Benzazepine derivatives containing five-membered heterocycle, preparation method and use thereof
A technology of phenyl and compound, applied in the field of compound with anti-tumor effect and its preparation, can solve the problems of genotoxicity, mutagenesis, low cure rate and the like
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Embodiment 2
[0047] Intermediate Ⅲ-2
[0048]
[0049] In a reaction flask equipped with stirring, condenser and thermometer, add 1.9g (0.010mol) N,N-dimethyl-2,3,4,5-tetrahydro-1H-benzo[b]azepine -5-Amine (II), 2.0g (0.020mol) potassium bicarbonate and 30ml acetonitrile, add dropwise 2.78g (0.02mol) 3-bromopropanol under stirring, reflux reaction for 12h, TLC shows that the reaction is complete, filter the insoluble matter, The filtrate was poured into distilled water, extracted with ethyl acetate (15ml×3), the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was evaporated, and the residue was separated by silica gel column chromatography to obtain a yellow solid with a yield of 82.5% and a purity of 97.5%. (HPLC normalization method), ESI-MS (m / z): 248.2.
Embodiment 3
[0051] Intermediate IV-1
[0052]
[0053] In a reaction flask equipped with stirring, condenser, and thermometer, add 2.34g (0.01mol) of intermediate III-1, 50ml of pyridine and stir to dissolve it. The solution is controlled below -5°C, and 2.28g (0.012mol) of ) p-toluenesulfonyl chloride, reacted at 0°C for 10h, TLC showed that the reaction was complete, the reaction solution was poured into cold water, solids were precipitated, filtered, the filter cake was washed with saturated brine (50ml×3), and dried in vacuo to obtain a white solid , yield 93.7%, purity 97.6% (HPLC normalization method), ESI-MS (m / z): 388.2.
[0054] Reference Example 4:
[0055] Intermediate Ⅳ-2
[0056]
[0057] In a reaction flask equipped with stirring, condenser and thermometer, add 2.48g (0.01mol) of intermediate III-2, 50ml of N,N-dimethylformamide and 2.52g (0.025mol) of triethylamine, stir to make Dissolve, control the solution below -5°C, add 2.28g (0.012mol) p-toluenesulfonyl chl...
Embodiment 1
[0059] 3-(2-(5-(Dimethylamino)-2,3,4,5-tetrahydro-1H-benzo[b]azepine-1-yl)ethylamino)-1H-pyrrole- 2-Carboxylic acid ethyl ester (compound Ⅰ-1)
[0060]
[0061] In the reaction flask equipped with stirring, condenser and thermometer, add 3.88g (0.01mol) intermediate IV-1, 0.8g (0.02mol) sodium hydroxide, 30ml ethanol and 1.54g (0.01mol) 3-amino -1H-pyrrole-2-carboxylic acid ethyl ester, reflux reaction for 6h, TLC showed that the reaction was complete, filtered off the insoluble matter, evaporated the solvent, and the residue was separated by silica gel column chromatography to obtain compound Ⅰ-1: white solid, yield 78%, purity 99.4% (HPLC normalization method), HRMS (m / z) [M+H] + : 371.2442.
[0062] Example 2:
[0063] 2-(2-(5-(Dimethylamino)-2,3,4,5-tetrahydro-1H-benzo[b]azepine-1-yl)ethylamino)-1H-pyrrole- 3-Carbonitrile (compound Ⅰ-2)
[0064]
[0065] In the reaction flask equipped with stirring, condenser and thermometer, add 3.88g (0.01mol) of intermediat...
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