Nitrobenzene → N,N,N',N'-tetra(3-biphenylyl)benzidine

HRID 481933

Reaction equation

HRID 481933 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11](I)=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[N+:21]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([O-])=O>[Cu]>[C:5]1([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:7][CH:2]=[C:3]([N:21]([C:10]2[CH:9]=[C:8]([C:5]3[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=3)[CH:13]=[CH:12][CH:11]=2)[C:24]2[CH:29]=[CH:28][C:27]([C:27]3[CH:28]=[CH:29][C:24]([N:21]([C:10]4[CH:9]=[C:8]([C:5]5[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=5)[CH:13]=[CH:12][CH:11]=4)[C:3]4[CH:4]=[C:5]([C:8]5[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=5)[CH:6]=[CH:7][CH:2]=4)=[CH:25][CH:26]=3)=[CH:26][CH:25]=2)[CH:4]=1

Participants

5

Reactant 3

HCID 7416NitrobenzeneHCID 11430Potassium CarbonateHCID 763484,4'-Diiodo-1,1'-biphenyl

Product 1

HCID 22013501N,N,N',N'-tetra(3-biphenylyl)benzidineYield 55.7%

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Procedure

A 500-ml reactor was charged with 44.5 g (0.139 mol) of di(3-biphenyl)amine, 27.6 g (0.0680 mol) of 4,4'-diiodobiphenyl, 34.3 g (0.249 mol) of potassium carbonate, 2.3 g of copper powder, and 180 ml of nitrobenzene. In an argon stream, the contents were heated under reflux for 24 hours. At the end of reaction, the insoluble was removed by filtration and the filtrate was distilled of the solvent. The still residue was purified through a silica gel column with a 3/1 mixture of n-hexane and toluene, obtaining 30 g of N,N,N',N'-tetra(3-biphenylyl)benzidine of primary purity grade (yield 55.7%). It was further purified by recrystallization from toluene, obtaining 6.0 g of a 99.58% pure fraction and 5.0 g of a 99.23% pure fraction (combined yield 20.496). Further purification by sublimation yielded 8.0 g of a 99.99% pure product.

Workup

  1. temperatureIn an argon stream, the contents were heated
  2. temperatureunder reflux for 24 hours
  3. customAt the end of reaction
  4. customthe insoluble was removed by filtration
  5. distillationthe filtrate was distilled of the solvent
  6. customThe still residue was purified through a silica gel column with a 3/1 mixture of n-hexane and toluene

Sources & evidence

ORD record
ord-ac37574bc2a1464ca3e20107cedb7833
Source dataset
uspto-grants-1998_08
Patent number
US05792557

Linked notes

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