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

HRID 369049Notes

Reaction equation

HRID 369049 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-0b193c8a4aeb42878e904e5455a9529b
Source dataset
uspto-grants-2000_10
Patent number
US06136800

Reaction notes

Loading…