反应详情

(Csende, F et al. Synthesis, 1995, 1240-1242) 7.0 g (35 mmol) of 13 was dissolved in 30 ml of acetonitrile in a 250 ml single-necked round bottom flask. 11.3 g (84 mmol, 2.4 equiv) of anhydrous copper (H) chloride Was added to the solution and the reaction mixture was heated to reflux for 2 hours. To control the HCl gas that formed during the course of the reaction, a NaOH solution was used to absorb the HCl that escapes from dry tube. The reaction mixture was cooled to ambient temperature, and placed into an ice-water bath. 150 mL of ice-water was added to quench the reaction. The mixture was stirred vigorously for 10 minutes to give a gray precipitate and blue liquid containing copper (I) chloride. The precipitate was then collected by filtration (pH of the filtrate is 0-1) and washed first with 1N HCl (100 mL), then with Milli-Q water (5×100 mL). To remove remaining copper by-products, the filter cake was stirred in 1N HCl (150 mL) for 0.5 h and then filtered. The filter cake was washed with water until the filtrate is at pH 7 (approximately 7 washes). The solid was dried over a medium flit sintered glass funnel in vacuo to give 14 as a light gray powder in 93.8% yield, 1H NMR (DMSO-d6): δ 7.95 (s, 1H), 7.85 (d, J=7.5 Hz; 2H), 7.47 (m, 2H), 7.43 (m, 1H), 2.13 (s, 3H). HPLC (tr/purity): 21.48 min, >97%; ESI m/z (MeOH) 187.36 (MH+).

1. temperaturethe reaction mixture was heated
2. temperatureto reflux for 2 hours
3. customformed during the course of the reaction
4. customto absorb the HCl that escapes
5. customfrom dry tube
6. customplaced into an ice-water bath
7. addition150 mL of ice-water was added
8. customto quench
9. customthe reaction
10. customto give a gray precipitate and blue liquid
11. filtrationThe precipitate was then collected by filtration (pH of the filtrate
12. washwashed first with 1N HCl (100 mL)
13. customTo remove
14. stirringthe filter cake was stirred in 1N HCl (150 mL) for 0.5 h
15. filtrationfiltered
16. washThe filter cake was washed with water until the filtrate
17. customThe solid was dried over a medium flit sintered glass funnel in vacuo