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【结 构 式】 
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【分子编号】40868 【品名】 【CA登记号】 |
【 分 子 式 】C24H34O5 【 分 子 量 】402.53096 【元素组成】C 71.61% H 8.51% O 19.87% |
合成路线1
该中间体在本合成路线中的序号：(IV)The reaction of cyanohydrineketal (I) with dimethyl(chloromethyl)silyl chloride (A), TEA and DMAP in THF gives the silylated cyanohydrine (II), which is treated with Li and 4,4'-di-tert-butylbiphenyl (DBB) in THF followed by acidification with HCl yields 17alpha-hydroxy-19-norpregna-4,9-diene-3,20-dione (III). The reaction of (III) with ethylene-glycol and TsOH afford the bis ethylenedioxy derivative (IV), which is epoxidized with H2O2 and trifluoroacetone in dichloromethane affording the monoepoxide (V). The Grignard condensation of (V) with 4-(dimethylamino)phenylmagnesium bromide in THF provides the 11-beta-(dimethylamino) derivative (VII), which is dehydrated and deprotected with sulfuric acid in refluxing ethanol to furnish 11-beta-[4-(dimethylamino)phenyl]-17alpha-hydroxy-19-norpregna-4,9-diene-3,20-dione (VIII). Finally, this compound is acetylated with AcOH and trifluoroacetic anhydride in dichloromethane.
| 【1】 Wronski, R.; et al.; A brain derived peptide preparation reduces the translation dependent loss of a cytoskeletal protein in primary cultured chicken neurons. J Neural Transm 2000, 59, 263. |
| 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) | 40865 | chloro(chloromethyl)dimethylsilane | 1719-57-9 | C3H8Cl2Si | 详情 | 详情 |
| (I) | 40864 | C21H27NO3 | 详情 | 详情 | ||
| (II) | 40866 | C24H34ClNO3Si | 详情 | 详情 | ||
| (III) | 40867 | (13S,17R)-17-acetyl-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | 14340-01-3 | C20H26O3 | 详情 | 详情 |
| (IV) | 40868 | C24H34O5 | 详情 | 详情 | ||
| (V) | 40869 | C24H34O6 | 详情 | 详情 | ||
| (VI) | 10863 | Bromo[4-(dimethylamino)phenyl]magnesium | 7353-91-5 | C8H10BrMgN | 详情 | 详情 |
| (VII) | 40870 | C32H45NO6 | 详情 | 详情 | ||
| (VIII) | 40871 | (13S,17R)-17-acetyl-11-[4-(dimethylamino)phenyl]-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | C28H35NO3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(IV)
| 【1】 Rao PN. 2000. A practical large-scale synthesis of 17 alpha-acetoxy-ll beta-(4-N,N-dimethylaminophenyl)-19-norpregna-4,9-diene-3,20-dione (CDB-2914). Steroids, 65 (7): 395～400 |
| 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) | 40864 | C21H27NO3 | 详情 | 详情 | ||
| (II) | 40866 | C24H34ClNO3Si | 详情 | 详情 | ||
| (III) | 40867 | (13S,17R)-17-acetyl-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | 14340-01-3 | C20H26O3 | 详情 | 详情 |
| (IV) | 40868 | C24H34O5 | 详情 | 详情 | ||
| (V) | 40869 | C24H34O6 | 详情 | 详情 | ||
| (VI) | 10863 | Bromo[4-(dimethylamino)phenyl]magnesium | 7353-91-5 | C8H10BrMgN | 详情 | 详情 |
| (VII) | 40870 | C32H45NO6 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(VI)
| 【1】 Dancsi L, Visky G, Tuba Z, et al.2007.Industrial process for the synthesis of 17α-acetoxy-11β-[4-(N,N-dimethylamino) Phenyl]-19-norpregna-4,9-diene-3,20-dione and new intermediates of the process. WO 2007144674 A1. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (V) | 67466 | 1-((8R,13R,14R)-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydrospiro[cyclopenta[a]phenanthrene-3,2'-[1,3]dioxolan]-17-yl)ethanone | C22H30O4 | 详情 | 详情 | |
| (I) | 30502 | 3,3-Ethylenedioxyestra-5(10),9(11)-dien-17-one | 5571-36-8 | C20H26O3 | 详情 | 详情 |
| (II) | 67463 | (8R,13R,14R,17S)-17-ethynyl-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydrospiro[cyclopenta[a]phenanthrene-3,2'-[1,3]dioxolan]-17-ol | C22H28O3 | 详情 | 详情 | |
| (III) | 67464 | (8R,13R,14R)-13-methyl-17-(2-(phenylsulfinyl)vinylidene)-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydrospiro[cyclopenta[a]phenanthrene-3,2'-[1,3]dioxolane] | C28H32O3S | 详情 | 详情 | |
| (IV) | 67465 | (8R,13R,14R)-17-(1-methoxyvinyl)-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydrospiro[cyclopenta[a]phenanthrene-3,2'-[1,3]dioxolan]-17-ol | C23H32O4 | 详情 | 详情 | |
| (VI) | 40868 | C24H34O5 | 详情 | 详情 | ||
| (VII) | 40869 | C24H34O6 | 详情 | 详情 | ||
| (VIII) | 40870 | C32H45NO6 | 详情 | 详情 | ||
| (IX) | 40871 | (13S,17R)-17-acetyl-11-[4-(dimethylamino)phenyl]-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | C28H35NO3 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(IV)
| 【1】 Kim Hyun K, San Antonio, Caemie Kirk, et al.1996.Method for preparing 17α-acetoxy-11β-(4-N,N-dimethylamino Phenyl)-19-norpregna-4,9-diene-3,20-dione, Intermediates useful in the method, and method for the preparation of such intermediates. US 9603660. |
| 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) | 40864 | C21H27NO3 | 详情 | 详情 | ||
| (II) | 40866 | C24H34ClNO3Si | 详情 | 详情 | ||
| (III) | 40867 | (13S,17R)-17-acetyl-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | 14340-01-3 | C20H26O3 | 详情 | 详情 |
| (IV) | 40868 | C24H34O5 | 详情 | 详情 | ||
| (V) | 40869 | C24H34O6 | 详情 | 详情 | ||
| (VI) | 40870 | C32H45NO6 | 详情 | 详情 | ||
| (VII) | 40871 | (13S,17R)-17-acetyl-11-[4-(dimethylamino)phenyl]-17-hydroxy-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | C28H35NO3 | 详情 | 详情 |