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

HRID 1037511

Reaktionsgleichung

Reaktionsgleichung von HRID 1037511
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11](I)=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[CH:15]1[C:27]2[NH:26][C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[C:19]=2[CH:18]=[CH:17][CH:16]=1.C([O-])([O-])=O.[K+].[K+].C1O[CH2:50][CH2:49]OCCOCCOCCOCCOC1>[Cu].C(Cl)Cl.ClC1C=CC=CC=1Cl>[CH:3]1[C:4]2[N:26]([C:25]3[CH:20]=[CH:21][C:22]([C:50]4[CH:49]=[CH:27][C:15]([N:26]5[C:25]6[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=6[C:19]6[C:27]5=[CH:15][CH:16]=[CH:17][CH:18]=6)=[CH:16][CH:17]=4)=[CH:23][CH:24]=3)[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:5]=2[CH:6]=[CH:7][CH:2]=1

Komponenten

8

Edukt 4

HCID 6854CarbazoleHCID 11430Potassium Carbonate2×HCID 2855718-Crown-6HCID 763484,4'-Diiodo-1,1'-biphenyl

Produkt 1

HCID 112487164,4'-Bis(9H-carbazol-9-yl)biphenyl

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23978CopperKatalysatorHCID 6344DichloromethaneLösungsmittelHCID 72391,2-DichlorobenzeneLösungsmittel

Reaktionsbedingungen

Temperatur
180 °C

Versuchsvorschrift

4,4′-Diiodobiphenyl (10.001 g, 24.63 mmol), carbazole (9.078 g, 54.29 mmol), K2CO3 (20.087 g, 145.34 mmol), 18-crown-6 (0.100 g, 0.34 mmol), and copper powder (10.051 g, 158.16 mmol) were combined in reaction flask. To the flask, o-dichlorobenzene (50 mL) was added. The reaction was heated under inert N2 atmosphere at 180° C. overnight. TLC showed evidence of limited di-substitution product which necessitated the addition of K2CO3 (4.994 g, 36.13 mmol) and Cu powder (5.223 g, 82.19 mmol) to the reaction flask to promote di-substitution. The reaction was allowed to proceed overnight. Additional reagents had no noticeable effect on the reaction so the reaction was stopped. Insoluble material was removed by vacuum filtration and washed with several portions of THF. On standing, a crystalline product crashed out of the filtrate. Further crystallization was promoted by the addition of a large amount of methanol. The precipitate was vacuum filtered to isolate. TLC (hexanes: DCM=8:2) confirmed precipitate was product with minor impurity. Purification was accomplished by dissolving the precipitate in hot boiling THF followed by filtration to obtain a green insoluble impurity. The product began to precipitate on standing and cooling. The filtrate/product mixture was dried under vacuum until the product started crashing out of solution and methanol was added to promote full precipitation. The product was isolated by vacuum filtration and air dried (24 hours). A cream colored flaky product was obtained (7.660 g, 64.2%).

Aufarbeitung

  1. customon the reaction so the reaction
  2. customInsoluble material was removed by vacuum filtration
  3. washwashed with several portions of THF
  4. customFurther crystallization
  5. additionwas promoted by the addition of a large amount of methanol
  6. filtrationfiltered
  7. customto isolate
  8. customPurification
  9. dissolutionby dissolving the precipitate
  10. filtrationfollowed by filtration
  11. customto obtain a green insoluble impurity
  12. customto precipitate
  13. temperaturecooling
  14. customThe filtrate/product mixture was dried under vacuum until the product
  15. additionwas added
  16. customprecipitation
  17. customThe product was isolated by vacuum filtration and air
  18. customdried (24 hours)
  19. customwas obtained (7.660 g, 64.2%)

Quellen und Nachweise

ORD-Eintrag
ord-61f3dbe1a16245648fd443679caa1887
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08546505B2

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