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

HRID 1285321ノート

反応式

HRID 1285321 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 (VA, Example 29, 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, dried 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. dry with materialdried 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-6846504055bb4fe48c533f02ab0193f4
出典データセット
uspto-grants-1986_01
特許番号
US04567001

反応ノート

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