反应详情

温度

110 °C

In a 350-mL pressure-glass was added 4-bromo-2,6-difluorophenol (23.82 g, 0.11 mol), triethylamine (55 mL, 0.39 mol), ethyl acrylate (34.27 g, 0.34 mol), DMF (50 mL), palladium (II) acetate (1.29 g, 5.75 mmol), and followed by tri-o-tolyphosphine (2.34 g, 7.6 mmol) under N2. The mixture in the sealed glass was stirred at 110° C. overnight (21 hours), cooled to room temperature and added EtOAc (150 mL) and stirred for 30 minutes, filtered through celite and rinsed with EtOAc (3×100 mL). The filtrate was acidified with 2N HCl to pH ˜2. The organic layer was separated, and the aqueous layer was extracted with EtOAc (2×50 mL). The organic layers were combined and washed with water (2×100 mL), brine (100 mL) and dried over sodium sulfate. After filtration, heptane (200 mL) was added and the solution was concentrated in vacuo. The resulting precipitate was filtered, washed with heptane (2×50 mL) and dried to afford the desired product as a light-yellow solid. The mother liquor was concentrated in vacuo to obtain additional desired product (10) as a pale-yellow solid. 1H NMR (400 MHz, CDCl3) δ: 7.50 (d, J=15.9 Hz, 1H), 7.09 (d, J=8.3 Hz, 2H), 6.29 (d, J=15.9 Hz, 1H), 5.54 (br, 1H), 4.26 (q, J=7.1 Hz, 2H), 1.33 (t, J=7.1 Hz, 3H).

1. temperaturecooled to room temperature
2. stirringstirred for 30 minutes
3. filtrationfiltered through celite
4. washrinsed with EtOAc (3×100 mL)
5. customThe organic layer was separated
6. extractionthe aqueous layer was extracted with EtOAc (2×50 mL)
7. washwashed with water (2×100 mL), brine (100 mL)
8. dry with materialdried over sodium sulfate
9. filtrationAfter filtration, heptane (200 mL)
10. additionwas added
11. concentrationthe solution was concentrated in vacuo
12. filtrationThe resulting precipitate was filtered
13. washwashed with heptane (2×50 mL)
14. customdried