Acetoacetic ester synthesis

Acetoacetic ester synthesis is a chemical reaction where ethyl acetoacetate is alkylated at the α-carbon to both carbonyl groups and then converted into a ketone, or more specifically an α-substituted acetone.

When heated with aqueous acid, the newly alkylated ester is hydrolyzed to a β-keto acid, which is decarboxylated to form a methyl ketone.

[1][2] The alkylated ester can undergo a second substitution to produce the dialkylated product.

The classical acetoacetatic ester synthesis utilizes the 1:1 conjugate base.

Ethyl acetoacetate is however diprotic:[3] The dianion (i.e., LiCH2C(O)CH(Na)CO2Et) adds electrophile to the terminal carbon as depicted in the following simplified form:[3]