Fused pyridones as kinase inhibitors
A compound, selected technology, applied in the direction of drug combination, organic chemistry, medical preparations containing active ingredients, etc.
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Embodiment 1
[0135] Embodiment 1: the preparation of compound 1
[0136] Step 1: Preparation of Compound 1-2
[0137]
[0138] The raw materials chloral hydrate (22g, 133.01mmol, 17.32mL) and sodium sulfate (168.20g, 1.18mol, 120.14mL) were dissolved in water (360mL), the system was heated to 35°C, and the raw materials 1-1( 25g, 131.57mmol) in aqueous solution (120mL), hydrochloric acid (12M, 14.80mL) and hydroxylamine hydrochloride (29.26g, 421.02mmol). After the addition was complete, the system was heated to 90°C for 16 hours. A yellow precipitate appeared in the system, the system was cooled to room temperature, filtered to obtain a filter cake, washed with water, dissolved in ethyl acetate (300mL), filtered, and the filtrate was concentrated to obtain compound 1-2, which was directly used in the next reaction without further purification .
[0139] MS(ESI)m / z(M+H) + =262.9.
[0140] Step 2: Preparation of Compound 1-3
[0141]
[0142] At 60°C, compound 1-2 (30.8g, 117.99...
Embodiment 2
[0228] Embodiment 2: the preparation of compound 2
[0229] Step 1: Preparation of compound 2-2
[0230]
[0231] Dissolve compound 1-13 (500mg, 0.96mmol), 2-1 (323.0mg, 1.252mmol), N,N-diisopropylethylamine (246.0mg, 1.926mmol) in acetonitrile (4mL), and add , the system was heated to 110°C and stirred for 10 h. After cooling the system, the system was concentrated to obtain a crude product. The crude product was purified by medium-pressure column chromatography (ethyl acetate / petroleum ether (v / v) = 0-25%) to obtain compound 2-2.
[0232] MS(ESI)m / z:(M+H) + =743.2
[0233] Step 2: Preparation of compound 2-3
[0234]
[0235] Compound 2-2 (115 mg, 0.155 mmol) and iron powder (30.0 mg, 0.5414 mmol) were dissolved in acetic acid (3.0 mL), and the system was heated to 80° C. and stirred for 2 h. After the system was cooled, the reaction was quenched with water, extracted with ethyl acetate (10mL x 2), the organic phases were combined, dried over anhydrous sodium sul...
Embodiment 3
[0266] Embodiment 3: the preparation of compound 3
[0267] Step 1: Preparation of compound 3-1
[0268]
[0269] Compound 2-6 (50mg, 0.087mmol), ((1H-benzo[d][1,2,3]triazol-1-yl)oxy)tris(dimethylamino)phosphonium hexafluorophosphate (V) (42.0 mg, 0.0957 mmol) and 1,8-diazabicycloundec-7-ene (55.0 mg, 0.36 mmol) were dissolved in N,N-dimethylformamide (2.0 mL), The system was heated to 100°C and stirred for 1 h. After the system was cooled, it was quenched with water, extracted with ethyl acetate (5mL x 2), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by a medium-pressure preparative column (methanol / dichloromethane (v / v)=0~10%), the target compound 3-1 was obtained.
[0270] MS(ESI)m / z:(M+H) + =692.2
[0271] Step 2: Preparation of compound 3-2
[0272]
[0273] Compound 1-19A (45mg, 0.39mmol) and sodium hydride (15.6mg, 0.39mmol, 60% purity) were di...
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