Nitrobenzene → 4'-ethyl-N-(4'-methoxy-[1,1'-biphenyl]-4-yl)-N-(4-methylphenyl)-[1,1'-biphenyl]-4-amine

HRID 52816Notes

Reaction equation

HRID 52816 reaction equation
[CH2:1]([C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][C:12]([NH:15][C:16]3[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][CH:17]=3)=[CH:11][CH:10]=2)=[CH:5][CH:4]=1)[CH3:2].[N+]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)([O-])=O.[C:32](=[O:35])([O-])[O-].[K+].[K+]>C1CCCCC1.C1(C)C=CC=CC=1.[Cu]>[CH2:1]([C:3]1[CH:4]=[CH:5][C:6]([C:9]2[CH:14]=[CH:13][C:12]([N:15]([C:29]3[CH:30]=[CH:31][C:26]([C:3]4[CH:8]=[CH:7][C:6]([O:35][CH3:32])=[CH:5][CH:4]=4)=[CH:27][CH:28]=3)[C:16]3[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][CH:17]=3)=[CH:11][CH:10]=2)=[CH:7][CH:8]=1)[CH3:2]

Participants

7

Reactant 3

HCID 7416NitrobenzeneHCID 11430Potassium CarbonateHCID 199639404'-ethyl-N-(4-methylphenyl)-[1,1'-biphenyl]-4-amine

Product 1

HCID 151001124'-ethyl-N-(4'-methoxy-[1,1'-biphenyl]-4-yl)-N-(4-methylphenyl)-[1,1'-biphenyl]-4-amine

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 1140TolueneSolventHCID 8078CyclohexaneSolvent

Conditions

Temperature
210 °C

Procedure

To 4.31 g (15.0 mmol) of the thus obtained 4'-ethyl-N-(4-methylphenyl) -[1,1'-biphenyl]-4-amine were added 60 ml of nitrobenzene, 5.58 g (18.0 mmol) of 4'-iodine-4'-methoxy-[1,1'-biphenyl], 4.15 g of potassium carbonate, and 0.48 g of copper powder. The mixture was placed in an ester pipe and azeotropically heated for dehydration, with stirring, at 210° C. for 11 hours as a nitrogen gas was caused to flow over the mixture. The reaction mixture was then cooled to room temperature and filtered through a Celite filter to obtain a filtrate. The nitrobenzene was distilled away from the filtrate under reduced pressure. The residue was extracted with toluene, washed with water, dried by use of magnesium sulfate, and condensed under reduced pressure, whereby orange brown crystals were obtained. The thus obtained product was subjected to a silica gel column chromatography by use of a mixed solvent of cyclohexane and toluene as an eluent, and recrystallized from a mixed solvent of ethanol and toluene, whereby 4'-ethyl-N-(4'-methoxy-[1,1'-biphenyl]-4-yl)-N-(4-methylphenyl)-[1,1'-biphenyl]-4-amine (Aminobiphenyl Compound No. 2-62 in Table 3) was obtained in the form of colorless needles with a yield of 4.00 g (56.8%). The melting point of the product was 159.5° C. to 161.5° C.

Workup

  1. temperatureazeotropically heated for dehydration
  2. temperatureThe reaction mixture was then cooled to room temperature
  3. filtrationfiltered through a Celite
  4. filtrationfilter
  5. customto obtain a filtrate
  6. distillationThe nitrobenzene was distilled away from the filtrate under reduced pressure
  7. extractionThe residue was extracted with toluene
  8. washwashed with water
  9. dry with materialdried by use of magnesium sulfate, and condensed under reduced pressure, whereby orange brown crystals
  10. customwere obtained
  11. customrecrystallized from a mixed solvent of ethanol and toluene

Sources & evidence

ORD record
ord-3f160b61d77544ccad66fe5ed850a087
Source dataset
uspto-grants-1997_04
Patent number
US05616801

Reaction notes

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