Disiloxane → Prednisolone 17,21-diacetate

HRID 259158

반응식

HRID 259158 반응식
C[Si](C)(C)[O:3][C@H:4]1[CH2:27][C@@:26]2([CH3:28])[C@@H:15]([CH2:16][CH2:17][C@:18]2([OH:29])[C:19](=[O:25])[CH2:20][O:21][C:22](=[O:24])[CH3:23])[C@H:14]2[C@H:5]1[C@:6]1([CH3:31])[C:11]([CH2:12][CH2:13]2)=[CH:10][C:9](=[O:30])[CH:8]=[CH:7]1.[C:34]([O-])(=[O:36])[CH3:35].[Na+].[SiH3]O[SiH3]>C(OC(C)=C)(=O)C>[CH3:23][C:22]([O:21][CH2:20][C:19]([C@:18]1([O:29][C:34]([CH3:35])=[O:36])[C@@:26]2([CH3:28])[CH2:27][C@H:4]([OH:3])[C@@H:5]3[C@:6]4([CH3:31])[C:11](=[CH:10][C:9]([CH:8]=[CH:7]4)=[O:30])[CH2:12][CH2:13][C@H:14]3[C@@H:15]2[CH2:16][CH2:17]1)=[O:25])=[O:24]

참가 물질

5

반응물 3

HCID 123318DisiloxaneHCID 517045Sodium AcetateHCID 2279852811beta-Trimethylsiloxy-17alpha-hydroxy-21-acetoxy-pregna-1,4-diene-3,20-dione

생성물 1

HCID 14233395Prednisolone 17,21-diacetate

시약·촉매·용매 1

HCID 7916Isopropenyl acetate용매

실험 절차

A mixture of 8 g of 11β -trimethylsiloxy-17α-hydroxy-21-acetoxy-pregna-1,4-diene-3,20 -dione (from Example 29), 8 g of paratoluenesulfonic acid monohydrate and 800 ml of isopropenyl acetate was allowed to stand for one week at room temperature. By this time TLC control indicated that almost all the starting material had reacted. 15 g of anhydrous sodium acetate was added and the mixture left stirring for another day. The supernatant was decanted from the salt crystals and the resulting solution -- after addition of 400 ml methyl-isobutyl ketone -- was washed twice, each time with 500 ml of water, then with 200 ml of saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and evaporated under reduced pressure to dryness. This residue was found to be 11β-trimethylsiloxy-17α,21-diacetoxypregna-1,4-diene-3,20-dione, about 90% pure, there was about 10% of a less polar artifact believed to be the result of a slight aromatization side reaction about ring A, followed by acetylation. The identity was proved by hydrolyzing off the silyl ether blocking group to give prednisolone 17,21-diacetate, identified by TLC with a sample obtained by the Ortho ester route.

후처리

  1. waitto stand for one week at room temperature
  2. customhad reacted
  3. waitthe mixture left
  4. customThe supernatant was decanted from the salt crystals
  5. additionthe resulting solution -- after addition of 400 ml methyl-isobutyl ketone
  6. washwas washed twice
  7. dry with materialeach time with 500 ml of water, then with 200 ml of saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate
  8. customevaporated under reduced pressure to dryness
  9. customresult of a slight aromatization side reaction about ring A,

출처 및 근거

ORD 기록
ord-031feb8dedac43f0b0d7de19f3e6e82c
출처 데이터셋
uspto-grants-1977_07
특허 번호
US04036831

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