反应详情

温度

0 °C

A suspension of 15.2 g (79.8 mmol) of copper iodide in 70 ml of dry tetrahydrofuran is cooled to 0° C., mixed with 28.7 g (330 mmol) of lithium bromide and 27.8 ml of DMPU, stirred first for 30 minutes at this temperature and then cooled to −30° C. While being stirred, 52 ml of methylmagnesium bromide in diethyl ether (3 molar solution) is then added in drops, stirred for another 30 minutes, and the gray-colored suspension is mixed with a solution that consists of 10.0 g (34.7 mmol) of 11β-fluoroestra-4,6-diene-3,17-dione, 24.3 ml of DMPU and 23 ml of trimethylsilyl chloride in 60 ml of dichloromethane. After the addition is completed, it is allowed to stir for another 1.5 hours between −30→−10° C., the cold bath is removed, and 35 ml of ethyl acetate is carefully added at room temperature while being stirred vigorously. For working-up, the reaction solution is diluted with ethyl acetate, washed with saturated aqueous ammonium chloride solution that is free of copper, and the organic phase is dried on sodium sulfate. The crude product is chromatographed on silica gel (hexane-ethyl acetate, gradient of up to 1:1), yield 3.1 g (30%).

1. temperaturecooled to −30° C
2. stirringWhile being stirred
3. stirringstirred for another 30 minutes
4. additionthe gray-colored suspension is mixed with a solution that
5. additionAfter the addition
6. stirringto stir for another 1.5 hours between −30→−10° C.
7. customthe cold bath is removed
8. addition35 ml of ethyl acetate is carefully added at room temperature
9. stirringwhile being stirred vigorously
10. additionthe reaction solution is diluted with ethyl acetate
11. washwashed with saturated aqueous ammonium chloride solution that
12. customthe organic phase is dried on sodium sulfate
13. customThe crude product is chromatographed on silica gel (hexane-ethyl acetate, gradient of up to 1:1), yield 3.1 g (30%)