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【结 构 式】 
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【分子编号】32653 【品名】(8S,9S,10R,13S,14S,16R,17R)-17-glycoloyl-17-hydroxy-10,13,16-trimethyl-9,10,12,13,14,15,16,17-octahydro-3H-cyclopenta[a]phenanthrene-3,11(8H)-dione 【CA登记号】 |
【 分 子 式 】C22H26O5 【 分 子 量 】370.44544 【元素组成】C 71.33% H 7.07% O 21.59% |
合成路线1
该中间体在本合成路线中的序号：(X)The dehydrogenation of 16alpha-methyl-17alpha,21-dihydroxypregna-1,4-diene-3,11,20-trione-21-acetate (VIII) with (II) in dioxane-HCl gives 16alpha-methyl-17alpha,21-dihydroxypregna-1,4,6-triene-3,11,20-trione-21-acetate (IX), which is hydrolyzed with aqueous NaHCO3 to the corresponding free diol (X). The reaction of (X) with triethyl orthopropionate (A) as before yields 16alpha-methyl-17alpha,21-dihydroxypregna-1,4,6-triene-3,11,20-trione-17,21-ethylorthopropionate (XI), which is hydrolyzed partially with acetic acid to 16alpha-methyl-17alpha,21-dihydroxypregna-1,4,6-triene-3,11,20-trione-17-propionate (XII). The acylation of (XII) with propionic anhydride yields the corresponding dipropionate (XIII), which is treated with dry HCl in dioxane to afford 16alpha-methyl-17alpha,21-dihydroxy-7alpha-chloropregna-1,4-diene-3,11,20-trione 17,21-dipropionate (XIV). Finally, this compound is reduced with NaSH4 in methanol - THF.
| 【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 |
| (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 |
| (VIII) | 32651 | 2-[(8S,9S,10R,13S,14S,16R,17R)-17-hydroxy-10,13,16-trimethyl-3,11-dioxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | C24H30O6 | 详情 | 详情 | |
| (IX) | 32652 | 2-[(8S,9S,10R,13S,14S,16R,17R)-17-hydroxy-10,13,16-trimethyl-3,11-dioxo-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl acetate | C24H28O6 | 详情 | 详情 | |
| (X) | 32653 | (8S,9S,10R,13S,14S,16R,17R)-17-glycoloyl-17-hydroxy-10,13,16-trimethyl-9,10,12,13,14,15,16,17-octahydro-3H-cyclopenta[a]phenanthrene-3,11(8H)-dione | C22H26O5 | 详情 | 详情 | |
| (XI) | 32654 | 2'-Ethoxy-2'-ethyl-16alpha-methylspiro[androsta-1,4,6-triene-17(R),4'-[1,3]dioxane]-3,5',11-trione | C27H34O6 | 详情 | 详情 | |
| (XII) | 32655 | (8S,9S,10R,13S,14S,16R,17R)-17-glycoloyl-10,13,16-trimethyl-3,11-dioxo-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl propionate | C25H30O6 | 详情 | 详情 | |
| (XIII) | 32656 | 2-oxo-2-[(8S,9S,10R,13S,14S,16R,17R)-10,13,16-trimethyl-3,11-dioxo-17-(propionyloxy)-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl]ethyl propionate | C28H34O7 | 详情 | 详情 | |
| (XIV) | 32657 | (7R,8S,9S,10R,13S,14S,16R,17R)-7-chloro-10,13,16-trimethyl-3,11-dioxo-17-[2-(propionyloxy)acetyl]-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl propionate | C28H35ClO7 | 详情 | 详情 |