2-Pyridinamine, 5-bromo-4-chloro-

To a stirred solution of 4-chloropyridin-2-amine (8 g, 62.2 mmol) inacetonitrile (600 mL) at rt was added NBS (11.08 g, 62.2 mmol) in portions andthe reaction was stirred for 14 h. The reaction mixture was concentrated under reduced pressure. The residue was reconstituted in ethyl acetate and water. The organics were extracted with ethyl acetate (3X50 mL). The combined organic layers were washed with water (100 mL), brine (100 mL), and dried over sodium sulphate. The organics were concentrated under reduced pressure to afford 5-bromo-4-chloropyridin-2-amine as yellow solid (13 g, 99 percent yield) that was used without further purification in the next step. LCMS (ESI) mle 207.0 [(M+H), calcd for C5H5BrC1N2 206.9]; LC/MS retention time (method B): tR = 0.8 mm; ‘H NMR (400 MHz, CDC13) ö 8.17 (s, 1H), 6.63 (s, 1H), 4.59 (s, 2H).To a stirred solution of 4-chloropyridin-2-amine (8 g, 62.2 mmol) in acetonitrile (600 mL) at rt was added A^-bromosuccinimide (11.08 g, 62.2 mmol) in portions and the reaction was stirred for 14 h. The reaction mixture was concentrated under reduced pressure. The residue was diluted with water (50 mL) and extracted with EtOAc (3x50 mL). The combined organic layers were washed with water (100 mL), brine (100 mL) and dried over sodium sulfate. The organics were concentrated under reduced pressure to afford 5-bromo-4-chloropyridin-2-amine as yellow solid (13 g, 99percent) that was used as is without further purification.A solution of 4-chloropyridin-2-amine (10 g, 78 mmol) in acetonitrile (400 mL) was treated dropwise with a solution of N-bromosuccinimide (14.09 g, 79 mmol) in acetonitrile (200 mL) . The mixture was stirred at ambient temperature for 16 hours and concentrated in vacuo. The crude product was purified by chromatography (silica gel, 3: 2 hexane /ethyl acetate) to afford the title compound (16 g, 77 mmol, 99percent yield) .To a 1 L 3 necked round bottomed flask equipped with a magnetic stirrer, cold bath, and NN-Bromosuccinimide (10.9 g, 61.3 mmol) was added to a solution of 4-chloro-2-aminopyridine (7.50 g, 58.3 mmol) in acetonitrile (130 mL) at RT under nitrogen atmosphere. The yellow solution was stirred for 3 hr. The solvent was evaporated under reduced pressure and the residue purified by chromatography on silica gel (cyclohexane/ethyl acetate) to give the title compound as a light yellow solid (10.0 g, 83percent). To a solution of 4-chloropyridin-2-amine (5.0 g, 39 mmol) in MeCN (200 mL) at 0 °C was added B (2.2 mL, 43 mmol) in portions over a period of 30 min. The reaction was warmed to rt and stirred overnight. The solid was filtered, washed with hexane (3x), and dried to afford Intermediate 12A (9.1 g, 81percent) as an off-white solid. LC-MS (ESI) m/z: 206.9/208.9 [M+H]To a solution of 2-amino-4-chloropyridine (0.50 g, 3.9 mmol) in acetonitrile (20 ml) was added dropwise a solution of N-bromosuccinimide (0.730 g, 4.1 mmol) in acetonitrile (10 ml). The reaction mixture was stirred at room temperature for 16 h then concentrated in vacuo. The crude product was purified by chromatography on silica gel (hexane/ethyl acetate 6:4) to give the title compound as a white solid (0.65 g, 80percent); General procedure: To a - 20°C solution of 2-aminopyridineor 2-amino-4-chloropyridine(1 equiv) in DMF was added N-bromosuccinimide(1.1 or 2.2 equiv.) in two portions. The reaction mixture was stirred for 16 hat room temperature and was then poured withstirring into a 1M solution of NaOH (50 mL). The phases were separated and theaqueous layer was extracted with EtOAc. The combined organic phases were washedwith water (2 x 50 mL) and brine (50 mL), dried over MgSO5.2.2.31 General procedure: To a mixture of 2-aminopyridine (0.5 mmol, 1 equiv), p-TSA (0.4 mmol, 0.8 equiv), 1-butylpyridinium bromide (1.5 mmol, 3 equiv) in a 50 mL Schlenk tube were added 1, 2-dimethoxyethane (2 mL) under air. Then H[0254] To a solution of 4-chloro-2-pyridylamine (6.0 g, 46.7 mmol) in chloroform(180 rαL) was added N-bromosuccinimide (8.3 g, 46.7 mmol). The solution was stirred in the dark for 2 hours, at which time it was added to CHSynthesis of 5-bromo-4-chloro-2-pyridylamine[0098] To a solution of 4-chloro-2-pyridylamine (6.0 g, 46.7 mmol) in chloroform(180 mL) was added N-bromosuccinimide (8.3 g, 46.7 mmol). The solution was stirred in the dark for 2 hours, at which time it was added to CH

Molecular Weight:207.45
XLogP3:1.8
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Exact Mass:205.92464
Monoisotopic Mass:205.92464
Topological Polar Surface Area:38.9
Heavy Atom Count:9
Complexity:101
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes