9alpha-Bromo-11beta-hydroxy-4-androstene-3,17-dione → 11beta-Hydroxyandrost-4-ene-3,17-dione

HRID 22062

反応式

HRID 22062 の反応式
Br[C@:2]12[C@@H:19]([OH:20])[CH2:18][C@@:16]3([CH3:17])[C@@H:12]([CH2:13][CH2:14][C:15]3=[O:21])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:23])[CH2:4][CH2:5][C:6](=[O:22])[CH:7]=1>C1COCC1>[OH:20][C@H:19]1[CH2:18][C@@:16]2([CH3:17])[C@@H:12]([CH2:13][CH2:14][C:15]2=[O:21])[C@H:11]2[C@H:2]1[C@:3]1([CH3:23])[C:8]([CH2:9][CH2:10]2)=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]1

参加物

3

反応物 1

HCID 111326859alpha-Bromo-11beta-hydroxy-4-androstene-3,17-dione

生成物 1

HCID 9414111beta-Hydroxyandrost-4-ene-3,17-dione

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

9α-Bromo-11β-hydroxyandrost-4-ene-3,17-dione (I, PREPARATION 2, 2.134 g) is dissolved in THF (THF 20ml) and degassed as described in EXAMPLE 1. This solution is added dropwise over 20 min to a freshly degassed slurry of chromic chloride hexahydrate (81 mg), thiovanic acid (0.70 ml) and zinc dust (555 mg) in DMF (4 ml) at 0° THF (about 8 ml) is used for rinse purposes. The slurry is stirred at 0° to 2° for 2.2 hr and then is slowly heated to 50°. The THF is removed by vacuum distillation and the remaining slurry is diluted with ethyl acetate (25 ml) and water (25 ml). The unreacted zinc is removed by filtration and is washed with aqueous ethyl acetate. The combined filtrate and wash is allowed to separate. The organic layer is washed with water (3×25 ml) and finally is concentrated under vacuum to a residue. The residue is recrystallized from 1 part toluene and 2 parts heptane to give the title compound, TLC Rf =0.45 (methanol/methylene chloride, 5/95); HPLC 96.7% (II), 2.9% ∆9(11).

後処理

  1. customdegassed
  2. additionThis solution is added dropwise over 20 min to a freshly degassed slurry of chromic chloride hexahydrate (81 mg), thiovanic acid (0.70 ml) and zinc dust (555 mg) in DMF (4 ml) at 0° THF (about 8 ml)
  3. washfor rinse purposes
  4. temperatureis slowly heated to 50°
  5. customThe THF is removed by vacuum distillation
  6. additionthe remaining slurry is diluted with ethyl acetate (25 ml) and water (25 ml)
  7. customThe unreacted zinc is removed by filtration
  8. washis washed with aqueous ethyl acetate
  9. washThe combined filtrate and wash
  10. customto separate
  11. washThe organic layer is washed with water (3×25 ml)
  12. concentrationfinally is concentrated under vacuum to a residue
  13. customThe residue is recrystallized from 1 part toluene and 2 parts heptane

出典と根拠

ORDレコード
ord-9f4906b82f104ab08ee7e55757ce1dce
出典データセット
uspto-grants-1995_06
特許番号
US05426198

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