Androsta-1,4-diene-3,17-dione → 1-Methyl-androsta-1,4-diene-3,17-dione-17-ethylene ketal

HRID 259893

반응식

HRID 259893 반응식
C[Al](C)C.C([C:9]1C=C(C)C=C(C(C)(C)C)[C:10]=1[OH:20])(C)(C)C.C[Al]C.[C:24](C1C=C(C)C=C(C(C)(C)C)C=1[O-])(C)(C)C.[CH3:40][C@:41]12[CH2:58][CH2:57][C@H:56]3[C@@H:46]([CH2:47][CH2:48][C:49]4[C@:54]3([CH3:55])[CH:53]=[CH:52][C:51](=[O:59])[CH:50]=4)[C@@H:45]1[CH2:44][CH2:43][C:42]2=[O:60]>CCCCCC.C(OCC)(=O)C.[Ni+2].C/C(/[O-])=C/C(C)=O.O>[CH2:10]1[O:20][C:51]2([CH:52]=[C:53]([CH3:24])[C@@:54]3([CH3:55])[C:49]([CH2:48][CH2:47][C@@H:46]4[C@@H:56]3[CH2:57][CH2:58][C@@:41]3([CH3:40])[C@H:45]4[CH2:44][CH2:43][C:42]3=[O:60])=[CH:50]2)[O:59][CH2:9]1

참가 물질

9

반응물 4

HCID 13472Androsta-1,4-diene-3,17-dioneHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 16682925TrimethylaluminumHCID 86749536Dimethylaluminum 2,6-di-tert-butyl-4-methylphenoxide

생성물 1

HCID 676856741-Methyl-androsta-1,4-diene-3,17-dione-17-ethylene ketal

시약·촉매·용매 4

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olate촉매HCID 962Water용매HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

실험 절차

32.22 (mmol) of a 10% solution of trimethylaluminum in hexane is introduced at room temperature under nitrogen atmosphere. With stirring, 6.6 g (30 mmol)-of 2,6-di-tert-butyl-4-methylphenol is added in portions. The solution is stirred for 30 more minutes at 35° C. This thus produced solution of dimethylaluminum-2,6-di-tert-butyl-4-methylphenoxide is added at 58° C. to a solution of 9.84 g (30 mmol) of androsta-1,4-diene-3,17-dione (ADD) and 430 mg (1.5 mmol) of nickel(II)-acetylacetonate in 60 ml of ethyl acetate (acetic acid-ethyl ester). The solution is stirred for 4 more hours at a temperature of 60° C. For hydrolysis, 5 ml of water is added with cooling. The inorganic solid is filtered off and rewashed twice with 20 ml of ethyl acetate. After concentration by evaporation of the ethyl acetate phases, 17 g of crude,material 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, 12.9 g of 1-methyl-androsta-1,4-diene-3,17-dione-17-ethylene ketal (28% of theory) of melting point 159° C. is obtained.

후처리

  1. stirringThe solution is stirred for 30 more minutes at 35° C
  2. stirringThe solution is stirred for 4 more hours at a temperature of 60° C
  3. additionis added
  4. temperaturewith cooling
  5. filtrationThe inorganic solid is filtered off
  6. concentrationAfter concentration
  7. customby evaporation of the ethyl acetate phases, 17 g of crude,material
  8. customis obtained
  9. customwhich is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion
  10. concentrationAfter concentration
  11. customby evaporation of the fractions, 12.9 g of 1-methyl-androsta-1,4-diene-3,17-dione-17-ethylene ketal (28% of theory) of melting point 159° C.
  12. customis obtained

출처 및 근거

ORD 기록
ord-1d06bafb8b36494b90e69c546821e4f7
출처 데이터셋
uspto-grants-1996_06
특허 번호
US05523428

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