Alkynyl pyrimidine or alkynyl pyridine compound as well as composition and application thereof
A technology of compounds and solvates, applied in the fields of drug combination, digestive system, organic chemistry, etc., can solve the problems of side effects that limit the clinical application of drugs and no inhibitory activity.
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[0071] Preparation of some intermediates
[0072] A series intermediates
[0073] Synthesis of Intermediate A1.5-iodo-N-(1-methyl-1H-pyrazol-4-yl)pyrimidin-2-amine
[0074]
[0075]Step 1: 4-nitropyrazole (1.13g, 10mmol), iodomethane (2.85g, 20mmol), potassium carbonate (4.14g, 30mmol) in acetone (10mL) was heated to 60°C for 12 hours, cooled, Filtration, concentration, and purification by column chromatography gave 1.1 g of the white solid product 1-methyl-4-nitro-1H-pyrazole with a yield of 85%.
[0076] Step 2: Add palladium (55% humidity on carbon, 10% mass content) to a solution of 1-methyl-4-nitro-1H-pyrazole (0.64g, 5mmol) in methanol (20mL), replace with hydrogen three times, The reaction was stirred at room temperature for 6 hours, filtered with celite, and the filtrate was concentrated to obtain 0.4 g of the target product 1-methyl-1H-pyrazol-4-amine, with a yield of 82%, MS: 98 [M+H]+.
[0077] Step 3: To a solution of 1-methyl-1H-pyrazol-4-amine (0.2g, 2mmol)...
Embodiment 1
[0152] Example 1. 4-methyl-3-((2-((1-methyl-1H-pyrazol-4-yl)amino)pyrimidin-5-yl)ethynyl)-N-(4-(( 4-Methylpiperazin-1-yl)methyl)-3-(trifluoromethyl)phenyl)benzamide
[0153] 5-iodo-N-(1-methyl-1H-pyrazol-4-yl)pyrimidin-2-amine (30mg, 0.1mmol), 3-ethynyl-4-methyl-N-(4-(( 4-Methylpiperazin-1-yl)methyl)-3-(trifluoromethyl)phenyl)benzamide (42mg, 0.1mmol), Pd(PPh 3 ) 2 Cl 2 (4mg, 0.005mmol), CuI (2mg, 0.01mmol), DMF (1.5mL) solution of triethylamine (1.5mL) was replaced by argon, heated to 65 degrees Celsius for 15 hours, cooled, extracted with ethyl acetate, Wash with saturated brine, dry the organic phase, concentrate, and prepare a thin-layer plate (supported on silica gel, dichloromethane:methanol=10:1) for purification to obtain 35 mg of a white solid product with a yield of 60%. 1 HNMR (400MHz, DMSO-d 6 )δ10.52(s,1H),9.91(s,1H),8.65(s,2H),8.21(d,J=2.2Hz,1H),8.13(d,J=1.9Hz,1H),8.07( dd,J=8.5,2.1Hz,1H),7.92-7.89(m,2H),7.71(d,J=8.5Hz,1H),7.52-7.50(m,2H),3.82(s,3H),3.57 (...
Embodiment 2
[0155] Example 2. 3-((2-((1-(2-hydroxyethyl)-1H-pyrazol-4-yl)amino)pyrimidin-5-yl)ethynyl)-4-methyl-N- (4-((4-methylpiperazin-1-yl)methyl)-3-(trifluoromethyl)phenyl)benzamide
[0156] 2-(4-((5-iodopyrimidin-2-yl)amino)-1H-pyrazol-1-yl)ethyl-1-ol (33mg, 0.1mmol), 3-ethynyl-4-methyl -N-(4-((4-methylpiperazin-1-yl)methyl)-3-(trifluoromethyl)phenyl)benzamide (42mg, 0.1mmol), Pd(PPh 3 ) 2 Cl 2 (4mg, 0.005mmol), CuI (2mg, 0.01mmol), DMF (1.5mL) solution of triethylamine (1.5mL) was replaced by argon, heated to 65 degrees Celsius for 15 hours, cooled, extracted with ethyl acetate, Wash with saturated brine, dry the organic phase, concentrate, prepare TLC plate (supported on silica gel, dichloromethane:methanol=10:1) and purify to obtain 31 mg of white solid product, yield 50%; 1 H NMR (400MHz, DMSO-d 6 )δ10.52(s,1H),9.92(s,1H),8.65(s,2H),8.21(d,J=2.2Hz,1H),8.13(d,J=2.0Hz,1H),8.06( d,J=8.2Hz,1H),7.98–7.87(m,2H),7.71(d,J=8.5Hz,1H),7.58–7.47(m,2H),4.87(t,J=5.3Hz,1H ), 4.11(t, J=5...
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