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

HRID 600118

反応式

HRID 600118 の反応式
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

参加物

9

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 23978Copper触媒HCID 962Water溶媒HCID 31260Isoamyl Alcohol溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-71c0a2f7086e482a881ab9f8dc376607
出典データセット
uspto-grants-2011_03
特許番号
US07897816B2

関連ノート

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