反应详情

A 2-liter flask was charged with 100 g (0.348 mol) of 4-amino-3-iodobenzotrifluoride, 40 g of CuCN and 750 mL of DMF. The mixture was heated to and then maintained at reflux for 1 hour. The reaction was cooled and poured into 3 L of water containing 300 mL of concentrated ammonium hydroxide. To the mixture was added 1 L CH2Cl2. The mixture was then filtered through Celite. The layers were separated and the aqueous layer was back extracted with CH2Cl2. The organic extracts were combined and the solvent removed under reduced pressure. The residue was dissolved in 1.5 L of ether and the resulting solution was washed with 1N ammonium hydroxide, aqueous sodium bisulfite, 1N aqueous HCl and brine. The solution was dried over anhydrous MgSO4 and filtered through a silica gel plug containing a layer of MgSO4 on top. The plug was washed with 0.5 L ether. The ether solutions were combined and concentrated to 750 mL and let stand at room temperature. After 2 days the resulting solids were collected, washed with hexanes and dried under reduced pressure to afford 2-amino-5-(trifluoromethyl)benzonitrile. 1H NMR (CDCl3, 500 MHz) δ 7.68 (s, 1H), 7.58 (d, J=8.5 Hz, 1H), 6.81 (d, J=8.5 Hz, 1H), 4.80 (br s, 2H).

1. temperatureThe mixture was heated to and
2. temperaturethen maintained
3. temperatureat reflux for 1 hour
4. temperatureThe reaction was cooled
5. filtrationThe mixture was then filtered through Celite
6. customThe layers were separated
7. extractionthe aqueous layer was back extracted with CH2Cl2
8. customthe solvent removed under reduced pressure
9. dissolutionThe residue was dissolved in 1.5 L of ether
10. washthe resulting solution was washed with 1N ammonium hydroxide, aqueous sodium bisulfite, 1N aqueous HCl and brine
11. dry with materialThe solution was dried over anhydrous MgSO4
12. filtrationfiltered through a silica gel plug
13. additioncontaining a layer of MgSO4 on top
14. washThe plug was washed with 0.5 L ether
15. concentrationconcentrated to 750 mL
16. customlet stand at room temperature
17. customAfter 2 days the resulting solids were collected
18. washwashed with hexanes
19. customdried under reduced pressure