Benzene → 4-Bromo-2-chlorobiphenyl

HRID 1777336Notes

Reaction equation

HRID 1777336 reaction equation
N(OCC(C)C)=O.[Br:8][C:9]1[CH:15]=[CH:14][C:12](N)=[C:11]([Cl:16])[CH:10]=1.S(=O)(=O)(O)O.[CH:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>>[Br:8][C:9]1[CH:15]=[CH:14][C:12]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[C:11]([Cl:16])[CH:10]=1

Participants

5

Reactant 4

HCID 241BenzeneHCID 1118Sulfuric AcidHCID 10958Isobutyl nitriteHCID 6101694-Bromo-2-chloroaniline

Product 1

HCID 134574164-Bromo-2-chlorobiphenyl

Conditions

Temperature
52.5 °C

Procedure

Isobutyl nitrite (121 g, 1.17 mol) and cupric chloride (21.2 g, 0.16 mol) are added to a solution of 4-bromo-2-chloroaniline (200 g, 0.97 mol) in benzene (500 mL) at 60-65° C. temperature. The reaction mixture is refluxed for 2 hrs. The reaction mixture is cooled to 50-55° C. temperature and to it a solution of aqueous sulfuric acid (92 mL conc. Sulfuric acid in 453 mL demineralized water). After refluxing for 1 hr the reaction mixture is cooled to room temperature and organic layer is separated. It is treated with an aqueous solution of urea (41 g in 127 mL water) and refluxed for 1 hr. Organic layer is separated, washed with demineralized water (2×200 mL) and dried over sodium sulfate. After removing the solvent under reduced pressure the residue is fractionally distilled to get 4-bromo-2-chlorobiphenyl.

Workup

  1. temperatureThe reaction mixture is refluxed for 2 hrs
  2. temperatureAfter refluxing for 1 hr the reaction mixture
  3. temperatureis cooled to room temperature
  4. customorganic layer is separated
  5. additionIt is treated with an aqueous solution of urea (41 g in 127 mL water)
  6. temperaturerefluxed for 1 hr
  7. customOrganic layer is separated
  8. washwashed with demineralized water (2×200 mL)
  9. dry with materialdried over sodium sulfate
  10. customAfter removing the solvent under reduced pressure the residue
  11. distillationis fractionally distilled

Sources & evidence

ORD record
ord-f2d136161a95472dbdac1c4a86d32c52
Source dataset
uspto-grants-2016_02
Patent number
US09266867B2

Reaction notes

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