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Methanesulfonic Acid → (2beta,3alpha,5alpha)-3-Hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnane-11,20-dione

HRID 233520
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HRID 233520 반응식
Cl[CH2:2][C:3](=[O:33])[C@@H:4]1[C@:21]2([CH3:22])[C@H:7]([C@H:8]3[C@H:18]([C:19](=[O:23])[CH2:20]2)[C@:16]2([CH3:17])[C@H:11]([CH2:12][C@H:13]([OH:32])[C@@H:14]([N:24]4[CH2:29][CH2:28][O:27][C:26]([CH3:31])([CH3:30])[CH2:25]4)[CH2:15]2)[CH2:10][CH2:9]3)[CH2:6][CH2:5]1.CS(O)(=O)=O.[S-:39][C:40]#[N:41].[K+].C(=O)([O-])[O-].[Na+].[Na+]>CO.O>[OH:32][C@@H:13]1[C@@H:14]([N:24]2[CH2:29][CH2:28][O:27][C:26]([CH3:31])([CH3:30])[CH2:25]2)[CH2:15][C@@:16]2([CH3:17])[C@@H:11]([CH2:10][CH2:9][C@@H:8]3[C@@H:18]2[C:19](=[O:23])[CH2:20][C@@:21]2([CH3:22])[C@H:7]3[CH2:6][CH2:5][C@@H:4]2[C:3](=[O:33])[CH2:2][S:39][C:40]#[N:41])[CH2:12]1
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참가 물질

7

반응물 4

HCID 6395Methanesulfonic AcidHCID 10340Sodium CarbonateHCID 516872Potassium thiocyanateHCID 10672358(2beta,3alpha,5alpha)-21-Chloro-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)pregnane-11,20-dione

생성물 1

HCID 10696819(2beta,3alpha,5alpha)-3-Hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnane-11,20-dione수율 17.6%

시약·촉매·용매 2

HCID 887Methanol용매HCID 962Water용매2회

실험 절차

To (2β,3α,5α)-21-chloro-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)pregnane-11,20-dione (3.1 g) was added a solution of methanesulfonic acid (615 mg) in methanol (63 ml) and then a solution of potassium thiocyanate (12.4 g) in water (32 ml). The resulting solution was stirred at room temperature for 24 h, poured into water and sodium carbonate was then added until the pH exceeded 9. The precipitated solid was filtered off, washed with water and dissolved in dichloromethane. This solution was dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was chromatographed on silica gel and the purified product was crystallised from diethyl ether and then from methanol to give (2β,3α,5α)-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnane-11,20-dione (572 mg). m.p. 197°-198° C.; [α]D +99.3° (c 0.8).

후처리

  1. additionwas then added until the pH
  2. filtrationThe precipitated solid was filtered off
  3. washwashed with water
  4. dissolutiondissolved in dichloromethane
  5. dry with materialThis solution was dried over sodium sulfate
  6. customthe solvent was removed under reduced pressure
  7. customThe residue was chromatographed on silica gel
  8. customthe purified product was crystallised from diethyl ether

출처 및 근거

ORD 기록
ord-27159a280d9542989db8091d57903fca
출처 데이터셋
uspto-grants-1997_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05593983

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