Nitrobenzene → 4,4'-Dibromo-2-bis(4-methoxyphenyl)amino-1,1'-biphenyl

HRID 11746

Reaction equation

HRID 11746 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([Br:14])=[CH:10][CH:9]=2)=[C:4]([NH2:15])[CH:3]=1.I[C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1.[C:25](=[O:28])([O-])[O-].[K+].[K+].[N+]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)([O-])=O>[Cu].C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11]([Br:14])=[CH:12][CH:13]=2)=[C:4]([N:15]([C:34]2[CH:39]=[CH:38][C:37]([O:28][CH3:25])=[CH:36][CH:35]=2)[C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)[CH:3]=1

Participants

7

Reactant 4

HCID 7416NitrobenzeneHCID 11430Potassium CarbonateHCID 696764-IodoanisoleHCID 45594205-Bromo-2-(4-bromophenyl)aniline

Product 1

HCID 219763144,4'-Dibromo-2-bis(4-methoxyphenyl)amino-1,1'-biphenyl

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 1140TolueneSolvent

Procedure

4,4′-Dibromo-2-amino-1,1′-biphenyl (16.35 g, 0.05 mol), 4-iodoanisole (28 g, 0.12 mol), potassium carbonate (−325 mesh fine powder, 16.6 g, 0.12 mole), copper dust (−150 mesh,1.0 g), and nitrobenzene (20 ml) were charged into a flask and stirred at gentle reflux for 15 hours. The dark reaction mixture was cooled to room temperature and extracted with 200 ml of toluene. The toluene solution was evaporated. The dark residue obtained was then mixed with 10 ml of toluene and chromatographed on a silica gel column using hexane and hexane/ethyl acetate (20:1) eluant. The portions containing the product were collected and evaporated. The residue was recrystallized twice from hexane/toluene (300 ml/60 ml) to yield 7.4 grams of off-white crystals of the desired monomer. 1H NMR (CDCl3): δ=6.8–7.5 (15H, multiple peaks); 3.78 (6H).

Workup

  1. temperatureat gentle reflux for 15 hours
  2. customThe dark reaction mixture
  3. extractionextracted with 200 ml of toluene
  4. customThe toluene solution was evaporated
  5. customThe dark residue obtained
  6. customchromatographed on a silica gel column
  7. additionThe portions containing the product
  8. customwere collected
  9. customevaporated
  10. customThe residue was recrystallized twice from hexane/toluene (300 ml/60 ml)

Sources & evidence

ORD record
ord-1b201015aa3a453fafae9c0c128bc49f
Source dataset
uspto-grants-2006_08
Patent number
US07098297B2

Linked notes

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