Sulfuric Acid → 3-Bromo-5-nitrophenol

HRID 2077262Notes

Reaction equation

HRID 2077262 reaction equation
N[C:2]1[C:7]([Br:8])=[CH:6][C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[OH:12].S(=O)(=O)(O)O.N([O-])=O.[Na+]>CCO>[Br:8][C:7]1[CH:2]=[C:3]([OH:12])[CH:4]=[C:5]([N+:9]([O-:11])=[O:10])[CH:6]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 23668193Sodium NitriteHCID 49766558HCID 49766558, compound

Product 1

HCID 104889843-Bromo-5-nitrophenolYield 85.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Compound 98 (33.0 g, 0.14 mol) was treated with sulfuric acid (13.7 mL) and was refluxed in EtOH (550 mL) for 0.5 hours, followed by addition of NaNO2 (23.8 g, 0.35 mol). The resulting mixture was refluxed for additional 1 hour and the volatile was evaporated. The residue was taken up with ethyl acetate and water. The layers were separated and the organic layer was washed with water, saturated sodium bicarbonate, and brine. After removal of solvent, the residue was purified by column chromatography on silica gel to afford the title compound (26 g, 85%); 1H NMR (500 MHz, CD3OD): δ 5.00 (brs, 1H), 7.58 (dd, 1H, J=1.7, 2.3 Hz), 7.47 (t, 1H, J=2.1 Hz), 7.69 (t, 1H, J=1.9 Hz); 13C NMR (125 MHz, CD3OD): δ 110.5, 118.1, 123.7, 125.6, 151.0, 160.5; HRMS (FAB) calcd for C6H4BrNO3 (M+) 216.9375, found 216.9374.

Workup

  1. temperatureThe resulting mixture was refluxed for additional 1 hour
  2. customthe volatile was evaporated
  3. customThe layers were separated
  4. washthe organic layer was washed with water, saturated sodium bicarbonate, and brine
  5. customAfter removal of solvent
  6. customthe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-8923048c4b1446ea83a6241bb12701aa
Source dataset
uspto-grants-2011_04
Patent number
US07928127B2

Reaction notes

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