N-bromobutanimide → Dimethyl bromomethylfumarate

HRID 83480Notes

Reaction equation

HRID 83480 reaction equation
[CH3:1][O:2][C:3](=[O:11])/[C:4](/[CH3:10])=[CH:5]\[C:6]([O:8][CH3:9])=[O:7].[Br:12]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[CH3:1][O:2][C:3](=[O:11])/[C:4](/[CH2:10][Br:12])=[CH:5]/[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 5355715Dimethyl citraconate

Product 1

HCID 10466666Dimethyl bromomethylfumarateYield 85.5%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of (Z)-2-methyl-2-butenedioic acid dimethyl ester (15.3 g) in carbon tetrachloride (300 ml) were added N-bromosuccinimide (25.8 g) and 2,2′-azobis(isobutyronitrile) (319 mg), and the mixture was stirred for 36 hours at reflux. After cooling the mixture to room temperature, the insoluble substance was filtered off, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=1/0 to 18/1) to give the titled compound (19.6 g).

Workup

  1. temperatureat reflux
  2. filtrationthe insoluble substance was filtered off
  3. concentrationthe filtrate was concentrated
  4. customThe resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=1/0 to 18/1)

Sources & evidence

ORD record
ord-9b68949a788e4e38b52d66d0a597807e
Source dataset
uspto-grants-2014_09
Patent number
US08846746B2

Reaction notes

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