Hydrogen Bromide → HCID 59445916, compound

HRID 1191572Notes

Reaction equation

HRID 1191572 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11](N)=[C:10]([I:15])[CH:9]=2)=[CH:4][CH:3]=1.N([O-])=O.[Na+].C(OCC)(=O)C.[BrH:26]>O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2].[Cu]>[Br:26][C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=2)=[CH:9][C:10]=1[I:15]

Participants

8

Reactant 4

HCID 260Hydrogen Bromide2×HCID 8857Ethyl AcetateHCID 23668193Sodium NitriteHCID 59445936HCID 59445936, compound

Product 1

HCID 59445916HCID 59445916, compound

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolvent

Conditions

Temperature
45 °C

Procedure

4′-Chloro-3-iodobiphenyl-4-ylamine (13.5 g, 0.041 mol) is ground to a fine powder and suspended in a mixture of 48% aqueous hydrogen bromide (54 ml) and distilled water (42 ml). This suspension is then heated to 45° C. for 30 minutes, then cooled to 0-5° C. and a solution of sodium nitrite (3.54 g, 0.0125 mol) in distilled water (6 ml) is added dropwise, maintaining internal temperature below 5° C. throughout. This mixture is then added portionwise to a second pre-formed suspension of copper(II) sulfate pentahydrate (15 g, 0.06 mol) and copper powder (5.29 g, 0.084 mol) in 48% aqueous hydrogen bromide (80 ml) at 80° C. When the addition is complete the reaction mixture is stirred at 80° C. for an additional 90 minutes. After cooling to room temperature, ethyl acetate is added and the reaction mixture is poured into distilled water and the two layers separated. The aqueous phase is further extracted with ethyl acetate (×2), and the combined organic extracts are washed with distilled water until a neutral pH is achieved, then dried over anhydrous magnesium sulfate. The mixture is filtered, the filtrate is evaporated in vacuo, and the residue is further purified by flash column chromatography on silica gel (hexane eluant) to afford 4-bromo-4′-chloro-3-iodobiphenyl (10.5 g) as a pale orange liquid.

Workup

  1. distillationdistilled water (42 ml)
  2. temperaturecooled to 0-5° C.
  3. temperaturemaintaining internal temperature below 5° C. throughout
  4. additionWhen the addition
  5. temperatureAfter cooling to room temperature
  6. additionthe reaction mixture is poured
  7. distillationinto distilled water
  8. customthe two layers separated
  9. extractionThe aqueous phase is further extracted with ethyl acetate (×2)
  10. washthe combined organic extracts are washed with distilled water until a neutral pH
  11. dry with materialdried over anhydrous magnesium sulfate
  12. filtrationThe mixture is filtered
  13. customthe filtrate is evaporated in vacuo
  14. customthe residue is further purified by flash column chromatography on silica gel (hexane eluant)

Sources & evidence

ORD record
ord-1f322e92505f4bc19f3cfc4caadfa8b8
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

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