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With ammonia; potassium carbonate In water; <i>tert</i>-butyl alcohol at 20 - 60℃;
(2e) 6-Chloro-5-methyl-3-nitro-2-pyridinamine [Formula 22]; A mixture of 2,6-dichloro-3-methyl-5- nitropyridine (10.41 g, 50.3 mmol), 28percent aqueous ammonia solution (17 ml, 0.25 mol), potassium carbonate (10.4 g, 75.5 mmol) and t-butanol (167 ml) was stirred overnight at 60°C under nitrogen atmosphere. After stirring at room temperature for 3 hours, a precipitate was filtered and then washed three times with water, thereby yielding the title compound (4.25 g, 22.7 mmol, 45percent) as a yellow solid. 1H NMR(400MHz, QMSO-D6) No. ppm; 2.23,(3H, s), 8.04(2H, br s), 8.39(1H, s).
With ammonia; potassium carbonate; In water; tert-butyl alcohol; at 20 - 60℃;
(2e) 6-Chloro-5-methyl-3-nitro-2-pyridinamine [Formula 22]; A mixture of 2,6-dichloro-3-methyl-5- nitropyridine (10.41 g, 50.3 mmol), 28% aqueous ammonia solution (17 ml, 0.25 mol), potassium carbonate (10.4 g, 75.5 mmol) and t-butanol (167 ml) was stirred overnight at 60C under nitrogen atmosphere. After stirring at room temperature for 3 hours, a precipitate was filtered and then washed three times with water, thereby yielding the title compound (4.25 g, 22.7 mmol, 45%) as a yellow solid. ¹H NMR(400MHz, QMSO-D6) No. ppm; 2.23,(3H, s), 8.04(2H, br s), 8.39(1H, s).
Example 3; 5- (2,2-Difluoroethoxy)-2-(((4-methoxy-3- methyl-2-pyridinyl) methyl)sulfinyl)-6-methyl-3H- imidazo [4,5-b]pyridine Sodium salt [Formula 28]; (3a) 6-(2,2-difluoroethoxy)-5-methyl-3-nitro-2- pyridineamine [Formula 29]; 2,2-Difluoro ethanol (418 mg, 5.1 mmol) was dissolved in tetrahydrofuran (15 ml), sodium hydride (60%) '(180 mg, 4.5 mmol) was added thereto under nitrogen atmosphere, and the reaction mixture was stirred for 30 minutes at room temperature. A solution of 6-chloro-5-methyl-3-nitro-2-pyridineamine (600 mg, 3.20 mmol) in tetrahydrofuran (15 ml) was dropped, and the mixture was stirred at room temperature overnight. Water was added to the reaction solution and extracted with ethyl acetate, and after washed with sodium bicarbonate solution, dried over magnesium sulfate. The residue obtained by evaporating the solvent was triturated with n-hexane to yield the'title compound (685 mg, 3.1 mmol, 96%) as an orange solid. ¹H NMR(400MHz, DMSO-d6) No. ppm; 2.05 (3H, s) , 4.56- 4.69 (2H, m), 6.29-6.60(1H, m), 8.03 (2H, s), 8.19(lH, s) .
(2f) 5-Methyl-3-nitro-6-(2,2,2-trifluoroethoxy)-2- pyridinamine [Formula 23]; 2,2,2-Trifluoroethanol (340 mg, 3.4 mmol) was dissolved in the tetrahydrofuran (10 ml), sodium hydride (60%) (120 mg, 3.0 mmol) was added thereto, and the reaction mixture was stirred for 30 minutes at room temperature under nitrogen atmosphere. A solution of 6-chloro-5-methyl-3-nitro-2-pyridineamine crude product (400 mg) in tetrahydrofuran (10 ml) was dropped, and the reaction mixture was stirred at room temperature for 2.5 days. Water was added to the' reaction solution and extracted with ethyl acetate, and after washed with a sodium bicarbonate solution, dried over magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (eluting solvent: ethyl acetate/n- hexane= 15/85) to yield the title compound (225 mg, 0.90 mmol) as a yellow solid. (at)H NMR (400MHz, DMSO-d6) No. ppm; 2.07 (3H, s), 5.06 (2H, J=9Hz), 8.05 (2H, s), 8.24(1H, s).
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