Acetone → HCID 86734344, compound

HRID 1974427Notes

Reaction equation

HRID 1974427 reaction equation
[C:1]([O:4][C:5]1[CH2:22][CH2:21][C@H:20]2[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[O:23]C(=O)C)[CH:6]=1)(=[O:3])[CH3:2].CC(C)=O.C([O-])(=O)C.[Na+].BrN1C(=O)CCC1=O>[Cl-].[Na+].O.CCCCCC.N1C=CC=CC=1.C(O)(=O)C.O>[C:1]([OH:4])(=[O:3])[CH3:2].[OH:23][C@H:14]1[CH2:13][CH2:12][C@H:11]2[C@H:10]3[C@H:19]([CH2:18][CH2:17][C@:15]12[CH3:16])[C@@H:20]1[C:7](=[CH:6][C:5](=[O:4])[CH2:22][CH2:21]1)[CH:8]=[CH:9]3

Participants

10

Reactant 4

HCID 180Acetone2×HCID 67184N-bromobutanimideHCID 517045Sodium AcetateHCID 11760130HCID 11760130, compound

Product 1

HCID 86734344HCID 86734344, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1049PyridineSolventHCID 8058HexaneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

The compound 3,17β-diacetoxyestr-3,5-diene, 60.0 g (0.158 mole) prepared as in Example 1, is placed in an acetone buffered solution containing 3,180 ml of acetone, 816 ml of water, 81.6 ml of acetic acid, 18 ml of pyridine, and 81.6 g of sodium acetate. The solution is cooled to 0°-5° C. using a salt-methanol-ice bath and 32.1 g (0.18 mole) of N-bromosuccinimide is added at one time. The reaction mixture is totally shielded from light and stirring continued for a period of 3 hours at 0°-5° C. The solution is poured onto 12 liters of cold brine and the product extracted with 1 liter of ether. The ether extract is washed with water, dried over anhydrous magnesium sulfate and concentrated under vacuum at temperatures below 20° C. The amber oil residue is dissolved in 75 ml of dimethylformamide and rapidly added to a vigorously refluxing suspension of 750 ml of dimethylformamide, 60 g of lithium bromide and 60 g of lithium carbonate under nitrogen. Residual ether is permitted to evaporate and the reaction mixture is refluxed for a period of one hour. On cooling, the suspension is filtered and the filtrate is poured into an ice-water mixture. The product is extracted into ether and the combined ether extracts are washed with water, 2 liters of a 5% sodium hydroxide solution and washed again with water. The solution is dried over anhydrous magnesium sulfate and concentrated under vacuum to yield a yellow solid which is layered with hexane and filtered to yield 34.6 g of the desired 17β-hydroxy-estra-4,6-dien-3-one acetate.

Workup

  1. temperatureThe solution is cooled to 0°-5° C.
  2. extractionthe product extracted with 1 liter of ether
  3. extractionThe ether extract
  4. washis washed with water
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under vacuum at temperatures below 20° C
  7. dissolutionThe amber oil residue is dissolved in 75 ml of dimethylformamide
  8. additionrapidly added to
  9. temperaturea vigorously refluxing
  10. additionsuspension of 750 ml of dimethylformamide, 60 g of lithium bromide and 60 g of lithium carbonate under nitrogen
  11. customto evaporate
  12. temperaturethe reaction mixture is refluxed for a period of one hour
  13. temperatureOn cooling
  14. filtrationthe suspension is filtered
  15. additionthe filtrate is poured into an ice-water mixture
  16. extractionThe product is extracted into ether
  17. washthe combined ether extracts are washed with water, 2 liters of a 5% sodium hydroxide solution
  18. washwashed again with water
  19. dry with materialThe solution is dried over anhydrous magnesium sulfate
  20. concentrationconcentrated under vacuum
  21. customto yield a yellow solid which
  22. filtrationfiltered

Sources & evidence

ORD record
ord-a9e7a5f746bf4aa1a8023e885f6a4145
Source dataset
uspto-grants-1976_12
Patent number
US04000273

Reaction notes

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