Hydrogen Bromide → Methyl 3-bromo-4-cyanobenzoate

HRID 746775Notes

Reaction equation

HRID 746775 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[N:11])=[C:6](N)[CH:5]=1.N([O-])=O.[Na+].[BrH:18]>S(=O)(=O)(O)O.C(O)(=O)C.[Cu](Br)Br>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[N:11])=[C:6]([Br:18])[CH:5]=1

Participants

7

Reactant 3

HCID 260Hydrogen BromideHCID 10261604Methyl 3-amino-4-cyanobenzoateHCID 23668193Sodium Nitrite

Product 1

HCID 23379143Methyl 3-bromo-4-cyanobenzoateYield 56%

Reagents, catalysts & solvents 3

HCID 24611Copper bromide (CuBr2)CatalystHCID 176Acetic AcidSolventHCID 1118Sulfuric AcidSolvent

Conditions

Temperature
90 °C

Procedure

Add 3-amino-4-cyano-benzoic acid methyl ester (1.1 g, 6.24 mmol) to a stirred solution of sodium nitrite (511 mg, 7.4 mmol) in concentrated sulfuric acid (5 ml) and glacial acetic acid (5 ml) at 40° C. After 30 min at 40° C., pour the resulting orange solution into a cold solution of copper bromide (1.42 g, 9.89 mmol) in 48% hydrobromic acid (5 ml). When the evolution of nitrogen is finished, heat the mixture to 90° C. for 30 min. Cool down to room temperature and pour the mixture onto crushed ice. Filter out the resulting dark solid, wash with water. Take this solid up in chloroform and filter the inorganic solid. Concentrate the filtrate to yield a crude yellow residue. Purification by flash chromatography (Silica gel-hexane/EtOAc) yields the title compound (56%).

Workup

  1. temperatureCool down to room temperature
  2. additionpour the mixture
  3. customonto crushed ice
  4. filtrationFilter out the resulting dark solid
  5. washwash with water
  6. filtrationfilter the inorganic solid
  7. concentrationConcentrate the filtrate
  8. customto yield a crude yellow residue
  9. customPurification by flash chromatography (Silica gel-hexane/EtOAc)

Sources & evidence

ORD record
ord-d919c9ba7577405dbb03d6e86917edd7
Source dataset
uspto-grants-2008_07
Patent number
US07393868B2

Reaction notes

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