1-Methylimidazole → 2-Bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole

HRID 1509631Notes

Reaction equation

HRID 1509631 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[NH:5][C:4]=2[CH:3]=1.C([O-])([O-])=O.[K+].[K+].CN1C=CN=C1.Br[C:28]1[CH:33]=[C:32]([C:34]([CH3:37])([CH3:36])[CH3:35])[CH:31]=[CH:30][N:29]=1>[Cu]I.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[N:5]([C:28]3[CH:33]=[C:32]([C:34]([CH3:37])([CH3:36])[CH3:35])[CH:31]=[CH:30][N:29]=3)[C:4]=2[CH:3]=1

Participants

7

Reactant 4

HCID 13901-MethylimidazoleHCID 11430Potassium CarbonateHCID 127170892-Bromo-9H-carbazoleHCID 131833052-Bromo-4-tert-butylpyridine

Product 1

HCID 1180072932-Bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

To a pressure vessel equipped with a magnetic stir bar was added 2-bromo-9H-carbazole (2461 mg, 10.0 mmol, 1.0 eq), CuI (762 mg, 4.0 mmol, 0.4 eq), and K2CO3 (2764 mg, 20.0 mmol, 2.0 eq). Then the vessel was evacuated and back-filled with nitrogen, and the evacuation and back-fill procedure was repeated twice. Then solvent toluene (60 mL), 1-methyl-1H-imidazole (792 uL, 10.0 mmol, 1.0 eq) and 2-bromo-4-tert-butylpyridine (5353 mg, 25.0 mmol, 2.5 eq) were added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 115-125° C. for 4 days. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using dichloromethane as an eluent to obtain the desired product, 2-bromo-9-(4-tert-butylpyridin-2-yl)-9H-carbazole, as a colorless sticky liquid (3635 mg in 96% yield). 1H NMR (DMSO-d6, 400 MHz): δ 1.39 (s, 9H), 7.36 (t, J=8.0 Hz, 1H), 7.48-7.55 (m, 3H), 7.71-7.73 (m, 2H), 7.94 (d, J=2.0 Hz, 1H), 8.23 (d, J=8.0 Hz, 1H), 8.28 (d, J=8.0 Hz, 1H), 8.66 (d, J=5.5 Hz, 1H).

Workup

  1. customTo a pressure vessel equipped with a magnetic stir bar
  2. customThen the vessel was evacuated
  3. additionback-filled with nitrogen
  4. temperatureThen the mixture was cooled to ambient temperature
  5. customThe solvent was removed under reduced pressure
  6. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-57fa6a1fa3274e9ea19afad6eb69c8cc
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

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