30% |
|
Phthalhydrazide (1b) (10g, 61.7 mmol) was dissolved in dried N,N-dimethylformamide (100 mL) in a round-bottom flask. Sodium hydride (1.63g, 67.9 mmol) was added at 0C, and then stirred for half an hour. Ethyl 3-chloromethylbenzoate (1c, purchased from Shanghai Shaoyuan Co. Ltd.) (13.49g, 67.9 mmol) dissolved in N,N-dimethylformamide (20 mL) solution was added slowly dropwise at room temperature and reacted for 24 hours, and then ethyl acetate was added. The reaction solution was successively washed with 50 mL saturated sodium bicarbonate and saturated sodium chloride solution for three times, the organic layer was dried and concentrated. Column chromatography was performed for the crude product (petroleum ether : ethyl acetate = 10:1) to give ethyl 3-(((4-oxo-3-1,4-dihydrophthalazin -1-yl)oxy)methyl)benzoate (1d), 6 g white solid (yield 30%). 1H NMR (600 MHz, DMSO-d6): delta 11.94 (s, 1H), 8.24 (d, 1H, J = 7.50 Hz), 7.97-7.95 (m, 1H),7.93-7.87 (m, 3H), 7.85-7.83 (m, 1H), 7.57-7.56 (m, 1H), 7.48-7.45 (m, 1H), 5.23 (s, 2H), 4.29-4.25 (m, 2H), 1.28-1.25 (m, 3H); ESI-MS m/z: calculated for 324.1, found 346.9 [M+Na]+. |
30% |
|
Phthalhydrazide (1b) (10 g, 61.7 mmol) was dissolved in dried N,N-dimethylformamide (100 mL) in a round-bottom flask. Sodium hydride (1.63 g, 67.9 mmol) was added at 0 C., and then stirred for half an hour. Ethyl 3-chloromethylbenzoate (1c, purchased from Shanghai Shaoyuan Co. Ltd.) (13.49 g, 67.9 mmol) dissolved in N,N-dimethylformamide (20 mL) solution was added slowly dropwise at room temperature and reacted for 24 hours, and then ethyl acetate was added. The reaction solution was successively washed with 50 mL saturated sodium bicarbonate and saturated sodium chloride solution for three times, the organic layer was dried and concentrated. Column chromatography was performed for the crude product (petroleum ether:ethyl acetate=10:1) to give ethyl 3-(((4-oxo-3-1,4-dihydrophthalazin-1-yl)oxy)methyl)benzoate (1d), 6 g white solid (yield 30%). 1H NMR (600 MHz, DMSO-d6): delta 11.94 (s, 1H), 8.24 (d, 1H, J=7.50 Hz), 7.97-7.95 (m, 1H), 7.93-7.87 (m, 3H), 7.85-7.83 (m, 1H), 7.57-7.56 (m, 1H), 7.48-7.45 (m, 1H), 5.23 (s, 2H), 4.29-4.25 (m, 2H), 1.28-1.25 (m, 3H); ESI-MS m/z: calculated for 324.1. found 346.9 [M+Na]+. |