Ammonium Chloride → N-butyl-2,2'-imino-bis(8-nitroquinoline)

Participants

Reaction Steps

2-chloro-8-nitroquinoline (122 mg; 0.59 mmol) and NaOtBu (77.5 mg; 0.81 mmol) are added to a violet suspension of N-butyl-8-nitro-2-quinoline amine (0.17 g; 0.69 mmol), tris(dibenzylidene-acetone)-dipalladium(0) (13 mg; 0.014 mmol) and rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (17 mg; 0.027 mmol) in 5 ml of toluene under argon. The medium is heated under reflux for 3 hours, then 2-chloro-8-nitroquinoline (22 mg; 0.11 mmol) is again added. Heating is continued for 2 hours 30 minutes then 10 ml of a saturated ammonium chloride solution are added. The product is extracted with 3×30 ml of CH2Cl2 and the solvent is evaporated under reduced pressure. The product is purified by silica gel chromatography, eluted with CH2Cl2/hexane (80/20, v/v) to yield N-butyl-2,2′-imino-bis(8-nitroquinoline) in the form of a yellow powder (0.11 g; 0.26 mmol, yield=38%). NMR-1H (250 MHz, CDCl3) δ, ppm: 8.14 (d, 3J (H, H)=9.0 Hz, 2H); 7.99 (dd, 3J (H, H)=7.5 Hz, 4J (H, H)=1.5 Hz, 2H); 7.93 (dd, 3J (H, H)=8.0 Hz, 4J (H, H)=1.5 Hz, 2H); 7.73 (d, 3J (H, H)=9.0 Hz, 2H); 7.43 (m, 2H); 4.45 (t, 3J (H, H)=7.5 Hz, 2H); 1.83 (m, 2H); 1.47 (m, 2H); 0.98 (t, 3J (H, H)=7.5 Hz, 3H). NMR-13C (63 MHz, CDCl3) δ, ppm: 156.2 (Cq); 146.4 (Cq); 138.7 (Cq); 137.0 (CH); 131.5 (CH); 126.2 (Cq); 124.2 (CH); 122.8 (CH); 117.3 (CH); 48.9 (CH2); 30.4 (CH2); 20.3 (CH2); 13.9 (CH3). MS (CID, NH3): m/z=418 (MH+). Analysis (%) for C22H19N5O4: calculated C, 63.30. H, 4.59. N, 16.78. found C, 63.18. H, 4.49. N, 16.39. 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)=210 (91,400), 226 (53,500, shoulder), 270 (42,100), 294 (26,700, shoulder), 383 (28,400).

Provenance & Evidence