Ammonium Chloride → 11beta-Trimethylsiloxy-21-acetoxy-6alpha-fluoro-16alpha-methyl-pregna-1,4-diene-3,20-dione

HRID 259155Notes

Reaction equation

HRID 259155 reaction equation
[Li].[CH3:2][Cu]C.[CH3:5][Si:6]([CH3:37])([CH3:36])[O:7][C@H:8]1[CH2:31][C@@:30]2([CH3:32])[C@@H:19]([CH2:20][CH:21]=[C:22]2[C:23](=[O:29])[CH2:24][O:25][C:26](=[O:28])[CH3:27])[C@H:18]2[C@H:9]1[C@:10]1([CH3:35])[C:15]([C@@H:16]([F:33])[CH2:17]2)=[CH:14][C:13](=[O:34])[CH:12]=[CH:11]1.[Cl-].[NH4+]>ClCCl>[CH3:37][Si:6]([CH3:5])([CH3:36])[O:7][C@H:8]1[CH2:31][C@@:30]2([CH3:32])[C@@H:19]([CH2:20][C@@H:21]([CH3:2])[C@@H:22]2[C:23](=[O:29])[CH2:24][O:25][C:26](=[O:28])[CH3:27])[C@H:18]2[C@H:9]1[C@:10]1([CH3:35])[C:15]([C@@H:16]([F:33])[CH2:17]2)=[CH:14][C:13](=[O:34])[CH:12]=[CH:11]1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 2279853111beta-Trimethylsiloxy-21-acetoxy-6alpha-fluoropregna-1,4,16-triene-3,20-dioneHCID 178477771HCID 178477771, compound

Product 1

HCID 2279853011beta-Trimethylsiloxy-21-acetoxy-6alpha-fluoro-16alpha-methyl-pregna-1,4-diene-3,20-dione

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

750 mg cuprous iodide was suspended in 10 ml dichloromethane in an atmosphere of nitrogen and cooled to -10° C. To this suspension under stirring and cooling was added 9 ml of a 2% solution of lithium-methyl by drop wise addition maintaining the temperature below -5°. To the so obtained lithium-dimethyl-copper solution was added 425 mg 11β-trimethylsiloxy-21-acetoxy-6α-fluoropregna-1,4,16-triene-3,20-dione obtained according to Example 8 dissolved in 3 ml dichloromethane. The temperature of the reaction mixture was kept below -1°, and the stirring was maintained for a period of 15 minutes. The reaction mixture was poured into an aqueous ammonium chloride solution, the organic phase separated and the aqueous phase re-extracted with dichloromethane. The organic extracts were combined, washed with water, dried over anhydrous sodium sulfate and concentrated to dryness under reduced pressure. Trituration with acetone afforded a crystalline product 11β-trimethylsiloxy-21-acetoxy-6α-fluoro-16α-methyl-pregna-1,4-diene-3,20-dione (compound 14) yield 320 mg TLC: homogeneous.

Workup

  1. temperaturecooling
  2. additionby drop wise addition
  3. temperaturemaintaining the temperature below -5°
  4. customobtained
  5. customwas kept below -1°
  6. temperaturethe stirring was maintained for a period of 15 minutes
  7. customthe organic phase separated
  8. extractionthe aqueous phase re-extracted with dichloromethane
  9. washwashed with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-2f0fec28d7ee463c898190a6631089de
Source dataset
uspto-grants-1977_07
Patent number
US04036831

Reaction notes

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