Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1399469Notes

Reaction equation

HRID 1399469 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.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 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Conditions

Temperature
180 °C

Procedure

Into a 300 mL three-neck flask were put 56 g (240 mmol) of p-dibromobenzene, 31 g (180 mmol) of 9H-carbazole, 4.6 g (24 mmol) of copper(I) iodide, 66 g (480 mmol) of potassium carbonate, and 2.1 g (8 mmol) of 18-crown-6-ether. Then, the atmosphere in the flask was replaced with nitrogen. Then, 8 mL of N,N′-dimethylpropyleneurea (abbreviation: DMPU) was added to the mixture, and the mixture was stirred at 180° C. for 6 hours. After the reaction mixture was cooled to room temperature, a precipitate was removed by suction filtration. The filtrate was washed with dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and a saturated saline solution in that order, and dried with magnesium sulfate. After being dried, the mixture was gravity filtered and then concentrated to give an oily substance. The obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) and recrystallized with chloroform and hexane, whereby 21 g of light-brown plate-shaped crystals of 9-(4-bromophenyl)-9H-carbazole which was the object of the synthesis was obtained in a yield of 35% (synthesis scheme (a-5)).

Workup

  1. customInto a 300 mL three-neck flask were put
  2. temperatureAfter the reaction mixture was cooled to room temperature
  3. customa precipitate was removed by suction filtration
  4. washThe filtrate was washed with dilute hydrochloric acid
  5. dry with materiala saturated aqueous sodium hydrogen carbonate solution, and a saturated saline solution in that order, and dried with magnesium sulfate
  6. customAfter being dried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give an oily substance
  10. customThe obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  11. customrecrystallized with chloroform and hexane, whereby 21 g of light-brown plate-shaped crystals of 9-(4-bromophenyl)-9H-carbazole which
  12. customwas obtained in a yield of 35% (synthesis scheme (a-5))

Sources & evidence

ORD record
ord-b354ab01c0a44db0a1e0701962614b2e
Source dataset
uspto-grants-2014_12
Patent number
US08906518B2

Reaction notes

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