Methane → Atamestane

HRID 259892

反応式

HRID 259892 の反応式
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

参加物

9

反応物 4

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

生成物 1

HCID 57050Atamestane収率 183.1%

試薬・触媒・溶媒 4

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olate触媒HCID 962Water溶媒HCID 6584Methyl Acetate溶媒HCID 8058Hexane溶媒

反応条件

温度
50 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-2ab5f6d35d9d4e0fa3429826d7c393c9
出典データセット
uspto-grants-1996_06
特許番号
US05523428

関連ノート

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