Carbazole → 9-(5-bromopyridin-3-yl)-9H-carbazole

HRID 520826Notes

Reaction equation

HRID 520826 reaction equation
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[Br:14][C:15]1[CH:16]=[N:17][CH:18]=[C:19](Br)[CH:20]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>CN(C=O)C.[Cu]>[Br:14][C:15]1[CH:20]=[C:19]([N:12]2[C:11]3[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=3[C:5]3[C:13]2=[CH:1][CH:2]=[CH:3][CH:4]=3)[CH:18]=[N:17][CH:16]=1

Participants

7

Reactant 4

HCID 6854CarbazoleHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 693693,5-Dibromopyridine

Product 1

HCID 594495909-(5-bromopyridin-3-yl)-9H-carbazoleYield 60%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 9H-carbazole (4.0 g, 24.1 mmol), 3,5-dibromopyridine (8.55 g, 36.1 mmol), copper powder (3.06 g, 48.2 mmol), potassium carbonate (13.3 g, 96.4 mmol) and 18-crown-6 (0.636 g, 2.4 mmol) in anhydrous DMF was degassed and heated at about 150° C. for about 40 hours. The crude mixture was then poured into water (200 mL), and then filtered. The solid was collected and dissolved in hot dichloromethane (500 mL) and an insoluble solid was then filtered off. The solution was absorbed on silica gel and purified by flash column (hexanes/ethyl acetate 12:1) to give a white solid product 2B (4.67 g, yield: 60%).

Workup

  1. customwas degassed
  2. additionThe crude mixture was then poured into water (200 mL)
  3. filtrationfiltered
  4. customThe solid was collected
  5. dissolutiondissolved in hot dichloromethane (500 mL)
  6. filtrationan insoluble solid was then filtered off
  7. customThe solution was absorbed on silica gel
  8. custompurified by flash column (hexanes/ethyl acetate 12:1)

Sources & evidence

ORD record
ord-d47d54d78e7a428fab7fa25bd0e9e728
Source dataset
uspto-grants-2016_05
Patent number
US09328094B2

Reaction notes

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