Mechanistic insight into alkylation of the ethyl acetoacetate anion with different ethyl halides

摘要: The alkylation reactions of the ambident ethyl acetoacetate anion with C2H5X (X = F, Cl, Br, and I) in O2, C3, O4 positions were investigated at B3LYP/6-311+G(d,p) level theory. It was found that ethylation reaction does not occur position O4, as well fluoride any anion, due to very high activation energies thermodynamic instability hypothetic products. for O2 are lower comparison but products C3 more stable than those implying C/O ratio is controlled by both kinetic factors, leading O2-product chloride, C3-product iodide leaving group.