Some reactions of substituted 2-bromopyridines was written by Berrie, A. H.;Newbold, G. T.;Spring, F. S.. And the article was included in Journal of the Chemical Society in 1952.Recommanded Product: 3-Aminopicolinamide This article mentions the following:
2-Hydroxy-3-nitropyridine (I) (14 g.), added to 50 g. PBr3 and 16 g. Br, heated 5 hrs. at 100°, cooled, treated dropwise with 100 cc. MeOH and then with 300 cc. H2O, and extracted with boiling C6H6 and the residue from the C6H6 extracted with petr. ether (b. 60-80°), gives 10 g. 2-bromo-3-nitropyridine (II), m. 125°; the 5-Cl derivative of I yields 59% of the 5-Cl derivative (III) of II, m. 75°; the 5-Br derivative of I gives 80% of 2,5-dibromo-3-nitropyridine (IV), m. 93°. II (1 g.) and 10 cc. conductivity HCl in 10 cc. AcOH, refluxed 3 hrs., give 0.5 g. 2-hydroxy-3-nitropyridine (V), pale yellow, m. 224°; III yields 54% of the 5-Cl derivative (VI) of V, yellow, m. 235°; IV, HCl, and AcOH give 64% of the 5-Br derivative (VII) of V, pale yellow, m. 242°; 10 g. 2-amino-5-bromo-3-nitropyridine (VIII) in 25 cc. H2SO4 (d. 1.84) at 0°, treated with 6 g. NaNO2 in 15 cc. H2O, kept 30 min. at 0°, and diluted with 150 cc. H2O, gives 6.05 g. VII. V (0.7 g.), 2 g. PCl5, and 1.5 cc. POCl3, heated 2 hrs. at 100°, give 0.2 g. 2-chloro-3-nitropyridine (IX), m. 101°; VI gives 52% 2,5-dichloro-3-nitropyridine (X), m. 43°; X results in 1.3 g. yield from 2-amino-5-chloro-3-nitropyridine. VII, PCl5, and POCl3 give 45% 5-bromo-2-chloro-3-nitropyridine (XI), m. 68° (51% from VIII). II (0.75 g.) and 0.7 g. CuCN, gradually heated to 150°, the pressure reduced to 1 mm., and the heat source removed after 15 sec., give 0.3 g. 3-nitropicolinonitrile (XII), m. 78°; III yields the 5-Cl derivative (XIII) of XII, m. 98°. IV gives 66% of the 5-Br derivative (XIV) of XII, m. 102°. 3-Amino-2-bromopyridine yields 32% 3-aminopicolinonitrile (XIVA), m. 149°; 5-Cl derivative (XIVB), m. 175°, 25%. XII (100 mg.) and 0.2 cc. H2SO4 (d. 1.84), heated 2 hrs. at 100°, give 50 mg. 3-nitropicolinamide (XV), m. 211°; XIII yields 55% of the 5-Cl derivative of XV, m. 230° and XIV gives-56% of the 5-Br derivative (XVA), m. 232-3° (decompn). II (1.45 g.), 2 g. Fe filings, and 12 cc. AcOH, heated 2 hrs. at 100°, diluted with 15 cc. H2O, basified with 30% NaOH, and the cooled product extracted with CHCl3, give 0.8 g. 3-amino-2-bromopyridine (XVI), m. 79°; 1.1 g. III yields 0.1 g. of the 2-Cl analog (XVII) of XVI, m. 79-80°; 1 g. XVI in 10 cc. HCl (d. 1.19), refluxed 3 hrs., gives 0.5 g. XVII. XV (20 mg.), 20 mg. Fe filings, and 0.12 cc. AcOH, heated 2 hrs. at 100°, give 10 mg. 3-aminopicolinamide (XVIII), m. 175-7°, sublimes at 100°/10-1 mm.; 120 mg. XIVA and 0.24 g. concentrated H2SO4, heated 2 hrs. at 100°, give 10 mg. XVIII. XIII, reduced in AcOH with Fe, gives 67% of the 5-Cl derivative (XIX) of XVIII, m. 168°; XIVB yields 11% XIX; 5-Br derivative of XVIII, m. 168°, 72 and 18% yield, resp. XI gives 81% 3-amino-2-bromo-5-chloropyridine (XX), m. 142°, absorption maximum at 2520 and 3140 A. (ε 11,500 and 5700); IV gives 84% 3-amino-2,5-dibromopyridine (XXI), m. 153°; 2,5-di-Cl analog, m. 129°; it results in 87% on reduction of X and in 0.2-g. yield on refluxing 2 hrs. 0.5 g. 3-amino-5-bromo-2-chloropyridine (XXII) in 10 cc. concentrated HCl. Reduction of XI with Fe in AcOH gives 85% XXII, m. 131°, absorption maximum at 2510 and 3140 A. (ε 7200 and 4700); 1 part XXI and 20 parts concentrated HCl, refluxed 2 hrs., give 35% XXII; 2.82 g. IV, 7 g. Sn, and 30 cc. HCl, refluxed until solution results, give 0.2 g. XXII. 2-Amino-5-bromo-3-nitropyridine, reduced with Sn and HCl, gives 21% 2,3-diamino-5-bromo-4(6)-chloropyridine, m. 164° (quinoxaline derivative from phenanthraquinone, C19H9N3ClBr, m. 270-2°). XXII (0.3 g.) in 10 cc. concentrated HCl, treated at 0° with 0.55 g. NaNO2 in 1.5 cc. H2O and then with 1.1 g. Cu, shaken 1 hr., almost neutralized with 30% NaOH, and the precipitate extracted with Me2CO and the residue from the Me2CO extracted with petr. ether, gives 100 mg. 5-bromo-2,3-dichloropyridine, m. 30-1°. XXI (1.26 g.) with NaNO2 in concentrated H2SO4 gives 0.6 g. 2,5-dibromo-3-hydroxypyridine, m. 195-7°. XVA (12.1 g.) and KOBr give 7 g. 2-amino-5-bromo-3-nitropyridine, yellow, m. 205°. In the experiment, the researchers used many compounds, for example, 3-Aminopicolinamide (cas: 50608-99-6Recommanded Product: 3-Aminopicolinamide).
3-Aminopicolinamide (cas: 50608-99-6) belongs to amides. In primary and secondary amides, the presence of N–H dipoles allows amides to function as H-bond donors as well. Thus amides can participate in hydrogen bonding with water and other protic solvents; the oxygen atom can accept hydrogen bonds from water and the N–H hydrogen atoms can donate H-bonds. Amides can be recrystallised from large quantities of water, ethanol, ethanol/ether, aqueous ethanol, chloroform/toluene, chloroform or acetic acid. The likely impurities are the parent acids or the alkyl esters from which they have been made. The former can be removed by thorough washing with aqueous ammonia followed by recrystallisation, whereas elimination of the latter is by trituration or recrystallisation from an organic solvent.Recommanded Product: 3-Aminopicolinamide
Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics