Azobisisobutyronitrile → Methyl 4-(bromomethyl)-3-chlorothiophene-2-carboxylate

HRID 2104427Notes

Reaction equation

HRID 2104427 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH3:11])[C:9]=1[Cl:10])=[O:4].[Br:12]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11][Br:12])[C:9]=1[Cl:10])=[O:4]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 2777567Methyl 3-chloro-4-methylthiophene-2-carboxylate

Product 1

HCID 18376575Methyl 4-(bromomethyl)-3-chlorothiophene-2-carboxylateYield 54.2%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

3-Chloro-4-methyl-2-thiophenecarboxylic acid methyl ester (3.81 g) was dissolved in carbon tetrachloride (40 mL). To the solution, N-bromosuccinimide (3.56 g) and α,α′-azobisisobutyronitrile (200 mg) were added, and the mixture was heated under reflux for 2.5 hours. The insoluble material was removed through filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate hexane=1:19→1:9), to thereby give the title compound (2.92 g) as a yellow oil.

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 2.5 hours
  3. customThe insoluble material was removed through filtration
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (ethyl acetate hexane=1:19→1:9)

Sources & evidence

ORD record
ord-38e18f289a1e402b8a7614aaeeeabd9b
Source dataset
uspto-grants-2009_08
Patent number
US07576135B2

Reaction notes

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