Synthesis
In a dry three-necked flask, 3-aminopyridine (20.0 g, 212.5 mmol), 4-dimethylaminopyridine (DMAP) (0.3 g, 2.1 mmol) and pyridine (33.6 g, 425.0 mmol) were dissolved in anhydrous dichloromethane (200 mL). Valeroyl chloride (28.2 g, 233.7 mmol) was added slowly and dropwise under cooling in an ice bath. The reaction mixture was kept stirred at 0 °C for 2 hours. After completion of the reaction, the reaction solution was slowly poured into ice water and the reaction was quenched with 1N hydrochloric acid solution. Subsequently, the mixture was extracted with dichloromethane (250 mL × 3), the organic phases were combined and washed with saturated saline (200 mL × 1). Finally, the solvent was removed by distillation under reduced pressure to afford 3-pivalamido pyridine (36.2 g) as a white solid in 95.5% yield.
References
[1] Synthesis, 1982, # 6, p. 499 - 500
[2] Tetrahedron, 2009, vol. 65, # 18, p. 3668 - 3672
[3] Patent: CN107382839, 2017, A. Location in patent: Paragraph 0005; 0012-0013; 0020-0021; 0028-0029; 0036-0037
[4] Patent: WO2014/198844, 2014, A1. Location in patent: Page/Page column 15; 16
[5] Patent: WO2014/198848, 2014, A2. Location in patent: Page/Page column 14; 15
