Methanol → Methyl 5-bromopyridine-3-carboxylate

A solution of 5-bromonicotinic acid (10 g, 49.5 mmol) in MeOH (200 mL) was cooled to 0° C. and conc. H2SO4 (5 mL) was added dropwise. The reaction mixture was heated to reflux for 12 h. After completion, the reaction mixture was concentrated under reduced pressure, diluted with water and the aqueous layer was washed with EtOAc. The resulting mixture was poured over an aqueous saturated NaHCO3 solution to adjust the pH 7-8, it was then extracted with EtOAc and the organic layer was dried over anhydrous Na2SO4. Solvent was evaporated under reduced pressure to get the solid product methyl 5-bromonicotinate as an off-white solid (7 g, yield 66%): 1H NMR (400 MHz, CDCl3) δ 9.14 (s, 1H), 8.86 (s, 1H), 8.45 (s, 1H), 3.98 (s, 3H)

1. temperatureThe reaction mixture was heated
2. temperatureto reflux for 12 h
3. concentrationAfter completion, the reaction mixture was concentrated under reduced pressure
4. additiondiluted with water
5. washthe aqueous layer was washed with EtOAc
6. additionThe resulting mixture was poured over an aqueous saturated NaHCO3 solution
7. extractionwas then extracted with EtOAc
8. dry with materialthe organic layer was dried over anhydrous Na2SO4
9. customSolvent was evaporated under reduced pressure

ORD record

ord-17dd942ee4ef4e64a517af5ddbb5844b

Source dataset

uspto-grants-2014_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08901156B2