Benzoyl Peroxide → 5-(Bromomethyl)-2-chlorobenzonitrile

HRID 508443Notes

Reaction equation

HRID 508443 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:10])=[C:6]([CH:9]=1)[C:7]#[N:8].[Br:11]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:11][CH2:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:10])=[C:6]([CH:9]=1)[C:7]#[N:8]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 125572002-Chloro-5-methylbenzonitrile

Product 1

HCID 140330355-(Bromomethyl)-2-chlorobenzonitrileYield 63.1%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 5-methyl-2-chlorobenzonitrile (200 mg, 1.32 mmol) in carbon tetrachloride (12 mL) was added N-bromosuccinimide (235 mg, 1.32 mmol) and benzoyl peroxide (32 mg, 0.132 mmol). The mixture was heated at reflux for 2 hours. The reaction was allowed to cool to room temperature and the solvent removed in vacuo. The resulting residue was partitioned between DCM and water. The organic layer was separated, dried over sodium sulphate and evaporated to give an orange oil. The oil was purified by silica gel chromatography eluting with 50% heptanes in DCM to afford the title compound (192 mg) as a 2:1:1 mixture with 5-methyl-2-chlorobenzonitrile and 2-chloro-5-(dibromomethyl)benzonitrile respectively, which was used in the next step without further purification.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 2 hours
  3. customthe solvent removed in vacuo
  4. customThe resulting residue was partitioned between DCM and water
  5. customThe organic layer was separated
  6. dry with materialdried over sodium sulphate
  7. customevaporated
  8. customto give an orange oil
  9. customThe oil was purified by silica gel chromatography
  10. washeluting with 50% heptanes in DCM

Sources & evidence

ORD record
ord-205e3575f5d9492db08d316aaefc5b11
Source dataset
uspto-grants-2015_08
Patent number
US09096500B2

Reaction notes

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