Pyridinecarboxylic acid derivatives. I. Syntheses of 4-substituted compounds of picolinic acid and 5-ethylpicolinic acid was written by Endo, Masaru;Nakashima, Tatsumi. And the article was included in Yakugaku Zasshi in 1960.HPLC of Formula: 24103-75-1 This article mentions the following:
2,4-Me(O2N)C5H3N(O) in MeOH, EtOH, or PhCH2OH with RONa gave 2,4-MeRC5H3N(O) (I) (R = MeO, EtO, PhO, and PhCH2O). I in CHCl3 at 0° treated with PCl5, stirred 1 hr. at room temperature, heated 30 min. on a H2O bath, the solvent removed in vacuo, the residue poured into ice H2O, and the product extracted with CHCl3 gave 2,4-MeRC5H3N (II) (R, % yield, b.p./mm. or m.p., and m.p. of picrate given): MeO, 59.9, 60°/5, 146-7°; EtO, 57.2, 86-9°/8, 135-6°; PhO, 67.9, 161°/1, 120-1°; PhCH2O, 84.5, 88-92°, 168°. II in H2O heated with KMnO4, the solution concentrated, adjusted to pH 4-4.8, saturated CuSO4 solution added, the precipitate filtered off, suspended in hot H2O, H2S gas passed in, the solution concentrated, and the residue recrystallized (EtOH) gave 4,2-R(HO2C)C5H3N (III) (R, % yield, and m.p. given): MeO, 25.2, 196° EtO, 7, 153-5°; PhO, 32.2, 178-9°. A solution of RONa in ROH treated with 2,4,5-Me(O2N)EtC5H2N(O), the mixture refluxed 2 hrs., the solvent removed, and the residue extracted with CHCl3 gave 2,4,5-MeREtC5H2N(O) (IV) (R = MeO or EtO). Also, 100 ml. AcCl treated with 20 g. 2,4,5-Me(O2N)EtC5H2N(O) portionwise, the mixture refluxed 10 min., the solution made alk. with Na2CO3, and the product extracted with CHCl3 gave 19.5 g. IV (R = Cl). IV and Ac2O heated at 100°, refluxed 15 min., and the product distilled gave 4,5,2-REt(AcOCH2)C5H2N (V) (R, % yield, and b.p./mm. given): MeO, 62.7, 140°/6 (picrate m. 119-21°); EtO, 53.5, 150-4°/7 [picrolonate m. 184-6° (decomposition)]; Cl, 47.6, 133-5°/6 [picrolonate m. 138-41° (decomposition)]. V and 10% HCl heated 1 hr. on a H2O bath, cooled, the solution made alk. with K2CO3, and the product extracted with CHCl3, gave 4,5,2-REt(HOCH2)C5H2N (VI) (R, % yield, b.p./mm. and m.p. of picrate given): MeO, 66.5, 140°/5, 73°; EtO, 59.3, 135-8°/4, 53-5°; Cl, 82.3, 132-4°/6, -. VI in CHCl3 and activated MnO2 stirred 2 hrs. and the CHCl3 layer concentrated gave 4,5,2-REt(OHC)C5H2N (VII) (R, % yield, b.p./mm. and m.p. of semicarbazone given): MeO, 48.4, 99-101°/6, 190-3°; EtO, 58.8, 109-10°/6, 175-8°; Cl, 52.5, 83-8°/6, 227-8°. AgNO3 (1.4 g.) in 14.1 ml. 20% NH4OH and 1.4 g. NaOH in 14.1 ml. H2O were mixed, stirred 1 hr. with 1 g. VII (R = MeO), kept overnight, the solution filtered, the filtrate acidified with HCl, evaporated to dryness, the residue taken up in EtOH, the EtOH removed, the residue in a small amount of H2O adjusted to pH 2-3, Cu(OAc)2 solution added, the precipitate decomposed with H2S, the solution concentrated, and the residue recrystallized (EtOH) gave 0.2 g. 4,5,2-REt(HO2C)C5H2N (VIII) (R = MeO), m. 150-2°. VII (R = EtO) (0.6 g.) in 8 ml. Me2CO and 0.5 ml. 30% H2O2 kept 1.5 hrs., kept overnight with 0.7 ml. addnl. H2O2, the Me2CO removed, the residue in 25 ml. H2O refluxed 1 hr., and the product concentrated gave 0.2 g. VIII (R = EtO), m. 148-9° (C6H6). Similarly, 1.5 g. VII (R = Cl) yielded 0.8 g. VIII (R = Cl), m. 134-6°. In the experiment, the researchers used many compounds, for example, 4-Methoxy-2-methylpyridine (cas: 24103-75-1HPLC of Formula: 24103-75-1).
4-Methoxy-2-methylpyridine (cas: 24103-75-1) belongs to pyridine derivatives. The ring atoms in the pyridine molecule are sp2-hybridized. The nitrogen is involved in the π-bonding aromatic system using its unhybridized p orbital. The lone pair is in an sp2 orbital, projecting outward from the ring in the same plane as the σ bonds. Several pyridine derivatives play important roles in biological systems. While its biosynthesis is not fully understood, nicotinic acid (vitamin B3) occurs in some bacteria, fungi, and mammals.HPLC of Formula: 24103-75-1