Azobisisobutyronitrile → 6-Bromomethyl-nicotinic acid methyl ester

HRID 131261

Reaction equation

HRID 131261 reaction equation
[CH3:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][N:3]=1.[Br:12]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.CCCCCC>C(Cl)(Cl)(Cl)Cl>[Br:12][CH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 8058HexaneHCID 67184N-bromobutanimideHCID 231548Methyl 6-methylnicotinate

Product 1

HCID 127522376-Bromomethyl-nicotinic acid methyl esterYield 35.5%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of methyl 6-methylnicotinate (6.3 g) in carbon tetrachloride (100 mL) is added successively N-bromosuccinimide (8.9 g) and 2,2′-azobisisobutyronitrile (342 mg), and the mixture is refluxed under heating for 6 hours. After cooling to room temperature, to the reaction mixture is added n-hexane (300 mL) and the insoluble materials are removed by filtration. The filtrate is concentrated in vacuo and the resultant crude product is purified by column chromatography on silica gel (Solvent; n-hexane:ethyl acetate=10:1) and stirred in n-hexane to give methyl 6-(bromomethyl)nicotinate (3.4 g, yield; 35%) as colorless crystals.

Workup

  1. temperaturethe mixture is refluxed
  2. temperatureunder heating for 6 hours
  3. customthe insoluble materials are removed by filtration
  4. concentrationThe filtrate is concentrated in vacuo
  5. customthe resultant crude product is purified by column chromatography on silica gel (Solvent; n-hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-88834c4755c14761a72f39e7f625bef1
Source dataset
uspto-grants-2008_06
Patent number
US07384952B2

Linked notes

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