Water → HCID 68140865, compound

HRID 1283724Notes

Reaction equation

HRID 1283724 reaction equation
[F:1][C@:2]12[C@@H:21]([OH:22])[CH2:20][C@@:19]3([CH3:23])[C@@H:12]([CH2:13][CH:14]=[C:15]3[C:16](=[O:18])[CH3:17])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:25])[CH2:4][CH2:5][C:6](=[O:24])[CH:7]=1.[OH2:26]>CS(C)=O.CO.Cl>[C:21]([C@@H:14]1[CH2:13][C@@H:12]2[C@:19]([CH3:23])([CH2:20][C@H:21]([OH:22])[C@@:2]3([F:1])[C@H:11]2[CH2:10][CH2:9][C:8]2[C@:3]3([CH3:25])[CH2:4][CH2:5][C:6](=[O:24])[CH:7]=2)[C@H:15]1[C:16](=[O:18])[CH3:17])(=[O:26])[C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:3]=1

Participants

6

Reactant 2

HCID 962WaterHCID 2394059-Fluoro-11-hydroxypregna-4,16-diene-3,20-dione

Product 1

HCID 68140865HCID 68140865, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 679Dimethyl SulfoxideSolvent2×HCID 887MethanolSolvent

Procedure

1-Phenyl-1-tetrahydropyranyloxyacetonitrile (1.3 g.) is added to a suspension of 57% sodium hydride-paraffin (275 mg.) in dry dimethylsulfoxide (20 ml.) in a nitrogen atmosphere. The mixture is stirred at room temperature for 90 minutes to yield a homogeneous solution of the anion. To the anion is added a solution of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione (1.04 g.) in dry dimethylsulfoxide. After 30 minutes, the mixture is poured into water and extracted with ethyl acetate. The extracts are combined, washed with water, dried over magnesium sulfate and evaporated to afford 2.55g. of a gum. This is dissolved in methanol (25 ml.), conc. hydrochloric acid (2 drops) is added and the solution is maintained in a bath at 55°-60°C for 5.0 hours. The methanol is evaporated in vacuo, the residue is dissolved in ethyl acetate, washed with a diluted sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated to afford the crude product as a gum. This is absorbed on a dry column of silica gel (40 g.) and the column is eluted successively with chloroform, ethyl acetate-chloroform (1:9) and ethyl acetate. Crystallization of the material (1.1 g.) eluted with ethyl acetate-chloroform from acetone-hexane affords the analytical specimen (690 mg.), melting point 250° -252°C, dec.

Workup

  1. customto yield a homogeneous solution of the anion
  2. waitAfter 30 minutes
  3. extractionextracted with ethyl acetate
  4. washwashed with water
  5. dry with materialdried over magnesium sulfate
  6. customevaporated
  7. customto afford 2.55g
  8. temperaturethe solution is maintained in a bath at 55°-60°C for 5.0 hours
  9. customThe methanol is evaporated in vacuo
  10. dissolutionthe residue is dissolved in ethyl acetate
  11. washwashed with a diluted sodium bicarbonate solution and water
  12. dry with materialdried over magnesium sulfate
  13. customevaporated

Sources & evidence

ORD record
ord-5d863f638c484d71869f311df68709b0
Source dataset
uspto-grants-1976_08
Patent number
US03976638

Reaction notes

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