Dimethylformamide → Fluocortin

HRID 2072191Notes

Reaction equation

HRID 2072191 reaction equation
[F:1][C@@H:2]1[C:22]2[C@:17]([CH3:24])([CH:18]=[CH:19][C:20](=[O:23])[CH:21]=2)[C@@H:16]2[C@H:4]([C@H:5]3[C@:13]([CH3:26])([CH2:14][C@@H:15]2[OH:25])[C@@H:8]([C:9](=[O:12])[CH:10]=[O:11])[C@H:7]([CH3:27])[CH2:6]3)[CH2:3]1.CN(C)C=[O:31].FCCO.[C-]#N.[K+]>[O-2].[Mn+4].[O-2].C(O)(=O)C>[F:1][C@@H:2]1[C:22]2[C@:17]([CH3:24])([CH:18]=[CH:19][C:20](=[O:23])[CH:21]=2)[C@@H:16]2[C@H:4]([C@H:5]3[C@:13]([CH3:26])([CH2:14][C@@H:15]2[OH:25])[C@@H:8]([C:9](=[O:12])[C:10]([OH:31])=[O:11])[C@H:7]([CH3:27])[CH2:6]3)[CH2:3]1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 9032Potassium CyanideHCID 97372-FluoroethanolHCID 86735083HCID 86735083, compound

Product 1

HCID 22875828Fluocortin

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 176Acetic AcidSolvent

Procedure

1.4 g. of 6α-fluoro-11β-hydroxy-3,20-dioxo-16α-methyl-1,4-pregnadien-21-al is dissolved in 14 ml. of dimethylformamide and combined with 5 ml. of 2-fluoroethanol, 1.4 ml. of concentrated acetic acid, 2.8 g. of active manganese (IV) oxide, and 225 mg. of potassium cyanide. The reaction mixture is agitated for 10 minutes at room temperature and then filtered off from the manganese (IV) oxide. The filtrate is poured into water and extracted with dichloromethane. The organic phase is washed with water, dried with sodium sulfate, and concentrated under vacuum. The residue is chromatographed on silica gel. With 31-33% acetone-hexane, after recrystallization from acetone/hexane, 630 mg. of the 2-fluoroethyl ester of 6α-fluoro-11β-hydroxy-3,20-dioxo-16α-methyl-1,4-pregnadien-21-oic acid is obtained; m.p. 188.0° C. [α]D25 = +141° (chloroform). UV: ε242 = 16,900 (methanol)

Workup

  1. filtrationfiltered off from the manganese (IV) oxide
  2. additionThe filtrate is poured into water
  3. extractionextracted with dichloromethane
  4. washThe organic phase is washed with water
  5. dry with materialdried with sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customThe residue is chromatographed on silica gel
  8. customWith 31-33% acetone-hexane, after recrystallization from acetone/hexane, 630 mg

Sources & evidence

ORD record
ord-2c0946b893fa45b2a8541cfbdd9ce654
Source dataset
uspto-grants-1977_09
Patent number
US04049804

Reaction notes

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