Ethanol → Ethyl 6-chloro-5-methylpicolinate

HRID 515227Notes

Reaction equation

HRID 515227 reaction equation
Cl[C:2]12[CH2:10][CH2:9][C:5]([CH3:11])([C:6]([Cl:8])=[N:7]1)[O:4][C:3]2=[O:12].[CH2:13]1CCN2C(=NCCC2)C[CH2:14]1.C(O)C>C(Cl)(Cl)Cl>[Cl:8][C:6]1[N:7]=[C:2]([C:3]([O:4][CH2:13][CH3:14])=[O:12])[CH:10]=[CH:9][C:5]=1[CH3:11]

Participants

5

Reactant 3

HCID 702EthanolHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 15014155HCID 15014155, compound

Product 1

HCID 9837074Ethyl 6-chloro-5-methylpicolinate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

4,6-Dichloro-1-methyl-2-oxa-5-azabicyclo[2.2.2]oct-5-en-3-one (26-3) (3.0 g, 14.4 mmol, 1 eq) was dissolved in chloroform (30 mL) and DBU (6.5 mL, 43 mmol, 3 eq) was added. After 5 minutes of stirring at ambient temperature, ethanol (0.84 mL, 16 mmol, 1.1 eq) was added and there was a slight exotherm. After 15 minutes of stirring at ambient temperature, the reaction mixture was concentrated and the crude residue was purified by flash chromatography (80 g SiO2, 0-100% EtOAc in hexanes) to afford ethyl 6-chloro-5-methylpyridine-2-carboxylate (26-4) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.97 (d, J=7.6 Hz, 1 H); 7.69 (d, J=7.6 Hz, 1 H); 4.47 (q, J=7.2 Hz, 2 H); 2.46 (s, 3 H); 1.43 (t, J=7.2 Hz, 3H). LRMS m/z (M+H) 200.0 found, 200.0 required.

Workup

  1. stirringAfter 15 minutes of stirring at ambient temperature
  2. concentrationthe reaction mixture was concentrated
  3. customthe crude residue was purified by flash chromatography (80 g SiO2, 0-100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-91f664eaf4a5403fba5bdb662188127b
Source dataset
uspto-grants-2015_08
Patent number
US09108937B2

Reaction notes

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