Azobisisobutyronitrile → Methyl 4-(bromomethyl)-3-fluorobenzoate

HRID 220769Notes

Reaction equation

HRID 220769 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[C:6]([F:11])[CH:5]=1.CC(N=NC(C#N)(C)C)(C#N)C.[Br:25]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][Br:25])=[C:6]([F:11])[CH:5]=1

Participants

5

Reactant 3

HCID 6547Azobisisobutyronitrile2×HCID 67184N-bromobutanimide2×HCID 18973767Methyl 3-fluoro-4-methylbenzoate

Product 1

HCID 18766370Methyl 4-(bromomethyl)-3-fluorobenzoateYield 41%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

3-Fluoro-4-methylbenzoic acid methyl ester from Example E3.1 (4.5 g, 26.6 mmol) was dissolved in carbon tetra-chloride (150 ml). AIBN (457 mg, 2.7 mmol) and N-bromosuccinimide (5.2 g, 29.3 mmol) were added and the mixture was heated at reflux for 18 h. The mixture was allowed to cool and further portions of AIBN (457 mg, 2.7 mmol) and N-bromosuccinimide (5.2 g, 29.3 mmol) were added. The mixture was heated at reflux for 56 h. The mixture was allowed to cool and evaporated in vacuo. The residue was purified by flash chromatography on silica gel (eluant; 10% EtOAc:90% pet ether) to yield the title compound (2.7 g, 41%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 18 h
  3. temperatureto cool
  4. temperatureThe mixture was heated
  5. temperatureat reflux for 56 h
  6. temperatureto cool
  7. customevaporated in vacuo
  8. customThe residue was purified by flash chromatography on silica gel (eluant; 10% EtOAc:90% pet ether)

Sources & evidence

ORD record
ord-ceedca7d4dee4d5a8e1f4f8cf1f2922c
Source dataset
uspto-grants-2012_06
Patent number
US08202858B2

Reaction notes

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