Carbazole → 9-(4-Bromophenyl)carbazole

HRID 426382Notes

Reaction equation

HRID 426382 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.[CH:9]1[C:21]2[NH:20][C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:13]=2[CH:12]=[CH:11][CH:10]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>[Cu](I)I.CN1CCCN(C)C1=O>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([N:20]2[C:21]3[CH:9]=[CH:10][CH:11]=[CH:12][C:13]=3[C:14]3[C:19]2=[CH:18][CH:17]=[CH:16][CH:15]=3)=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 6854CarbazoleHCID 78041,4-DibromobenzeneHCID 11430Potassium CarbonateHCID 2855718-Crown-6

Product 1

HCID 223613909-(4-Bromophenyl)carbazoleYield 35.7%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Conditions

Temperature
180 °C

Procedure

56.3 g (0.24 mol) of 1,4-dibromobenzene, 31.3 g (0.18 mol) of carbazole, 4.6 g (0.024 mol) of copper iodide, 66.3 g (0.48 mol) of potassium carbonate, and 2.1 g (0.008 mol) of 18-crown-6-ether were put into a 300 mL three-neck flask, and the atmosphere of the flask was substituted with nitrogen. Thereafter, 8 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: DMPU) was added, and then the mixture was stirred for 6 hours at 180° C. After the reaction mixture was cooled to room temperature, the precipitate was removed by suction filtration. The filtrate was washed with a diluted hydrochloric acid, a saturated sodium bicarbonate aqueous solution, and then brine, and dried with magnesium sulfate. After drying, the mixture was filtered, and the filtrate was concentrated to yield an oil which was purified by silica gel column chromatography (hexane:ethyl acetate=9:1). The resulting solid was recrystallized with chloroform and hexane, obtaining 20.7 g of N-(4-bromophenyl)carbazole as a light brown plate-like crystal in 35% yield. By the nuclear magnetic resonance measurement (NMR), it was confirmed that this compound was N-(4-bromophenyl)carbazole.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. customthe precipitate was removed by suction filtration
  3. washThe filtrate was washed with a diluted hydrochloric acid
  4. dry with materiala saturated sodium bicarbonate aqueous solution, and then brine, and dried with magnesium sulfate
  5. customAfter drying
  6. filtrationthe mixture was filtered
  7. concentrationthe filtrate was concentrated
  8. customto yield an oil which
  9. customwas purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  10. customThe resulting solid was recrystallized with chloroform and hexane

Sources & evidence

ORD record
ord-ed2b171da6bd45939e335b24e98b7328
Source dataset
uspto-grants-2012_01
Patent number
US08106392B2

Reaction notes

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