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

HRID 600119
ノート
印刷プレビュー

反応式

HRID 600119 の反応式
[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
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 23978Copper触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
45 °C

実験手順

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%. The crystals were purified by column chromatography (carrier: silica gel, eluate: toluene/n-hexane=1/2) to obtain 5.47 g (HPLC purity: 100.0%, column purification yield: 61.3%) of N,N′-bis[4-{bis(biphenyl-4-yl)amino}biphenyl-4′-yl]-N,N′-diphenyl-4,4″-diamino-p-terphenyl. The melting point was 204.5° C. Identification of the product was performed by NMR analysis, elemental analysis and IR analysis. The elemental analysis values are as follows: carbon; measured value; 90.22% (theoretical value; 90.37%), hydrogen; measured value; 5.73% (theoretical value; 5.50%), nitrogen; measured value; 4.05% (theoretical value; 4.13%). The results of NMR analysis were as follows: 7.637-7.396 ppm (40H), 7.336-7.172 (32H), 7.081-7.029 ppm (2H).

後処理

  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

出典と根拠

ORDレコード
ord-d1dc7a39e9c44fa7b5637047b9c11cb5
出典データセット
uspto-grants-2011_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07897816B2

反応ノート

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