反应详情

To a solution of 2,4-difluorobenzaldehyde (2.27 g) in methylene chloride (6 mL) was added concentrated sulfuric acid (6 mL) under ice-cooling, and the mixture was stirred for 15 minutes. To the mixture was added fuming nitric acid (1 mL) under ice-cooling, and the mixture was stirred at the same temperature for 30 minutes. Then the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate. To the mixture was added water, and the organic layer was separated. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution twice, water and brine successively, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane−n-hexane/ethyl acetate=7/3) to give 2,4-difluoro-5-nitrobenzaldehyde (2.63 g). The obtained 2,4-difluoro-5-nitrobenzaldehyde (1 g) was dissolved in tetrahydrofuran (15 mL). To the solution was added sodium borohydride (0.3 g), and the mixture was stirred at room temperature for 5 minutes. To the reaction mixture was added 1 mol/L hydrochloric acid, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane −n-hexane/ethyl acetate=1/1) to give the title compound (0.76 g)

1. temperaturecooling
2. temperaturecooling
3. stirringthe mixture was stirred at the same temperature for 30 minutes
4. stirringThen the mixture was stirred at room temperature for 1 hour
5. customthe organic layer was separated
6. washThe organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution twice
7. dry with materialwater and brine successively, and dried over anhydrous magnesium sulfate
8. customThe solvent was removed under reduced pressure
9. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane−n-hexane/ethyl acetate=7/3)