Ethanol → 2,5-Di(3-(trimethylsilyl)phenyl)pyridine

HRID 1522728Notes

Reaction equation

HRID 1522728 reaction equation
[CH3:1][Si:2]([CH3:13])([CH3:12])[C:3]1[CH:4]=[C:5](B(O)O)[CH:6]=[CH:7][CH:8]=1.Br[C:15]1[CH:20]=[CH:19][C:18](Br)=[CH:17][N:16]=1.[CH2:22](O)[CH3:23].C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][Si:2]([CH3:13])([CH3:12])[C:3]1[CH:4]=[C:5]([C:15]2[CH:20]=[CH:19][C:18]([C:23]3[CH:22]=[CH:7][CH:8]=[C:3]([Si:2]([CH3:13])([CH3:12])[CH3:1])[CH:4]=3)=[CH:17][N:16]=2)[CH:6]=[CH:7][CH:8]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 693532,5-DibromopyridineHCID 45771813-(Trimethylsilyl)phenylboronic acid

Product 1

HCID 692364992,5-Di(3-(trimethylsilyl)phenyl)pyridineYield 94%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A solution of (22) (5.70 g, 29.4 mmol) and 2,5-dibromopyridine (2.32 g, 9.8 mmol) in a mixture of toluene (120 cm3), ethanol (40 cm3) and aqueous sodium carbonate (2 M, 40 cm3) was deoxygenated with argon. Tetrakis(triphenylphosphine)palladium(0) (566 mg, 0.49 mmol) was added, and the solution was deoxygenated with argon again, then heated at reflux for 16 hours. Water (200 cm3) and dichloromethane (200 cm3) were added, and the layers were separated. The aqueous layer was extracted with dichloromethane (3×50 cm3). The combined organic extracts were washed with brine (500 cm3) and dried over magnesium sulfate, and the solvent was removed to leave a black oil. The crude product was purified by column chromatography using dichloromethane: light petroleum (1:1) as eluent, to give (23) as a white solid (3.48 g, 94%).

Workup

  1. customwas deoxygenated with argon
  2. customthe solution was deoxygenated with argon again
  3. temperatureheated
  4. temperatureat reflux for 16 hours
  5. additionWater (200 cm3) and dichloromethane (200 cm3) were added
  6. customthe layers were separated
  7. extractionThe aqueous layer was extracted with dichloromethane (3×50 cm3)
  8. washThe combined organic extracts were washed with brine (500 cm3)
  9. dry with materialdried over magnesium sulfate
  10. customthe solvent was removed
  11. customto leave a black oil
  12. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-bbe5446fe82f46a9a0b2f348b95fa062
Source dataset
uspto-grants-2015_07
Patent number
US09078330B2

Reaction notes

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