Hydrochloric Acid → 17-Methyleneestra-4-EN-3-one

HRID 1585859Notes

Reaction equation

HRID 1585859 reaction equation
Cl.O.C[O:4][C:5]1[CH2:6][C:7]2[CH2:8][CH2:9][C@@H:10]3[C@@H:19]([C:20]=2[CH2:21][CH:22]=1)[CH2:18][CH2:17][C@@:15]1([CH3:16])[C@H:11]3[CH2:12][CH2:13][C:14]1=[CH2:23].C(=O)(O)[O-].[Na+]>CO.CC(C)=O>[CH2:23]=[C: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)[CH2:8][CH2:9]3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 516892Sodium BicarbonateHCID 5433836617-Methylenestra-2,5(10)-dien-3-yl methyl ether

Product 1

HCID 1587099217-Methyleneestra-4-EN-3-one

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 887MethanolSolvent

Procedure

Con. hydrochloric acid (6.0 mL) and water (6.0 mL) were added to a solution of 17-methylenestra-2,5(10)-dien-3-yl methyl ether (15, 702.8 mg. 2.471 mmol) in methanol (6 mL) and acetone (20 mL). See Example 17. After stirring 1 h, sodium bicarbonate (7.50 g) was added cautiously. The mixture was concentrated under reduced pressure once effervescence had ceased and water (50 mL) was added. The mixture was extracted three times with 25 mL portions of methylene chloride. The combined organic extracts were washed with 50 mL of brine, dried over magnesium sulfate, and filtered through diatomaceous earth. The residue was washed with 10 mL of methylene chloride and the combined filtrates were concentrated under reduced pressure. The product was purified by decolorization with charcoal, flash chromatography (20% ethyl acetate/hexanes on silica gel), and recrystallization from aqueous ethanol to give a white powder (302.8 mg. 1.120 mmol, 45%), m.p. 83-89° C. (NA-1994A-271)

Workup

  1. concentrationThe mixture was concentrated under reduced pressure once effervescence
  2. additionwater (50 mL) was added
  3. extractionThe mixture was extracted three times with 25 mL portions of methylene chloride
  4. washThe combined organic extracts were washed with 50 mL of brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered through diatomaceous earth
  7. washThe residue was washed with 10 mL of methylene chloride
  8. concentrationthe combined filtrates were concentrated under reduced pressure
  9. customThe product was purified by decolorization with charcoal, flash chromatography (20% ethyl acetate/hexanes on silica gel), and recrystallization from aqueous ethanol
  10. customto give a white powder (302.8 mg. 1.120 mmol, 45%), m.p. 83-89° C. (NA-1994A-271)

Sources & evidence

ORD record
ord-22852159985a432e92e6378f4ffb02ea
Source dataset
uspto-grants-1999_08
Patent number
US05939570

Reaction notes

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