Methyl 6-bromopicolinate

Chemical Properties

White to off-white solid

Uses

Methyl 6-bromopicolinate, also known as Methyl 6-bromopyridine-2-carboxylate, is a halogenated pyridine derivative that can be used in esterolysis reactions to form 6-Bromopicolinic acid.It can also be used in substitution reactions or cross-couplings to synthesise other pyridine compounds.

Synthesis

The general procedure for the synthesis of methyl 6-bromo-2-pyridinecarboxylate from methanol and 6-bromo-2-pyridinecarboxylic acid is as follows: 1. 6-bromo-2-pyridine carboxylic acid (6.000 g) was dissolved in methanol (180 mL) containing concentrated hydrochloric acid and heated to reflux. 2. Sulfuric acid (2 mL) was added and the reaction continued to reflux for 4 hours. 3. Upon completion of the reaction, the reaction mixture was cooled to about 0°C and concentrated. 4. Ammonia (4.8 mL) was added to the concentrated mixture. 5. The resulting solution was evaporated to give a white solid residue. 6. 6. The white solid was dissolved in a solvent mixture of dichloromethane (100 mL) and brine (100 mL), and the organic layer was separated with sufficient shaking. 7. The organic layer was dried with magnesium sulfate and the solvent was evaporated to give the white solid product methyl 6-bromo-2-pyridinecarboxylate (6.300 g, 98% yield). Product characterization data: 1H NMR (400 MHz, CDCl3) δ 4.00 (3H, s), 7.66-7.74 (2H, m), 8.07-8.13 (1H, m).

References

[1] Patent: WO2003/84917, 2003, A1. Location in patent: Page/Page column 26
[2] Journal of Agricultural and Food Chemistry, 2016, vol. 64, # 18, p. 3533 - 3537
[3] Patent: WO2017/9798, 2017, A1. Location in patent: Page/Page column 92
[4] Journal of Medicinal Chemistry, 2017, vol. 60, # 2, p. 722 - 748
[5] Inorganic Chemistry, 2018, vol. 57, # 13, p. 7512 - 7515