Water → Atamestane

HRID 259890

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HRID 259890 반응식
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

참가 물질

8

반응물 4

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

생성물 1

HCID 57050Atamestane수율 20.1%

시약·촉매·용매 3

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olate촉매HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

반응 조건

온도
58 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-06b8b65a39714bd68e070459dc430221
출처 데이터셋
uspto-grants-1996_06
특허 번호
US05523428

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