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【结 构 式】 
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【分子编号】32647 【品名】(8S,9S,10R,11S,13S,14S,16R,17R)-17-glycoloyl-11,17-dihydroxy-10,13,16-trimethyl-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-3-one 【CA登记号】13954-10-4 |
【 分 子 式 】C22H28O5 【 分 子 量 】372.46132 【元素组成】C 70.94% H 7.58% O 21.48% |
合成路线1
该中间体在本合成路线中的序号：(IV)The dehydrogenation of 16alpha-methyl-11beta,17alpha,21-trihydroxypregna-1,4-diene-3,20-dione-21-acetate (I) with dichlorodicyanobenzoquinone (II) in dioxane HCl gives 16alpha-methyl-11beta,17alpha,21-trihydroxypregna-1,4,6-triene-3,20-dione-21-acetate (III), which is hydrolyzed with aqueous NaHCO3 to the corresponding free triol (IV). The reaction of (IV) with triethyl orthopropionate (A) by means of p-toluenesulfonic acid in DMSO yields 16alpha-methyl-11beta,17alpha,21-trihydroxypregna-1,4,6-triene-3,20-dione-17,21-ethylorthopropionate (V), which is hydrolyzed partially with acetic acid to 16alpha-methyl-11beta,17alpha,21-trihydroxypregna-1,4,6-triene-3,20-dione-17-propionate (VI). The acylation of (VI) with propionic anhydride affords 16alpha-methyl-11beta,17alpha,21-trihydroxypregna-1,4,6-triene-3,20-dione-17,21-dipropionate (VII), which is finally treated with dry HCl in dioxane.
| 【1】 Green, M.J.; et al. (Schering Corp.); 7alpha-Halogeno-3,20-dioxo-1,4-pregnadienes, methods for their manufacture, their use as anti-inflammatory agents, and pharmaceutical formulations useful therefor. US 4124707 . |
| 【2】 Green, M.J.; et al. (Schering Corp.); Process for the preparation of 7{60 -halogeno-3-oxo-4-dehydro steroids and novel 7{60 -halogeno derivatives produced thereby. CA 1099254; US 4076708 . |
| 【3】 Van Wagenen, B.C.; Barmore, R.M. (NPS Pharmaceuticals, Inc.); Chiral reductions of imines leading to the syntheses of optically active amines. WO 9711934 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 20095 | propionic anhydride | 123-62-6 | C6H10O3 | 详情 | 详情 | |
| (A) | 10395 | 1,1,1-Triethoxypropane; 1,1-Diethoxypropyl ethyl ether; Triethyl orthopropionate | 115-80-0 | C9H20O3 | 详情 | 详情 |
| (I) | 32645 | 2-[(8S,9S,10R,11S,13S,14S,16R,17R)-11,17-dihydroxy-10,13,16-trimethyl-3-oxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | C24H32O6 | 详情 | 详情 | |
| (II) | 21890 | 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; 4,5-dichloro-3,6-dioxo-1,4-cyclohexadiene-1,2-dicarbonitrile | 84-58-2 | C8Cl2N2O2 | 详情 | 详情 |
| (III) | 32646 | 2-[(8S,9S,10R,11S,13S,14S,16R,17R)-11,17-dihydroxy-10,13,16-trimethyl-3-oxo-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | 13796-64-0 | C24H30O6 | 详情 | 详情 |
| (IV) | 32647 | (8S,9S,10R,11S,13S,14S,16R,17R)-17-glycoloyl-11,17-dihydroxy-10,13,16-trimethyl-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-3-one | 13954-10-4 | C22H28O5 | 详情 | 详情 |
| (V) | 32648 | 2'-Ethoxy-2'-ethyl-11beta-hydroxy-16alpha-methylspiro[androsta-1,4,6-triene-17(R),4'-[1,3]dioxane]-3,5'-dione | 67212-72-0 | C27H36O6 | 详情 | 详情 |
| (VI) | 32649 | (8S,9S,10R,11S,13S,14S,16R,17R)-17-glycoloyl-11-hydroxy-10,13,16-trimethyl-3-oxo-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl propionate | C25H32O6 | 详情 | 详情 | |
| (VII) | 32650 | (8S,9S,10R,11S,13S,14S,16R,17R)-11-hydroxy-10,13,16-trimethyl-3-oxo-17-[2-(propionyloxy)acetyl]-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl propionate | 67212-74-2 | C28H36O7 | 详情 | 详情 |