Bromobenzene → 4-Chlorobiphenyl

HRID 1937039Notes

Reaction equation

HRID 1937039 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](B(O)O)=[CH:4][CH:3]=1.Br[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[Na+].[Na+].[Cl-].[Li+]>O1CCCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 7961BromobenzeneHCID 10340Sodium CarbonateHCID 742994-Chlorophenylboronic acidHCID 433294Lithium Chloride

Product 1

HCID 163234-ChlorobiphenylYield 97%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 100 mmol of p-chlorophenylboronic acid (15.7 g), 98 mmol of bromobenzene (15.4 g), 110 mmol of anhydrous sodium carbonate (11.7 g), 0.1 mmol of trans-di-μ-acetato-bis[2-[bis(1,1-dimethylethyl)phosphino]-2 methylpropyl-C,P]dipalladium (0.2 mol %), 10 mmol of lithium chloride (0.43 g) and 100 ml of tetrahydrofuran was refluxed for 2.5 hours. After distilling off as much of the THF as possible under atmospheric pressure and replacing it by 100 ml of toluene, the mixture was hydrolyzed with 150 ml of water. The aqueous phase was extracted with a further 50 ml of toluene and the organic phase was washed with 50 ml of water. Distillation of the combined organic phases gave 4-chlorobiphehyl in a yield of 97% (based on bromobenzene).

Workup

  1. temperaturewas refluxed for 2.5 hours
  2. distillationAfter distilling off as much of the THF as possible under atmospheric pressure
  3. extractionThe aqueous phase was extracted with a further 50 ml of toluene
  4. washthe organic phase was washed with 50 ml of water
  5. distillationDistillation of the combined organic phases
  6. customgave 4-chlorobiphehyl in a yield of 97% (based on bromobenzene)

Sources & evidence

ORD record
ord-7d85a1302dc642438c76044ebba01f48
Source dataset
uspto-grants-2002_05
Patent number
US06392047B1

Reaction notes

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