Benzoyl Peroxide → Methyl 3-(bromomethyl)-4-chlorobenzoate

HRID 1356587Notes

Reaction equation

HRID 1356587 reaction equation
[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].[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:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[Cl:1])[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 7015786Benzoic acid, 4-chloro-3-methyl-, methyl ester

Product 1

HCID 12144656Methyl 3-(bromomethyl)-4-chlorobenzoateYield 53%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
90 °C

Procedure

To a suspension of methyl 4-chloro-3-methylbenzoate I (19.9 g, 108 mmol) and N-bromosuccinimide (NBS, 20.2 g, 114 mmol) in carbon tetrachloride (500 mL) was added benzoyl peroxide (1.30 g, 5.4 mmol), and the mixture was stirred at 90° C. overnight. The mixture was then cooled and the white precipitate was removed by filtration. The filtrate was concentrated and the resulting solid was re-crystallized from ethyl acetate to give methyl 3-bromomethy-4-chlorobenzoate II (15.0 g, 57 mmol, 53%) as a white solid: 1H NMR (CDCl3) δ 3.95 (s, 3H), 4.63 (s, 2H), 7.49 (d, J=8.3 Hz, 1H), 7.94 (dd, J=2.1, 8.3 Hz, 1H), 8.15 (d, J=2.1 Hz, 1H).

Workup

  1. temperatureThe mixture was then cooled
  2. customthe white precipitate was removed by filtration
  3. concentrationThe filtrate was concentrated
  4. customthe resulting solid was re-crystallized from ethyl acetate

Sources & evidence

ORD record
ord-0845532cf2a74e47bb5233d337d35281
Source dataset
uspto-grants-2003_07
Patent number
US06586623B2

Reaction notes

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