反应详情

1 g (5.2 mmol) of 5H-dibenz(b,f)azepine was suspended in 40 ml of dry ether and 9.7 ml (15.5 mmol) of a 1.6M solution of n-butyllithium in hexane was dropped thereinto under stirring at room temperature. After 24 hours, the reaction mixture was cooled in a dry ice-acetone bath and 2 ml of a solution of 0.93 g (7.8 mmol) of isobutyl nitrate in dry ether was dropped thereinto. After stirring at room temperature for 30 minutes, 2 ml of acetic acid was added thereto. Then the reaction mixture was poured into 50 ml of water and extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated. Then the residue was purified by silica gel column chromatography to thereby give 4-nitro-5H-dibenz(b,f)azepine. This product was dissolved in 50 ml of tetrahydrofuran and 1 g of zinc dust was added. Under stirring, conc. hydrochloric acid was dropped thereinto. When the reaction mixture turned from reddish brown into pale yellow, the addition was ceased and the formed insoluble matters were filtered off. The filtrate was made basic by adding diluted aqueous ammonia and then extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated and the residue was purified by silica gel column chromatography. Thus 45 mg of the title compound was obtained.

1. temperaturethe reaction mixture was cooled in a dry ice-acetone bath
2. stirringAfter stirring at room temperature for 30 minutes
3. extractionextracted with ethyl acetate
4. washThe organic layer was washed with water
5. dry with materialdried over magnesium sulfate
6. concentrationconcentrated
7. customThen the residue was purified by silica gel column chromatography to thereby give 4-nitro-5H-dibenz(b,f)azepine
8. dissolutionThis product was dissolved in 50 ml of tetrahydrofuran
9. addition1 g of zinc dust was added
10. stirringUnder stirring
11. additionconc. hydrochloric acid was dropped
12. additionthe addition
13. filtrationthe formed insoluble matters were filtered off
14. additionby adding diluted aqueous ammonia
15. extractionextracted with ethyl acetate
16. washThe organic layer was washed with water
17. dry with materialdried over magnesium sulfate
18. concentrationconcentrated
19. customthe residue was purified by silica gel column chromatography