Azobisisobutyronitrile → 5-(Bromomethyl)pyridine-2-carbonitrile

HRID 1190957Notes

Reaction equation

HRID 1190957 reaction equation
CC(N=NC(C#N)(C)C)(C#N)C.[CH3:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]#[N:21])=[N:18][CH:19]=1.C1C(=O)N([Br:29])C(=O)C1>C(Cl)(Cl)(Cl)Cl>[Br:29][CH2:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]#[N:21])=[N:18][CH:19]=1

Participants

5

Reactant 3

HCID 6547Azobisisobutyronitrile2×HCID 67184N-bromobutanimideHCID 741835-Methylpicolinonitrile

Product 1

HCID 219277275-(Bromomethyl)pyridine-2-carbonitrileYield 44%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

Add AIBN (0.25 g, 1.5 mmol) to a slurry of 5-methyl-pyridine-2-carbonitrile (2.5 g, 21.1 mmol) and NBS (3.7 g, 21.1 mmol) in carbon tetrachloride (150 mL) at reflux under a nitrogen atmosphere. Add AIBN (3×0.25 g, 3×1.5 mmol) to the reaction in 0.25 g portions every hour for 3 h. Stir the resulting mixture for one additional hour at reflux. Cool the mixture to room temperature and wash with saturated aqueous NaHCO3 (30 mL). Collect the organic phase, concentrate in vacuo and purify the residue by chromatography on silica gel (330 g) eluting with DCM to obtain the desired intermediate (1.8 g, 44%). MS (ES+) m/z: 199 (M+2)+.

Workup

  1. temperatureat reflux under a nitrogen atmosphere
  2. temperatureat reflux
  3. washwash with saturated aqueous NaHCO3 (30 mL)
  4. customCollect the organic phase
  5. concentrationconcentrate in vacuo
  6. custompurify the residue by chromatography on silica gel (330 g)
  7. washeluting with DCM

Sources & evidence

ORD record
ord-9d2b734de22a4ba18e9c48a2e654bfe4
Source dataset
uspto-grants-2014_03
Patent number
US08680091B2

Reaction notes

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