Methanol → Methyl 2-chloro-3-nitrobenzoate

HRID 2369918Notes

Reaction equation

HRID 2369918 reaction equation
[Cl:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].S(Cl)(Cl)=O.[CH3:18]O>>[Cl:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([O:6][CH3:18])=[O:5]

Participants

4

Reactant 3

HCID 887Methanol2×HCID 198702-Chloro-3-nitrobenzoic acidHCID 24386Thionyl Chloride

Product 1

HCID 10751184Methyl 2-chloro-3-nitrobenzoateYield 98%

Procedure

To a stirred solution of 2-chloro-3-nitrobenzoic acid (1.0 g, 5.0 mmol) in anhydrous methanol (10 mL) at 0° C. was added thionyl chloride (0.5 mL, 7.4 mmol) dropwise and the reaction mixture was stirred overnight at reflux. The mixture was diluted with methanol and concentrated under reduced pressure to remove the excess thionyl chloride. The residue was then re-dissolved in ethyl acetate, washed with saturated aqueous sodium bicarbonate, re-extracted with ethyl acetate, dried (Na2SO4), filtered, and concentrated under reduced pressure to give methyl 2-chloro-3-nitrobenzoate (1.1 g, 98%) as a white foam that was used in the next step without further purification: 1H NMR (300 MHz, DMSO-d6) δ 8.21 (d, J=1.5 Hz, 1H), 8.07 (dd, J=7.8, 1.5 Hz, 1H), 7.73 (t, J=8.1 Hz, 1H), 3.91 (s, 3H).

Workup

  1. temperatureat reflux
  2. concentrationconcentrated under reduced pressure
  3. customto remove the excess thionyl chloride
  4. dissolutionThe residue was then re-dissolved in ethyl acetate
  5. washwashed with saturated aqueous sodium bicarbonate
  6. extractionre-extracted with ethyl acetate
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b30c998f2818407f8b849916a3c36238
Source dataset
uspto-grants-2014_04
Patent number
US08710046B2

Reaction notes

Loading…