Potassium Carbonate → 4-(9-Phenyl-9h-carbazol-3-yl)diphenylamine

HRID 2061319Notes

Reaction equation

HRID 2061319 reaction equation
[CH:1]1[CH:6]=[CH:5][C:4]([NH:7][C:8]2[CH:13]=[CH:12][C:11](Br)=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.[C:15]1([N:21]2[C:33]3[CH:32]=[CH:31][C:30](B(O)O)=[CH:29][C:28]=3[C:27]3[C:22]2=[CH:23][CH:24]=[CH:25][CH:26]=3)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[K+].[K+].C(O)C1C(Cl)=C(Cl)C(Cl)=C(Cl)C=1Cl>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)C.C1(C)C=CC=CC=1>[CH:1]1[CH:6]=[CH:5][C:4]([NH:7][C:8]2[CH:13]=[CH:12][C:11]([C:30]3[CH:31]=[CH:32][C:33]4[N:21]([C:15]5[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=5)[C:22]5[C:27]([C:28]=4[CH:29]=3)=[CH:26][CH:25]=[CH:24][CH:23]=5)=[CH:10][CH:9]=2)=[CH:3][CH:2]=1

Participants

9

Reactant 5

HCID 11430Potassium CarbonateHCID 276412,3,4,5,6-PentachlorobenzenemethanolHCID 80271Tri-o-tolylphosphineHCID 64257864-BromodiphenylamineHCID 513584509-Phenyl-9H-carbazole-3-boronic acid

Product 1

HCID 598279834-(9-Phenyl-9h-carbazol-3-yl)diphenylamine

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

In a 500-mL three-neck flask, 6.5 g (26 mmol) of 4-bromodiphenylamine, 7.5 g (26 mmol) of 9-phenyl-9H-carbazol-3-boronic acid, and 400 mg (1.3 mmol) of tri(o-tolyl)phosphine were added, and the atmosphere in the flask was substituted by nitrogen. Then, 100 mL of toluene, 50 mL of ethanol, and 14 mL of aqueous solution of potassium carbonate (2.0 mol/L) were added to this mixture. The mixture was degassed while stirring under reduced pressure, which is followed by the addition of 67 mg (0.3 mmol) of palladium(II) acetate. This mixture was refluxed at 100° C. for 10 hours. After the reflux, the organic layer was separated from the aqueous layer, the aqueous layer was extracted with toluene, and the extract and the organic layer were combined and washed with brine. The organic layer was dried with magnesium sulfate, subjected to gravity filtration. The resulting filtrate was concentrated to give a pale brown oily product. The oily product was purified by silica gel column chromatography (the developing solvent containing a 4:6 ratio of hexane to toluene), and a white solid obtained after the purification was recrystallized with a mixed solvent of dichloromethane and hexane to give a white solid which was the desired substance. The yield was 4.9 g and 45%. The synthetic scheme of PCBA is shown in the scheme (C-4).

Workup

  1. customThe mixture was degassed
  2. customAfter the reflux, the organic layer was separated from the aqueous layer
  3. extractionthe aqueous layer was extracted with toluene
  4. extractionthe extract
  5. washwashed with brine
  6. dry with materialThe organic layer was dried with magnesium sulfate
  7. filtrationsubjected to gravity filtration
  8. concentrationThe resulting filtrate was concentrated
  9. customto give a pale brown oily product
  10. customThe oily product was purified by silica gel column chromatography (the developing solvent
  11. additioncontaining a 4:6 ratio of hexane to toluene), and a white solid
  12. customobtained
  13. customafter the purification
  14. customwas recrystallized with a mixed solvent of dichloromethane and hexane
  15. customto give a white solid which

Sources & evidence

ORD record
ord-af7edf3dcef54b859735df12cf348330
Source dataset
uspto-grants-2012_10
Patent number
US08283055B2

Reaction notes

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