4-Aminobiphenyl → [1,1'-Biphenyl]-4-amine, N,N-bis(3,4-dimethylphenyl)-

HRID 1301

Reaction equation

HRID 1301 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.I[C:15]1[CH:16]=[C:17]([CH3:22])[C:18]([CH3:21])=[CH:19][CH:20]=1.[OH-].[K+]>C1(C)C=CC=CC=1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1>[CH3:22][C:17]1[CH:16]=[C:15]([N:1]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[C:17]([CH3:22])[CH:16]=2)[C:2]2[CH:3]=[CH:4][C:5]([C:8]3[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=3)=[CH:6][CH:7]=2)[CH:20]=[CH:19][C:18]=1[CH3:21]

Participants

6

Reactant 3

HCID 71024-AminobiphenylHCID 14797Potassium HydroxideHCID 1416464-Iodo-1,2-dimethylbenzene

Product 1

HCID 10595766[1,1'-Biphenyl]-4-amine, N,N-bis(3,4-dimethylphenyl)-Yield 70%

Reagents, catalysts & solvents 2

HCID 13181,10-PhenanthrolineCatalystHCID 1140TolueneSolvent

Conditions

Temperature
130 °C

Procedure

In a 250 milliliter round-bottomed flask equipped with mechanical stirrer and fitted with a Dean-Stark trap under a reflux condenser were placed 8.46 grams (0.05 mole) of 4-aminobiphenyl, 25.53 grams (0.11 mole) of 4-iodo-ortho-xylene, 0.25 gram (0.0025 mole) of cuprous chloride, 0.45 gram (0.0025 mole) of 1,10-phenanthroline, 22.4 grams (0.4 mole) of flake potassium hydroxide and 30 milliliters of toluene solvent. The reaction was heated quickly to a reflux temperature of 130° C. and maintained at this temperature for 4 hours, after which time chromatographic analysis revealed the reaction to be complete. The reaction mixture was allowed to attain room temperature, about 25° C., and was partitioned between 200 milliliters of toluene and 150 milliliters of deionized water. The resulting organic layer was separated and water was removed by azeotropic distillation of water under a Dean-Stark trap. The product was decolorized by slurry treating the toluene solution with 36 grams of Filtrol-24™, an acid-washed clay, and 24 grams of Alcoa CG-20 alumina. After 3 hours stirring at reflux, the solution was cooled to room temperature and filtered. The product of N,N-bis(3,4-dimethylphenyl)-4-biphenylamine was recovered from the filtrate by evaporation of the solvent. Recrystallization from 40 milliliters of a one to one mixture of ethylacetate-isopropanol provided 13.2 grams (70 percent) of the above product. Chromatographic analysis by high performance liquid chromatography illustrated an excellent product purity of 99.8 percent and a melting temperature, which was determined by differential scanning calorimetry to be 113.21° C.

Workup

  1. customIn a 250 milliliter round-bottomed flask equipped with mechanical stirrer
  2. customfitted with a Dean-Stark trap under a reflux condenser
  3. temperaturemaintained at this temperature for 4 hours
  4. customthe reaction
  5. customto attain room temperature, about 25° C.
  6. customwas partitioned between 200 milliliters of toluene and 150 milliliters of deionized water
  7. customThe resulting organic layer was separated
  8. customwater was removed by azeotropic distillation of water under a Dean-Stark trap
  9. additiontreating the toluene solution with 36 grams of Filtrol-24™
  10. temperatureat reflux
  11. temperaturethe solution was cooled to room temperature
  12. filtrationfiltered
  13. customThe product of N,N-bis(3,4-dimethylphenyl)-4-biphenylamine was recovered from the filtrate by evaporation of the solvent
  14. customRecrystallization from 40 milliliters of a one
  15. additionto one mixture of ethylacetate-isopropanol

Sources & evidence

ORD record
ord-c73a1583f23e4b29be1a2f3ab4c01786
Source dataset
uspto-grants-1998_03
Patent number
US05723671

Linked notes

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