Sulfuric Acid → 2-broMo-5-hydroxybenzoic acid Methyl ester

HRID 1363405Notes

Reaction equation

HRID 1363405 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8](N)[CH:7]=[CH:6][C:5]=1[Br:11].S(=O)(=O)(O)[OH:14].N([O-])=O.[Na+]>O.S([O-])([O-])(=O)=O.[Cu+2]>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([OH:14])[CH:7]=[CH:6][C:5]=1[Br:11]

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 245495Methyl 5-amino-2-bromobenzoateHCID 23668193Sodium Nitrite

Product 1

HCID 189336882-broMo-5-hydroxybenzoic acid Methyl ester

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent

Conditions

Temperature
2.5 °C

Procedure

Compound of example 151 (12 g, 52.1 mmol) was added to 10% aqueous sulfuric acid (110 mL) at 0° C. An aqueous solution (40 mL) of NaNO2 (4.3 g, 62.32 mmol) was added dropwise, with stirring at 0-5° C. The reaction mixture was stirred for 10 min. and was added to an ice cold aqueous solution of copper sulfate (156 g, 1 L, 625 mmol) containing Cu2O (6.8 g, 47.55 mmol). The resultant mixture was stirred at 0° C. for 10 min. It was diluted with water and extracted using EtOAc (3×500 mL). The organic extract was washed with water, dried (anhydrous Na2SO4), concentrated and purified using a silica gel column and 2% EtOAc in petroleum ether (60-80° C.) as eluant to obtain the title compound.

Workup

  1. stirringThe reaction mixture was stirred for 10 min.
  2. extractionextracted
  3. extractionThe organic extract
  4. washwas washed with water
  5. dry with materialdried (anhydrous Na2SO4)
  6. concentrationconcentrated
  7. custompurified
  8. customa silica gel column and 2% EtOAc in petroleum ether (60-80° C.)

Sources & evidence

ORD record
ord-08de6767ac80468d96d03632bf6b848f
Source dataset
uspto-grants-2011_02
Patent number
US07884127B2

Reaction notes

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