C-2 substituted Aldisin derivative and medicinal salt thereof, their pharmaceutical composition, and application in preparation of antitumor drug thereof
A derivative, C-2 technology, applied in the direction of drug combination, antineoplastic drugs, active ingredients of heterocyclic compounds, etc., can solve the problems of poor stability and high cytotoxicity, and achieve the effect of low cost and easy operation
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preparation Embodiment 1
[0066] Preparation Example 1: Synthesis of 2-(4-bromobenzyl)-6,7-dihydropyrrole[2,3-c]azepine-4,8(1H,5H)-dione (Compound 5)
[0067] Pyrrole (100mmol, 6.7g), [bmim] + [BF 4 ] (20mL), K 2 CO 3 (16mmol, 2.208g) was added to 12mL of dry acetonitrile to obtain a mixed solution I, and p-bromobenzyl bromide (10mmol, 5.0g) was mixed with 25mL of dry acetonitrile to form II, and II was slowly added dropwise to I under reflux at 80°C , and vigorously stirred for 6.5h. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure, extracted with ethyl acetate, the organic phases were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, and filtered to remove Na 2 SO 4 , and the solvent was removed by rotary evaporation under reduced pressure, and the crude product was separated and purified by flash column chromatography (petroleum ether, then petroleum ether: ethyl acetate=20:1) to obtain light yellow oily liqui...
preparation Embodiment 2
[0073] Preparation Example 2: Synthesis of 2-(biphenyl-4-methylene)-6,7-dihydropyrrole[2,3-c]azepine-4,8(1H,5H)-dione
[0074] In a 10mL reaction tube, dissolve compound 5 (0.2mmol, 66.6mg) and phenylboronic acid (0.4mmol, 48.8mg) in degassed 2mL THF, mix well and then add Pd(PPh 3 ) 4 (0.015mmol, 17.0mg) and 2mol / L degassed K 2 CO 3 solution (1.0mL), filled with N 2 , quickly cover the reaction tube, and react at 90°C for 8 hours. After the reaction is completed and cooled, pour the reaction solution into 20 mL of distilled water, extract it with ethyl acetate several times, combine the organic phases, dry them with anhydrous sodium sulfate, and remove them by suction filtration. Sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was separated and purified by flash column chromatography (petroleum ether: ethyl acetate=1:1, 1% CH 3 COOH), to obtain 31 mg of white powdery solid, yield: 47%.
[0075] 1 H NMR (400MHz,...
preparation Embodiment 3
[0076] Preparation Example 3: 2-(4'-(methyl)biphenyl-4-methylene)-6,7-dihydropyrrole[2,3-c]azepine-4,8(1H,5H )-Diketone Synthesis
[0077] The synthesis method is the same as that of Preparation Example 2, except that 4-methylphenylboronic acid is used instead of phenylboronic acid. After purification, 34 mg of white powdery solid was obtained, with a yield of 49%.
[0078] 1 H NMR (300MHz, DMSO) δ: 12.13(s, 1H), 8.20(s, 1H), 7.53(dd, J=10.0, 8.1Hz, 4H), 7.33(d, J=7.9Hz, 2H), 7.23 (d, J=8.1Hz, 2H), 6.26(s, 1H), 3.93(s, 2H), 2.65(s, 2H), 2.33(s, 3H).EI-MS: m / z=344[M ] + .
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