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

HRID 58934

Reaction equation

HRID 58934 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-])(=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

8

Reactant 4

HCID 11430Potassium CarbonateHCID 80271Tri-o-tolylphosphineHCID 64257864-BromodiphenylamineHCID 513584509-Phenyl-9H-carbazole-3-boronic acid

Product 1

HCID 598279834-(9-Phenyl-9h-carbazol-3-yl)diphenylamineYield 45.9%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Into a 500 mL three-neck flask were put 6.5 g (26 mmol) of 4-bromodiphenylamine, 7.5 g (26 mmol) of 9-phenyl-9H-carbazole-3-boronic acid, and 400 mg (1.3 mmol) of tri(o-tolyl)phosphine. The atmosphere in the flask was replaced with nitrogen. To the mixture were added 100 mL of toluene, 50 mL of ethanol, and 14 mL (0.2 mol/L) of potassium carbonate aqueous solution. Under reduced pressure, this mixture was degassed while being stirred. After the degassing, 67 mg (30 mmol) of palladium(II) acetate was added to the mixture. This mixture was refluxed at 100° C. for 10 hours. After the reflux, an aqueous layer of this mixture was extracted with toluene, and the extract was combined with an organic layer and then washed with a saturated saline solution. The organic layer was dried with magnesium sulfate. After the drying, this mixture was subjected to gravity filtration. The obtained filtrate was condensed to give an oily light brown substance. This oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane:toluene=4:6). A white solid obtained after the purification was recrystallized with dichloromethane/hexane to give 4.9 g of a white solid, which was the object of the synthesis, in a yield of 45%.

Workup

  1. customInto a 500 mL three-neck flask were put
  2. customUnder reduced pressure, this mixture was degassed
  3. extractionAfter the reflux, an aqueous layer of this mixture was extracted with toluene
  4. washwashed with a saturated saline solution
  5. dry with materialThe organic layer was dried with magnesium sulfate
  6. filtrationAfter the drying, this mixture was subjected to gravity filtration
  7. customcondensed
  8. customto give an oily light brown substance
  9. customThis oily substance was purified by silica gel column chromatography (a developing solvent
  10. customA white solid obtained
  11. customafter the purification
  12. customwas recrystallized with dichloromethane/hexane

Sources & evidence

ORD record
ord-fb6d9460738e4bb5a47455c44e7d6a4f
Source dataset
uspto-grants-2016_09
Patent number
US09437824B2

Linked notes

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