Benzoyl Peroxide → Ethyl 2-(bromomethyl)-5-chlorobenzoate

HRID 1640006Notes

Reaction equation

HRID 1640006 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([CH:12]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8].[Br:14]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>ClCCCl>[Br:14][CH2:13][C:5]1[CH:4]=[CH:3][C:2]([Cl:1])=[CH:12][C:6]=1[C:7]([O:9][CH2:10][CH3:11])=[O:8]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 21269135Ethyl 5-chloro-2-methylbenzoate

Product 1

HCID 13272463Ethyl 2-(bromomethyl)-5-chlorobenzoateYield 69.2%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
75 °C

Procedure

A mixture of ethyl 5-chloro-2-methylbenzoate (3.20 g, 16.1 mmol), N-bromosuccinimide (3.15 g, 17.7 mmol) and benzoyl peroxide (0.39 g, 1.61 mmol) in 1,2-dichloroethane (90 mL) was heated to 75° C. in an oil bath for 4 h. After this time, the mixture was cooled to room temperature and the organic layer was washed with water (45 mL) and brine (45 mL). The organic layer was then dried over magnesium sulfate and concentrated under reduced pressure. Purification by flash chromatography (silica, 1:20 ethyl acetate/hexanes) afforded ethyl 2-(bromomethyl)-5-chlorobenzoate (3.09 g, 68%) as a clear oil: 1H NMR (500 MHz, CDC13) 7.94 (d, J=2.5 Hz, 1H), 7.46 (dd, J=8.5, 2.5 Hz, 1H), 7.40 (d, J=8.0 Hz, 1H), 4.91 (s, 2H), 4.42 (q, J=7.0 Hz, 2H), 1.43 (t, J=7.0 Hz, 3H); ESI MS m/z 279 [(M+2)+H]+.

Workup

  1. temperatureAfter this time, the mixture was cooled to room temperature
  2. washthe organic layer was washed with water (45 mL) and brine (45 mL)
  3. dry with materialThe organic layer was then dried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customPurification by flash chromatography (silica, 1:20 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-df0590a0be1340c3a625f52c44e55cf8
Source dataset
uspto-grants-2012_02
Patent number
US08110681B2

Reaction notes

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