Dodecane → N,N'-bis[4-{bis(biphenyl-4-yl)amino}biphenyl-4'-yl]-N,N'-diphenyl-4,4''-diamino-p-terphenyl

HRID 1158221Notes

Reaction equation

HRID 1158221 reaction equation
[C:1]1([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH:6]=[CH:5][C:4]([N:7]([C:27]2[CH:32]=[CH:31][C:30]([C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)=[CH:29][CH:28]=2)[C:8]2[CH:13]=[CH:12][C:11]([C:14]3[CH:19]=[CH:18][C:17]([NH:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)=[CH:16][CH:15]=3)=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.I[C:46]1[CH:51]=[CH:50][C:49]([C:52]2[CH:57]=[CH:56][C:55]([C:58]3[CH:63]=[CH:62][C:61](I)=[CH:60][CH:59]=3)=[CH:54][CH:53]=2)=[CH:48][CH:47]=1.C(=O)([O-])[O-].[K+].[K+].[CH3:71][CH2:72][CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH3:82]>C1(C)C=CC=CC=1.[Cu].C(OCC)(=O)C>[C:30]1([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[CH:31]=[CH:32][C:27]([N:7]([C:4]2[CH:3]=[CH:2][C:1]([C:39]3[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=3)=[CH:6][CH:5]=2)[C:8]2[CH:9]=[CH:10][C:11]([C:14]3[CH:19]=[CH:18][C:17]([N:20]([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:46]4[CH:51]=[CH:50][C:49]([C:52]5[CH:57]=[CH:56][C:55]([C:58]6[CH:63]=[CH:62][C:61]([N:20]([C:80]7[CH:81]=[CH:82][C:77]([C:76]8[CH:71]=[CH:72][C:73]([N:7]([C:8]9[CH:9]=[CH:10][C:11]([C:14]%10[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=%10)=[CH:12][CH:13]=9)[C:4]9[CH:5]=[CH:6][C:1]([C:39]%10[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=%10)=[CH:2][CH:3]=9)=[CH:74][CH:75]=8)=[CH:78][CH:79]=7)[C:21]7[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=7)=[CH:60][CH:59]=6)=[CH:54][CH:53]=5)=[CH:48][CH:47]=4)=[CH:16][CH:15]=3)=[CH:12][CH:13]=2)=[CH:28][CH:29]=1

Participants

8

Reactant 4

HCID 8182DodecaneHCID 11430Potassium CarbonateHCID 35635834,4''-Diiodo-p-terphenylHCID 23140819N4,N4-di([1,1'-biphenyl]-4-yl)-N4'-phenyl-[1,1'-biphenyl]-4,4'-diamine

Product 1

HCID 59510919N,N'-bis[4-{bis(biphenyl-4-yl)amino}biphenyl-4'-yl]-N,N'-diphenyl-4,4''-diamino-p-terphenylYield 65.9%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
45 °C

Procedure

There were mixed 12.68 g (0.022 mole) of N,N-bis(bi-phenyl-4-yl)-N′-phenyl-4,4′-diaminobiphenyl, 5.00 g (0.01 mole) of 4,4″-diiodo-p-terphenyl, 4.14 g (0.030 mole) of anhydrous potassium carbonate, 0.32 g (0.005 mole) of copper powder and 10 ml of n-dodecane, followed by reaction at 195 to 210° C. for 30 hours. The reaction product was extracted with 800 ml of toluene, and the insoluble matter was removed by filtration. Then, the filtrate was concentrated. After the concentration, 100 ml of methanol was added to perform crystallization, and suction filtration was performed to obtain crude crystals. The crude crystals were dissolved in 300 ml of toluene under reflux, and allowed to cool down to 45° C. Then, 300 ml of ethyl acetate was added dropwise to perform crystallization, thereby obtaining crystals. N,N′-bis[4-{bis(biphenyl-4-yl)amino}biphenyl-4′-yl]-N,N′-diphenyl-4,4″-diamino-p-terphenyl was obtained in an amount of 9.43 g. The yield was 65.9%, and the HPLC purity was 94.7%.

Workup

  1. customfollowed by reaction at 195 to 210° C. for 30 hours
  2. extractionThe reaction product was extracted with 800 ml of toluene
  3. customthe insoluble matter was removed by filtration
  4. concentrationThen, the filtrate was concentrated
  5. concentrationAfter the concentration, 100 ml of methanol
  6. additionwas added
  7. customcrystallization, and suction filtration
  8. customto obtain crude crystals
  9. temperatureunder reflux
  10. customcrystallization
  11. customobtaining crystals

Sources & evidence

ORD record
ord-4ad7474df4284c278aacb13870baf970
Source dataset
uspto-grants-2010_10
Patent number
US07807274B2

Reaction notes

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