Hydrochloric Acid → 6-Methylene-16-(phenylsulfinylmethyl)pregna-4,16-diene-3,20-dione

HRID 65407ノート

反応式

HRID 65407 の反応式
[C:1]([C@:4]1(O)[C:9](=[CH2:10])[CH2:8][C@H:7]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:5]12[CH3:6])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH2:17][CH2:18]1)[C:13](=[CH2:25])[CH2:12]3)(=[O:3])[CH3:2].CN(C)C.[C:31]1([S:37](Cl)(=[O:39])=O)[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.Cl>C(Cl)Cl>[CH2:25]=[C:13]1[C:14]2[C@:19]([CH3:20])([CH2:18][CH2:17][C:16](=[O:24])[CH:15]=2)[C@@H:21]2[C@H:11]([C@H:7]3[C@:5]([CH3:6])([CH2:23][CH2:22]2)[C:4]([C:1](=[O:3])[CH3:2])=[C:9]([CH2:10][S:37]([C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)=[O:39])[CH2:8]3)[CH2:12]1

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 1146Trimethylamine2 回HCID 7369Benzenesulfonyl chloride3 回HCID 1331493117alpha-Acetyl-17beta-hydroxy-6,16-dimethyleneandrost-4-en-3-one

生成物 1

HCID 137303406-Methylene-16-(phenylsulfinylmethyl)pregna-4,16-diene-3,20-dione

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

17α-Acetyl-17β-hydroxy-6,16-dimethyleneandrosta-4-en-3-one (Example 5, 8.0 g) is dissolved in methylene chloride (66 ml) and cooled to -20°. Trimethylamine (2.56 ml) at -20° and methylene chloride (5 ml) are mixed and the trimethylamine mixture transferred by syringe to the steroid solution. To the cold steroid solution was added phenylsulfonylchloride (1.0 equivalent) by a syringe pump over 1 hr. TLC shows the reaction approximately 80-85% complete. Phenylsulfonylchloride (0.25 equivalent) was added over approximately 10 min., TLC showing the reaction to be approximately 95% complete. Phenylsulfonylchloride (0.10 equivalent) was then added for a total of 1.35 equivalence, at which time TLC shows the reaction to be complete. Hydrochloric acid (10%, 40 ml) was added all at once, the temperature now being 7°, and the mixture stirred for about 10 min. The phases are separated. The aqueous portion is back-extracted with methylene chloride (10 ml). The organic extracts are washed with phosphate buffer (25 ml) and back-extracted with methylene chloride (10 ml). The organic extracts are combined, dired over sodium sulfate overnight at 20°-25°. This mixture is filtered and the filtrate concentrated under reduced pressure to an oil, which is the title compound.

後処理

  1. temperaturecooled to -20°
  2. customthe reaction approximately 80-85% complete
  3. customthe reaction
  4. customthe reaction
  5. customnow being 7°
  6. customThe phases are separated
  7. extractionThe aqueous portion is back-extracted with methylene chloride (10 ml)
  8. washThe organic extracts are washed with phosphate buffer (25 ml)
  9. extractionback-extracted with methylene chloride (10 ml)
  10. customdired over sodium sulfate overnight at 20°-25°
  11. filtrationThis mixture is filtered
  12. concentrationthe filtrate concentrated under reduced pressure to an oil, which

出典と根拠

ORDレコード
ord-07dad5d65ceb4deab29eed308f16bb51
出典データセット
uspto-grants-1986_09
特許番号
US04614621

反応ノート

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