Water → 2-Bromo-4-nitrobenzoic acid

HRID 1739140Notes

Reaction equation

HRID 1739140 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH3:11].N1C=CC=CC=1.[O-:18][Mn](=O)(=O)=O.[K+].[OH2:24]>>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11]([OH:18])=[O:24]

Participants

5

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 821892-Bromo-4-nitrotolueneHCID 516875Potassium Permanganate

Product 1

HCID 3135342-Bromo-4-nitrobenzoic acid

Conditions

Temperature
60 °C

Procedure

2-bromo-4-nitrotoluene (5.00 g, 23.14 mmol) was dissolved into pyridine (23 ml) and water (46 ml). The heterogeneous mixture was heated to 60° C. and KMnO4 (18.29 g, 115.7 mmol) was added carefully. The mixture was then heated under reflux overnight. The reaction mixture was filtered and washed with boiling water. The solution was then made acidic and extracted into ethyl acetate, dried over Na2SO4, and the solvent was removed in vacuo. A crude NMR revealed remaining starting material so the solid was taken up in NaOH and washed with hexanes. The aqueous phase was made acidic and the product was extracted into ethyl acetate. The ethyl acetate fractions were combined and dried over Na2SO4 and the solvent was removed in vacuo to yield 3.72 g (65.4%). mp 158-160° C.; 1H NMR (CD3OD) 7.81 (1H, d, J=8.5 Hz), 8.08 (1H, d, J=8.5 Hz), 8.30 (1H, s); 13C NMR (CD3OD) 121.96, 122.75, 129.36, 132.24, 139.52, 149.54, 167.75; anal. calc. for C7H4BrNO4 +0.1 ethyl acetate, C: 34.88, H: 1.90, N: 5.50; found, C: 34.68, H: 1.86, N: 5.82.

Workup

  1. temperatureThe mixture was then heated
  2. temperatureunder reflux overnight
  3. filtrationThe reaction mixture was filtered
  4. washwashed with boiling water
  5. extractionmade acidic and extracted into ethyl acetate
  6. dry with materialdried over Na2SO4
  7. customthe solvent was removed in vacuo
  8. washwashed with hexanes
  9. extractionthe product was extracted into ethyl acetate
  10. dry with materialdried over Na2SO4
  11. customthe solvent was removed in vacuo
  12. customto yield 3.72 g (65.4%)

Sources & evidence

ORD record
ord-db4568f1a27240d6aa0127a0031cf6e6
Source dataset
uspto-grants-1999_10
Patent number
US05965539

Reaction notes

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