反应详情

温度

50 °C

To concentrated hydrochloric acid (30 mL) was added 4-chloro-3-nitroaniline (5.18 g) under ice-cooling, and the mixture was stirred at the same temperature for 5 minutes. To the mixture was added a solution of sodium nitrite (3.1 g) in water (30 mL). The mixture was heated to 50° C. To the mixture was added a solution of potassium O-ethyl dithiocarbonate (14.4 g) in water (60 mL), and the mixture was stirred at 50° C. for 1 hour. The reaction mixture was cooled to room temperature, and the mixture was extracted with diethyl ether twice. The extracts were combined and washed with 1 mol/L aqueous sodium hydroxide solution, 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 O-ethyl S-(4-chloro-3-nitrophenyl) dithiocarbonate (2.96 g). This material was dissolved in tetrahydrofuran (50 mL). The solution was added to a suspension of lithium aluminum hydride (1.62 g) in tetrahydrofuran (50 mL) under ice-cooling, and the mixture was stirred at room temperature for 10 minutes. The reaction mixture was cooled in ice. To the mixture were added water (1.8 mL), 15% aqueous sodium hydroxide solution (1.8 mL) and water (5.4 mL), and the mixture was stirred at room temperature for 30 minutes. The insoluble material was removed by filtration, and the filtrate was diluted with ethyl acetate. The resulting mixture was washed with 1 mol/L hydrochloric acid, 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/ethyl acetate=9/1−1/9) to give the title compound (1.28 g).

1. temperaturecooling
2. stirringthe mixture was stirred at 50° C. for 1 hour
3. temperatureThe reaction mixture was cooled to room temperature
4. extractionthe mixture was extracted with diethyl ether twice
5. washwashed with 1 mol/L aqueous sodium hydroxide solution, water and brine successively
6. dry with materialdried over anhydrous magnesium sulfate
7. customThe solvent was removed under reduced pressure
8. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane−n-hexane/ethyl acetate=7/3)