Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1464873Notes

Reaction equation

HRID 1464873 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 36.2%

Reagents, catalysts & solvents 2

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

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 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 condensed, 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 an objective light brown plate-shaped crystal of 9-(4-bromophenyl)carbazole 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 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. customcondensed
  8. customan obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  9. customrecrystallized with chloroform and hexane

Sources & evidence

ORD record
ord-220cf5e9801340649b534d5f1e9df15e
Source dataset
uspto-grants-2015_04
Patent number
US08999520B2

Reaction notes

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