反应详情

To the resulting nitroaniline (5.80 g, 23.7 mmol) was added concentrated hydrochloric acid (10 ml) with ice cooling and, with stirring, a solution of sodium nitrite (4.27 g, 61.9 mmol) in water (5 ml) was dropped into the resulting suspension during 10 minutes. The mixture was stirred for 1 hour in an ice bath, adjusted to pH, 7 with a saturated aqueous solution of sodium bicarbonate, then sodium thiomethoxide (2.00 g, 28.5 mmol) was added thereto, and the mixture was stirred for 5 minutes. This was stirred at 80° C. for 10 minutes more, the reaction solution was allowed to cool to room temperature, extracted with chloroform, the organic layer was washed with water and a saturated sodium chloride solution successively and dried over anhydrous sodium sulfate and the solvent was evaporated. The residue was purified by a silica gel column chromatography (150 g of silica gel; developing solvent, hexane:benzene=2:1) and the resulting crude crystals were recrystallized from ethyl acetate-hexane to provide 0.87 g (yield 19.8%) of 2-methylthio-6-nitrophenol as pale yellowish brown needles.

1. stirringThe mixture was stirred for 1 hour in an ice bath
2. stirringthe mixture was stirred for 5 minutes
3. stirringThis was stirred at 80° C. for 10 minutes more
4. extractionextracted with chloroform
5. washthe organic layer was washed with water
6. dry with materiala saturated sodium chloride solution successively and dried over anhydrous sodium sulfate
7. customthe solvent was evaporated
8. customThe residue was purified by a silica gel column chromatography (150 g of silica gel; developing solvent, hexane:benzene=2:1)
9. customthe resulting crude crystals were recrystallized from ethyl acetate-hexane