Formic Acid → Butanoic acid, 2-[(dimethylamino)methylene]-4,4,4-trifluoro-3-oxo-, ethyl ester

Participants

Reaction Steps

To a stirred mixture of ethyl trifluoroacetoacetate (4.6 g, 0.025 mol) and formic acid (2.3 g, 0.05 mol) in 15 ml of THF, DMF dimethyl acetal (6.2 g, 0.05 mol) was added dropwise at a rate which maintained the reaction temperature below 35° C. After stirring the mixture at ambient temperature for 45 minutes to complete the reaction (TLC), it was poured into water and extracted with ether. The ether extract was washed with water, brine solution, then dried (MgSO4), and concentrated. The residual yellow oil was column-chromatographed on silica gel (Hexanes:Ethyl acetate/7:3) to give ethyl 2-trifluoroacetyl-3-(N,N-dimethylamino)-2-propenoate (Compound 2; Rf=0.3) as the major product; 3.2 g (53%). Ethyl 3-(N,N-dimethylamino)-2-propenoate (Compound 4, Rf=0.5) was obtained as the minor product in the form of an oil; 0.85 g (23.7%).

Provenance & Evidence