Methane → Atamestane

HRID 259892

Reaktionsgleichung

Reaktionsgleichung von HRID 259892
C[Al](C)C.[C:5](C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.C.[CH3:22][C@:23]12[CH2:40][CH2:39][C@H:38]3[C@@H:28]([CH2:29][CH2:30][C:31]4[C@:36]3([CH3:37])[CH:35]=[CH:34][C:33](=[O:41])[CH:32]=4)[C@@H:27]1[CH2:26][CH2:25][C:24]2=[O:42]>CCCCCC.C(OC)(=O)C.[Ni+2].C/C(/[O-])=C/C(C)=O.O>[CH3:5][C:35]1[C@@:36]2([CH3:37])[C:31]([CH2:30][CH2:29][C@@H:28]3[C@@H:38]2[CH2:39][CH2:40][C@@:23]2([CH3:22])[C@H:27]3[CH2:26][CH2:25][C:24]2=[O:42])=[CH:32][C:33](=[O:41])[CH:34]=1

Komponenten

9

Edukt 4

HCID 297MethaneHCID 13472Androsta-1,4-diene-3,17-dioneHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 16682925Trimethylaluminum

Produkt 1

HCID 57050AtamestaneAusbeute 183,1 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olateKatalysatorHCID 962WaterLösungsmittelHCID 6584Methyl AcetateLösungsmittelHCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

86.4 ml (80 mmol) of a 10% solution of trimethylaluminum in hexane is introduced at room temperature under nitrogen atmosphere. With stirring, 17.4 g (80 mmol) of 2,6-di-tert-butyl-4-methylphenol is added in portions. The solution is stirred for 30 more minutes and subsequently stirred until the end of the methane generation. 28.4 g (100 mmol) of androsta-1,4-diene-3,17-dione (ADD) in 200 ml of methyl acetate is added at 25° C. The solution is heated to 50° C. 1.43 g (5 mmol) of nickel(II)-acetylacetonate is added at 50° C. The solution is stirred for 50 more minutes at a temperature of 50° C. For hydrolysis, 15 ml of water is added with cooling, for completion, it is stirred for 15 more minutes. The inorganic solid is filtered off and rewashed twice with 50 ml of methyl acetate. After concentration by evaporation Of the methyl acetate phases, 43.71 g of crude product is obtained, which is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion. After concentration by evaporation of the fractions, 6.5 g of 1-methyl-androsta-1,4-diene-3,17-dione (23% of theory) of melting point 168° C. is obtained.

Aufarbeitung

  1. stirringThe solution is stirred for 30 more minutes
  2. stirringThe solution is stirred for 50 more minutes at a temperature of 50° C
  3. additionis added
  4. temperaturewith cooling, for completion, it
  5. stirringis stirred for 15 more minutes
  6. filtrationThe inorganic solid is filtered off
  7. concentrationAfter concentration
  8. customby evaporation Of the methyl acetate phases

Quellen und Nachweise

ORD-Eintrag
ord-2ab5f6d35d9d4e0fa3429826d7c393c9
Quelldatensatz
uspto-grants-1996_06
Patentnummer
US05523428

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