反应详情

To 9.0 mL (135 mmol, Fisher) of chlorosulfonic acid was added dropwise with stirring at room temperature 5.00 g (35.0 mmol, Lancaster) of 3-methyl-quinoline over ~5 minutes. The addition was exothermic. The resulting dark solution was heated to 140°-145°, stirring for 5 h, then cooled to 125°. To the cooled reaction mixture was added dropwise over 15 rain 3.3 mL (45 mmol, Mallinckrodt) of thionyl chloride, and the reaction mixture was then heated to 1400 for 1 h. The reaction mixture was cooled to room temperature, then cooled in an ice-bath and added slowly to 50 g of ice. Chloroform (50 mL) was added to the resulting slurry and stirred until the ice melted to give two layers. The aqueous layer was separated and extracted with 30 mL of chloroform. The chloroform layers were combined, washed with two-50 mL portions of 5% aqueous sodium bicarbonate solution, 50 mL of water, dried (sodium sulfate) and concentrated in vacuo to give 4.6 g of a crude light brown solid. The crude material was recrystallized (~20 mL toluene), and the crystals were washed with hexane and dried in vacuo to afford 2.89 g (12.0 mmol, 34%) of title compound as small pale brown crystals, mp 158°-159°.

1. additionThe addition
2. temperatureThe resulting dark solution was heated to 140°-145°
3. temperaturecooled to 125°
4. customTo the cooled reaction mixture
5. temperaturethe reaction mixture was then heated to 1400 for 1 h
6. temperaturecooled in an ice-bath
7. customto give two layers
8. customThe aqueous layer was separated
9. extractionextracted with 30 mL of chloroform
10. washwashed with two-50 mL portions of 5% aqueous sodium bicarbonate solution, 50 mL of water
11. dry with materialdried (sodium sulfate)
12. concentrationconcentrated in vacuo
13. customto give 4.6 g of a crude light brown solid
14. customThe crude material was recrystallized (~20 mL toluene)
15. washthe crystals were washed with hexane
16. customdried in vacuo