N-bromobutanimide → 2-Bromo-5-bromomethylpyridine

HRID 373617Notes

Reaction equation

HRID 373617 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1.[Br:9]N1C(=O)CCC1=O>N(C(C)(C)C#N)=NC(C)(C)C#N.C(Cl)(Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][Br:9])=[CH:4][N:3]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 5642162-Bromo-5-methylpyridine

Product 1

HCID 64246602-Bromo-5-bromomethylpyridineYield 110.3%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 296.3 g (1.72 mol) of 2-bromo-5-picoline from step 3 in 6L of carbon tetrachloride was treated with 306.5 g (1.72 mol) of N-bromosuccinimide (NBS) and 28.3 g (173 mmol) of azobisisobutyronitrile (AIBN). The reaction was stirred at reflux under nitrogen for 3 h, filtered, and concentrated in vacuo providing 476 g of crude 2-bromo-5-bromomethylpyridine as a brownish yellow solid (NMR indicates that this material is only 69% monobromomethyl product): NMR (CDCl3) δ 4.42 (s, 2H), 7.48 (d, J=9 Hz, 1H), 7.60 (dd, J=9 and 3 Hz, 1H), 8.37 (d, J=3 Hz, 1H).

Workup

  1. temperatureat reflux under nitrogen for 3 h
  2. filtrationfiltered
  3. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8a5a319febdf4c679d2167d5b731961f
Source dataset
uspto-grants-1992_11
Patent number
US05164403

Reaction notes

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