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15.33 : Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis

Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an alkylated β-keto acid. Under high-temperature conditions, the β-keto acid undergoes decarboxylation to form a ketone. However, if the alkylation is repeated before hydrolysis and decarboxylation steps, a disubstituted ketone is obtained.

Tags
AlkylationketoesterEnolate IonAcetoacetic Ester SynthesisAlkyl HalidesAlkoxide BaseSN2 ProcessAlkylated Ester IntermediateC C BondHydrolysisAcidificationAlkylated keto AcidDecarboxylationDisubstituted Ketone

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15.33 : Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis

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15.2 : Reactivity of Enolate Ions

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15.3 : Types of Enols and Enolates

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