Carbazole → 4,4'-Bis(9H-carbazol-9-yl)biphenyl

HRID 16033

Reaktionsgleichung

Reaktionsgleichung von HRID 16033
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([C:21]2[CH:26]=[CH:25][C:24](Br)=[CH:23][CH:22]=2)=[CH:17][CH:16]=1.[CH3:28][C:29]([CH3:32])([O-])[CH3:30].[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[CH:10]1[C:11]2[N:12]([C:15]3[CH:20]=[CH:19][C:18]([C:21]4[CH:26]=[CH:25][C:24]([N:12]5[C:11]6[CH:10]=[CH:9][CH:8]=[CH:7][C:32]=6[C:29]6[C:30]5=[CH:2][CH:1]=[CH:13][CH:28]=6)=[CH:23][CH:22]=4)=[CH:17][CH:16]=3)[C:13]3[C:5](=[CH:4][CH:3]=[CH:2][CH:1]=3)[C:6]=2[CH:7]=[CH:8][CH:9]=1

Komponenten

7

Edukt 3

HCID 6854CarbazoleHCID 71104,4'-DibromobiphenylHCID 23676156Sodium t-butoxide

Produkt 1

HCID 112487164,4'-Bis(9H-carbazol-9-yl)biphenylAusbeute 75.527,898 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 83681Tris(1,1-dimethylethyl)phosphineKatalysatorHCID 167845palladium(II) acetateKatalysatorHCID 1140TolueneLösungsmittel3×

Versuchsvorschrift

Tri-tert-butylphosphine (304 mg, 1.50 mmol) in toluene (38 ml) was added under nitrogen to a deoxygenated mixture of carbazole (16.9 g, 0.100 mmol), 4,4′-dibromobiphenyl (15.7 g, 50.4 mmol), sodium tert-butoxide (30.9 g, 321 mmol) and palladium acetate (115 mg, 0.512 mmol) in toluene (50 ml) and the resulting mixture was heated at reflux under nitrogen for 10 days. The reaction mixture was cooled to room temperature and then diluted with more toluene (200 ml). The reaction mixture was filtered to remove the sodium salts. The filtrate was concentrated to dryness to give the crude product as a pale brown solid. The crude product was purified first by chromatography on silica using dichloromethane as the eluent followed by recrystallisation from toluene. The material was then sublimed at 280-281° C. at 10−6 mm Hg to give the product 4,4′-bis(carbazol-9-yl)biphenyl (1) (18.3 g, 75%), as an off-white solid with melting point 280-281° C. (lit. m.p. 281° C.).

Aufarbeitung

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux under nitrogen for 10 days
  3. filtrationThe reaction mixture was filtered
  4. customto remove the sodium salts
  5. concentrationThe filtrate was concentrated to dryness
  6. customto give the crude product as a pale brown solid
  7. customThe crude product was purified first by chromatography on silica
  8. customfollowed by recrystallisation from toluene
  9. customwas then sublimed at 280-281° C. at 10−6 mm Hg

Quellen und Nachweise

ORD-Eintrag
ord-cde1b627deb84233936c4eac8d7f92d5
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07736534B2

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