Dichloromethane → Methyl 2-chloropyridine-4-carboxylate

2-Chloro-isonicotinic acid (10 g, 63.5 mmol)) was refluxed in thionylchloride (40 mL) under argon for 6 hr. The SOCl2 was evaporated under reduced pressure, twice toluene (30 mL) was added and evaporated. The residue was dried under high vacuum and set under argon. MeOH (50 mL) was added and the mixture was heated to reflux for 1 hr. and stirred overnight at r.t. The solvent was evaporated. To the residue were added saturated NaHCO3 and ether. The etheral phase was separated, washed with water, brine, dried over MgSO4 and evaporated. The residue was purified by column chromatography using CH2Cl2 as eluent to give 9.1 g (84%) of the white and crystalline product. Rf (CH2Cl2)=0.51. 1H NMR (599 MHz, CDCl3) δ 8.52 (d, 1H, J=5.26 Hz, pyridine), 7.87 (d, 1H, J=1.31 Hz, pyridine) 7.75 (dd, 1H, J=5.26, 1.31 Hz, pyridine), 3.95 (s, 3H, methyl ester). 13C NMR (150 MHz, CDCl3) δ 164.5, 152.7, 150.8, 140.4, 124.3, 121.8, 53.2. HRMS (MALDI-FTMS): MH+ calculated: 172.016; found: 172.0161

1. customThe SOCl2 was evaporated under reduced pressure, twice toluene (30 mL)
2. additionwas added
3. customevaporated
4. customThe residue was dried under high vacuum
5. additionMeOH (50 mL) was added
6. temperaturethe mixture was heated
7. temperatureto reflux for 1 hr
8. customThe solvent was evaporated
9. additionTo the residue were added saturated NaHCO3 and ether
10. customThe etheral phase was separated
11. washwashed with water, brine
12. dry with materialdried over MgSO4
13. customevaporated
14. customThe residue was purified by column chromatography
15. customto give 9.1 g (84%) of the white and crystalline product

ORD record

ord-31bbb048a4b64e49987423a82d65f94f

Source dataset

uspto-grants-2009_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07579350B2