Reaktion #93623

ord-d1cbf3bc997146c8ba55f3de17402c48

Reaktionsgleichung

O=S(=O)([O-])O.[K+]
KHSO4
CC(C)=O
acetone
C=C(Oc1ccccc1)[C@@]1(O)CC[C@H]2[C@@H]3CCC4=CC(=O)CC[C@]4(C)C3=CC[C@@]21C
17α-hydroxy-20-phenoxypregna-4,9(11),20-trien-3-one
O=P([O-])([O-])[O-].[K+].[K+].[K+]
potassium phosphate
O=S([O-])OO.[K+]
OXONE
→
CC(=O)OCC(=O)[C@@]1(O)CC[C@H]2[C@@H]3CCC4=CC(=O)CC[C@]4(C)C3=CC[C@@]21C
17α-hydroxy-21 -acetoxy-pregna-4,9(11)-diene-3,20-dione

Edukte

O=S(=O)([O-])O.[K+]
KHSO4
CC(C)=O
acetone
C=C(Oc1ccccc1)[C@@]1(O)CC[C@H]2[C@@H]3CCC4=CC(=O)CC[C@]4(C)C3=CC[C@@]21C
17α-hydroxy-20-phenoxypregna-4,9(11),20-trien-3-one
O=P([O-])([O-])[O-].[K+].[K+].[K+]
potassium phosphate
O=S([O-])OO.[K+]
OXONE

Reagenzien

CCCC[N+](CCCC)(CCCC)CCCC.[Br-]
Tetra n-butylammonium bromide

Lösungsmittel

ClCCl
methylene chloride
O
water

Reaktionsbedingungen

Temperatur
15°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Filtrationfiltered
  2. 2
    Sonstigeplaced in an addition funnel
  3. 3
    workup.ADDITIONThe OXONE solution is added dropwise
  4. 4
    Temperaturwhile maintaining the pH between 6.8 and 7.2 with 30% potassium hydroxide
  5. 5
    workup.ADDITIONFifty ml of water is added
  6. 6
    Filtrationthe reaction mixture is filtered
  7. 7
    WaschenThe filtered solids are rinsed with methylene chloride and water
  8. 8
    Sonstigethe layers are separated
  9. 9
    Filtrationthe methylene chloride layer is filtered
  10. 10
    Filtrationfilter
  11. 11
    workup.ADDITIONTwo ml of glacial acetic acid are added
  12. 12
    workup.STIRRINGthe mixture is stirred for 1 hour

Vorschrift

17α-hydroxy-20-phenoxypregna-4,9(11),20-trien-3-one (4.05 grams, 10 mmoles) is slurried in a 250 ml round bottom flask, in an aqueous pH 8 potassium phosphate buffer (20 ml, 0.05M in PO4≡) prepared as in Example 1. Tetra n-butylammonium bromide (0.64 grams, 2.0 mmole), acetone (20 ml), methylene chloride (40 ml) are added and the mixture cooled to 15° C. 18.42 grams, 30 mmoles of OXONE® (2KHSO5.KHSO4.K2SO4) is dissolved in 62 ml of water filtered and placed in an addition funnel. The OXONE solution is added dropwise with stirring while maintaining the pH between 6.8 and 7.2 with 30% potassium hydroxide. The reaction is run to completion. Fifty ml of water is added and the reaction mixture is filtered. The filtered solids are rinsed with methylene chloride and water, the layers are separated and the methylene chloride layer is filtered thru a solka flok filter. Two ml of glacial acetic acid are added and the mixture is stirred for 1 hour to yield 2.5 grams of 17α-hydroxy-21 -acetoxy-pregna-4,9(11)-diene-3,20-dione at room temperature.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04613463uspto-grants-1986_09