Acetic Acid → 4-(Bromomethyl)picolinonitrile

HRID 899990Notes

Reaction equation

HRID 899990 reaction equation
C(O)(=O)C.[C:5]([C:7]1[CH:12]=[C:11]([CH3:13])[CH:10]=[CH:9][N:8]=1)#[N:6].[Br:14]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[C:5]([C:7]1[CH:12]=[C:11]([CH2:13][Br:14])[CH:10]=[CH:9][N:8]=1)#[N:6]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 887392-Cyano-4-methylpyridine

Product 1

HCID 106317764-(Bromomethyl)picolinonitrileYield 24.6%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
50 °C

Procedure

0.146 ml of acetic acid is added to a solution of 0.236 g of 2-cyano-4-methylpyridine in 5 ml of carbon tetrachloride, under an inert atmosphere of argon at a temperature in the region of 20° C. The mixture is brought, with stirring, to a temperature of 50° C. 0.712 g of N-bromosuccinimide and 0.096 g of benzoyl peroxide are successively added at this temperature. The mixture is maintained at 80° C. for about 18 hours. After cooling, the reaction medium is placed on a cartridge 27 mm in diameter packed with 25 g of 20-40 μm silica not conditioned beforehand, and then eluted with dichloromethane at a flow rate of 10 ml/minute. The fractions between 140 and 175 ml are concentrated to dryness under reduced pressure. 0.097 g of 2-cyano-4(bromomethyl)pyridine is thus obtained.

Workup

  1. temperatureThe mixture is maintained at 80° C. for about 18 hours
  2. temperatureAfter cooling
  3. washeluted with dichloromethane at a flow rate of 10 ml/minute
  4. concentrationThe fractions between 140 and 175 ml are concentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-4425797e98dd4ed297ed0e7baf70ec79
Source dataset
uspto-grants-2008_04
Patent number
US07354933B2

Reaction notes

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