Oxalic Acid → 17-Difluoromethylene-estra-1,3,5(10),6-tetraen-3-ol

HRID 850827Notes

Reaction equation

HRID 850827 reaction equation
[F:1][C:2]([F:28])=[C:3]1[CH2:8][CH2:7][C@H:6]2[C@H: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[CH: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@H: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[CH:11]=[CH:10]3

Participants

5

Reactant 2

HCID 971Oxalic AcidHCID 18397082HCID 18397082, compound

Product 1

HCID 988285117-Difluoromethylene-estra-1,3,5(10),6-tetraen-3-olYield 69.7%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

A suspension of 1.1 g of 17-difluoromethylene-3-tetrahydropyranyloxy-estra-1,3,5(10),6-tetraene in 25 ml of methanol and 2.5 ml of water is refluxed at a bath temperature of 100° C. with 1.1 mg of oxalic acid for 1.5 hours. Then, it is added to water, extracted with dichloromethane, 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),6-tetraen-3-ol is obtained as colorless crystals with a melting point of 132-134° C., [α]D22 =-167.9° (c=0.505% in. pyridine).

Workup

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

Sources & evidence

ORD record
ord-82477920614941bc955c0a1668f0bb41
Source dataset
uspto-grants-2000_01
Patent number
US06018062

Reaction notes

Loading…