Oxalic Acid → 17-Difluoromethylene-estra-1,3,5(10),7-tetraen-3-ol

HRID 850833Notes

Reaction equation

HRID 850833 reaction equation
[F:1][C:2]([F:28])=[C:3]1[CH2:8][CH2:7][C@H:6]2[C:9]3[C@H:18]([CH2:19][CH2:20][C@:4]12[CH3:5])[C:17]1[CH:16]=[CH:15][C:14]([O:21]C2CCCCO2)=[CH:13][C:12]=1[CH2:11][CH:10]=3.C(O)(=O)C(O)=O>CO.O>[F:1][C:2]([F:28])=[C:3]1[CH2:8][CH2:7][C@H:6]2[C:9]3[C@H:18]([CH2:19][CH2:20][C@:4]12[CH3:5])[C:17]1[CH:16]=[CH:15][C:14]([OH:21])=[CH:13][C:12]=1[CH2:11][CH:10]=3

Participants

5

Reactant 2

HCID 971Oxalic AcidHCID 15307272HCID 15307272, compound

Product 1

HCID 1530727317-Difluoromethylene-estra-1,3,5(10),7-tetraen-3-olYield 80.7%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A suspension of 950 mg of 17-difluoromethylene-3-tetrahydropyranyloxy-estra-1,3,5(10),7-tetraene in 20 ml of methanol and 2.0 ml of water is refluxed with 950 mg of oxalic acid for 0.5 hour at a bath temperature of 100° C. Then, it is concentrated by evaporation in a vacuum diluted with ethyl acetate, washed with water, sodium bicarbonate solution as well as with saturated sodium chloride solution, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/ethyl acetate. 0.6 g of 17-difluoromethylene-estra-1,3,5(10),7-tetraen-3-ol is obtained as colorless crystals with a melting point of 126-129° C., [α]D22 =+163.7° (c=0.505% in pyridine)

Workup

  1. concentrationThen, it is concentrated by evaporation in a vacuum
  2. additiondiluted with ethyl acetate
  3. washwashed with water, sodium bicarbonate solution as well as with saturated sodium chloride solution
  4. customdried on sodium sulfate
  5. concentrationconcentrated by evaporation in a vacuum
  6. customchromatographed on silica gel with hexane/ethyl acetate

Sources & evidence

ORD record
ord-6a97ed94f7d24512a32218b268bb8e0d
Source dataset
uspto-grants-2000_01
Patent number
US06018062

Reaction notes

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