Diarylpyrazole compound and its preparation method and application
A technology of diarylpyrazoles and compounds, applied in the field of diarylpyrazoles and their preparation, can solve the problems of prostate cancer no longer effective, solid-state re-emergence, etc.
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Embodiment 1
[0067] The preparation of embodiment 1 intermediate compound 14
[0068] Weighing Weigh 12mmol (1eq) of the intermediate compound 3-(4-fluorophenyl)-1-methyl-1H-pyrazole-5-ethyl carboxylate 5 into a 100mL eggplant-shaped flask, and dissolve it in 30mL of tetrahydrofuran. Weigh 36mmol (1.37g, 3eq) of lithium aluminum hydride, add to the reaction solution in portions under ice bath conditions, react at room temperature for 15 minutes, when no intermediate 4 is detected by TLC, the reaction is complete, and add to the reaction solution under ice bath conditions Add 50mL of ice water dropwise to the solution, evaporate THF under reduced pressure, adjust the pH to 1 with 1mol / L HCl, when the solution is no longer a colloid, extract with ethyl acetate (50mL×3), combine the organic phases, and wash the organic phases with saturated chlorine Wash with sodium chloride, dry, filter, and evaporate the organic solvent under reduced pressure to obtain a white solid.
[0069] The intermedi...
Embodiment 2
[0071] The preparation of embodiment 2 intermediate compound 15
[0072] Weigh 0.8mmol of intermediate compound 14 in a 50mL eggplant-shaped bottle, dissolve it with 10mL of dichloromethane, slowly drop into 1.6mmol of thionyl chloride, and react at room temperature for 1 hour. When no intermediate compound 14 is detected by TLC, the reaction is completed and reduced Dichloromethane and thionyl chloride were evaporated under pressure to obtain a pale yellow solid.
[0073]The intermediate compound 14 used is 3-(4-fluorophenyl)-1-methyl-1H-5-pyrazolyl)methanol, and correspondingly, the obtained intermediate compound is 5-chloromethyl-3-(4- Fluorophenyl)-1-methyl-1H-pyrazole, specifically as follows;
[0074] 5-Chloromethyl-3-(4-fluorophenyl)-1-methyl-1H-pyrazole (15); pale yellow solid, yield: 100%; Mp: 124-126°C; 1 H-NMR (400MHz, DMSO-d 6 )δ (ppm): 7.799 (t, J = 7.2Hz, 2H), 7.227 (t, J = 7.2Hz, 2H), 6.800 (s, 1H), 4.953 (s, 2H), 3.891 (s, 3H) .
Embodiment 3
[0075] The preparation of embodiment 3 target compound 16
[0076] Weigh 0.8mmol (1eq) of substituted aniline in a 50mL eggplant-shaped flask, dissolve it in 12mL of acetone, add 4mmol (553mg, 5eq) of anhydrous potassium carbonate and 0.08mmol (13mg, 0.1eq) of potassium iodide, and dissolve 0.8mmol (179mg, 1eq) ) Intermediate compound 15 was added therein, stirred at room temperature for 8 hours, when the TLC reaction was completed, the reaction was stopped, acetone was evaporated under reduced pressure, the solid was dissolved with 50mL water and 50mL ethyl acetate, the water phase was separated, and the organic phase was saturated with sodium chloride (30mL×1), washed, dried, filtered, the filtrate was taken, the organic solvent in the filtrate was evaporated under reduced pressure, and the obtained solid was separated and purified by silica gel column chromatography to obtain the target compound 16. The elution system is petroleum ether:ethyl acetate=10:1;
[0077] The sub...
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