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Sulfuric Acid → 17-Difluoromethylene-18-methyl-estra-1,3,5(10)-trien-3-ol

HRID 369065
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 369065
[F:1][C:2]([F:24])=[C:3]1[CH2:9][CH2:8][C@H:7]2[C@H:10]3[C@H:19]([CH2:20][CH2:21][C@:4]12[CH2:5][CH3:6])[C:18]1[CH:17]=[CH:16][C:15]([O:22]C)=[CH:14][C:13]=1[CH2:12][CH2:11]3.[H-].C([Al+]CC(C)C)C(C)C.S(=O)(=O)(O)O>C1(C)C=CC=CC=1>[F:1][C:2]([F:24])=[C:3]1[CH2:9][CH2:8][C@H:7]2[C@H:10]3[C@H:19]([CH2:20][CH2:21][C@:4]12[CH2:5][CH3:6])[C:18]1[CH:17]=[CH:16][C:15]([OH:22])=[CH:14][C:13]=1[CH2:12][CH2:11]3
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 3

HCID 1118Sulfuric AcidHCID 21225700DiisobutylaluminumhydrideHCID 7019755717-Difluoromethylene-3-methoxy-18-methyl-estra-1,3,5(10)-triene

Produkt 1

HCID 7020076817-Difluoromethylene-18-methyl-estra-1,3,5(10)-trien-3-olAusbeute 94 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140Toluene
Lösungsmittel
2×

Versuchsvorschrift

A solution of 5 g of 17-difluoromethylene-3-methoxy-18-methyl-estra-1,3,5(10)-triene in 95 ml of toluene is refluxed with 95 ml of a 1.6 M diisobutylaluminum hydride solution in toluene for 3 hours at a bath temperature of 140° C. Then, it is cooled to room temperature, slowly added to 200 g of ice, mixed with 400 ml of 1 M sulfuric acid, stirred for 1 hour at room temperature, extracted three times with ethyl acetate, the organic phases are washed with water 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. 4.5 g of 17-difluoromethylene-18-methyl-estra-1,3,5(10)-trien-3-ol is obtained as colorless crystals with a melting point of 120-121° C., [α]D22 =+37.8° (c=0.5% in pyridine).

Aufarbeitung

  1. extractionextracted three times with ethyl acetate
  2. washthe organic phases are washed with water 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

Quellen und Nachweise

ORD-Eintrag
ord-e0ce40836abd429e8607a4f626dcb743
Quelldatensatz
uspto-grants-2000_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06136800

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