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

HRID 906838Notes

Reaction equation

HRID 906838 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 irradiated 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. customAgain, the mix was irradiated
  5. temperatureto reflux for a period of 2 hours
  6. additionAfter this period the reaction mix
  7. temperaturewas chilled to ambient temperature
  8. filtrationfiltered
  9. customThe filtrate was evaporated in vacuo
  10. customthe resulting crude residue was purified

Sources & evidence

ORD record
ord-9eb9da79362c4ec982af333101cd6aeb
Source dataset
uspto-grants-2011_09
Patent number
US08013001B2

Reaction notes

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