Benzoyl Peroxide → 4-Bromo-1-(bromomethyl)-2-chlorobenzene

HRID 1455205Notes

Reaction equation

HRID 1455205 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[C:4]([Cl:9])[CH:3]=1.[Br:10]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][Br:10])=[C:4]([Cl:9])[CH:3]=1

Participants

5

Reactant 3

HCID 7187Benzoyl Peroxide2×HCID 67184N-bromobutanimideHCID 27355544-Bromo-2-chlorotoluene

Product 1

HCID 219144864-Bromo-1-(bromomethyl)-2-chlorobenzeneYield 60%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

4-Bromo-2-chloro-1-methyl-benzene (2.5 mL, 18.7 mmoles) and N-bromosuccinimide (4.0 g, 22.5 mmoles) were dissolved into 50 mL of CCl4. To this stirring mix was added benzoyl peroxide (0.5 g, 2.1 mmoles) and the solution was irradiated using white light. Enough light intensity was utilized to affect gentle reflux for 2 hours. After this period the mixture was cooled to ambient temperature and benzoyl peroxide (0.5 g, 2.1 mmoles) was added. Again, the mix was irridiated to reflux for a period of 2 hours. After this period the reaction mix was chilled to ambient temperature and was gravity filtered. The filtrate was evaporated in vacuo and the resulting crude residue was purified using flash silica chromatography (0-1% EtOAc/Hexane) to yield 4-bromo-1-bromomethyl-2-chloro-benzene (3.04 g, 60%) as a clear liquid. 1H-NMR (CDCl3): δ 7.57 (d, J=2.0 Hz, 1H), 7.39 (dd, J′=8.3 Hz, J″=1.8 Hz, 1H), 7.31 (d, J=8.1 Hz, 1H), 4.53 (s, 2H).

Workup

  1. additionTo this stirring mix
  2. customthe solution was irradiated
  3. temperatureto affect gentle reflux for 2 hours
  4. temperatureto reflux for a period of 2 hours
  5. additionAfter this period the reaction mix
  6. temperaturewas chilled to ambient temperature
  7. filtrationfiltered
  8. customThe filtrate was evaporated in vacuo
  9. customthe resulting crude residue was purified

Sources & evidence

ORD record
ord-e87d743d2df045f18c8ee505e758e042
Source dataset
uspto-grants-2009_01
Patent number
US07482366B2

Reaction notes

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