Benzoyl Peroxide → Methyl 3-(bromomethyl)-2-fluorobenzoate

HRID 2369932Notes

Reaction equation

HRID 2369932 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 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 22049929Methyl 2-fluoro-3-methylbenzoate

Product 1

HCID 22050044Methyl 3-(bromomethyl)-2-fluorobenzoateYield 56.6%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of methyl 2-fluoro-3-methylbenzoate (13.8 g, 82.3 mmol) from Step A above and N-bromosuccinimide (16.0 g, 90.6 mmol) in carbon tetrachloride (82 mL) at room temperature was added a catalytic amount of benzoyl peroxide. The yellow mixture was heated under reflux until the reaction was complete by TLC (overnight) and then it was concentrated and purified by column chromatography (silica gel, 9:1 hexanes/ethyl acetate) to afford methyl 3-(bromomethyl)-2-fluorobenzoate as a light yellow oil (11.5 g, 56%): 1H NMR (500 MHz, CDCl3) δ 7.90 (t, J=8.0 Hz, 1H), 7.59 (t, J=7.5 Hz, 1H), 7.19 (t, J=7.5 Hz, 1H), 4.53 (s, 2H), 3.90 (s, 3H).

Workup

  1. temperatureThe yellow mixture was heated
  2. temperatureunder reflux until the reaction
  3. customwas complete by TLC (overnight)
  4. concentrationit was concentrated
  5. custompurified by column chromatography (silica gel, 9:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-f0faca8807264bb1adc3c0e9c5330a75
Source dataset
uspto-grants-2014_04
Patent number
US08710046B2

Reaction notes

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