反応 #347074

反応方程式

methane

trimethylaluminum

androsta-1,4-diene-3,17-dione

2,6-di-tert-butyl-4-methylphenol

→

crude product

収率 183.1%

1-Methyl-androsta-1,4 -diene-3,17-dione

収率 183.1%

溶媒

hexane

water

methyl acetate

反応条件

後処理

1. 1
   workup.STIRRINGThe solution is stirred for 30 more minutes
2. 2
   workup.STIRRINGThe solution is stirred for 50 more minutes at a temperature of 50° C
3. 3
   workup.ADDITIONis added
4. 4
   温度with cooling, for completion, it
5. 5
   workup.STIRRINGis stirred for 15 more minutes
6. 6
   ろ過The inorganic solid is filtered off
7. 7
   濃縮After concentration
8. 8
   その他by evaporation Of the methyl acetate phases

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.

出典