Azobisisobutyronitrile → 3-Bromomethyl-5-iodo-2-methoxypyridine

HRID 1432875Notes

Reaction equation

HRID 1432875 reaction equation
[I:1][C:2]1[CH:3]=[C:4]([CH3:10])[C:5]([O:8][CH3:9])=[N:6][CH:7]=1.C1C(=O)N([Br:18])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl>[Br:18][CH2:10][C:4]1[C:5]([O:8][CH3:9])=[N:6][CH:7]=[C:2]([I:1])[CH:3]=1

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 534159905-Iodo-2-methoxy-3-methylpyridine

Product 1

HCID 538965933-Bromomethyl-5-iodo-2-methoxypyridineYield 55%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A solution containing 5-iodo-3-methyl-2-methoxy-pyridine (1.00 g, 4.00 mmol) and NBS (0.78 g, 4.40 mmol) in CCl4 (20 mL) is warmed to reflux. AIBN is added in 5 mg portions (0.03 mmol) every hour. After 3 h, the reaction mixture is cooled and then concentrated in vacuo. The residue is dissolved in EtOAc (150 mL) and washed successively with aqueous Na2S2O3 (100 mL), water (100 mL), brine then dried over anhydrous Na2SO4, filtered and concentrated. The crude product ispurified by silica gel flash column chromatography (hexane/diethyl ether, 19:1) to provide 0.72 g (55%) of the title compound as a white solid. 1H NMR (300 MHz, CDCl3) δ3.97 (s, 3H), 4.38 (s, 2H), 7.83 (d, J=2.2 Hz, 1H), 8.27 (d, J=2.2 Hz, 1H) ppm; MS (EI): m/z 327 (M+).

Workup

  1. temperatureis warmed to reflux
  2. temperaturethe reaction mixture is cooled
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue is dissolved in EtOAc (150 mL)
  5. washwashed successively with aqueous Na2S2O3 (100 mL), water (100 mL), brine
  6. dry with materialthen dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-d22900b731c943c78293e18dbc1bc638
Source dataset
uspto-grants-2009_11
Patent number
US07612075B2

Reaction notes

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