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

HRID 1831933Notes

Reaction equation

HRID 1831933 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-6fad3a7e9ee6479b8cf4345abd46ce04
Source dataset
uspto-grants-2006_06
Patent number
US07067540B2

Reaction notes

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