5-Bromo-2-methyl-3-pyridinamine

To a solution of 5-bromo-2-methyl-3-nitropyridine (13.8 g, 63.9 mmol) in industrial methylated spirit (330 mL) at 40° C. was added iron powder (20 g) (portionwise to avoid clumping) followed by concentrated aqueous hydrochloric acid (5 mL). The dark brown mixture was stirred vigorously at reflux for 2 hours and then cooled and filtered through Celite.(R). (which was washed with 1 L of industrial methylated spirit). The solvent was then removed in vacuo and the residue taken up in ethyl acetate (200 mL) and washed with a saturated aqueous solution of sodium bicarbonate (200 mL), dried over magnesium sulfate and solvent removed in vacuo to give 5-bromo-2-methylpyridin-3-amine as an orange solid (10.7 g, 90percent). To a solution of 5- bromo-2-methyl-3-nitropyridine (1) (15 g, 69.4 mmol) in EtOH (300 mL) and water (70 ml), was added iron powder (46.7 g, 833 mmol) and ammonium chloride (4.5 g, 83.4 mmol) successively at rt. The reaction mixture was heated to 90 °C for 40 min. The reaction was filtered hot and rinsed with EtOAc. The filtrate was washed with a saturated aqueous solution of sodium bicarbonate (200 mL), brine, dried over magnesium sulfate and solvent removed in vacuo to give the title compound as an orange solid, (11.7 g, 62.9 mmol, 90percent). LCMS (ESI) calc'd for CTo a solution of 5-bromo-2-methyl-3-nitropyridine (1) (15 g, 69.4 mmol) in EtOH (300 mL) and water (70 ml), was added iron powder (46.7 g, 833 mmol) and ammonium chloride (4.5 g, 83.4 mmol)successively at room temperature. The reaction mixture was heated to 90 °C for 40 mm. Thereaction was filtered hot and rinsed with EtOAc. The filtrate was washed with a saturated aqueous solution of sodium bicarbonate (200 mL), washed with brine, dried over magnesium sulfate and solvent removed in vacuo to give the title compound as an orange solid, (11.7 g, 62.9 mmol, 90percent). LCMS (ESI) calc’d for C6H7BrN2 [M+H]: 187, found: 187, 188.To a solution of 5-bromo-2-methyl-3-nitropyridine (13.8 g, 63.9 mmol) in industrial methylated spirit (330 mL) at 40° C. was added iron powder (20 g) (portionwise to avoid clumping) followed by concentrated aqueous hydrochloric acid (5 mL).To a solution of 5-bromo-2-methyl-3-nitropyridine (13.8 g, 63.9 mmol) in industrial methylated spirit (330 mL) at 40 °C was added iron powder (20 g)(portionwise to avoid clumping) followed by concentrated aqueous hydrochloric acid (5 mL). The dark brown mixture was stirred vigorously at reflux for 2 hours and then cooled and filtered through CeliteIron powder (15.4 g, 276 mmol) and ammonium chloride (14.8 g, 276 mmol) are added to a solution of 20.0 g (92.2 mmol) C-2 in 180 mL EtOH. The mixture is stirred and heated until reflux for 3 h. The mixture is filtered through Celite and the solvent is evaporated under reduced pressure. The crude product is taken up with water and DCM, the organic phase is separated, dried over MgS0Iron powder (15.4 g, 276 mmol) and ammonium chloride (14.8 g, 276 mmol) are added to a solution of 20.0 g (92.2 mmol) C-2 in 180 mL EtOH. The mixture is stirred and heated until reflux for 3 h. The mixture is filtered through Celite and the solvent is evaporated under reduced pressure. The crude product is taken up with water and DCM, the organic phase is separated, dried over MgS0Iron powder (15.4 g, 276 mmol) and ammonium chloride (14.8 g, 276 mmol) are added to a solution of 20.0 g (92.2 mmol) C-2 in 180 mL EtOH. The mixture is stirred and heated until reflux for 3 h. The mixture is filtered through Celite and the solvent is evaporated under reduced pressure. The crude product is taken up with water and DCM, the organic phase is separated, dried over MgSOIron powder (15.4 g, 276 mmol) and ammonium chloride (14.8 g, 276 mmol) are added to a solution of 20.0 g (92.2 mmol) C-2 in 180 mL EtOH. b) 5-bromo-2-methyl-3-pyridinamine; A mixture of 5-bromo-2-methyl-3-nitropyridine (5.68 g, 26.2 mmol) and tin (II) chloride dihydrate in ethyl acetate (200 mL) was refluxed for 2 hours and concentrated in vacuo. The residue was diluted with 6N NaOH (200 mL), water (100 mL), and dichloromethane (300 mL) and stirred at room temperature. The mixture was filtered through filter paper to remove small amounts of undissolved solid and the biphasic mixture was transferred to a separatory funnel. The layers were separated and the organic layer was washed with saturated NaCl, dried over Nab) 5 -bromo-2-methyl-3 -pyridinamine; A mixture of 5-bromo-2-methyl-3-nitropyridine (5.68 g, 26.2 mmol) and tin (II) chloride dihydrate in EtOAc (200 mL) was heated at reflux for 2 hours and concentrated in vacuo. The residue was diluted with 6 N NaOH (200 mL), water (100 mL), and dichloromethane (300 mL) and stirred at room temperature. The mixture was filtered through filter paper to remove small amounts of undissolved solid and the biphasic mixture was transferred to a separatory funnel. The layers were separated and the organic layer was washed with brine, dried over Na5 -Bromo-2-methyl-3 -pyridinamine A mixture of 5-bromo-2-methyl-3-nitropyridine (5.68 g, 26.2 mmol) and tin (II) chloride dihydrate in EtOAc (200 mL) was refluxed for 2 hours and concentrated in vacuo. The residue was diluted with 6N NaOH (200 mL), water (100 mL), and dichloromethane (300 mL) and stirred at room temperature. The mixture was filtered through filter paper to remove small amounts of undissolved solid and the biphasic mixture was transferred to a separatory funnel. The layers were separated and the organic layer was washed with saturated NaCl, dried over NaTo a stirred mixture of iron filings (5 g, 89.29 mmol, 3.88 equiv) and ammonium chloride (1 g, 18, 70 mmol, 0.81 equiv) in ethanol (66 mL) and water (33 mL) was added a solution of 5-bromo-2- methyl-3-nitropyridine (5 g, 23.04 mmol, 1 .00 equiv) in ethanol (50 mL) dropwise at 90 °C. The reaction mixture was stirred for 1 0 min at 90 °C and then cooled to rt. The solid material was removed by filtration. The filtrate was concentrated under vacuum and the residue was purified on a si lica gel column eluted with ethyl acetate/petroleum ether ( 1 :2) to yield 1 .6 g (37percent) of the title compound as a yellow solid. LC/MS (Method I, ESI). RT= 0.81 min, m z =- 187.0; 189.0 [M+H]To a stirred mixture of iron filings (5 g, 89.29 mmol, 3.88 equiv) and ammonium chloride (1 g, 18, 70 mmol, 0.81 equiv) in ethanol (66 mL) and water (33 mL) was added a solution of 5-bromo-2- methyl-3-nitropyridine (5 g, 23.04 mmol, 1 .00 equiv) in ethanol (50 mL) dropwise at 90 °C. The reaction mixture was stirred for 1 0 min at 90 °C and then cooled to rt. The solid material was removed by filtration. The filtrate was concentrated under vacuum and the residue was purified on a si lica gel column eluted with ethyl acetate/petroleum ether ( 1 :2) to yield 1 .6 g (37percent) of the title compound as a yellow solid. LC/MS (Method I, ESI). RT= 0.81 min, m z =- 187.0; 189.0 [M+H][0200] Step 1. 5-Bromo-2-methyl-pyridin-3-ylamine. To a stirred mixture of iron filings (5 g, 89.29 mmol, 3.88 equiv) and ammonium chloride (1 g, 18.70 mmol, 0.81 equiv) in ethanol (66 mL) and water (33 mL) was added a solution of 5-bromo-2-methyl-3- nitropyridine (5 g, 23.04 mmol, 1.00 equiv) in ethanol (50 mL) dropwise at 90 °C. The reaction mixture was stirred for 10 mm at 90 °C and then cooled to rt. The solid material was removed by filtration. The filtrate was concentrated under vacuum and the residue was purified on a silica gel column eluted with ethyl acetate/petroleum ether (1:2) to yield 1.6 g (37percent) of the title compound as a yellow solid. LC/MS (Method I, ESI): RT= 0.81 mm, m/z = 187.0; 189.0 [M+Hf’.

Molecular Weight:187.04
XLogP3:1.3
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Exact Mass:185.97926
Monoisotopic Mass:185.97926
Topological Polar Surface Area:38.9
Heavy Atom Count:9
Complexity:97.1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes