb, U. (Schering AG); Novel spironolactones and process for their preparation. DE 2652761; US 4129564 . |
| 【2】 Serradell, M.N.; Robinson, C.P.; Castaner, J.; Spirorenone. Drugs Fut 1985, 10, 6, 478. |
| 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) | 29663 | 1-(3-methoxyphenyl)acetone | 3027-13-2 | C10H12O2 | 详情 | 详情 |
| (IX) | 29696 | (4aR,4bS,6aS,7aS,8aS,8bS,8cR)-9-hydroxy-4a,6a-dimethyl-7-oxo-1,2,3,4,4a,4b,5,6,6a,7,7a,8,8a,8b,8c,9-hexadecahydrocyclopropa[4,5]cyclopenta[1,2-a]phenanthren-2-yl pivalate | C25H36O4 | 详情 | 详情 | |
| (XVII) | 29705 | (8R,9S,10R,13S,14S)-3-hydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | C19H28O2 | 详情 | 详情 | |
| (XVIII) | 29702 | (7S,8R,9S,10R,13S,14S,15S)-3,7,15-trihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | C19H28O4 | 详情 | 详情 | |
| (XIX) | 29703 | (2aS,5aS,10aR,10bS,12aS,12bS,12cR)-8-hydroxy-4,4,10a,12a-tetramethyl-2,2a,5a,7,8,9,10,10a,10b,11,12,12a,12b,12c-tetradecahydro-1H-benzo[h]indeno[1,7,6-def][1,3]benzodioxepin-1-one | C22H32O4 | 详情 | 详情 | |
| (XX) | 29706 | (8R,9S,10R,13S,14S,15S)-3,7,15-trihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | C19H28O4 | 详情 | 详情 | |
| (XXI) | 29704 | (8R,9S,10R,13S,14S,15S)-15-[(2,2-dimethylpropanoyl)oxy]-7-hydroxy-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl pivalate | C29H44O6 | 详情 | 详情 |