2-Bromo-5-methylpyridine → 3-Methyl-2,2'-bipyridine

HRID 1772761Notes

Reaction equation

HRID 1772761 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1.C([Sn](CCCC)(CCCC)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1)CCC>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[C:4]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)=[N:3][CH:2]=[CH:7][CH:6]=1

Participants

5

Reactant 2

HCID 5642162-Bromo-5-methylpyridineHCID 6077842-(Tributylstannyl)pyridine

Product 1

HCID 1824573-Methyl-2,2'-bipyridineYield 76.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 2-bromo-5-methylpyridine (5.0 g, 29 mmol), 2-tributylstannylpyridine (10 g, 27 mmol) and Pd(PPh3)4 (2.0 g, 1.7 mmol) in dry toluene (250 mL) was stirred for 48 h at 110° C. The reaction mixture was filtered over Celite and evaporated under reduced pressure. The residue was dissolved in EtOAc and washed with saturated aqueous NaHCO3 solution, and the organic layer was dried over MgSO4 and concentrated under reduced pressure. Flash column chromatography (0.5% MeOH in CH2Cl2) afforded methyl-2,2′-bipyridine (3.5 g, 75%) as a colorless oil. 1H-NMR (500 MHz, CDCl3): 2.47 (s, 3H), 7.35 (dd, 1H), 7.70 (dd, 1H), 7.87 (m, 1H), 8.36 (d, 1H), 8.43 (d, 1H), 8.58 (d, 1H), 8.74 (dd, 1H).

Workup

  1. filtrationThe reaction mixture was filtered over Celite
  2. customevaporated under reduced pressure
  3. dissolutionThe residue was dissolved in EtOAc
  4. washwashed with saturated aqueous NaHCO3 solution
  5. dry with materialthe organic layer was dried over MgSO4
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-15d032be5c3a4bbc8831a52969cae9a1
Source dataset
uspto-grants-2016_02
Patent number
US09249408B2

Reaction notes

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