Cyclopropanone → HCID 67896746, 화합물

HRID 329362

반응식

HRID 329362 반응식
[C:1]1(=[O:4])[CH2:3][CH2:2]1.[CH2:5]([O:12][C@H:13]1[CH2:30][CH2:29][C@@:28]2([CH3:31])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:27]2[CH2:26][CH2:25][C@@:23]2([CH3:24])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[SH:32])[CH2:14]1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>ClCCl>[CH2:5]([O:12][C@H:13]1[CH2:30][CH2:29][C@@:28]2([CH3:31])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:27]2[CH2:26][CH2:25][C@@:23]2([CH3:24])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[S:32][C:1]2([OH:4])[CH2:3][CH2:2]2)[CH2:14]1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

참가 물질

4

반응물 2

HCID 138404CyclopropanoneHCID 88492213HCID 88492213, 화합물

생성물 1

HCID 67896746HCID 67896746, 화합물

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

실험 절차

3β-Benzyloxyandrost-5-en-17β-thiol is obtained starting from dehydroepiandrosterone. The dehydroepiandrosterone is reacted with one equivalent of sodium hydride and benzyl chloride by standard procedures for making benzyl ethers to give 3-benzyloxyandrost-5-en-17-one. This benzyloxy compound is then reacted with Lawesson's reagent (4-methoxyphenylthiophosphine sulfide dimer) according to the procedure described in M. Feiser, "Feiser and Feiser's Reagents for Organic Synthesis", John Wiley & Sons, New York, 1980, p. 327; also B. S. Pedersen et al., Bull. Soc. Chim. Belg., 87, 223 (1978). This gives 3β-benzyloxyandrost-5-ene-17-thione and this thione is then reduced with lithium aluminum hydride by standard procedures to give the desired 17β-thiol. Then, to a solution of cyclopropanone in dichloromethane under nitrogen at -50° C., there is added rapidly 1.1 equivalent of the above thiol in dichloromethane. The temperature is allowed to rise to -30° C. and, after 16 hours, most of the solvent is evaporated. Dry ether is added to precipitate by-product polyketene. The by-product is removed by filtration, the solvent is distilled from the filtrate, and the residue is purified by flash chromatography to give 3β-benzyloxy-17β-(1-hydroxycyclopropylthio)androst-5-ene.

후처리

  1. customis evaporated
  2. additionDry ether is added
  3. customto precipitate by-product polyketene
  4. customThe by-product is removed by filtration
  5. distillationthe solvent is distilled from the filtrate
  6. customthe residue is purified by flash chromatography

출처 및 근거

ORD 기록
ord-9a7f09f31ffd40bb9615f3bc058e0b40
출처 데이터셋
uspto-grants-1990_01
특허 번호
US04891367

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