反应详情

The product has already been described in: V. M. Dziomko et al., Yakugaku Zasshi 1951, 71, 452-455; but using a different method of synthesis. Caesium carbonate (156 mg; 0.48 mmol), 8-bromoquinoline (32 μl; 50 mg; 0.24 mmol) and CuCl2.2H2O (4.1 mg; 0.024 mmol) are added to a solution under argon of 8-hydroxyquinoline (71 mg; 0.49 mmol) in 2.0 ml of dry DMF. The mixture is heated under reflux for 72 hours. After cooling, 5 ml of CH2Cl2 and 5 ml of a 0.12 M aqueous solution of EDTA disodium salt are added. The organic phase is recovered and the aqueous phase is subsequently extracted with CH2Cl2 (2×5 ml). The organic phases are combined and washed once with 5 ml of 0.12 M EDTA in H2O then in water. The volume is reduced under reduced pressure then the reaction crude product is purified by silica gel chromatography, eluted with a gradient of 50 to 100% of ethyl acetate in toluene (v/v) then with 100% of CH3OH and the solvent is evaporated to recover 15, from the methanol phase, in the form of a white powder (13 mg; 0.046 mmol, yield=19%). NMR-1H (250 MHz, CDCl3) δ, ppm: 8.95 (dd, 3J (H, H)=4.0 Hz, 4J (H, H)=1.5 Hz, 2H); 8.21 (dd, 3J (H, H)=8.5 Hz, 4J (H, H)=1.5 Hz, 2H); 7.61 (dd, 3J (H, H)=8.0 Hz, 4J (H, H)=1.0 Hz, 2H); 7.46 (dd, 3J (H, H)=4.0 Hz and 8.5 Hz, 2H); 7.42 (dd, 3J (H, H)=7.5 Hz and 8.0 Hz, 2H); 7.14 (dd, 3J (H, H)=7.5 Hz, 4J (H, H)=1.0 Hz, 2H). MS (CID, NH3): m/z=273 (MH+). UV/vis [CH3OH/20 mM Tris-HCl pH=7.4 containing 150 mM NaCl (1/1, v/v)]: λ nm (ε M−1 cm−1)=232 (53,300), 240 (42,900), 2994 (9,400), 327 (5,800, shoulder).

1. customa different method of synthesis
2. temperatureThe mixture is heated
3. temperatureunder reflux for 72 hours
4. temperatureAfter cooling
5. customThe organic phase is recovered
6. extractionthe aqueous phase is subsequently extracted with CH2Cl2 (2×5 ml)
7. washwashed once with 5 ml of 0.12 M EDTA in H2O
8. customthe reaction crude product
9. customis purified by silica gel chromatography
10. washeluted with a gradient of 50 to 100% of ethyl acetate in toluene (v/v)
11. customwith 100% of CH3OH and the solvent is evaporated
12. customto recover 15
13. additionUV/vis [CH3OH/20 mM Tris-HCl pH=7.4 containing 150 mM NaCl (1/1