Tris(4-bromophenyl)amine → N,N-bis(4-bromophenyl)-N',N'-bis(4-butylphenyl)-1,4-phenylenediamine

HRID 1845979Notes

Reaction equation

HRID 1845979 reaction equation
CC(C)([O-])C.[Na+].Br[C:8]1[CH:13]=[CH:12][C:11]([N:14]([C:22]2[CH:27]=[CH:26][C:25]([Br:28])=[CH:24][CH:23]=2)[C:15]2[CH:20]=[CH:19][C:18]([Br:21])=[CH:17][CH:16]=2)=[CH:10][CH:9]=1.[CH2:29]([C:33]1[CH:38]=[CH:37][C:36]([NH:39][C:40]2[CH:45]=[CH:44][C:43]([CH2:46][CH2:47][CH2:48][CH3:49])=[CH:42][CH:41]=2)=[CH:35][CH:34]=1)[CH2:30][CH2:31][CH3:32]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].C1(C)C=CC=CC=1>[Br:21][C:18]1[CH:19]=[CH:20][C:15]([N:14]([C:22]2[CH:27]=[CH:26][C:25]([Br:28])=[CH:24][CH:23]=2)[C:11]2[CH:12]=[CH:13][C:8]([N:39]([C:40]3[CH:41]=[CH:42][C:43]([CH2:46][CH2:47][CH2:48][CH3:49])=[CH:44][CH:45]=3)[C:36]3[CH:35]=[CH:34][C:33]([CH2:29][CH2:30][CH2:31][CH3:32])=[CH:38][CH:37]=3)=[CH:9][CH:10]=2)=[CH:16][CH:17]=1

Participants

7

Reactant 3

HCID 258027Tris(4-bromophenyl)amineHCID 145138624-Butyl-N-(4-butylphenyl)anilineHCID 23676156Sodium t-butoxide

Product 1

HCID 58099117N,N-bis(4-bromophenyl)-N',N'-bis(4-butylphenyl)-1,4-phenylenediamineYield 24%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 15826098Cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;iron(2+)CatalystHCID 1140TolueneSolvent

Procedure

Under an inert atmosphere, in a 300 mL three-necked flask, 0.24 g (0.27 mmol) of tris(dibenzylideneacetone)dipalladium, 0.22 g (0.4 mmol) of diphenylphosphinoferrocene, 2.56 g (26.7 mmol) of sodium tertiary butoxide and 125 mL of toluene were charged, followed by stirring at room temperature for 10 minutes. Subsequently, 12.9 g (26.7 mmol) of tris-(4-bromophenyl)amine was charged, followed by stirring at room temperature for 10 minutes. Thereafter, 5 g (17.8 mmol) of bis(4-butylphenyl) amine was charged, and the mixture was heated to 125° C. and refluxed for 9 hours. After the completion of the reaction, the reaction solution was filtered to remove insolubles, passed through a short column of silica gel and then purified by a silica gel column using cyclohexane as an eluent to obtain N,N-bis(4-bromophenyl)-N′,N′-bis(4-butylphenyl)-1,4-phenylenediamine (aromatic amine A) (2.96 g, yield: 24%).

Workup

  1. stirringby stirring at room temperature for 10 minutes
  2. temperaturethe mixture was heated to 125° C.
  3. temperaturerefluxed for 9 hours
  4. customAfter the completion of the reaction
  5. filtrationthe reaction solution was filtered
  6. customto remove insolubles
  7. custompurified by a silica gel column

Sources & evidence

ORD record
ord-9201dad65c2049fb9bd7deebf526c6f0
Source dataset
uspto-grants-2015_02
Patent number
US08951646B2

Reaction notes

Loading…