1-Bromo-4-nitrobenzene → 4-Nitro-1,1'-biphenyl

HRID 1955962Notes

Reaction equation

HRID 1955962 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[C:11]1([Sn])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>CN(C=O)C.C1COCC1>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:3][CH:4]=1)([O-:10])=[O:9].[C:2]1([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 114661-Bromo-4-nitrobenzeneHCID 5477253HCID 5477253, compound

Product 2

HCID 7095BiphenylYield 5%HCID 71144-Nitro-1,1'-biphenylYield 85%

Reagents, catalysts & solvents 1

HCID 21974620tetrahydrofuran N,N-dimethylformamideSolvent

Procedure

A preparative reaction was conducted with 0.40 g of p-bromonitrobenzene (2 mmol) and 2.97 g of phenyltin reactant 1a (2.4 mmol) in 10 mL 1/1 DMF/THF at 80° C. for approximately 22 hours. Both reactants were consumed according to TLC analysis. After azeotropic evaporation with toluene at 75° C. (to remove some of the solvent), a three-phase extraction was conducted as described above. The methylene chloride phase was then washed three more times with water and FC-72 (together) to remove DMF and fluorous products. The crude organic product was purified by flash chromatography to provide 337 mg (85%) of 4-nitrobiphenyl and 17 mg (5%) of biphenyl. The crude fluorous tin chloride (99%) from the FC-72 phase was reacted with phenyl magnesium bromide to provide 2.85 g (96% overall) of the original tin reactant la after purification by passing through a short column of neutral alumina.

Workup

  1. customA preparative reaction
  2. customBoth reactants were consumed
  3. customAfter azeotropic evaporation with toluene at 75° C. (
  4. customto remove some of the solvent),
  5. extractiona three-phase extraction
  6. washThe methylene chloride phase was then washed three more times with water and FC-72 (together)
  7. customto remove DMF and fluorous products
  8. customThe crude organic product was purified by flash chromatography

Sources & evidence

ORD record
ord-cdc3a3ca9eef4ddcbdcb640469bf9a51
Source dataset
uspto-grants-1998_07
Patent number
US05777121

Reaction notes

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