Substituted pyrimidine derivatives, and preparation method and application thereof
A technology of derivatives and pyrimidines, applied in the treatment of human immunodeficiency virus, replacing the field of pyrimidine derivatives, can solve the problem of slow attenuation
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Embodiment 1
[0065] Example 1: Preparation of 4-((6-chloro-2-((4-cyanophenyl)amino)pyrimidin-4-yl)oxy)-3,5-dimethylbenzonitrile (3)
[0066] Weigh 2,4,6-trichloropyrimidine (2.0g, 10.9mmol), 4-hydroxyl-3,5-dimethylbenzonitrile (1.6g, 10.9mmol) and N,-diisopropylethylamine ( 3.6ml, 21.8mmol) in 25mL of 1,4-dioxane solution, stirred at 70°C for 2h. TLC detects that the reaction is complete. After the reaction solution is cooled, 100 mL of water is slowly added thereto, continued to stir for 30 min, filtered, and dried in a vacuum oven to obtain a white solid that is compound 4-((2,6-dichloropyrimidin-4-yl )oxy)-3,5-dimethylbenzonitrile (2), yield 91.8%. 1 H NMR (400MHz, DMSO-d 6 , ppm) δ: 7.76 (2H, s, Ph–H), 7.64 (1H, s, pyrimidine-H), 2.12 (6H, s, CH 3 ).ESI–MS: m / z 294.28(M+1).C 13 h 9 Cl 2 N 3 O(293.01), mp:207–209℃.
[0067] Intermediate 2 (2.0g, 6.8mmol) and 4-aminobenzonitrile (0.8g, 6.8mmol) were dissolved in N-methylpyrrolidone (10mL) at 0–5°C, then tert-butanol was added in ...
Embodiment 2
[0068] Example 2: n=2,5-((6-(4-cyano-2,6-dimethylphenoxy)-2-((4-cyanophenyl)amino)pyrimidin-4-yl ) amino) valeric acid (LTb2) preparation
[0069] Intermediate 3 (1.0g, 2.66mmol) and 5-aminovaleric acid (0.55g, 5.32mmol) were dissolved in N-methylpyrrolidone (5mL), and reacted at 130°C for 20min under microwave conditions. After the reaction was completed, the reaction solution was dropped into 50 ml of ice water, and a white solid was precipitated, filtered, vacuum-dried, and then flash column chromatographed to obtain the intermediate LTb2 with a yield of 52.5%.
Embodiment 3
[0070] Example 3: n=2,5-((6-(4-cyano-2,6-dimethylphenoxy)-2-(((4-cyanophenyl)amino)pyrimidine-4- base) amino)-N-hydroxypentanamide (IA-1-2) preparation
[0071]1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.10g, 0.54mmol) and 1-hydroxybenzotriazole (0.15g, 0.54mmol) were dissolved in 5ml DMF , stirred in an ice bath for 30 min, and then the intermediate LTb2 (0.20 g, 0.45 mmol) and O-(tetrahydropyran-2-yl) hydroxylamine (0.064 g, 0.54 mmol) were added to the reaction solution, and the stirring was continued at room temperature for 8 h . After the reaction was completed, it was extracted with ethyl acetate (3×20ml), washed with saturated sodium chloride solution, and the organic layer was separated and dried over anhydrous sodium sulfate. Then flash column chromatography was carried out to obtain a white solid which is the intermediate LTb2a. Intermediate LTb2a (0.10g, 0.18mmol) was dissolved in 5ml of anhydrous methanol, p-toluenesulfonic acid (0.032g, 0.18mmo...
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