2-AMINO-5-BROMO-NICOTINONITRILE

Light brown solid

2-amino-5-bromopyridine-3--carbonitrile (2); [00140] 2-aminopyridine-3-carbonitrile 1 (0.56g, 4.6 mmol) was dissolved in 10 mL HOAc, to which one equivalent of NaTo a solution of 2-aminonicotinonitrile (10 g, 84 mmol) in dry MeCN (200 ml) NH4Ac (0.64 g, 8.2 mmol) was added. The reaction was cooled to 0 °C and NBS (16.44 g, 92.4 mmol) was added all at once. After 12 h, solvent was removed under the reduced pressure and 5percent hydrochloric acid (360 ml) was added until most of product was redissolved. Resulting solution was filtered, cooled to 0 °C, and basified to pH > 10 with 6 M NaOH (200 ml).In 20 min, crystals were collected, washed on the filter with large amount of water and dried in vacuo affording 2-amino-5-bromo-3-pyridinecarbonitrile (Lacbay et al.2014). White crystal; yield 98percent; 193–194 °C; 1H NMR (400 MHz, DMSO-d6) δ 8.27 (d, J = 2.5 Hz, 1H, H-4), 8.14 (d, J = 2.5 Hz, 1H, H-6), 7.13 (s, 2H, NH2); 13C NMR(100 MHz, DMSO-d6) δ 159.22 (C-2), 154.16 (C-6), 144.01(C-4), 116.19 (C≡N), 104.28 (C-3), 91.39 (C-5); HRMS(ESI) m/z: calculated for C6H5BrN3+ [M + H]+: 197.9667; found: 197.9670.8.1 Compound 9: 2-Aminonicotinonitrile 8 (100 g, 0.839 mol) was dissolved in HOAc (800 mL) . To the solution was added NaCompound 9: 2-Aminonicotinonitrile 8 (100 g, 0.839 mol) was dissolved in HOAc (800 mL). To the solution was added NaStep 1: Preparation of 2-amino-5-bromonicotinonitrile (42) 2-Aminonicotinonitrile (95.0 g, 0.80 mol, 1.0 eq) was dissolved in HOAc (2 L) and then NaTo a solution of 2-aminonicotinonitrile (1.5 g, 12.5 mmol, 1.0 eq.) in AcOH (30 mL) was added Na2003 (1.3 g, 12.5 mmol). Bromine (0.7 ml, 13.8 mmol) was added drop wise to the resulting suspension and reaction mixture was stirred at rt for 1 h. The orange precipitate formed was collected by filtration, washed with water and dried to afford 2.0 g (80percent) of 1-34 as a yellow solid. NMR (400 MHz, DMSO) 6 8.27 (5, 1 H), 8.15 (5, 1 H), 7.12 (brs, 2H).Bromine (1.1 mL, 21 mmol) in ACOH (3 mL) was added dropwise to a solution of 2-AMINO-NICOTINONITRILE (1.00 g, 8.4 mmol) in ACOH (20 mL) at 10 °C. The orange mixture was stirred for 22 hours at ambient temperature then diluted with ether (100 mL). The resultant precipitated salt was filtered, washed with ether and dried on air. The precipitate was suspended in water (100 mL), neutralized with 1N NAOH, filtered, washed with water and dried on air to give 1.29 g (78percent) title COMPOUND. LH NMR (300 MHz, DMSO-d6) 8 8.27 (d, J= 2. 5HZ, 1H), 8. 14 (d, J= 2. 5HZ, 1H), 7.13 (s, br, 2H). MS (ESI) INULE : 197.9655 (M+H) +.1.1 2-Amino-5-bromo-nicotinonitrile To a solution of 2-amino-nicotinonitrile (0.50 g; 4.11 mmol) in acetic acid (10 mL) was added sodium carbonate (0.48 g; 4.52 mmol) at 0 °C followed by the dropwise addition of bromine (0.74 g; 4.52 mmol). The reaction mixture was stirred at ambient temperature for 2 h. The solvent was evaporated under vacuum, the residue was suspended in water (50 mL), filtered by suction and dried to afford the title compound (0.60 g; 73percent). The product was used in the next step without further purification; 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

Molecular Weight:198.02
XLogP3:1.5
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Exact Mass:196.95886
Monoisotopic Mass:196.95886
Topological Polar Surface Area:62.7
Heavy Atom Count:10
Complexity:162
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes