反应详情

A solution of sodium sulfite (3.31 g, 47.94 mmol) in water (5 ml) was added dropwise to a mixture of 3-amino-6,7,8,9-tetrahydro-5H-benzocyclohepten-5-one (8.00 g, 45.65 mmol) and 35% hydrochloric acid (20 ml) under ice-cooling and stirred under ice-cooling for 20 minutes. Sodium acetate trihydrate (33 g) was added to the reaction mixture and the resulting mixture was added dropwise to a 15% aqueous sodium thiomethoxide solution (42.67 g, 91.31 mmol). The reaction mixture was stirred at 80° C. for 1.5 hours, adjusted to pH 9 with an aqueous sodium hydroxide solution and then extracted with ethyl acetate. The extract solution was washed with water and a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was purified by a silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/30) to obtain 4.33 g of 3-methylthio-6,7,8,9-tetrahydro-5H-benzocyclohepten-5-one.

1. temperaturecooling
2. temperaturecooling for 20 minutes
3. stirringThe reaction mixture was stirred at 80° C. for 1.5 hours
4. extractionextracted with ethyl acetate
5. washThe extract solution was washed with water
6. dry with materiala saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate
7. distillationThe solvent was distilled off under reduced pressure
8. customthe resulting residue was purified by a silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/30)