Ethyl Acetoacetate → Ethyl 2-acetyl-3-(dimethylamino)acrylate

HRID 1109443Notes

Reaction equation

HRID 1109443 reaction equation
CO[CH:3](OC)[N:4]([CH3:6])[CH3:5].[C:9]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:10][C:11]([CH3:13])=[O:12]>O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH2:16]([O:15][C:9](=[O:14])[C:10](=[CH:3][N:4]([CH3:5])[CH3:6])[C:11]([CH3:13])=[O:12])[CH3:17]

Participants

4

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 78373Dimethylformamide dimethyl acetal

Product 1

HCID 3806790Ethyl 2-acetyl-3-(dimethylamino)acrylateYield 71.6%

Reagents, catalysts & solvents 1

HCID 521998p-Toluenesulfonic acid monohydrateCatalyst

Procedure

A mixture of 200 g (1.68 moles) of N,N-dimethylformamide dimethyl acetal, 145.68 g (1.12 moles) of ethyl acetoacetate, and 0.5 g (0.003 mole) of p-toluenesulfonic acid monohydrate was heated in a water bath with stirring for three hours. The color of the reaction mixture changed progressively from orange to red and finally to brown. Heating was discontinued, and the reaction mixture was allowed to sit at room temperature for approximately 18 hours. At the conclusion of this period, the mixture was distilled under vacuum, and six fractions having a boiling point in the range 145°-150° C. were analyzed by NMR spectroscopy. The NMR spectrum of each fraction was consistent with the proposed structure. These fractions were combined, yielding a total of 148.51 g of ethyl-2-dimethylaminomethyleneacetoacetate.

Workup

  1. temperaturewas heated in a water bath
  2. temperatureHeating
  3. waitto sit at room temperature for approximately 18 hours
  4. distillationAt the conclusion of this period, the mixture was distilled under vacuum, and six fractions
  5. customin the range 145°-150° C.

Sources & evidence

ORD record
ord-55fbc1a225d746229b8752b252c92745
Source dataset
uspto-grants-1994_06
Patent number
US05321002

Reaction notes

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