2-Bromo-5-methylpyridine → 5-Methyl-[2,2']bipyridinyl

HRID 1866463Notes

Reaction equation

HRID 1866463 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1>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>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)=[N:3][CH:4]=1

Participants

4

Reactant 1

HCID 5642162-Bromo-5-methylpyridine

Product 1

HCID 110738485-Methyl-[2,2']bipyridinylYield 193%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A solution of 2-(tributyltin)pyridine (9.20 g, 25 mmol) and 2-bromo-5-methylpyridine (4.3 g, 25 mmol) in toluene was bubbled with argon gas for 10 min. The catalyst Pd(PPh3)4 (0.29 g, 0.25 mmol, 1 mol %) was added and the mixture was refluxed under argon atmosphere for 3 days. Removal of solvent gave an oil that was purified by chromatography over silica gel eluted with CH2Cl2 and then EtOAc. The brown liquid obtained was dried overnight under high vacuum providing 4.1073 g of 5-methyl-[2,2′]bipyridinyl as a brown liquid (24.13 mmol, yield 96.5%). 1H NMR (CDCl3, 300.16 MHz) δ (ppm) 8.66 (ddd, J=4.8, 1.8 & 0.9 Hz, 1H), 8.51 (dt, J=2.9 & 0.7 Hz, 1H), 8.35 (dt, J=8.0 & 1.1 Hz, 1H), 8.28 (d, J=8.1 Hz, 1H), 7.80 (td, J=7.7 & 1.8 Hz, 1H), 7.63 (ddd, J=8.1, 1.5 & 0.7 Hz, 1H), 7.28 (ddd, J=7.5, 4.8 & 1.2 Hz, 1H) and 2.39 (s, 3H). MS (ESI) m/z: 171 (M+1)+ and (2M+23)+.

Workup

  1. temperaturethe mixture was refluxed under argon atmosphere for 3 days
  2. customRemoval of solvent
  3. customgave an oil that
  4. customwas purified by chromatography over silica gel
  5. washeluted with CH2Cl2
  6. customThe brown liquid obtained
  7. customwas dried overnight under high vacuum

Sources & evidence

ORD record
ord-55139af07d0a471eba3601930aa2d147
Source dataset
uspto-grants-2009_12
Patent number
US07629375B2

Reaction notes

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