A kind of imidazopyridine derivatives
A technology of pyridine derivatives and imidazolo, which is applied in the field of small molecules that can inhibit Trk activity, and can solve problems such as stability and insufficient activity
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Embodiment 1
[0093] Example 1-Compound 1
[0094] Prepare M1
[0095]
[0096] (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(3-benzylureido)pyridine
[0097] (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(diphenoxycarbonyl)aminopyridine (2g, 3.5mmol) , benzylamine (0.56g, 5.3mmol) and sodium carbonate (0.74g, 7mmol) were suspended in 25mL of acetonitrile and stirred at room temperature for 12 hours. After the reaction was detected by TLC, 20 ml of water was added to quench the reaction, extracted with ethyl acetate (3×50 ml), the organic phases were combined, dried, and spin-dried to obtain a crude product. The crude product was purified by a silica gel column (ethyl acetate / petroleum ether=1 / 3, V / V) to obtain 1.4 g of a yellow solid product with a yield of 85.7%. LC-MS(ESI)m / z:454[M+H] + .
[0098]
[0099] (R)-N-Benzyl-5-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3H-imidazo[4,5-b]pyridine-3-carboxamide
[0100] Intermediate M1 (200 mg, 0.44 mmol) was dissolv...
Embodiment 2
[0103] Example 2-Compound 2
[0104]
[0105] (R)-5-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-N-(4-fluorobenzyl)-3H-imidazo[4,5-b]pyridine- 3-formamide
[0106] Step A: (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(3-(4-fluorobenzyl)ureido) Preparation of pyridine. Prepared as in the preparation of M1, using 4-fluorobenzylamine instead of benzylamine.
[0107] Step B: (R)-5-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-N-(4-fluorobenzyl)-3H-imidazo[4,5-b ] Preparation of pyridine-3-carboxamide. The intermediate (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(3-(4-fluorobenzyl)ureido) Pyridine (300 mg, 0.63 mmol) was dissolved in 5 mL of THF, 10% palladium on carbon (30 mg) was added, hydrogen was replaced, and stirred at room temperature for 12 hours. After the reaction was detected by TLC, it was filtered and spin-dried to obtain the crude product. The crude product was dissolved in 5 mL of triethyl orthoformate, p-toluenesulfonic acid (15 mg) was added,...
Embodiment 3
[0110] Example 3-Compound 3
[0111]
[0112] (R)-N-(3,5-difluorobenzyl)-5-(2-(3,5-difluorophenyl)pyrrolidin-1-yl)-3H-imidazo[4,5-b ]pyridine-3-carboxamide
[0113] Step A: (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(3-(3,5-difluorobenzyl) Preparation of ureido)pyridines. Prepared as in the preparation of M1, using 3,5-difluorobenzylamine instead of benzylamine.
[0114] Step B: Add (R)-6-(2-(2,5-difluorophenyl)pyrrolidin-1-yl)-3-nitro-2-(3-(3,5-difluorobenzyl )ureido)pyridine (200mg, 0.41mmol) was dissolved in 5mL THF, 10% palladium carbon (20mg) was added to replace the hydrogen, and stirred at room temperature for 12 hours. TLC detection, after the reaction was completed, filtered and spin-dried to obtain the crude product. The crude product was dissolved in 5 mL of triethyl orthoformate, p-toluenesulfonic acid (10 mg) was added, and reacted at 135° C. for 4 hours. TLC detection, after the reaction, the reaction solution was concentrated and purified b...
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