Potassium Phosphate, Tribasic → 2-(4-phenylpyridin-2-yl)-9H-carbazole

HRID 1509632Notes

Reaction equation

HRID 1509632 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:21]=[CH:20][C:19]3[C:18]4[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=4)[NH:12][C:11]=3[CH:10]=2)O1.Cl[C:24]1[CH:29]=[C:28]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[CH:27]=[CH:26][N:25]=1.C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:30]1([C:28]2[CH:29]=[CH:24][N:25]=[C:26]([C:9]3[CH:21]=[CH:20][C:19]4[C:18]5[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=5)[NH:12][C:11]=4[CH:10]=3)[CH:27]=2)[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

6

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 75806TricyclohexylphosphineHCID 27628422-Chloro-4-phenylpyridineHCID 467380132-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

Product 1

HCID 1181139652-(4-phenylpyridin-2-yl)-9H-carbazole

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
102.5 °C

Procedure

To a three-necked flask equipped with a magnetic stir bar was added 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (682 mg, 2.32 mmol, 1.1 eq), 2-chloro-4-phenylpyridine (400 mg, 2.11 mmol, 1.0 eq), Pd2(dba)3 (21 mg, 0.023 mmol, 0.01 eq), PCy3 (14 mg, 0.051 mmol, 0.024 eq) and K3PO4 (761 mg, 3.59 mmol, 1.7 eq). Then the flask was evacuated and back-filled with nitrogen, and the evacuation and back-fill procedure was repeated twice. Then solvent dioxane (8 mL) and water (3.8 mL) were added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100-105° C. for 16 hours. Then the mixture was cooled to ambient temperature and diluted with ethyl acetate. The organic layer was separated and dried over sodium sulfate, and filtered, the filtrate was concentrated under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (5:1-3:1-2:1) as an eluent to obtain the desired product, 2-(4-phenylpyridin-2-yl)-9H-carbazole, as a brown solid (675 mg in 99% yield). 1H NMR (DMSO-d6, 400 MHz): δ 7.20 (t, J=7.6 Hz, 1H), 7.41-7.45 (m, 1H), 7.51-7.61 (m, 4H), 7.68 (dd, J=4.8, 1.2 Hz, 1H), 7.96-7.98 (m, 2H), 8.05 (dd, J=7.6, 1.6 Hz, 1H), 8.18 (d, J=7.6 Hz, 1H), 8.24 (d, J=8.0 Hz, 1H), 8.31 (s, 1H), 8.35 (d, J=0.4 Hz, 1H), 8.77 (d, J=5.2 Hz, 1H), 11.37 (s, 1H).

Workup

  1. customTo a three-necked flask equipped with a magnetic stir bar
  2. customThen the flask was evacuated
  3. additionback-filled with nitrogen
  4. additionThen solvent dioxane (8 mL) and water (3.8 mL) were added under the protection of nitrogen
  5. temperatureThen the mixture was cooled to ambient temperature
  6. additiondiluted with ethyl acetate
  7. customThe organic layer was separated
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-55ad341f34b141e98c9d4038b225c82e
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

Loading…