Carbazole → 9-(4-Bromophenyl)carbazole

HRID 521542Notes

Reaction equation

HRID 521542 reaction equation
[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:14][C:15]1[CH:20]=[CH:19][C:18](I)=[CH:17][CH:16]=1.C([O-])([O-])=O.[K+].[K+]>[Cu].CN(C=O)C>[Br:14][C:15]1[CH:20]=[CH:19][C:18]([N:12]2[C:11]3[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=3[C:5]3[C:13]2=[CH:1][CH:2]=[CH:3][CH:4]=3)=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 6854CarbazoleHCID 11430Potassium CarbonateHCID 115221-Bromo-4-iodobenzene

Product 1

HCID 223613909-(4-Bromophenyl)carbazoleYield 96.3%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
130 °C

Procedure

Compound 4 was prepared as follows: a mixture of carbazole (6.30 g, 37.7 mmol), 1-bromo-4-iodobenzene (15.99 g, 56.52 mmol), copper powder (4.79 g, 75.4 mmol), K2CO3 (20.83 g, 150.7 mmol) and anhydrous DMF (100 mL) was degassed with argon for about 1 h while stirring. The stirring reaction mixture was then maintained under argon at about 130° C. for about 42 h. Upon confirming consumption of the starting material by TLC (SiO2, 4:1 hexanes-dichloromethane), the mixture was cooled to RT, filtered, the filtrant washed copiously with EtOAc (ca. 200 mL) and the resulting filtrate concentrated in vacuo. Purification of the crude product by flash chromatography (SiO2, hexanes) afforded compound 4 (11.7 g, 96% yield) as a pale yellow solid. (See Xu, H.; Yin, K.; Huang, W. Chem. Eur. J., 2007, 13(36), 10281-10293.)

Workup

  1. customCompound 4 was prepared
  2. customwas degassed with argon for about 1 h
  3. customThe stirring reaction mixture
  4. customconsumption of the starting material by TLC (SiO2, 4:1 hexanes-dichloromethane)
  5. temperaturethe mixture was cooled to RT
  6. filtrationfiltered
  7. washthe filtrant washed copiously with EtOAc (ca. 200 mL)
  8. concentrationthe resulting filtrate concentrated in vacuo
  9. customPurification of the crude product by flash chromatography (SiO2, hexanes)

Sources & evidence

ORD record
ord-0991254c31334be387c34ed8619382b5
Source dataset
uspto-grants-2016_05
Patent number
US09328086B2

Reaction notes

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