反应详情

n-Butyllithium (10 ml of a 2.5M solution) and tetrahydrofuran (THF, 10 ml) were placed in a 250 ml 3-neck flask under nitrogen and chilled to -60° C. (dry ice/acetone). Acetonitrile (1 g) in tetrahydrofuran (10 ml) was added in one portion. A precipitate formed in a short time. Thirty minutes thereafter, a solution of 1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine (4.5 g) in tetrahydrofuran (20 ml) was added. The cold bath was then removed and the reaction mixture was stirred for 2 hours. The mixture was diluted with ethyl acetate (350 ml) and poured into saturated ammonium chloride solution (500 ml). The organic phase was separated and washed with brine (50%, 500 ml). The insolubles were collected by filtration. The ethyl acetate solution was dried over anhydrous sodium sulfate and concentrated to a solid. The solids were combined and purified by flash chromatography (silica, 80 g, eluted with dichloromethane) to afford 4.2 g of product. Recrystallization from a large volume of ethanol/isopropanol gave 2.48 g of crystalline product, m.p. 218°-220° C.

1. customA precipitate formed in a short time
2. customThe cold bath was then removed
3. additionThe mixture was diluted with ethyl acetate (350 ml)
4. additionpoured into saturated ammonium chloride solution (500 ml)
5. customThe organic phase was separated
6. washwashed with brine (50%, 500 ml)
7. filtrationThe insolubles were collected by filtration
8. dry with materialThe ethyl acetate solution was dried over anhydrous sodium sulfate
9. concentrationconcentrated to a solid
10. custompurified by flash chromatography (silica, 80 g, eluted with dichloromethane)