Heterocycle type derivative and preparing method and pharmaceutical application thereof
A technology of heterocyclic groups and compounds, which is applied in the fields of heterocyclic derivatives and their preparation and their application in medicine, and can solve the problems of insufficient research and disclosure of anti-tumor tumors such as liver cancer
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Embodiment 1
[0182] N-(4-((3-(2,6-dichloro-3,5-dimethoxyphenyl)-1-(3-(dimethylamino)propyl)-2-oxo-1 , 2-dihydro-1,6-naphthyridin-7-yl)amino)tetrahydrofuran-3-yl)acrylamide
[0183]
[0184] first step
[0185] 6-Chloro-4-((3-(dimethylamino)propyl)amino)nicotinic acid ethyl ester
[0186] 4,6-Dichloronicotinic acid ethyl ester 1a (30.1g, 136.99mmol) and N 1 , N 1 Dimethylpropane-1,3-diamine 1b (18.95 mL, 150.46 mmol) was dissolved in 300 mL tetrahydrofuran, and reacted at 60°C for 2 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent: system A) to obtain 6-chloro-4-((3-(dimethylamino)propyl)amino)nicotinic acid Ethyl ester 1c (22.84 g, white solid), yield: 58.5%.
[0187] MS m / z(ESI): 286.0[M+1]
[0188] second step
[0189] (6-Chloro-4-((3-(dimethylamino)propyl)amino)pyridin-3-yl)methanol
[0190] Dissolve ethyl 6-chloro-4-((3-(dimethylamino)propyl)amino)nicotinate 1c (16.5g, 57.7...
Embodiment 2
[0218] N-(2-((3-(2,6-dichloro-3,5-dimethoxyphenyl)-1-(3-(dimethylamino)propyl)-2-oxo-1 , 2-dihydro-1,6-naphthyridin-7-yl)amino-3-fluorophenyl)acrylamide
[0219]
[0220]
[0221] first step
[0222] 3-(2,6-dichloro-3,5-dimethoxyphenyl)-1-(3-(dimethylamino)propyl)-7-((2-fluoro-6-nitrobenzene Base)amino)-1,6-naphthyridin-2(1H)-one
[0223] Under argon protection, 7-chloro-3-(2,6-dichloro-3,5-dimethoxyphenyl)-1-(3-(dimethylamino)propyl)-1,6 -Naphthyridin-2(1H)-one 1h (200mg, 0.425mmol), 2-fluoro-6-nitroaniline 2a (94mg, 0.467mmol), 4,5-bisdiphenylphosphine-9,9-bis Methyl xanthene (49 mg, 0.085 mmol), tris(dibenzylideneacetone) dipalladium (39 mg, 0.0425 mmol) and cesium carbonate (415 mg, 1.270 mmol) were dissolved in 10 mL of toluene, heated to 120 ° C for 4 hours . The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel thin layer chromatography (developing solvent: system C) to obtain 3-(2,6-dichloro-3,5-di...
Embodiment 3
[0243] N-(2-((3-(2,6-dichloro-3,5-dimethoxyphenyl)-1-(3-(dimethylamino)propyl)-2-oxo-1 , 2-dihydro-1,6-naphthyridin-7-yl)amino-5-morpholinylphenyl)acrylamide
[0244]
[0245]
[0246] first step
[0247] N-(4-Bromo-2-nitrophenyl)acetamide
[0248] 4-Bromo-2-nitroaniline 3a (30.3g, 138mmol) was dissolved in 240mL of acetic acid, acetic anhydride (22.44g, 220.2mmol) was added, and heated to 95°C for 7.5 hours. The reaction solution was cooled to room temperature and poured into 600mL of ice water. After the ice melted, it was extracted with dichloromethane (90mL×3). The solid was dissolved in 600mL of dichloromethane. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was decompressed. Concentration gave N-(4-bromo-2-nitrophenyl)acetamide 3b (35.4 g, orange solid), yield: 99.1%.
[0249] MS m / z(ESI): 258.8[M+1]
[0250] second step
[0251] N-(4-morpholino-2-nitrophenyl)acetamide
[0252] Under argon protection, N-(4-br...
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