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【结 构 式】 
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【分子编号】34085 【品名】(6R,8S,9R,10S,11S,13S,14S,17R)-17-[2-(acetoxy)acetyl]-2,9-dibromo-6-fluoro-11-hydroxy-10,13-dimethyl-3-oxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl acetate 【CA登记号】57781-13-2 |
【 分 子 式 】C25H29Br2FO7 【 分 子 量 】620.3074632 【元素组成】C 48.41% H 4.71% Br 25.76% F 3.06% O 18.05% |
合成路线1
该中间体在本合成路线中的序号：(X)The starting product being 21-acetoxy-11alpha,17alpha-dihydroxy-pregn-4-ene-3,20-dione (I). The first step is the ketalization of (I) giving the ethylenedioxy derivative (II), which is epoxidized with monoperphthalic acid (B) to the epoxide (III), then the epoxide ring is opened with HF giving the fluoro derivative (IV); its bromination in dioxane affords (V), which by reaction with methanesulfonyl chloride gives the mesyl ester (VI). This compound is acetylated with acetic anhydride to the triacetoxy derivative (VII), which by treatment first with sodium acetate and then with bromine gives the mono unsaturated dibromo compound (VIII). This product by treatment with lithium carbonate and lithium bromide is converted into the triene derivative (IX); this product by treatment with 1,3-dibromo-5,5-dimethylhydantoine (C) adds BrOH giving (X), which is epoxidized by treatment with potassium carbonate yielding (Xl). This epoxide ring is finally opened with HF.
| 【1】 Riva, M.; Toscano, L.; 2-Bromo-6beta-fluoropregna-1,4-3,20-diones. BE 0826030; DE 2533377; ES 455934; FR 2261776; GB 1499822 . |
| 【2】 Castaner, J.; de Angelis, L.; Halopredone diacetate. Drugs Fut 1976, 1, 11, 526. |
| 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) | 11295 | Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol | 107-21-1 | C2H6O2 | 详情 | 详情 |
| (B) | 34077 | 2-carboperoxybenzoic acid | C8H6O5 | 详情 | 详情 | |
| (I) | 34075 | 2-[(8S,10R,11R,14S,17R)-11,17-dihydroxy-10-methyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | C22H30O6 | 详情 | 详情 | |
| (II) | 34076 | C25H36O7 | 详情 | 详情 | ||
| (III) | 34078 | (5α,6α,11α)-21-(acetyloxy)-5,6-epoxy-11,17-dihydroxypregnane-3,20-dione cyclic 3-(1,2-ethanediyl acetal) | 57781-08-5 | C25H36O8 | 详情 | 详情 |
| (IV) | 34079 | 2-[(5R,6R,8S,10R,11R,13S,14S,17R)-6-fluoro-5,11,17-trihydroxy-10,13-dimethyl-3-oxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | 913-49-5 | C23H33FO7 | 详情 | 详情 |
| (V) | 34080 | 2-[(2R,5R,6R,8S,10R,11R,13S,14S,17R)-2-bromo-6-fluoro-5,11,17-trihydroxy-10,13-dimethyl-3-oxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | 57781-10-9 | C23H32BrFO7 | 详情 | 详情 |
| (VI) | 34081 | 2-((2R,5R,6R,8S,10R,11R,13S,14S,17R)-2-bromo-6-fluoro-5,17-dihydroxy-10,13-dimethyl-11-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-3-oxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)-2-oxoethyl acetate | C26H38BrFO7S | 详情 | 详情 | |
| (VII) | 34082 | (2R,5R,6R,8S,10R,11R,13S,14S,17R)-5-(acetoxy)-17-[2-(acetoxy)acetyl]-2-bromo-6-fluoro-10,13-dimethyl-11-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-3-oxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl acetate | C30H42BrFO9S | 详情 | 详情 | |
| (VIII) | 34083 | (6R,8S,10R,11R,13S,14S,17R)-17-[2-(acetoxy)acetyl]-2,2-dibromo-6-fluoro-10,13-dimethyl-11-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl acetate | C28H37Br2FO7S | 详情 | 详情 | |
| (IX) | 34084 | (6R,8S,10R,13S,14S,17R)-17-[2-(acetoxy)acetyl]-2-bromo-6-fluoro-10,13-dimethyl-3-oxo-6,7,8,10,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl acetate | 57808-78-3 | C25H28BrFO6 | 详情 | 详情 |
| (X) | 34085 | (6R,8S,9R,10S,11S,13S,14S,17R)-17-[2-(acetoxy)acetyl]-2,9-dibromo-6-fluoro-11-hydroxy-10,13-dimethyl-3-oxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl acetate | 57781-13-2 | C25H29Br2FO7 | 详情 | 详情 |
| (XI) | 34086 | (4aS,4bS,5aS,6aS,7R,9aS,9bS,11R)-7-[2-(acetoxy)acetyl]-3-bromo-11-fluoro-4a,6a-dimethyl-2-oxo-2,4a,5a,6,6a,7,8,9,9a,9b,10,11-dodecahydrocyclopenta[7,8]phenanthro[4b,5-b]oxiren-7-yl acetate | C25H28BrFO7 | 详情 | 详情 | |
| (C) | 31277 | 1,3-dibromo-5,5-dimethyl-2,4-imidazolidinedione | 77-48-5 | C5H6Br2N2O2 | 详情 | 详情 |