Acetyl chloride → Methyl 4-fluoro-3-nitrobenzoate

HRID 1867090Notes

Reaction equation

HRID 1867090 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].[C:14](Cl)(=O)C>CO>[F:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([O:8][CH3:14])=[O:7])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12]

Participants

4

Reactant 2

HCID 6367Acetyl chlorideHCID 679874-Fluoro-3-nitrobenzoic acid

Product 1

HCID 5219721Methyl 4-fluoro-3-nitrobenzoateYield 75.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A 1 L 3-necked round bottomed flask equipped with a nitrogen inlet, stirbar, addition funnel and thermocouple was charged with 4-fluoro-3-nitrobenzoic acid (50 g, 0.27 mol) and methanol (300 mL). The system was cooled to 0 C and acetyl chloride (27 mL, 0.37 mol) was added dropwise. The system was warmed to room temperature, the addition funnel was replaced with a reflux condenser, and was heated to reflux for 1.5 h. The reaction mixture was cooled to room temperature, quenched with saturated aqueous NaHCO3, and extracted with ethyl acetate. The organic extract was washed with brine, dried with Na2SO4 and concentrated in vacuo to give methyl 4-fluoro-3 nitrobenzoate as an orange solid (40.6 g, 75%). 1H NMR (400 MHz, CD3OD) δ 8.67 ((dd, J=2.2 and 6.8 Hz, 1H), 8.34 (dddd, J=2.2, 4.4, 6.4 and 8.8 Hz, 1H), 7.55 (dd, J=8.8 and 10.8 Hz, 1H), 3.94 (s, 3H) ppm. ES-HRMS m/z 200.02446 (M+H calcd for C8H7FNO4 requires 200.0354).

Workup

  1. customA 1 L 3-necked round bottomed flask equipped with a nitrogen inlet
  2. additionstirbar, addition funnel
  3. additionwas added dropwise
  4. customthe addition funnel was replaced with a reflux condenser
  5. temperaturewas heated
  6. temperatureto reflux for 1.5 h
  7. temperatureThe reaction mixture was cooled to room temperature
  8. customquenched with saturated aqueous NaHCO3
  9. extractionextracted with ethyl acetate
  10. extractionThe organic extract
  11. washwas washed with brine
  12. dry with materialdried with Na2SO4
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f2ce421b561c4bce9ebec676eabe8a19
Source dataset
uspto-grants-2009_12
Patent number
US07629363B2

Reaction notes

Loading…