Ethanol → Ethyl 4-bromo-3-hydroxybenzoate

HRID 908059Notes

Reaction equation

HRID 908059 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]=1[OH:11].[CH3:12][CH2:13]O.CS(O)(=O)=O>C1C=CC=CC=1>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([O:8][CH2:12][CH3:13])=[O:7])=[CH:4][C:3]=1[OH:11]

Participants

5

Reactant 3

HCID 702EthanolHCID 6395Methanesulfonic AcidHCID 64209734-Bromo-3-hydroxybenzoic acid

Product 1

HCID 12134897Ethyl 4-bromo-3-hydroxybenzoateYield 90%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a mixture containing 4-bromo-3-hydroxybenzoic acid (5.0 g, 0.023 mol) and 5 ml of EtOH in 150 ml of benzene was added 1 ml of MeSO3H. The mixture was heated at reflux for 10 h using a Dean-Stark trap to collect water, then concentrated. The residue was dissolved in CH2Cl2, washed (water, 5% NaHCO3, and brine), dried (Na2SO4), and concentrated. The crude product was chromatographed (EtOAc/hexane) to gave a white solid (5.1 g, 90%): 1H NMR (300 MHz, CDCl3) δ 1.39 (t, J=7.2 Hz, 3 H), 4.37 (q, J=7.2 Hz, 2 H), 5.75 (s, 1 H), 7.48 (d, J=8.1 Hz, 1 H), 7.55 (d, J=8.1 Hz, 1 H), 7.68 ppm (s, 1 H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 10 h
  3. customto collect water
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in CH2Cl2
  6. washwashed (water, 5% NaHCO3, and brine)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. customThe crude product was chromatographed (EtOAc/hexane)

Sources & evidence

ORD record
ord-8ccfc5203bd449389630e75b8ad8a43a
Source dataset
uspto-grants-2011_09
Patent number
USRE042700E1

Reaction notes

Loading…