Sodium Carbonate → (2beta,3alpha,5alpha)-3-Hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnan-20-one

HRID 233519Notes

Reaction equation

HRID 233519 reaction equation
CS(O)(=O)=O.Cl[CH2:7][C:8](=[O:37])[C@@H:9]1[C@:26]2([CH3:27])[C@H:12]([C@H:13]3[C@H:23]([CH2:24][CH2:25]2)[C@:21]2([CH3:22])[C@H:16]([CH2:17][C@H:18]([OH:36])[C@@H:19]([N:28]4[CH2:33][CH2:32][O:31][C:30]([CH3:35])([CH3:34])[CH2:29]4)[CH2:20]2)[CH2:15][CH2:14]3)[CH2:11][CH2:10]1.[S-:38][C:39]#[N:40].[K+].C(=O)([O-])[O-].[Na+].[Na+]>CO.O>[OH:36][C@@H:18]1[C@@H:19]([N:28]2[CH2:33][CH2:32][O:31][C:30]([CH3:35])([CH3:34])[CH2:29]2)[CH2:20][C@@:21]2([CH3:22])[C@@H:16]([CH2:15][CH2:14][C@@H:13]3[C@@H:23]2[CH2:24][CH2:25][C@@:26]2([CH3:27])[C@H:12]3[CH2:11][CH2:10][C@@H:9]2[C:8](=[O:37])[CH2:7][S:38][C:39]#[N:40])[CH2:17]1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 516872Potassium thiocyanateHCID 86750181(2beta,3alpha,5alpha)-21-Chloro-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)pregnan-20-one methanesulfonate

Product 1

HCID 53898985(2beta,3alpha,5alpha)-3-Hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnan-20-one

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

To a mixture of (2β,3α,5α)-21-chloro-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)pregnan-20-one methanesulfonate (1:1) salt (1.5 g) in methanol (63 ml) was added a solution of potassium thiocyanate (5.14 g) in water (32 ml). The resulting solution was stirred at room temperature for 72 h, then poured into water and sodium carbonate was added until the pH exceeded 9. The precipitated solid was filtered off, washed with water and dissolved in dichloromethane. The 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 methanol and then from diethyl ether to give (2β,3α,5α)-3-hydroxy-2-(2,2-dimethyl-4-morpholinyl)-21-thiocyanatopregnan-20-one (497 mg). m.p. 165.5°-166.5° C.; [α]D +121.1° (c 1.3).

Workup

  1. additionwas added until the pH
  2. filtrationThe precipitated solid was filtered off
  3. washwashed with water
  4. dissolutiondissolved in dichloromethane
  5. dry with materialThe 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 methanol

Sources & evidence

ORD record
ord-53d507414b7e4a24991f7451606f31e8
Source dataset
uspto-grants-1997_01
Patent number
US05593983

Reaction notes

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