1-Methylimidazole → 9-(4-methylpyridin-2-yl)-2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole

HRID 1509639Notes

Reaction equation

HRID 1509639 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[C:11]1[CH:12]=[C:13]([CH:28]=[CH:29][CH:30]=1)[O:14][C:15]1[CH:27]=[CH:26][C:25]2[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[NH:18][C:17]=2[CH:16]=1.C([O-])([O-])=O.[K+].[K+].Br[C:38]1[CH:43]=[C:42]([CH3:44])[CH:41]=[CH:40][N:39]=1.CN1C=CN=C1>[Cu]I.C1(C)C=CC=CC=1>[CH3:44][C:42]1[CH:41]=[CH:40][N:39]=[C:38]([N:18]2[C:17]3[CH:16]=[C:15]([O:14][C:13]4[CH:28]=[CH:29][CH:30]=[C:11]([C:2]5[CH:3]=[CH:4][C:5]6[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=6)[N:1]=5)[CH:12]=4)[CH:27]=[CH:26][C:25]=3[C:24]3[C:19]2=[CH:20][CH:21]=[CH:22][CH:23]=3)[CH:43]=1

Participants

7

Reactant 4

HCID 13901-MethylimidazoleHCID 11430Potassium CarbonateHCID 27340872-Bromo-4-methylpyridineHCID 1181142092-(3-(quinolin-2-yl)phenoxy)-9H-carbazole

Product 1

HCID 1021416579-(4-methylpyridin-2-yl)-2-(3-(quinolin-2-yl)phenoxy)-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 dry pressure vessel equipped with a magnetic stir bar was added 2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole (773 mg, 2.0 mmol, 1.0 eq), CuI (76 mg, 0.4 mmol, 0.2 eq), and K2CO3 (553 mg, 4.0 mmol, 2.0 eq). The vessel was evacuated and back-filled with nitrogen. The evacuation and back-fill procedure was repeated twice. Then 2-bromo-4-methylpyridine (1032 mg, 6.0 mmol, 3.0 eq), 1-methyl-1H-imidazole (158 uL, 2.0 mmol, 1.0 eq) and solvent toluene (32 mL) were added under nitrogen. After bubbling with nitrogen for 25 minutes, the mixture was stirred in an oil bath at a temperature of 120° C. for three days, and cooled to ambient temperature. The solid was filtered off and washed with ethyl acetate. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-5:1-3:1) as an eluent to afford the desired product Ligand ON11Me as a sticky liquid (955 mg) in 99%. 1H NMR (DMSO-d6, 400 MHz): δ 2.38 (s, 3H), 7.09 (dd, J=8.4, 2.4 Hz, 1H), 7.18 (dd, J=8.4, 2.4 Hz, 1H), 7.25 (d, J=5.2 Hz, 1H), 7.32 (t, J=7.6 Hz, 1H), 7.43 (t, J=7.6 Hz, 1H), 7.50 (d, J=2.0 Hz, 1H), 7.54-7.60 (m, 3H), 7.72-7.77 (m, 2H), 7.97-8.04 (m, 4H), 8.13 (d, J=9.2 Hz, 1H), 8.21 (d, J=7.6 Hz, 1H), 8.27 (d, J=8.0 Hz, 1H), 8.44 (d, J=8.8 Hz, 1H), 8.49 (d, J=4.8 Hz, 1H).

Workup

  1. customTo a dry pressure vessel equipped with a magnetic stir bar
  2. customThe vessel was evacuated
  3. additionback-filled with nitrogen
  4. customAfter bubbling with nitrogen for 25 minutes
  5. temperaturecooled to ambient temperature
  6. filtrationThe solid was filtered off
  7. washwashed with ethyl acetate
  8. concentrationThe filtrate was concentrated
  9. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-3f60f323c187476a825df4912dc0e64c
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

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