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

HRID 2168554Notes

Reaction equation

HRID 2168554 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-815fefd4c1014c5d8181696a8d68d0dd
Source dataset
uspto-grants-2015_06
Patent number
US09045501B2

Reaction notes

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