Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1873444Notes

Reaction equation

HRID 1873444 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.CN1C(=O)N(C)CCC1>[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%

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 placed in a 300-mL three-neck flask, and nitrogen substitution was carried out. 8 mL of DMPU was added, and the mixture was stirred for 6 hours at 180° C. After cooling the reaction mixture to room temperature, the precipitate was removed by suction filtration. The filtrate was washed with dilute hydrochloric acid, a saturated sodium hydrogen carbonate solution, and a saturated saline solution, in this order, and then dried with magnesium sulfate. After drying, the reaction mixture was filtered naturally, the filtrate was concentrated, and the oily substance obtained was purified by silica gel column chromatography (hexane:ethyl acetate=9:1). After recrystallization with chloroform and hexane, 20.7 g of light brown plate-shaped crystals were obtained as N-(4-bromophenyl)carbazole in the yield of 35%.

Workup

  1. temperatureAfter cooling the reaction mixture to room temperature
  2. customthe precipitate was removed by suction filtration
  3. washThe filtrate was washed with dilute hydrochloric acid
  4. dry with materiala saturated sodium hydrogen carbonate solution, and a saturated saline solution, in this order, and then dried with magnesium sulfate
  5. customAfter drying
  6. filtrationthe reaction mixture was filtered naturally
  7. concentrationthe filtrate was concentrated
  8. customthe oily substance obtained
  9. customwas purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  10. customAfter recrystallization with chloroform and hexane, 20.7 g of light brown plate-shaped crystals

Sources & evidence

ORD record
ord-5279de55d8e54d778c854b3e170f2b24
Source dataset
uspto-grants-2012_11
Patent number
US08304094B2

Reaction notes

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