反应详情

温度

58 °C

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.

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