Toluene → 2-(o-Tolyl)pyridine

HRID 1897554Notes

Reaction equation

HRID 1897554 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[C:8]1([CH3:17])[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1B(O)O.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O>[C:8]1([CH3:17])[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 79732-BromopyridineHCID 62657Potassium Phosphate, TribasicHCID 27332672-Methylphenyl boronic acid

Product 1

HCID 825102-(o-Tolyl)pyridineYield 68.9%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalystHCID 962WaterSolvent

Procedure

A mixture of 8.1 g (51.5 mmol) of 2-bromopyridine, 7 g (51.5 mmol) o-tolylboronic acid, 0.47 g (0.51 mmol) of Pd2(dba)3, 0.84 g (2.06 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl and 32 g (154.5 mmol) of potassium phosphate tribasic, 100 mL of toluene and 30 mL of water was purged with nitrogen. The solution was heated to reflux for 12 hours. Upon cooling, the organic layer was separated, and dried with MgSO4. The product was separated by column chromatography using hexanes/ethyl acetate (5% ethyl acetate) as the eluent. The solvent was removed by rotary evaporation, and the product was dried under vacuum resulting in 6 g (35.5 mmol) of 2-(o-tolyl)pyridine.

Workup

  1. customwas purged with nitrogen
  2. temperatureThe solution was heated
  3. temperatureto reflux for 12 hours
  4. temperatureUpon cooling
  5. customthe organic layer was separated
  6. dry with materialdried with MgSO4
  7. customThe product was separated by column chromatography
  8. customThe solvent was removed by rotary evaporation
  9. customthe product was dried under vacuum

Sources & evidence

ORD record
ord-cf60f238972248bbb263ee69ab210240
Source dataset
uspto-grants-2013_08
Patent number
US08519130B2

Reaction notes

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