p-Toluenesulfonic acid → Methyl 3-bromo-5-hydroxybenzoate

HRID 2188930Notes

Reaction equation

HRID 2188930 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([OH:11])[CH:10]=1)[C:5]([OH:7])=[O:6].[CH3:12]C1C=CC(S(O)(=O)=O)=CC=1.C([O-])(O)=O.[Na+]>CO>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([OH:11])[CH:10]=1)[C:5]([O:7][CH3:12])=[O:6]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 516892Sodium BicarbonateHCID 157355113-Bromo-5-hydroxybenzoic acid

Product 1

HCID 53216607Methyl 3-bromo-5-hydroxybenzoateYield 627.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of 3-bromo-5-hydroxybenzoic acid (3.8 g, 18 mmol) and p-TsOH (350 mg, 2.0 mmol) in MeOH (100 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature. Saturated aqueous NaHCO3 (100 mL) was added and the mixture was extracted with dichloromethane (100 mL×3). The combined organic layers were washed with brine and water, dried over anhydrous Na2SO4, and concentrated under vacuum to afford methyl 3-bromo-5-hydroxybenzoate (2.9 g, 73%) as a white solid. 1H NMR (300 MHz, CDCl3) δ 7.74 (t, J=1.5 Hz, 1H), 7.50 (dd, J=1.2, 2.4 Hz, 1H), 7.23 (t, J=2.1, 1H), 5.68 (brs, 1H), 3.92 (s, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. extractionthe mixture was extracted with dichloromethane (100 mL×3)
  4. washThe combined organic layers were washed with brine and water
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-280a0b175e494d4b999b8f5cfbe2d84e
Source dataset
uspto-grants-2012_12
Patent number
US08324207B2

Reaction notes

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