A class of kinase inhibitors
A compound and pharmaceutical technology, applied in the field of aminopyrimidine ring derivatives and their pharmaceutically acceptable salts, can solve problems such as dose-dependent toxicity
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Embodiment 1
[0227] N-(2-((2-(dimethylamino)ethyl)(methyl)amino)-6-methoxy-5-(4-(1-methyl-1H-indole-3- Base) pyrimidin-2-ylamino) pyridin-3-yl) acrylamide (1)
[0228] 6-Chloro-2-methoxy-3-nitropyridine (1a)
[0229] To a solution of 2,6-dichloro-3-nitropyridine (5.79g, 30.0mmol) in dry tetrahydrofuran (30mL), add methanol (1.15mL, 28.5mmol) at 0°C, and then add hydrogenation in 4 batches Sodium (60%, 1.20 g, 30.0 mmol). After stirring at 0° C. for 1 h, it was stirred at room temperature for 1 h. The mixture was diluted with water (50 mL) and extracted with ethyl acetate (2×30 mL). The extract was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated to dryness, and the residue was recrystallized from n-hexane to obtain 6-chloro-2-methoxy-3-nitropyridine (1a) as a pale yellow solid (4.04 g, 71%).
[0230] N 1 -(6-methoxy-5-nitropyridin-2-yl)-N 1 ,N 2 ,N 2 -Trimethylethane-1,2-diamine (1b)
[0231] 6-Chloro-2-methoxy-3-nitropyridine (1a...
Embodiment 2
[0245] N-(6-methoxy-2-(methyl(2-(methylamino)ethyl)amino)-5-((4-(1-methyl-1H-indole-3- Base) pyrimidin-2-yl) amino) pyridin-3-yl) acrylamide (2)
[0246] tert-butyl 2-((6-methoxy-5-nitropyridin-2-yl)(methyl)amino)ethyl(methyl)carbamate (2b)
[0247] 1a (4.00g, 21.3mmol) and tert-butylmethyl (2-(methylamino) ethyl) carbamate (2a, 4.38g, 22.3mmol) (prepared according to literature, J.Med.Chem., 1992, 35,565) in ethanol (47 mL) was heated to reflux for 3 h, the solvent was evaporated to dryness under reduced pressure, and the residue was purified by silica gel column chromatography with 15-30% ethyl acetate / n-hexane as the eluent to obtain tert-butyl 2-(( 6-Methoxy-5-nitropyridin-2-yl)(methyl)amino)ethyl(methyl)carbamate (2b) (4.65 g, 63%) as a yellow solid. MS-ESI(m / z):341[M+1] + .
[0248] tert-butyl 2-((3-bromo-6-methoxy-5-nitropyridin-2-yl)(methyl)amino)ethyl(methyl)carbamate Esters (2c)
[0249] At 0 ° C, to tert-butyl 2-((6-methoxy-5-nitropyridin-2-yl) (methy...
Embodiment 3
[0261] N-(2-((2-(Ethyl(methyl)amino)ethyl)(methyl)amino)-6-methoxy-5-((4-(1-methyl-1H- Indol-3-yl)pyrimidin-2-yl)amino)pyridin-3-yl)acrylamide (3)
[0262] At room temperature, in N-(6-methoxy-2-(methyl(2-(methylamino)ethyl)amino)-5-((4-(1-methyl-1H-indole-3 -yl)pyrimidin-2-yl)amino)pyridin-3-yl)acrylamide (2) (15.4mg, 0.0317mmol) in 1,2-dichloroethane (1mL) solution was added acetaldehyde (water content 40 %, 9.0mg, 0.082mmol) and sodium triacetoxyborohydride (8.7mg, 0.041mmol), the mixture was stirred at room temperature for 1h, diluted with saturated aqueous sodium bicarbonate (5mL), extracted with dichloromethane (2×5mL ), the extract was dried over sodium sulfate, the solvent was evaporated to dryness under reduced pressure, the residue was purified by silica gel column chromatography, and the eluent was dichloromethane / methanol / ammonia (95:4:1), to obtain N-(2-( (2-(Ethyl(methyl)amino)ethyl)(methyl)amino)-6-methoxy-5-((4-(1-methyl-1H-indol-3-yl)pyrimidine -2-yl)ami...
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