Methanol → Methyl 2-bromo-4-methylbenzoate

HRID 1487974Notes

Reaction equation

HRID 1487974 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].S(=O)(=O)(O)O.[CH3:17]O>>[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:3]=1[C:4]([O:6][CH3:17])=[O:5]

Participants

4

Reactant 3

HCID 887MethanolHCID 1118Sulfuric AcidHCID 2262922-Bromo-4-methylbenzoic acid

Product 1

HCID 21779704Methyl 2-bromo-4-methylbenzoateYield 99%

Conditions

Temperature
70 °C

Procedure

A solution of 2-bromo-4-methylbenzoic acid (10.0 g, 46.5 mmol) in MeOH (50 mL) was cooled to 0° C., then concentrated sulfuric acid (10 mL) was carefully added. The mixture was heated at 70° C. for 2 hours. After cooling to room temperature, the volatile organics were removed under reduced pressure, and the residue was poured onto ice-water (100 mL). The mixture was extracted with EtOAc (×2) and the combined organic extracts were washed with aq. NaHCO3, brine, dried (MgSO4), filtered, and concentrated to yield 10.5 g (99%) of the title compound as a clear oil. 1H NMR (400 MHz, Chloroform-d) δ 7.73 (d, 1H), 7.50 (d, 1H), 7.19-7.11 (m, 1H), 3.92 (s, 3H), 2.36 (s, 3H).

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe volatile organics were removed under reduced pressure
  3. additionthe residue was poured onto ice-water (100 mL)
  4. extractionThe mixture was extracted with EtOAc (×2)
  5. washthe combined organic extracts were washed with aq. NaHCO3, brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-0706de861294474e81660d3f26fff5fd
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

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