Betamethasone → 9-Fluoro-11beta-hydroxy-16beta-methylandrosta-1,4-diene-3,17-dione

HRID 434480

Reaction equation

HRID 434480 reaction equation
[F:1][C@:2]12[C@@H:22]([OH:23])[CH2:21][C@@:20]3([CH3:24])[C@@H:12]([CH2:13][C@H:14]([CH3:26])[C@:15]3([OH:25])C(=O)CO)[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:28])[CH:4]=[CH:5][C:6](=[O:27])[CH:7]=1.[O-][Bi](=O)=O.[Na+]>C(O)(=O)C.C(Cl)(Cl)Cl>[F:1][C@:2]12[C@@H:22]([OH:23])[CH2:21][C@@:20]3([CH3:24])[C@@H:12]([CH2:13][C@H:14]([CH3:26])[C:15]3=[O:25])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:28])[CH:4]=[CH:5][C:6](=[O:27])[CH:7]=1

Participants

5

Reactant 2

HCID 9782BetamethasoneHCID 4063671Sodium bismuthate

Product 1

HCID 2431519-Fluoro-11beta-hydroxy-16beta-methylandrosta-1,4-diene-3,17-dioneYield 65.2%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6212ChloroformSolvent

Procedure

A solution of 4.7 g (12.0 mmole) of 9-fluoro-16β-methyl-11β,17,21-trihydroxypregna-1,4-diene-3,20-dione in 50% acetic acid (600 ml) was stirred with 18 g of sodium bismuthate at room temperature for 2 hours. The brown suspension was filtered through a bed of deactivated silica powder and washed with 100 ml of 50% acetic acid. The filtrate was concentrated in vacuo to 100 ml, diluted with 100 ml of 20% hydrochloric acid and extracted with chloroform. The chloroform solution was washed with 20% hydrochloric acid and water, dried over anhydrous Na2SO4 and evaporated in vacuo to give a solid. This was dissolved in chloroform and chromatographed on a 30 g silica gel column, eluting successively with chloroform and 1:4 ethyl acetate-chloroform to give 2.6 g of the title compound, melting point 281°-283° C., dec.

Workup

  1. filtrationThe brown suspension was filtered through a bed of deactivated silica powder
  2. washwashed with 100 ml of 50% acetic acid
  3. concentrationThe filtrate was concentrated in vacuo to 100 ml
  4. additiondiluted with 100 ml of 20% hydrochloric acid
  5. extractionextracted with chloroform
  6. washThe chloroform solution was washed with 20% hydrochloric acid and water
  7. dry with materialdried over anhydrous Na2SO4
  8. customevaporated in vacuo
  9. customto give a solid
  10. customchromatographed on a 30 g silica gel column
  11. washeluting successively with chloroform and 1:4 ethyl acetate-chloroform

Sources & evidence

ORD record
ord-11528d974ea74b82a6e25f3d8d90ef4f
Source dataset
uspto-grants-1983_08
Patent number
US04397782

Linked notes

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