Iodine → HCID 54056135, compound

HRID 848027Notes

Reaction equation

HRID 848027 reaction equation
[C:1]([O-:4])(=[O:3])[CH3:2].[C:5]([O-:8])(=[O:7])[CH3:6].[C:9]([O-:12])(=O)[CH3:10].[C:13]([O-])(=O)[CH3:14].[Pb+4].C(=O)([O-])[O-].[Ca+2].C(O[C@H:27]1[CH2:46][C@@]2(C)[C@@H:38]([CH2:39][CH2:40][C@@H:41]2[CH:42]([OH:44])[CH3:43])[C@H:37]2[C@H:28]1[C@:29]1([CH3:52])[C:34](=[CH:35][CH2:36]2)[CH2:33]C2(OCCO2)C[CH2:30]1)(=O)C.II.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O>C1CCCCC1.CC(C)=O>[C:1]([O:4][C@H:27]1[CH2:46][C@@:10]2([CH2:9][OH:12])[C@@H:38]([CH2:39][CH2:40][C@@H:41]2[C:42](=[O:44])[CH3:43])[C@H:37]2[C@H:28]1[C@:29]1([CH3:52])[C:34](=[CH:35][CH2:36]2)[CH2:33][C:5]2([O:8][CH2:14][CH2:13][O:7]2)[CH2:6][CH2:30]1)(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 807Iodine2×HCID 10112Calcium CarbonateHCID 54126633HCID 54126633, compoundHCID 131709961Jones' reagentHCID 178418268HCID 178418268, compound

Product 1

HCID 54056135HCID 54056135, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8078CyclohexaneSolvent

Procedure

A mixture of 21.7 g of lead tetraacetate and 9.8 g of calcium carbonate in 1000 ml of cyclohexane is heated at reflux under argon for 1 hour and then cooled. To the resulting suspension is added 8.2 g of 11β-acetoxy-3,3-ethylenedioxypregn-5-en-20-ol and 2.5 g of iodine and the resulting purple suspension is heated to reflux and irradiated with a 275 W sunlamp until the color of the iodine has faded (1-1.5 hours). The mixture is then cooled and filtered through Celite and the filtrate is washed with aqueous sodium bisulfite, water, aqueous sodium bicarbonate and brine. The organic solution is then dried and concentrated and the residue obtained is dissolved in acetone and treated with 10 ml of standard Jones reagent at 0° C. for 1 hour. Excess Jones reagent is destroyed by the addition of 2-propanol and the resulting mixture is filtered to remove the precipitated inorganic salts. The filtrate is then concentrated to a small volume and the residue is partitioned between ether and water. The aqueous solution is extracted with ether and the ether solutions are combined, washed with aqueous sodium bicarbonate, dried and concentrated. The residue is dissolved in water:dioxane (1:9, 700 ml) and 7.2 g of silver acetate is added. The mixture is stirred and heated rapidly to 60°-65° C. and then maintained at that temperature for 4 hours. The mixture is then cooled, filtered and concentrated. The residue is dissolved in ether, filtered again and concentrated. The resulting material is chromatographed on silica gel to give 11β-acetoxy-3,3-ethylenedioxy-18-hydroxypregn-5-en-20-one.

Workup

  1. temperatureis heated
  2. temperatureat reflux under argon for 1 hour
  3. temperaturecooled
  4. temperaturethe resulting purple suspension is heated
  5. temperatureto reflux
  6. custom(1-1.5 hours)
  7. temperatureThe mixture is then cooled
  8. filtrationfiltered through Celite
  9. washthe filtrate is washed with aqueous sodium bisulfite, water, aqueous sodium bicarbonate and brine
  10. customThe organic solution is then dried
  11. concentrationconcentrated
  12. customthe residue obtained
  13. customExcess Jones reagent is destroyed by the addition of 2-propanol
  14. filtrationthe resulting mixture is filtered
  15. customto remove the precipitated inorganic salts
  16. concentrationThe filtrate is then concentrated to a small volume
  17. customthe residue is partitioned between ether and water
  18. extractionThe aqueous solution is extracted with ether
  19. washwashed with aqueous sodium bicarbonate
  20. customdried
  21. concentrationconcentrated
  22. dissolutionThe residue is dissolved in water:dioxane (1:9, 700 ml)
  23. addition7.2 g of silver acetate is added
  24. temperatureheated rapidly to 60°-65° C.
  25. temperaturemaintained at that temperature for 4 hours
  26. temperatureThe mixture is then cooled
  27. filtrationfiltered
  28. concentrationconcentrated
  29. dissolutionThe residue is dissolved in ether
  30. filtrationfiltered again
  31. concentrationconcentrated
  32. customThe resulting material is chromatographed on silica gel

Sources & evidence

ORD record
ord-f34919c86bcd4d6ca9f81464bb25416f
Source dataset
uspto-grants-1981_10
Patent number
US04293548

Reaction notes

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