Carbazole → 9-(4-Bromophenyl)carbazole

HRID 1408278Notes

Reaction equation

HRID 1408278 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>[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

6

Reactant 4

HCID 6854CarbazoleHCID 78041,4-DibromobenzeneHCID 11430Potassium CarbonateHCID 2855718-Crown-6

Product 1

HCID 223613909-(4-Bromophenyl)carbazoleYield 35%

Reagents, catalysts & solvents 1

HCID 83717Copper iodideCatalyst

Conditions

Temperature
180 °C

Procedure

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 into a 300 mL three-necked flask, and nitrogen was substituted for the content of the flask. Then, 8 mL of N—N′-dimetylpropyleneurea was added thereto, and this mixture was stirred for 6 hours at 180° C. to be reacted. After the reaction, cooling of the reaction mixture to the room temperature was performed, and the precipitated object 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, filtration was performed, and an oily substance that was obtained by concentrating the filtrate was purified by silica column chromatography. For the column purification, a mixed solvent of hexane:ethyl acetate=9:1 was used as a developing solvent. After the column purification, an obtained solution was re-crystallized with chloroform and hexane, whereby 21 g of a light brown solid of 9-(4-bromophenyl)carbazole was obtained in the yield of 35% (Synthesis Scheme (k-1)).

Workup

  1. customto be reacted
  2. customAfter the reaction
  3. temperaturecooling of the reaction mixture to the room temperature
  4. customthe precipitated object was removed by suction filtration
  5. washThe filtrate was washed with dilute hydrochloric acid
  6. dry with materiala saturated sodium hydrogen carbonate solution, and a saturated saline solution, in this order, and then dried with magnesium sulfate
  7. customAfter drying
  8. filtrationfiltration
  9. customan oily substance that was obtained
  10. concentrationby concentrating the filtrate
  11. customwas purified by silica column chromatography
  12. customFor the column purification
  13. customAfter the column purification
  14. customan obtained solution was re-crystallized with chloroform and hexane, whereby 21 g of a light brown solid of 9-(4-bromophenyl)carbazole
  15. customwas obtained in the yield of 35% (Synthesis Scheme (k-1))

Sources & evidence

ORD record
ord-5a4fadd63bd64e50bcad4f1e96ee4744
Source dataset
uspto-grants-2014_12
Patent number
US08920941B2

Reaction notes

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