New imidazo[ 4,5-b]pyridine-7-carboxamides 704
A technology of imidazo and pyridine, which is applied in the field of preparation compounds, can solve problems such as lithium poisoning and narrow therapeutic window
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Embodiment 1
[0182] Methyl 4-(6-bromo-3H-imidazo[4,5-b]pyridin-2-yl)benzoate
[0183]
[0184] Add DIPEA (16.6 mL, 95.7 mmol) to 5-bromopyridine-2,3-diamine (6.0 g, 31.9 mmol), monomethyl terephthalate (6.89 g, 38.3 mmol) and HBTU (14.5 g, 38.3 mmol) in MeCN (100 mL), then the reaction mixture was stirred at room temperature for 1 h. The precipitate formed was collected and washed with MeCN. The solid was partitioned into microwave vials using HOAc (4 mL) and heated to +200 °C for 5 min. The product precipitated at room temperature, was filtered, washed with HOAc and MeCN, and dried to afford 8.58 g (81% yield) of the title compound.
[0185] 1 H NMR (CDCl 3 )δppm; 8.15(d, J=1.52Hz, 1H), 8.07-8.09(m, 2H), 7.97(d, J=8.84Hz, 2H), 7.59(d, J=1.52Hz, 1H), 3.75( s, 3H); MS (APPI) m / z (M+1) 332, 334.
Embodiment 2
[0187] Methyl 4-(6-chloro-3H-imidazo[4,5-b]pyridin-2-yl)benzoate
[0188]
[0189] Add DIPEA (21.9 mL, 126 mmol) to 5-chloropyridine-2,3-diamine (6.0 g, 42.0 mmol), monomethyl terephthalate (9.06 g 50.3 mmol) and HBTU (19.1 g 50.3 mmol) suspension in MeCN (100 mL), the reaction mixture was then stirred at room temperature for 1 h. The precipitate formed was collected and washed with MeCN. The solid was partitioned into microwave vials using HOAc (4 mL) and heated to +200 °C for 10 min. The product precipitated at room temperature, was filtered, washed with HOAc and MeCN, and dried to afford 10.3 g (85% yield) of the title compound.
[0190] 1 H NMR (CDCl 3 )δppm; 7.92-7.98(m, 3H), 7.84(d, J=8.84Hz, 2H), 7.38(d, J=1.77Hz, 1H), 3.59-3.63(m, 3H); MS(APPI)m / z(M+1)288, 290.
Embodiment 3
[0192] Methyl 4-(6-bromo-7-chloro-3H-imidazo[4,5-b]pyridin-2-yl)benzoate
[0193]
[0194] Methyl 4-(6-bromo-3H-imidazo[4,5-b]pyridin-2-yl)benzoate (6.7 g, 20.2 mmol) obtained in Example 1 and m-chloroperbenzoic acid (70 %, 17.75 g, 60.3 mmol) was stirred in HOAc at room temperature for 18 hours. Another 2 equivalents of m-chloroperbenzoic acid (70%, 9.06 g, 40.6 mmol) were added to the reaction mixture and stirring was continued for 6 hours. The solvent was evaporated in vacuo and the residue was crystallized from EtOH. The resulting solid was mixed with POCl 3 Mix and heat at +120°C for 5 minutes in a microwave reactor. After cooling to room temperature, the mixture was poured into an ice / water mixture and the formed precipitate was collected, washed with water and dried to afford 6.1 g (83% yield) of the title compound.
[0195] 1 H NMR (400MHz, DMSO-d 6 )δppm; 8.59(s, 1H), 8.40(d, J=8.53Hz, 2H), 8.15(d, J=8.53Hz, 2H), 3.91(s, 3H); MS(APPI) m / z(M +1)368.
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