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

HRID 40436

Reaktionsgleichung

Reaktionsgleichung von HRID 40436
[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

Komponenten

8

Edukt 4

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

Produkt 1

HCID 598279834-(9-Phenyl-9h-carbazol-3-yl)diphenylamineAusbeute 45,9 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 702EthanolLösungsmittelHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

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 inmol) 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 of an aqueous solution of potassium carbonate (0.2 mol/L). 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, the organic layer of the mixture was separated, the aqueous layer was extracted with toluene, and the extracted solution was combined with the organic layer and then washed with a saturated aqueous sodium chloride 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). After the purification, the substance was condensed to give a white solid. The white solid was recrystallized with a mixed solvent 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.

Aufarbeitung

  1. customInto a 500 mL three-neck flask were put
  2. customUnder reduced pressure, this mixture was degassed
  3. customAfter the reflux, the organic layer of the mixture was separated
  4. extractionthe aqueous layer was extracted with toluene
  5. washwashed with a saturated aqueous sodium chloride 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. customAfter the purification
  12. customcondensed
  13. customto give a white solid
  14. customThe white solid was recrystallized with a mixed solvent of dichloromethane and hexane

Quellen und Nachweise

ORD-Eintrag
ord-8a3d96703ddf482bb34b891056c3f5c0
Quelldatensatz
uspto-grants-2013_09
Patentnummer
US08530060B2

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