Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1942977Notes

Reaction equation

HRID 1942977 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.CC1N(C(N(C)C)=O)C1>[Cu](I)I>[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 5

HCID 6854CarbazoleHCID 78041,4-DibromobenzeneHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 11007919N,N,2-trimethylaziridine-1-carboxamide

Product 1

HCID 223613909-(4-Bromophenyl)carbazoleYield 35%

Reagents, catalysts & solvents 1

HCID 83717Copper iodideCatalyst

Conditions

Temperature
180 °C

Procedure

First, 56 g (240 mmol) of p-dibromobenzene, 31 g (180 mmol) of carbazole, 4.6 g (24 mmol) of copper iodide, 66 g (480 mmol) of potassium carbonate, and 2.1 g (8 mmol) of 18-crown-6-ether were put in a 300-mL three-neck flask, and nitrogen was substituted for air in the flask. Then, 8 mL of N,N-dimethylpropyleneurea (abbreviation: DMPU) was added therein, 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 sodium hydrogen-carbonate aqueous solution, and a saturated saline solution in this order and dried with magnesium sulfate. After being dried, the solution was filtered naturally and concentrated, and an obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) and recrystallized with chloroform and hexane; thus, 21 g of a light brown plate-shaped crystal of 9-(4-bromophenyl)carbazole that was an object was obtained (yield: 35%).

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. customa precipitate was removed by suction filtration
  3. washThe filtrate was washed with dilute hydrochloric acid
  4. dry with materiala saturated sodium hydrogen-carbonate aqueous solution, and a saturated saline solution in this order and dried with magnesium sulfate
  5. customAfter being dried
  6. filtrationthe solution was filtered naturally
  7. concentrationconcentrated
  8. customan obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  9. customrecrystallized with chloroform and hexane
  10. customwas obtained (yield: 35%)

Sources & evidence

ORD record
ord-4bf1b54c7345464b97208d5f6c04c32d
Source dataset
uspto-grants-2013_03
Patent number
US08389735B2

Reaction notes

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