Ochiai, Eiji published the artcilePolarization of aromatic heterocyclic compounds. CV. 4-Substituted derivatives of α-picoline, Application of 4-Amino-2-picoline, the publication is Pharmaceutical Bulletin (1954), 147-9, database is CAplus.
cf. C.A. 48, 10746c. PCl3 (10 g.) added portionwise with ice cooling to 10 g. 4-nitro-α-picoline N-oxide in 200 ml. of CHCl3, the mixture warmed at 50° for 10 min., cooled, poured onto ice, neutralized with Na2CO3, extracted with CHCl3, dried over Na2SO4, and evaporated gave 7 g. 4-nitro-α-picoline (I), m. 42-5° (from petr. ether). I (1 g.) dissolved in MeOH and reduced over Pd-C gave 4-amino-α-picoline, purified through the picrate, m. 193°. 4-Bromo-α-picoline (II) (picrate, m. 184-5°) was prepared by 4 methods: (1) I (1 g.) heated at 150-70° for 8 hrs. with 5 g. 48% HBr, the mixture evaporated under reduced pressure, alkalinized with Na2CO3, extracted with Et2O, dried over Na2SO4 and evaporated gave 0.2 g. II, an oily residue, which was converted to the picrate. (2) I (5 g.), 26 g. of (H2N)2CO and 30 ml. 48% HBr refluxed 7 hrs., diluted with H2O, alkalinized with Na2CO3, steam distilled, the distillate saturated with NaCl, extracted with Et2O, the Et2O extract dried over Na2SO4, the Et2O removed, and the residue distilled gave 1.2 g. II, b5 47-56°. (3) I (3 g.) and 5 ml. AcBr heated 6 hrs. on a water bath (a red color developed), the mixture evaporated in vacuo, diluted with H2O, alkalinized with Na2CO3, and extracted with Et2O, and the extract distilled gave 1.2 g. II. (4) 4-Hydroxy-α-picoline N-oxide (10 g.) in 60 ml. CHCl3 cooled and treated portionwise with 25 g. PBr3 in 20 ml. CHCl3; after the reaction subsided the mixture was refluxed 6 hrs. on a water bath and a sirupy mass precipitated The CHCl3 layer extracted with H2O, the sirupy residue treated with 200 ml. ice water, the aqueous solutions mixed, alkalinized with Na2CO3, steam distilled, the distillate saturated with NaCl, extracted with Et2O, and the extract distilled in vacuo gave 7.8 g. II. CuCN (dried at 110° for 36 hrs.) (2.5 g.) added to 4.5 g. II, the mixture gradually heated to 150-60° when the mixture melted with darkening, the temperature raised to 180° then cooled to 120°, 1 g. CuCN added, the mixture heated 0.25 hrs. at 170-80° and distilled gave 2.2 g. 4-cyano-α-picoline (III), b11-15 about 75°, m. 45.5-6.5° (from petr. ether); picrate, decompose 163-4° (from EtOH). III (1.5 g.) reduced over Pd-C in acid solution gave 1.6 g. 4-amino-αpicoline, decompose 274° (from MeOH); picrate, m. 195-6° (from MeOH); benzoate, m. 81-3° (from benzene).
Pharmaceutical Bulletin published new progress about 18437-58-6. 18437-58-6 belongs to pyridine-derivatives, auxiliary class Pyridine,Amine, name is 4-Amino-2-picoline, and the molecular formula is C6H8N2, Application of 4-Amino-2-picoline.
Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem