Diethyl Ether → Ethyl (2e)-3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)-2-propenoate

HRID 2221603Notes

Reaction equation

HRID 2221603 reaction equation
[O:1]=[CH:2][CH:3]=[CH:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH3:10][C:11](=[N:15]O)[C:12](=O)[CH3:13].[ClH:17].C(OCC)(=O)C.C(OCC)C>C(OCC)(=O)C.CCCCCC>[Cl:17][CH2:10][C:11]1[N:15]=[C:2](/[CH:3]=[CH:4]/[C:5]([O:7][CH2:8][CH3:9])=[O:6])[O:1][C:12]=1[CH3:13]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 63989692-Oxime 2,3-butanedioneHCID 21866389Hydrogen chloride-ethyl acetateHCID 53438123Ethyl 4-oxobut-2-enoate

Product 1

HCID 131726861Ethyl (2e)-3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)-2-propenoateYield 55%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A mixture of ethyl 4-oxobutenate (25.31 g), 2,3-butanedione-2-oxime (20.02 g) and 4N hydrogenchloride-ethyl acetate solution (300 mL) was stirred at room temperature for 4 days. After concentration of the reaction mixture, diethyl ether was added to the residue, and the residue was decanted and washed. Tetrahydrofuran (300 mL) was added to the residue, and thionyl chloride (35.33 g) was further added. The mixture was heated under reflux for 2 hrs. After concentration of the reaction mixture, ethyl acetate was added to the residue. The ethyl acetate layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give from a fraction eluted with ethyl acetate-hexane (1:8, v/v), ethyl (2E)-3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)-2-propenoate as colorless crystals (24.98 g, yield 55%). Recrystallization from hexane gave prism crystals. melting point: 53-54° C.

Workup

  1. customthe residue was decanted
  2. washwashed
  3. additionTetrahydrofuran (300 mL) was added to the residue, and thionyl chloride (35.33 g)
  4. additionwas further added
  5. temperatureThe mixture was heated
  6. temperatureunder reflux for 2 hrs
  7. additionAfter concentration of the reaction mixture, ethyl acetate was added to the residue
  8. washThe ethyl acetate layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. concentrationconcentrated
  11. customto give from a fraction

Sources & evidence

ORD record
ord-902b5a743b8d4ee8a2425e7961f1d8c2
Source dataset
uspto-grants-2008_05
Patent number
US07368578B2

Reaction notes

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