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

HRID 369043Notes

Reaction equation

HRID 369043 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-211dbf26d58a421fb68a5a5085536f0b
Source dataset
uspto-grants-2000_10
Patent number
US06136800

Reaction notes

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