Toluene → Bis(4-diphenylaminophenyl)amine

HRID 324717

反応式

HRID 324717 の反応式
[C:1]1([N:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:8]2[CH:14]=[CH:13][C:11]([NH2:12])=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[Ca+2].[Cl-].[Cl-].[Al+3].[Cl-].[Cl-].[C:28]1(C)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>CCCCCCCCCCCCC>[C:1]1([N:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:8]2[CH:14]=[CH:13][C:11]([NH:12][C:11]3[CH:13]=[CH:14][C:8]([N:7]([C:28]4[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=4)[C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)=[CH:9][CH:10]=3)=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

参加物

6

反応物 4

HCID 1140TolueneHCID 75371N,N-Diphenyl-p-phenylenediamineHCID 5284359Calcium ChlorideHCID 6451240Aluminum(III) Chloride

生成物 1

HCID 9870733Bis(4-diphenylaminophenyl)amine収率 66.9%

試薬・触媒・溶媒 1

HCID 12388Tridecane溶媒

実験手順

In a 500-ml four-necked flask were charged 68 ml of tridecane (boiling point: 234° C.) as a solvent and 130.2 g (0.50 mol) of 4-diphenylaminoaniline, followed by the addition of 15.4 g (0.138 mol) of anhydrous calcium chloride and 18.5 g (0.138 mol) of anhydrous aluminum chloride under stirring. The resulting mixture was reacted at 210 to 220° C. for 3 hours under a nitrogen atmosphere. After cooling, the reaction mixture was added with 114 ml of toluene, followed by charging in 144 g of ice water. The resulting mixture was stirred and allowed to stand, and then the resulting water layer was separated out. The organic layer was washed successively with 90 ml of a 5% aqueous solution of hydrochloric acid, 60 ml of a 5% aqueous solution of sodium bicarbonate and 60 ml of water. After removal of the organic solvent by distillation under reduced pressure, 72 ml of isopropyl alcohol was added to the residue and the mixture was crystallized overnight at −3 to −8C. The resulting crude crystals were collected by filtration, washed with 27 ml of isopropyl alcohol and then dried, whereby 84.2 g (yield: 66.9%) of the title compound was obtained as pale yellow crystals. As a result of HPLC. analysis (column: YMC-A-312, detection UV: 280 nm, flow rate: 1.0 ml/min, eluent: methanol/tetrahydrofuran=99/1), the compound was found to have a purity of 99.7%.

後処理

  1. customThe resulting mixture was reacted at 210 to 220° C. for 3 hours under a nitrogen atmosphere
  2. temperatureAfter cooling
  3. stirringThe resulting mixture was stirred
  4. customthe resulting water layer was separated out
  5. washThe organic layer was washed successively with 90 ml of a 5% aqueous solution of hydrochloric acid, 60 ml of a 5% aqueous solution of sodium bicarbonate and 60 ml of water
  6. customAfter removal of the organic solvent
  7. distillationby distillation under reduced pressure, 72 ml of isopropyl alcohol
  8. additionwas added to the residue
  9. customthe mixture was crystallized overnight at −3 to −8C
  10. filtrationThe resulting crude crystals were collected by filtration
  11. washwashed with 27 ml of isopropyl alcohol
  12. customdried

出典と根拠

ORDレコード
ord-50382a95a19b4a58a15cb176bd38f5b1
出典データセット
uspto-grants-2001_04
特許番号
US06218576B1

関連ノート

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