1,2-Dibromobenzene → 4-Bromotriphenylamine

HRID 2104470Notes

Reaction equation

HRID 2104470 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[Br:21]>C1(C)C=CC=CC=1>[Br:21][C:16]1[CH:17]=[CH:18][C:19]([N:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[CH:20][CH:15]=1

Participants

4

Reactant 2

HCID 114141,2-DibromobenzeneHCID 11487Diphenylamine

Product 1

HCID 6428384-BromotriphenylamineYield 40%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

In a two-neck round bottom flask, diphenylamine (50 g, 0.30 mol), dibromobenzene (104 g, 0.44 mol), BINAP[2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl] (7.4 g, 4% mol), Pd(OAc)2[Palladium(II)acetate] (2.0 g, 3% mol), and NaOtBu[Sodium tert-butoxide] (42.6 g, 0.44 mol) are dissolved in toluene (400 mL), and then are maintained for 24 hours by reflux. On completion of the reaction, the flask having the resultant solution is cooled, and then toluene, a solvent of the reaction, is removed from the resultant solution. After that, the resultant solution having no toluene reacts on methylene-chloride and water, and then methylene-chloride is removed therefrom, and is performed by silica gel column chromatography with a solvent of methylene-chloride and hexane at a ratio of 3 to 1. After that, the solvent is removed from the resultant solution of completing silica gel column chromatography, and is recrystallized and filtered with methylene-chloride and petroleum ether, thereby obtaining a white solid, (4-bromo-phenyl)-diphenyl-amine (36.5 g, 40%).

Workup

  1. temperatureare maintained for 24 hours
  2. temperatureby reflux
  3. customOn completion of the reaction
  4. temperatureis cooled
  5. customis removed from the resultant solution
  6. customreacts on methylene-chloride and water
  7. custommethylene-chloride is removed
  8. customAfter that, the solvent is removed from the resultant solution of completing silica gel column chromatography
  9. customis recrystallized
  10. filtrationfiltered with methylene-chloride and petroleum ether

Sources & evidence

ORD record
ord-bf6836eacbe147fb95375eeb5a0ce65c
Source dataset
uspto-grants-2009_08
Patent number
US07576484B2

Reaction notes

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