Ethyl 4,4,4-trifluoroacetoacetate → Ethyl 3-(N,N-dimethylamino)acrylate

HRID 1533430Notes

Reaction equation

HRID 1533430 reaction equation
FC(F)(F)C([C:5](=[CH:11][N:12]([CH3:14])[CH3:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=O.FC(F)(F)C(=O)CC(OCC)=O>C(O)(=O)C>[CH3:13][N:12]([CH:11]=[CH:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:14]

Participants

4

Reactant 2

HCID 67793Ethyl 4,4,4-trifluoroacetoacetate2×HCID 53979199Butanoic acid, 2-[(dimethylamino)methylene]-4,4,4-trifluoro-3-oxo-, ethyl ester3×

Product 1

HCID 121015Ethyl 3-(N,N-dimethylamino)acrylate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

I have found surprisingly conditions which allow the preparation of ethyl 2-trifluoroacetyl-3-(N,N-dimethylamino)-2-propenoate (2) from ethyl trifluoroacetoacetate and DMF acetals according to a general one-step reaction. Specifically, I found that compound 2 can be prepared in good yields (61-85%) by reacting ethyl trifluoroacetoacetate with DMF acetals in the presence of an organic acid such as acetic acid. While not wishing to be bound by theory, the success of this reaction condition appears to lie in the suppression of the loss of the trifluoroacetyl group from (2) through the attack of the alcohol by-products. In the absence of the organic acid, ethyl 3-(N,N-dimethylamino)-2-propenoate (4) is formed as the major product in all cases. My overall result is shown in Scheme 2.

Workup

  1. customto a general one-step reaction
  2. customcan be prepared
  3. customin good yields (61-85%)

Sources & evidence

ORD record
ord-89da67ca858c46daa210cb3d4801029b
Source dataset
uspto-grants-2001_03
Patent number
US06207828B1

Reaction notes

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