反应详情

温度

0 °C

To a solution of 9-bromo-5-aminomethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione hydrochloride (300 mg, 0.866 mmol)in a 1:1 mixture of dichloromethane and DMF (10 mL)in the presence of triethylamine (0.3 mL, 2.16 mmol) was added ethyl chlorooxalate (0.102 mL, 0.909 mmol) at 0° C. The mixture was stirred for 15 min at 0° C. and for 10 h at room temperature and then water was added. The mixture was extracted with ethyl acetate. The aqueous layer was acidified with 1N hydrochloric acid to pH 1 and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, and concentrated. The residual solid was recrystallized from ethanol-ether to give 75 mg of the title compound (21%): mp 214.5~220.5° C.; 1H NMR (270 MHz, DMSO-d6) δ12.01 (s, 1H), 9.11 and 9.04 (two triplet, 1H, J=6 Hz), 7.19 (s, 1H), 7.14 (s, 1H), 4.98~5.07 (m, 1H), 4.21 (q, 2H, J=7.5 Hz), 3.17~3.57 (m, 2H), 3.01 (ddd, 1H, J=17.1, 13.5, 4.5 Hz), 2.79, (dm, 1H, J=17.1 Hz), 2.10 (dm, 1H, 13.5 Hz), 1.70~1.85 (m, 1H), 1.26 (t, 3H, J=7.5 Hz).

1. extractionThe mixture was extracted with ethyl acetate
2. extractionextracted with ethyl acetate
3. washThe combined organic layers were washed with brine
4. dry with materialdried over magnesium sulfate
5. concentrationconcentrated
6. customThe residual solid was recrystallized from ethanol-ether