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

HRID 22062

반응식

HRID 22062 반응식
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

참가 물질

3

반응물 1

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-9f4906b82f104ab08ee7e55757ce1dce
출처 데이터셋
uspto-grants-1995_06
특허 번호
US05426198

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