N-bromobutanimide → Methyl 3-(bromomethyl)-2-fluorobenzoate

HRID 1866917Notes

Reaction equation

HRID 1866917 reaction equation
[F:1][C:2]1[C:11]([CH3:12])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[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:11]1[C:2]([F:1])=[C:3]([CH:8]=[CH:9][CH:10]=1)[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 22049929Methyl 2-fluoro-3-methylbenzoate

Product 1

HCID 22050044Methyl 3-(bromomethyl)-2-fluorobenzoateYield 41.4%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

To a mixture of methyl 2-fluoro-3-methylbenzoate (1.5 g, 8.9 mmol) and N-bromosuccinimide (1.67 g, 9.4 mmol) was added carbon tetrachloride (24 mL) and benzoyl peroxide (5 mg), and the mixture was heated at reflux for 16 h. The reaction mixture was cooled, filtered, and concentrated under reduced pressure. Purification by flash column chromatography (silica, eluent 5:95 to 60:40 EtOAc/hexanes) afforded methyl 3-bromomethyl-2-fluorobenzoate as a light yellow solid (0.91 g, 41%): 1H NMR (300 MHz, CDCl3) δ 7.93-7.88 (m, 1H), 7.61-7.56 (m, 1H), 7.20 (t, J=8 Hz, 1H), 4.53 (d, J=3 Hz, 2H), 3.94 (s, 3H).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 16 h
  3. temperatureThe reaction mixture was cooled
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurification by flash column chromatography (silica, eluent 5:95 to 60:40 EtOAc/hexanes)

Sources & evidence

ORD record
ord-d6da7f443cde4ad382e59dc3898899d1
Source dataset
uspto-grants-2009_12
Patent number
US07629363B2

Reaction notes

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