反应详情

温度

23 °C

A slurry of N-bromosuccinimide (167 g), 3-fluoro-4-nitrotoluene (135 g), 2,2′-azoisobutyronitrile (17.1 g) and 1,2-dichloroethane (1120 g) is stirred at 60° C. for 2 hours and then at 80° C. for 30 min. The reaction mixture is cooled to 23° C. and water (300 ml) is added. The phases are separated and the aqueous is washed with methylene chloride (300 ml). The combined organics are concentrated. Methanol (400 ml) is added and the mixture is cooled to −5° C. Morpholine (218 g) is added slowly while maintaining −5 to 14° C. While maintaining 6 to 14° C., 37% hydrochloric acid (113 ml) is added to adjust the observed pH from 8 to 6. Water (650 ml) and toluene (650 ml) are added and the mixture is warmed to 25° C. The phases are separated and the aqueous is washed with toluene (2×600 ml). To the combined organics is added water (400 ml) followed by 37% hydrochloric acid (53 g). The phases are separated and the organic is washed with water (500 ml). At room temperature, the pH of the combined aqueous is slowly adjusted to pH of 9 with 50% aqueous sodium hydroxide to yield a yellow slurry. The precipitate is collected by filtration, washed with water (200 ml) and is dried in a nitrogen stream to afford a yellow solid (104 g). Physical characteristics: 1H NMR (400 MHz, CDCl3) δ2.47, 3.56, 3.73, 7.27, 7.35, 8.02; 13C NMR (100 MHz, CDCl3) δ53.55, 61.99, 66.83, 118.08, 124.33, 126.01, 148.10, 155.64; MS (EI) m/z 240; Anal. Found: C, 54.84; H, 5.47; N, 11.62.

1. customThe phases are separated
2. washthe aqueous is washed with methylene chloride (300 ml)
3. concentrationThe combined organics are concentrated
4. additionMethanol (400 ml) is added
5. temperaturethe mixture is cooled to −5° C
6. additionMorpholine (218 g) is added slowly
7. temperaturewhile maintaining −5 to 14° C
8. temperatureWhile maintaining 6 to 14° C.
9. addition37% hydrochloric acid (113 ml) is added
10. additionWater (650 ml) and toluene (650 ml) are added
11. temperaturethe mixture is warmed to 25° C
12. customThe phases are separated
13. washthe aqueous is washed with toluene (2×600 ml)
14. additionTo the combined organics is added water (400 ml)
15. customThe phases are separated
16. washthe organic is washed with water (500 ml)
17. customAt room temperature
18. customto yield a yellow slurry
19. filtrationThe precipitate is collected by filtration
20. washwashed with water (200 ml)
21. customis dried in a nitrogen stream