Water → Atamestane

HRID 259890

反応式

HRID 259890 の反応式
C[Al](C)C.[C:5](C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.[CH3:21][C@:22]12[CH2:39][CH2:38][C@H:37]3[C@@H:27]([CH2:28][CH2:29][C:30]4[C@:35]3([CH3:36])[CH:34]=[CH:33][C:32](=[O:40])[CH:31]=4)[C@@H:26]1[CH2:25][CH2:24][C:23]2=[O:41].O>CCCCCC.C(OCC)(=O)C.[Ni+2].C/C(/[O-])=C/C(C)=O>[CH3:5][C:34]1[C@@:35]2([CH3:36])[C:30]([CH2:29][CH2:28][C@@H:27]3[C@@H:37]2[CH2:38][CH2:39][C@@:22]2([CH3:21])[C@H:26]3[CH2:25][CH2:24][C:23]2=[O:41])=[CH:31][C:32](=[O:40])[CH:33]=1

参加物

8

反応物 4

HCID 962WaterHCID 13472Androsta-1,4-diene-3,17-dioneHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 16682925Trimethylaluminum

生成物 1

HCID 57050Atamestane収率 20.1%

試薬・触媒・溶媒 3

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olate触媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
58 °C

実験手順

12 ml (12 mmol) of trimethylaluminum of a 10% solution in hexane is introduced at room temperature under nitrogen atmosphere. With stirring, 2.64 g of 2,6-di-tert-butyl-4-methylphenol is added in portions. The solution is stirred for 30 more minutes and 2.84 g (10 mmol) of androsta-1,4-diene-3,17-dione in 20 ml of ethyl acetate is added at 25° C. The solution is heated to 58° C. At 58° C., 143 mg of nickel(II)-acetylacetonate is added. The solution is stirred for 2.5 more hours at a temperature of 60° C. After cooling, 1.1 ml of water is added for hydrolysis and stirred for 15 minutes. The inorganic solid is filtered off and rewashed twice with 50 ml of ethyl acetate. After concentration by evaporation of the ethyl acetate phases, a crude product is obtained, which is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion. 1.5 g of initial material is recovered. 0.60 g of 1-methyl-androsta-1,4-diene-3,17-dione of melting point 168°-170° C. is obtained. The yield is 20% of theory or 42% taking into consideration the initial material recovered.

後処理

  1. additionis added at 25° C
  2. stirringThe solution is stirred for 2.5 more hours at a temperature of 60° C
  3. temperatureAfter cooling
  4. stirringstirred for 15 minutes
  5. filtrationThe inorganic solid is filtered off
  6. concentrationAfter concentration
  7. customby evaporation of the ethyl acetate phases
  8. customa crude product is obtained
  9. customwhich is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion
  10. custom1.5 g of initial material is recovered

出典と根拠

ORDレコード
ord-06b8b65a39714bd68e070459dc430221
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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