Sulfuric Acid → (3beta,5beta,15alpha,16alpha)-15,16-Dihydro-3,5-dihydroxy-3'H-cycloprop(15,16)androsta-6,15-dien-17-one

HRID 391170

Reaktionsgleichung

Reaktionsgleichung von HRID 391170
[OH:1][C@@:2]12[CH2:19][C@@H:18]([O:20]C(=O)C(C)(C)C)[CH2:17][CH2:16][C@:15]1([CH3:27])[C@@H:14]1[C@H:5]([C@H:6]3[C@@:10]([CH2:12][CH2:13]1)([CH3:11])[C:9](=[O:28])[C@H:8]1[CH2:29][C@@H:7]31)[CH:4]=[CH:3]2.[OH-].[K+].O.Cl([O-])(=O)(=O)=O.[Na+].S(=O)(=O)(O)O>O1CCCC1.CO.O>[OH:20][C@H:18]1[CH2:17][CH2:16][C@@:15]2([CH3:27])[C@:2]([OH:1])([CH:3]=[CH:4][C@@H:5]3[C@@H:14]2[CH2:13][CH2:12][C@@:10]2([CH3:11])[C@H:6]3[C@@H:7]3[CH2:29][C@@H:8]3[C:9]2=[O:28])[CH2:19]1

Komponenten

8

Edukt 4

HCID 1118Sulfuric AcidHCID 14797Potassium HydroxideHCID 516899Sodium perchlorate monohydrateHCID 130759725-Hydroxy-15 beta,16 beta-methylene-3 beta-pivaloyloxy-5 beta-androst-6-en-17-one

Produkt 1

HCID 13075974(3beta,5beta,15alpha,16alpha)-15,16-Dihydro-3,5-dihydroxy-3'H-cycloprop(15,16)androsta-6,15-dien-17-one

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
1 °C

Versuchsvorschrift

5-Hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androst-6-en-17-one (80.00 g, 0.200 mol) is suspended under nitrogen in tetrahydrofuran (800 mL), mechanically stirred and cooled to 0-2° C. A solution of potassium hydroxide (85%, 27.69 g, 0.419 mol) in methanol (410 mL) is added dropwise below 5° C. followed by sodium perchlorate monohydrate (7.85 g, 0.056 mol). The mixture is stirred at room temperature for 3-4 hours. After cooling to 4-5° C., water (400 mL) is added followed by 20% sulfuric acid in water (90 mL) adjusting the pH to 7 and the mixture is stirred for 10-15 minutes. Tetrahydrofuran and methanol are then removed at 40° C. under reduced pressure and the residue is diluted with water (300 mL). The suspension is stirred at 5° C. for 30 minutes and the solid is filtered, washed with water and dried at 45° C. in a vacuum oven for 16 hours. The title compound is obtained as a colourless solid (61.00 g, 0.192 mol, 97%) and is used in the next step without purification.

Aufarbeitung

  1. stirringThe mixture is stirred at room temperature for 3-4 hours
  2. temperatureAfter cooling to 4-5° C.
  3. stirringthe mixture is stirred for 10-15 minutes
  4. customTetrahydrofuran and methanol are then removed at 40° C. under reduced pressure
  5. additionthe residue is diluted with water (300 mL)
  6. stirringThe suspension is stirred at 5° C. for 30 minutes
  7. filtrationthe solid is filtered
  8. washwashed with water
  9. customdried at 45° C. in a vacuum oven for 16 hours

Quellen und Nachweise

ORD-Eintrag
ord-9755c0cba9164bec9e611d126fa0aa0c
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08383809B2

Verknüpfte Notizen

Wird geladen…