Carbazole STAT3 inhibitor crystal form I and preparation method thereof
A technology of carbazole and crystal form, which is applied in the field of medicinal chemistry, can solve the problems that affect the process of prescription preparations, storage methods, pharmacokinetic performance in vivo, and affect the safety and effectiveness of drugs, and achieve good stability.
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Embodiment 1
[0043] Example 1 Preparation of 2-aminomethyl-4H-chromen-4-one hydrochloride
[0044] Step 1 Preparation of 2-acetoxyacetophenone
[0045]
[0046] Add 2-hydroxyacetophenone (100mmol), acetyl chloride (250mmol) and potassium carbonate (500mmol) into the reaction flask, add 300ml of acetone, and react under reflux for 12h. After the reaction is over, the solvent is evaporated under reduced pressure, water and ethyl acetate are added. Ester extraction, drying with anhydrous sodium sulfate, and concentration to obtain an oily substance, which was directly cast to the next step.
[0047] Step 2 Preparation of 2-methyl-4H-chromen-4-one
[0048]
[0049] Weigh 2-acetoxyacetophenone (50mmol) into the reaction flask, add 100ml DMSO to dissolve it, add sodium hydrogen (150mmol) in batches at 0-5°C, after the addition, warm to room temperature and stir for 3h. Add water to the reaction solution, adjust the pH to weak acidity with dilute hydrochloric acid, extract with ethyl acetate, dry with a...
Embodiment 2
[0059] Example 2 Preparation of 2,4-Dichloro-6-(4-nitrophenyl)-1,3,5-triazine
[0060] Step 1 Preparation of methyl 4-nitrobenzoate
[0061]
[0062] Weigh 4-nitrobenzoic acid (250mmol) into the reaction flask, add 300mL methanol to dissolve it, add thionyl chloride (375mmol) dropwise, and reflux reaction for 12h. After the reaction is complete, spin dry under reduced pressure and add saturated hydrogen carbonate The sodium solution was adjusted to pH 7-8, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated to obtain the title compound, which was directly cast to the next step.
[0063] Step 2 Preparation of 6-(4-nitrophenyl)-1,3,5-triazine-2,4-(1H,3H)-dione
[0064]
[0065] Weigh the biuret (100mmol) in the reaction flask, add 150mL of ethylene glycol dimethyl ether to dissolve it, add sodium hydride (83.4mmol) in batches at 0-5℃, after the addition, stir and react at 50℃ for 1h, then add Methyl 4-nitrobenzoate (83.4mmol), after the addition, heated ...
Embodiment 3
[0071] Example 3 4-Chloro-6-(4-nitrophenyl)-N-(2-methyl-4H-chromen-4-one)-1,3,5-triazin-2-amine preparation
[0072]
[0073] Weigh the 2,4-dichloro-6-(4-nitrophenyl)-1,3,5-triazine (50mmol) obtained in Example 2 into the reaction flask, add 100mL tetrahydrofuran to dissolve it, and add it to Example 1. The resultant 2-aminomethyl-4H-chromene-4-one hydrochloride 2-(trifluoromethyl)-pyridine-4-amine (55mmol), sodium carbonate (100mmol), reflux reaction for 72h, filter, column Purify by chromatography to obtain the title compound.
[0074] ES: M / Z 416[M+H] + .
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