Benzoyl Peroxide → Methyl 2-(bromomethyl)-5-fluorobenzoate

HRID 2252806Notes

Reaction equation

HRID 2252806 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[Br:13]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:13][CH2:12][C:5]1[CH:4]=[CH:3][C:2]([F:1])=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 7187Benzoyl Peroxide2×HCID 67184N-bromobutanimide2×HCID 23555748Methyl 5-fluoro-2-methylbenzoate

Product 1

HCID 15155455Methyl 2-(bromomethyl)-5-fluorobenzoate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

With no precautions to maintain a dry atmosphere, methyl 5-fluoro-2-methylbenzoate (Maybridge, 5 g, 29.7 mmole) was dissolved in CCl4 (50 mL). N-bromosuccinimide (5.82 g, 32.7 mmol) and benzoyl peroxide (0.36 g, 1.48 mmole) were added and the reaction brought to reflux overnight. An additional 0.3 eq of NBS and 0.01 eq of benzoyl peroxide was added and the reaction refluxed for 4 hrs, then cooled, filtered and concentrated. The residue was chromatographed on silica eluting with a gradient of 0-10% EtOAc/Hexanes. The fractions were collected to give the product, which was a mixture of mono and bis-brominated materials, as a clear oil.

Workup

  1. temperatureto reflux overnight
  2. temperaturethe reaction refluxed for 4 hrs
  3. temperaturecooled
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was chromatographed on silica eluting with a gradient of 0-10% EtOAc/Hexanes
  7. customThe fractions were collected
  8. customto give the product, which
  9. additiona mixture of mono and bis-brominated materials

Sources & evidence

ORD record
ord-bf0c18cac8fb420ab5afbaf7857b43fd
Source dataset
uspto-grants-2008_01
Patent number
US07323460B2

Reaction notes

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