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【结 构 式】 
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【分子编号】37105 【品名】(1S,3aS,3bR,10aR,10bS,12aS)-1,6,10a,12a-tetramethyl-2,3,3a,3b,4,5,10,10a,10b,11,12,12a-dodecahydro-1H-cyclopenta[7,8]phenanthro[3,2-d]isoxazol-1-ol 【CA登记号】 |
【 分 子 式 】C22H31NO2 【 分 子 量 】341.49368 【元素组成】C 77.38% H 9.15% N 4.1% O 9.37% |
合成路线1
该中间体在本合成路线中的序号：(V)The reaction of 17beta-hydroxy-17-methylandrost-4-en-3-one (I) with thiophenol (A) and formaldehyde by means of triethylamine in refluxing ethanol gives 17beta-hydroxy-17-methy-4-(phenylthiomethyl)androst-4-en-3-one (II), which is desulfurized by treatment with Raney-Ni in water yielding 17beta-hydroxy-4,17-dimethylandrost-4-en-3-one (III). The reaction of (III) with methyl formate by means of sodium methoxide in methanol affords 17beta-hydroxy-4,17-dimethyl-2-hydroxymethyleneandrost-4-en-3-one (IV), which by cyclization with hydroxylamine in acetic acid-sodium acetate is converted into 4,17-dimethylandrosta-2,4-dieno[2,3-d]isoxazol-17beta-ol (V). The epoxidation of (V) with m-chloroperbenzoic acid in methylene chloride gives 4alpha,5alpha-epoxy-4,17-dimethylandrost-2-eno [2,3-d]isoxazol-17beta-ol (VI), which is finally isomerized by treatment with sodium methoxide in THF.
| 【1】 Christiansen, R.G. (Sanofi-Synthelabo); Steroid cyanoketones and intermediates. US 4160027 . |
| 【2】 Castaner, J.; Hillier, K.; Blancafort, P.; Serradell, M.N.; WIN-32,729. Drugs Fut 1982, 7, 9, 661. |
| 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) | 12951 | Benzenethiol; Phenylmercaptan; Phenylhydrosulfide | 108-98-5 | C6H6S | 详情 | 详情 |
| (I) | 34383 | (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13,17-trimethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one | 58-18-4 | C20H30O2 | 详情 | 详情 |
| (II) | 37102 | (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13,17-trimethyl-4-[(phenylsulfanyl)methyl]-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one | C27H36O2S | 详情 | 详情 | |
| (III) | 37103 | (8R,9S,10R,13S,14S,17S)-17-hydroxy-4,10,13,17-tetramethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one | C21H32O2 | 详情 | 详情 | |
| (IV) | 37104 | (8R,9S,10R,13S,14S,17S)-17-hydroxy-2-[(Z)-hydroxymethylidene]-4,10,13,17-tetramethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-one | C22H32O3 | 详情 | 详情 | |
| (V) | 37105 | (1S,3aS,3bR,10aR,10bS,12aS)-1,6,10a,12a-tetramethyl-2,3,3a,3b,4,5,10,10a,10b,11,12,12a-dodecahydro-1H-cyclopenta[7,8]phenanthro[3,2-d]isoxazol-1-ol | C22H31NO2 | 详情 | 详情 | |
| (VI) | 37106 | (1S,3aS,3bS,5aS,6aS,10aR,10bS,12aS)-1,6a,10a,12a-tetramethyl-1,2,3,3a,3b,4,5,6a,10,10a,10b,11,12,12a-tetradecahydrocyclopenta[7,8]oxireno[2',3':10a,1]phenanthro[3,2-d]isoxazol-1-ol | C22H31NO3 | 详情 | 详情 |