反应详情

A mixture prepared from 1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]-benzodiazepin-6-one (8.3 gm, 35 mmole) and sodium hydride (1.65 gm, 50% in oil, 1.0 eq) in dimethylformamide (DMF, 80 ml) was stirred at room temperature for 1.5 hours under N2. It was cooled to ~0° C. To this solution was charged propargyl bromide (16.5 gm, 80% in toluene, 3 eq) and the mixture was stirred for another 1.5 hours at 0° C. At the end of the reaction, the solution was poured into 10% NaOH (250 ml), and extracted with dichloromethane (DCM 1 l). The DCM solution was washed with NaOH (250 ml), water (2×300 ml) and brine (2×300 ml), then dried over MgSO4 and concentrated to an oil. Purification was accomplished by flash chromatography (SiO2 column, 200 gm, eluted with 1:1 hexane:DCM, 4 l). The material thus purified weighed 7.1 gm, (74%) as an oil. It turned to solid upon trituration with ether. A 3 gram portion of this material was recrystallized from ether (150 ml) to afford 1.9 gm of yellow crystals, m.p. 104°-105° C.

1. temperatureIt was cooled to ~0° C
2. stirringthe mixture was stirred for another 1.5 hours at 0° C
3. customAt the end of the reaction
4. extractionextracted with dichloromethane (DCM 1 l)
5. washThe DCM solution was washed with NaOH (250 ml), water (2×300 ml) and brine (2×300 ml)
6. dry with materialdried over MgSO4
7. concentrationconcentrated to an oil
8. customPurification
9. washwas accomplished by flash chromatography (SiO2 column, 200 gm, eluted with 1:1 hexane:DCM, 4 l)
10. customThe material thus purified
11. customA 3 gram portion of this material was recrystallized from ether (150 ml)