Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1359896Notes

Reaction equation

HRID 1359896 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%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
180 °C

Procedure

First, 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 in a three-neck flask of 300 mL. After nitrogen was substituted for air in the three-neck flask, 8 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) was added thereto, and the mixture was stirred at 180° C. for 6 hours. The reactive mixture was cooled to a room temperature, and then a precipitate was removed by suction filtration. Then, the filtrate was washed with diluted hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline in this order. After the washing, the filtrate was dried with magnesium sulfate. After the drying, the reactive mixture was naturally filtrated. After the filtration, the filtrate was concentrated. Then, the thus-obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1), and thereafter, it was recrystallized by chloroform and hexane. Thus, 20.7 g (yield: 35%) of a light brown plate crystal, which was target matter, was obtained.

Workup

  1. additionwas added
  2. temperatureThe reactive mixture was cooled to a room temperature
  3. customa precipitate was removed by suction filtration
  4. washThen, the filtrate was washed with diluted hydrochloric acid
  5. dry with materialAfter the washing, the filtrate was dried with magnesium sulfate
  6. filtrationAfter the drying, the reactive mixture was naturally filtrated
  7. filtrationAfter the filtration
  8. concentrationthe filtrate was concentrated
  9. customThen, the thus-obtained oily substance was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)
  10. customit was recrystallized by chloroform and hexane
  11. customwas obtained

Sources & evidence

ORD record
ord-790ad713b35940aaaf9fff2629247e17
Source dataset
uspto-grants-2011_02
Patent number
US07879464B2

Reaction notes

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