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

HRID 2061199Notes

Reaction equation

HRID 2061199 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 air 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 an aqueous solution of potassium carbonate. 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 organic layer of the mixture was separated, an aqueous layer was extracted with toluene, and the extracted solution was combined with the organic layer and then washed with a saturated saline solution. The combined 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 a mixed solution of dichloromethane and hexane to give 4.9 g of a white solid, which was the object of the synthesis, in a yield of 45%. A synthesis scheme of Step 2 is shown in (a-2) given below.

Workup

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

Sources & evidence

ORD record
ord-cd8700983d7c494c918eda9dee881bc2
Source dataset
uspto-grants-2012_10
Patent number
US08278649B2

Reaction notes

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