반응식
C(OC(=O)C)(=O)C.N1C=CC=CC=1.C[O:15][C:16]1[CH:33]=[CH:32][C:31]2[C@@H:30]3[C@H:21]([C@H:22]4[C@@:26]([CH2:28][CH2:29]3)([CH3:27])[C@@H:25]([O:34]C(=O)C)[C@:24](O)([CH2:38][CH3:39])[CH2:23]4)[CH2:20][CH2:19][C:18]=2[CH:17]=1.COC1C=CC2[C@@H]3[C@H]([C@H]4[C@@](CC3)(C)C(=O)[C@@H](CC)C4)CCC=2C=1.[BH4-].[Na+].COC1C=CC2[C@@H]3[C@H]([C@H]4[C@@](CC3)(C)[C@@H](O)[C@@H](CC)C4)CCC=2C=1.[Li].N.Cl.CO>C(O)C.[Zn]>[OH:34][C@H:25]1[C@@H:24]([CH2:38][CH3:39])[CH2:23][C@H:22]2[C@H:21]3[C@H:30]([CH2:29][CH2:28][C@:26]12[CH3:27])[C@@H:31]1[C:18](=[CH:17][C:16](=[O:15])[CH2:33][CH2:32]1)[CH2:19][CH2:20]3참가 물질
반응물 8
생성물 1
시약·촉매·용매 2
실험 절차
These compounds can be prepared in a 10-stage process from 3-methoxy-1,3,5(10)-estratrien-17-one as starting material. In this process, 3-methoxy-1,3,5(10)-estratrien-17-one is enolized and acylated with acetic anhydride. The thus-obtained Δ16 -enol acetate is epoxidized with m-chloroperbenzoic acid and split in the presence of acetic acid. The resultant 16α-acetoxy-3-methoxy-1,3,5(10)-estratrien-17-one is saponified with sodium hydroxide solution in methanol and rearranged into 17β-hydroxy-3-methoxy-1,3,5(10)-estratrien-16-one. Subsequent Grignard reaction with ethylmagnesium iodide yields 3-methoxy-16,17β-dihydroxy-16α-ethyl-1,3,5(10)-estratriene, which is partially esterified with acetic anhydride/pyridine. The thus-obtained 3-methoxy-17β-acetoxy-16β-hydroxy-16α-ethyl-1,3,5(10)-estratriene is subjected to a Serini reaction with zinc/toulene and heating. The resultant 3-methoxy-16β-ethyl-1,3,5(10)-estratrien-17-one is reduced with sodium borohydride in ethanol. The ensuing 3-methoxy-16β-ethyl-1,3,5(10)-estratrien-17β-ol is reduced with lithium in liquid ammonia and then treated with hydrochloric acid/methanol, yielding the desired 17β-hydroxy-16β-ethyl-4-estren-3-one in a yield of barely 20% of theory.
후처리
- temperatureheating
출처 및 근거
- ORD 기록
- ord-354a86a0bc1f40b9886118c78d7aebcb
- 출처 데이터셋
- uspto-grants-1981_11
- 특허 번호
- US04298538
연결된 노트
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