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【结 构 式】 
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【分子编号】20019 【品名】3-Oxo-cyclopropa[1',2':15-beta,16-beta]pregna-4,6-diene-21,17-carbolactone 【CA登记号】 |
【 分 子 式 】C23H28O3 【 分 子 量 】352.47352 【元素组成】C 78.38% H 8.01% O 13.62% |
合成路线1
该中间体在本合成路线中的序号：(V)The condensation of 3,5-dihydroxy-15beta, 16beta-methyleneandrost-6-ene-17-one (I) with propargyl alcohol (II) by means of potassium ethoxide in THF gives 17alpha-(3-hydroxypropynyl)-15beta, 16beta-methyleneandrost-6-ene-3beta,5beta,17beta-triol (III), which is hydrogenated with H2 over RaNi in methanol yielding the 3-hydroxypropyl derivative (IV). The oxidation, with simultaneous cyclization and dehydration of (IV) with pyridine - CrO3, affords 15beta,16beta-methylene-3-oxo-17alpha-pregna-4,6-diene-21,17-carbolactone (V), which is treated with thioacetic acid in methanol - water to give the 7alpha-acetylthio derivative (VI). Finally, this compound is dehydrogenated with dicyano-dichloro-benzoquinone (DDQ) in refluxing benzene.
| 【1】 Nickisch, K.; Bittler, D.; Laurent, H.; Losert, W.; Casals-Stenzel, J.; Nishino, Y.; Schillinger, E.; Wiechert, R.; Aldosterone antagonists. 2. New 7alpha-(acetylthio)-15,16-methylene spirolactones. J Med Chem 1987, 30, 8, 1403. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 20015 | (4aR,4bS,6aS,7aS,8aS,8bR,8cR)-2,10a-dihydroxy-4a,6a-dimethyl-2,3,4,4a,4b,5,6,6a,7a,8,8a,8b,8c,10a-tetradecahydrocyclopropa[4,5]cyclopenta[1,2-a]phenanthren-7(1H)-one | C20H28O3 | 详情 | 详情 | |
| (II) | 16664 | Propargyl Alcohol; 2-propyn-1-ol | 107-19-7 | C3H4O | 详情 | 详情 |
| (III) | 20017 | (4aR,4bS,6aS,7S,7aS,8aS,8bR,8cR)-7-(3-hydroxy-1-propynyl)-4a,6a-dimethyl-2,3,4,4a,4b,5,6,6a,7,7a,8,8a,8b,8c-tetradecahydrocyclopropa[4,5]cyclopenta[1,2-a]phenanthrene-2,7,10a(1H)-triol | C23H32O4 | 详情 | 详情 | |
| (IV) | 20018 | (4aR,4bS,6aS,7S,7aS,8aS,8bR,8cR)-7-(3-hydroxypropyl)-4a,6a-dimethyl-2,3,4,4a,4b,5,6,6a,7,7a,8,8a,8b,8c-tetradecahydrocyclopropa[4,5]cyclopenta[1,2-a]phenanthrene-2,7,10a(1H)-triol | C23H36O4 | 详情 | 详情 | |
| (V) | 20019 | 3-Oxo-cyclopropa[1',2':15-beta,16-beta]pregna-4,6-diene-21,17-carbolactone | C23H28O3 | 详情 | 详情 | |
| (VI) | 20020 | 7-Alpha-(Acetylsulfanyl)-3-oxo-cyclopropa[1',2':15-beta,16-beta]pregn-4-ene-21,17-carbolactone | C25H32O4S | 详情 | 详情 |