1,3-Dibromobenzene → 1,3-Di(5-methyl-2-pyridyl)benzene

HRID 425239Notes

Reaction equation

HRID 425239 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4](Br)[CH:3]=1.[CH3:9][C:10]1[CH:11]=[CH:12][C:13]([Sn](CCCC)(CCCC)CCCC)=[N:14][CH:15]=1.[Cl-].[Li+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1>[CH3:9][C:10]1[CH:11]=[CH:12][C:13]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([C:13]3[CH:12]=[CH:11][C:10]([CH3:9])=[CH:15][N:14]=3)[CH:3]=2)=[N:14][CH:15]=1

Participants

6

Reactant 3

HCID 79271,3-DibromobenzeneHCID 433294Lithium ChlorideHCID 111327115-Methyl-2-(tri-n-butylstannyl)pyridine

Product 1

HCID 586373401,3-Di(5-methyl-2-pyridyl)benzene

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 1,3-dibromobenzene (1.88 g, 8 mmol), 5-methyl-2-tri-n-butylstannylpyridine (7.18 g, 18.8 mmol), lithium chloride (28 g, 0.67 mol), bis(triphenylphosphine)palladium dichloride (360 mg, 0.5 mmol) and toluene (150 cm3) was degassed by bubbling argon through the mixture for 15 minutes. The reaction mixture was heated under reflux for 24 h. The mixture was then allowed to cool to room temperature and was filtered through small pad of silica gel, which was then washed with ethyl acetate. The filtrate was evaporated to dryness and the product was purified by column chromatography (silica gel, hexane/ethyl acetate, 1/1) to give the title product as a colourless solid. Yield 728 mg, 35%. δH (270 MHz; CDCl3): 2.36 (6H, s, 2×CH3), 7.54 (1H, t, J 8.0, 5-H), 7.56 (2H, dd, J 8.2 and 2.1, 2×py 4-H), 7.72 (2H, d, J 8.2, 2×py 3-H), 7.99 (2H, dd, J 8.0 and 1.8, 4-H, 6-H), 8.52 (2H, d, J 2.1, 2×py 6-H), 8.54 (1H, t, J 1.8, 2-H).

Workup

  1. customwas degassed
  2. customby bubbling argon through the mixture for 15 minutes
  3. temperatureThe reaction mixture was heated
  4. temperatureunder reflux for 24 h
  5. filtrationwas filtered through small pad of silica gel, which
  6. washwas then washed with ethyl acetate
  7. customThe filtrate was evaporated to dryness
  8. customthe product was purified by column chromatography (silica gel, hexane/ethyl acetate, 1/1)

Sources & evidence

ORD record
ord-29c27d82229c4a3286f1d2cf8fb024e0
Source dataset
uspto-grants-2012_01
Patent number
US08106193B2

Reaction notes

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