反应详情

A mixture of 23.2 g (0.955 mol) of magnesium and 50 mg of iodine in 200 ml of ether was stirred while a solution of 167 g (0.954 mol) of 4-bromofluorobenzene in 600 ml of ether was added at a rate that maintained gentle reflux. After another 2 hours at reflux, the solution was cooled in ice and stirred while a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, chilled in ice, treated with 24 ml of isopropanol), stirred another 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes was added, the resulting slurry was filtered, and the hexanes filtrate was evaporated to leave an oil. Analysis by nmr showed the presence of unreacted chlorosilane, so the oil was dissolved in hexanes containing 30 ml of isopropanol, and the solution was chilled in ice and treated with a solution of 42 ml (0.30 mol) of triethylamine in hexanes. The resulting slurry was stirred at room temperature for 3 hours and filtered, and the filtrate was evaporated to leave an oil. Distillation provided 44.8 g (43%) of the title compound as a colorless liquid: bp 120°-140° (0.1 mm); nD22 1.5211; nmr (CDCl3) 1.2 (6H, d), 3.2 (2H, s), 4.1 (1H, septet), 7.1 (4H, t), 7.7 (4H, d of d).

1. additionwas added at a rate that
2. temperaturemaintained gentle reflux
3. temperatureAfter another 2 hours at reflux
4. temperaturethe solution was cooled in ice
5. additionwas added dropwise over 40 minutes
6. temperaturechilled in ice
7. stirringstirred another 10 minutes
8. filtrationfiltered
9. concentrationThe filtrate was concentrated to a gummy solid, hexanes
10. additionwas added
11. filtrationthe resulting slurry was filtered
12. customthe hexanes filtrate was evaporated
13. customto leave an oil
14. temperaturethe solution was chilled in ice
15. stirringThe resulting slurry was stirred at room temperature for 3 hours
16. filtrationfiltered
17. customthe filtrate was evaporated
18. customto leave an oil
19. distillationDistillation