Alkylation of ethyl 4,4,4-trifluoroacetoacetate. First example of a reversible O-alkylation process leading to C-alkylation

Abstract

In aprotic polar solvents the ratio of O vs. C alkylation products of ethyl 4,4,4-trifluoroacetoacetate (ETFAA)can be dependent on reaction time; in hexamethylphosphoric triamide (HMPA) or acetone, the S_N2 cleavage of enol ethers of ETFAA with sodium iodide was observed with concomitant formation of the sodium enolate and the corresponding iodides, and in the case of an activated iodide the mono- and di-alkylation products resulted quantitatively.