Purine derivative as well as preparation method and medical application thereof
A technology of derivatives and prodrugs, applied in the field of novel purine derivatives
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Embodiment 1
[0165] N-cyclopropyl-4-(2-(4-methoxyphenoxy)-6-(((tetrahydro-2H-pyran-4-yl)methyl)amino)-9H-purine-9 -yl)-2-methylbenzamide (compound 1)
[0166]
[0167] Step 1: 2,6-dichloro-9-(tetrahydro-2H-pyran-2-yl)-9H-purine (compound 1-2)
[0168] Add 2,6-dichloro-9H-purine (1.89g, 10mmol) into 100mL ethyl acetate, add TsOH (172mg, 1mmol), dihydropyran (100mg, 1.2mmol), and keep warm at 50°C for reaction 2 Hour. The reaction solution was washed with saturated aqueous sodium bicarbonate solution, washed with saturated brine, dried over anhydrous sodium sulfate, and the concentrated residue was separated and purified by column chromatography to obtain 1.63 g of the title compound.
[0169] ESI-MS(m / z):273.2[M+H] +
[0170] Step 2: 2-chloro-9-(tetrahydro-2H-pyran-2-yl)-N-((tetrahydro-2H-pyran-4-yl)methyl)-9H-purin-6-amine (Compounds 1-3)
[0171] Compound 1-2 (272 mg, 1 mmol), 4-aminomethyltetrahydropyran (138 mg, 1.2 mmol), and triethylamine (202 mg, 2 mmol) were dissolved in te...
Embodiment 2
[0183] N-cyclopropyl-4-(2-(2,3-difluoro-4-methoxyphenoxy)-6-(((tetrahydro-2H-pyran-4-yl)methyl)amino )-9H-purin-9-yl)-2-methylbenzamide (compound 19)
[0184]
[0185] Step 1: 2-(2,3-difluoro-4-methoxyphenoxy)-9-(tetrahydro-2H-pyran-2-yl)-N-((tetrahydro-2H-pyran -4-yl)methyl)-9H-purin-6-amine (compound 19-1)
[0186] Compound 1-3 (70.2mg, 0.2mmol), 2,3-difluoro-4-methoxyphenol (40mg, 0.24mmol), Pd 2 (dba) 3 (18.3mg, 0.02mmol), di-tBuxphos (17mg, 0.04mmol), Cs 2 CO 3 (130.3mg, 0.4mmol) was added to toluene (5mL), under nitrogen protection, and reacted at 120°C for 12 hours. Cool to room temperature, add water, extract with ethyl acetate, combine the organic phases, and dry over anhydrous sodium sulfate. The concentrated residue is purified by column chromatography to obtain 78 mg of the title compound. ESI-MS(m / z):477.2[M+H] +
[0187] Step 2: 2-(2,3-difluoro-4-methoxyphenoxy)-N-((tetrahydro-2H-pyran-4-yl)methyl)-9H-purin-6-amine (Compound 19-2)
[0188] Compound 1...
Embodiment 3
[0194] N-cyclopropyl-4-(2-(4-methoxyphenoxy)-6-((3,3,3-trifluoropropyl)amino)-9H-purin-9-yl)-2 -Toluamide (compound 14)
[0195]
[0196] Step 1: 2-chloro-9-(tetrahydro-2H-pyran-2-yl)-N-(3,3,3-trifluoropropyl)-9H-purin-6-amine (compound 14-1 )
[0197] Add compound 1-2 (272mg, 1mmol), 3,3,3-trifluoropropylamine (136mg, 1.2mmol), triethylamine (202mg, 2mmol) into tetrahydrofuran (5mL), and react at room temperature for 2.0 hours. Water and ethyl acetate were added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the concentrated residue was purified by column chromatography to obtain 312 mg of the title compound.
[0198] ESI-MS(m / z):350.2[M+H] +
[0199] Step 2: 2-(4-methoxyphenoxy)-9-(tetrahydro-2H-pyran-2-yl)-N-(3,3,3-trifluoropropyl)-9H-purine -6-amine (compound 14-2)
[0200] Compound 14-1 (69mg, 0.2mmol), 4-methoxyphenol (29.8mg, 0.24mmol), Pd 2 (dba) 3 (18.3mg, 0.02mmol), di-tBuxphos (17mg, 0.04mmol), Cs 2 CO 3 (130....
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