1,2-Dibromoethene → 3beta-Ethynyl-3alpha-hydroxy-17beta-methoxy-5beta-androstane

HRID 1837116ノート

反応式

HRID 1837116 の反応式
Br[CH:2]=[CH:3]Br.[Li]CCCC.[CH3:10][O:11][C@H:12]1[CH2:17][CH2:16][C@H:15]2[C@H:18]3[C@H:28]([CH2:29][CH2:30][C@:13]12[CH3:14])[C@:26]1([CH3:27])[C@@H:21]([CH2:22][C:23](=[O:31])[CH2:24][CH2:25]1)[CH2:20][CH2:19]3>C1COCC1.C(Cl)Cl>[C:2]([C@@:23]1([OH:31])[CH2:24][CH2:25][C@@:26]2([CH3:27])[C@H:21]([CH2:20][CH2:19][C@@H:18]3[C@@H:28]2[CH2:29][CH2:30][C@@:13]2([CH3:14])[C@H:15]3[CH2:16][CH2:17][C@@H:12]2[O:11][CH3:10])[CH2:22]1)#[CH:3]

参加物

6

反応物 3

HCID 108971,2-DibromoetheneHCID 1493938617beta-Methoxy-5beta-androstan-3-oneHCID 178418339Butyllithium

生成物 1

HCID 154079183beta-Ethynyl-3alpha-hydroxy-17beta-methoxy-5beta-androstane収率 78.3%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of 1,2-dibromoethylene (1.6 mL, 3.7 g, 19.71 mmol) in dry THF (10 mL) was treated with n-BuLi (16.4 mL, 2.4M in THF, 39.4 mmol) at −75° C. After stirring the mixture at −78° C. for 0.25 hr, a solution of 17β-methoxy-5β-androstan-3-one (2 g, 6.57 mmol) in THF (20 mL) was added and the mixture was stirred at −78° C. for 15 min. The cooling bath was then removed and the mixture was quenched with NH4Cl solution (3 mL). The solvents were removed and the residue was extracted with EtOAc. The organic layer was washed with water, and brine. After drying over anhyd. MgSO4 the solution was filtered and evaporated to yield the crude product. This crude product was then dissolved in a small amount of CH2Cl2 and poured on a column of silica gel. Elution with toluene:acetone mixture (95:5) gave 3β-ethynyl-3α-hydroxy-17β-methoxy-5β-androstane (1.70 g) as a colorless solid; mp 62-65° C.; TLC Rf (toluene:acetone 95:5)=0.23.

後処理

  1. stirringthe mixture was stirred at −78° C. for 15 min
  2. customThe cooling bath was then removed
  3. customthe mixture was quenched with NH4Cl solution (3 mL)
  4. customThe solvents were removed
  5. extractionthe residue was extracted with EtOAc
  6. washThe organic layer was washed with water, and brine
  7. customAfter drying over anhyd
  8. filtrationMgSO4 the solution was filtered
  9. customevaporated
  10. customto yield the crude product
  11. additionpoured on a column of silica gel
  12. washElution with toluene

出典と根拠

ORDレコード
ord-5ddd73292fc848ba84b29dd5661ffe90
出典データセット
uspto-grants-2004_08
特許番号
US06780853B1

反応ノート

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