Toluene → N4,N4,N4'-Triphenyl-[1,1'-biphenyl]-4,4'-diamine

HRID 2091440

Reaction equation

HRID 2091440 reaction equation
[C:1]1([N:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:8]2[CH:13]=[CH:12][C:11](B(O)O)=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:24]1[CH:36]=[CH:35][C:27]([NH:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[CH:26][CH:25]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O>[C:1]1([N:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:8]2[CH:13]=[CH:12][C:11]([C:32]3[CH:33]=[CH:34][C:29]([NH:28][C:27]4[CH:35]=[CH:36][CH:24]=[CH:25][CH:26]=4)=[CH:30][CH:31]=3)=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 62657Potassium Phosphate, TribasicHCID 64257864-BromodiphenylamineHCID 121669344-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 22013295N4,N4,N4'-Triphenyl-[1,1'-biphenyl]-4,4'-diamineYield 81.4%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalystHCID 962WaterSolvent

Procedure

4-(diphenylamino)phenylboronic acid (4.87 g, 16.8 mmol), 4-bromo-N-phenylaniline (3.5 g, 14 mmol), potassium phosphate (9.2 g, 42 mmol), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (0.23 g, 0.56 mmol) were added to a three-neck flask under nitrogen. 200 mL of toluene and 20 mL of water was then added. The solution was degassed with nitrogen for 20 minutes. Pd2(dba)3 (0.13 g, 0.14 mmol) was added to the mixture. The mixture was then heated up to reflux overnight. After cooled to room temperature, the organic layer was separated and dried over magnesium sulfate. After evaporating solvent, the residue was purified by column chromatography using 1:2 dichloromethane and hexanes as eluent. 4.7 g of desired product was obtained. (81% yield)

Workup

  1. customThe solution was degassed with nitrogen for 20 minutes
  2. temperatureThe mixture was then heated up
  3. temperatureto reflux overnight
  4. customthe organic layer was separated
  5. dry with materialdried over magnesium sulfate
  6. customAfter evaporating solvent
  7. customthe residue was purified by column chromatography

Sources & evidence

ORD record
ord-e54bba8890714effaf8a5159aeabcd93
Source dataset
uspto-grants-2013_05
Patent number
US08440326B2

Linked notes

Loading…