Acetoacetic Ester Synthesis

Acetoacetic ester synthesis is a synthetic procedure used to convert a compound that has the general structural formula 1 into a ketone that has the general structural formula 2.


R1 = alkyl

L = leaving group

The group —CH2COCH3 in 2 is contributed by an acetoacetic ester, hence the term acetoacetic ester synthesis.


R2 = alkyl, aryl

Acetoacetic ester synthesis consists of four consecutive reactions that can be carried out in the same pot.

reaction 1: acid-base reaction
reaction 2: nucleophilic substitution
reaction 3: ester hydrolysis (using saponification)
reaction 4: decarboxylation

eg:



reaction 1:



reaction 2:



reaction 3:



reaction 4:

acetoacticestersynthesis



A more direct method to convert 3 to 4 is the reaction of 3 with the enolate ion (5) of acetone.



However, the generation of 5 from acetone quantitatively in high yield is not an easy task because the reaction requires a very strong base, such as LDA, and must be carried out at very low temperature under strictly anhydrous conditions.



Acetoacetic ester synthesis provides a more convenient alternative to convert 3 to 4.

Acetoacetic ester synthesis can be adapted to synthesize compounds that have the general structural formula 6.

R3, R4 = identical or different alkyl groups

eg:



reaction 1:



reaction 2:



reaction 1 (repeat):



reaction 2 (repeat):



reaction 3:



reaction 4:



See also Malonic ester synthesis.

 

 

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