2-Bromopyridine → 2-(o-Tolyl)pyridine

HRID 1737196Notes

Reaction equation

HRID 1737196 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1B(O)O.C(=O)(O)[O-].[Na+]>COCCOC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 3

HCID 79732-BromopyridineHCID 516892Sodium BicarbonateHCID 27332672-Methylphenyl boronic acid

Product 1

HCID 825102-(o-Tolyl)pyridineYield 82%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a degassed solution of 2-bromopyridine (1.9 mL, 20 mmol) in ethylene glycol dimethyl ether (60 mL) under argon, tetrakis(triphenylphosphane) palladium (o) (700 mg, 0.6 mmol) was added. After stirring for 10 min, 2-methylphenyl boronic acid (2.9 g, 22 mmol) was added, followed by sodium bicarbonate solution (5.04 g, 60 mmol in 60 mL water). The mixture was heated to reflux (~85° C.) and stirred overnight. After cooling to room temperature, the solvent was evaporated, the residue was partitioned between water and ether, and the aqueous layer was extracted twice with ether. The combined organic layers were dried (Na2SO4), and the solvent was evaporated to give a black oil. This oil was distilled at <1 Torr at ~95° C. to give title compound (2.75 g, 82% yield) as a clear oil. ##STR91##

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux (~85° C.)
  3. stirringstirred overnight
  4. customthe solvent was evaporated
  5. customthe residue was partitioned between water and ether
  6. extractionthe aqueous layer was extracted twice with ether
  7. dry with materialThe combined organic layers were dried (Na2SO4)
  8. customthe solvent was evaporated
  9. customto give a black oil
  10. distillationThis oil was distilled at <1 Torr at ~95° C.

Sources & evidence

ORD record
ord-0dd00ed2b1834693b03dbf14257a3d2e
Source dataset
uspto-grants-1999_10
Patent number
US05962440

Reaction notes

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