Dodecane → N4,N4-di([1,1'-biphenyl]-4-yl)-N4'-phenyl-[1,1'-biphenyl]-4,4'-diamine

HRID 1158220Notes

Reaction equation

HRID 1158220 reaction equation
IC1C=CC([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[N:14](C(=O)C)C2C=CC=CC=2)=CC=1.[C:24]1([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH:29]=[CH:28][C:27]([NH:30][C:31]2[CH:36]=[CH:35][C:34]([C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)=[CH:33][CH:32]=2)=[CH:26][CH:25]=1.C(=O)([O-])[O-].[K+].[K+].[CH3:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH3:66].[OH-].[K+]>C(O)CC(C)C.[Cu].O>[C:34]1([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH:35]=[CH:36][C:31]([N:30]([C:64]2[CH:65]=[CH:66][C:61]([C:60]3[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=3)=[CH:62][CH:63]=2)[C:27]2[CH:26]=[CH:25][C:24]([C:43]3[CH:44]=[CH:45][C:46]([NH:14][C:9]4[CH:10]=[CH:11][CH:12]=[CH:13][CH:8]=4)=[CH:47][CH:48]=3)=[CH:29][CH:28]=2)=[CH:32][CH:33]=1

Participants

9

Reactant 5

HCID 8182DodecaneHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 504244Bis-biphenyl-4-yl-amineHCID 23140821N-(4'-iodobiphenylyl)acetanilide

Product 1

HCID 23140819N4,N4-di([1,1'-biphenyl]-4-yl)-N4'-phenyl-[1,1'-biphenyl]-4,4'-diamineYield 69.9%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 962WaterSolventHCID 31260Isoamyl AlcoholSolvent

Procedure

There were mixed 20.70 g (0.050 mole) of N-(4′-iodobiphenylyl)acetanilide, 19.95 g (0.060 mole) of N,N-bis(biphenyl-4-yl)amine, 10.40 g (0.075 mole) of anhydrous potassium carbonate, 0.20 g (0.003 mole) of copper powder and 10 ml of n-dodecane, followed by reaction at 200 to 212° C. for 15 hours. The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration. Then, the filtrate was concentrated to obtain crude crystals. The crude crystals were dissolved in 80 ml of isoamyl alcohol, and 5 ml of water and 5.00 g (0.075 mole) of 85% potassium hydroxide were added, followed by hydrolysis at 130° C. After isoamyl alcohol was removed by steam distillation, extraction with 250 ml of toluene was performed, and the organic layer was washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier: silica gel, eluate: toluene/n-hexane=1/2) to obtain 24.2 g (yield: 69.9%, HPLC purity: 98.0%) of N,N-bis(biphenyl-4-yl)-N′-phenyl-4,4′-diaminobiphenyl. The melting point was 145.8 to 146.0° C.

Workup

  1. customfollowed by reaction at 200 to 212° C. for 15 hours
  2. extractionThe reaction product was extracted with 200 ml of toluene
  3. customthe insoluble matter was removed by filtration
  4. concentrationThen, the filtrate was concentrated
  5. customto obtain crude crystals
  6. customfollowed by hydrolysis at 130° C
  7. customAfter isoamyl alcohol was removed by steam distillation, extraction with 250 ml of toluene
  8. washthe organic layer was washed with water
  9. customdried
  10. concentrationconcentrated
  11. customThe concentrate was purified by column chromatography (carrier: silica gel, eluate: toluene/n-hexane=1/2)

Sources & evidence

ORD record
ord-02aec482b20d4481b906f14edc364258
Source dataset
uspto-grants-2010_10
Patent number
US07807274B2

Reaction notes

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