Surf Wiki
Save to docs
general/carbon-carbon-bond-forming-reactions

From Surf Wiki (app.surf) — the open knowledge base

Acetoacetic ester synthesis

Chemical reaction

Acetoacetic ester synthesis

Chemical reaction

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. This is very similar to malonic ester synthesis.

Acetoacetic ester synthesis equation

Mechanism

A strong base deprotonates the dicarbonyl α-carbon. This carbon is preferred over the methyl carbon because the formed enolate is conjugated and thus resonance stabilized. The carbon then undergoes nucleophilic substitution. When heated with aqueous acid, the newly alkylated ester is hydrolyzed to a β-keto acid, which is decarboxylated to form a methyl ketone. The alkylated ester can undergo a second substitution to produce the dialkylated product.

Acetoacetic ester synthesis

Double deprotonation of ethyl acetoacetate

The classical acetoacetatic ester synthesis utilizes the 1:1 conjugate base. Ethyl acetoacetate is however diprotic: :CH3C(O)CH2CO2Et + NaH → CH3C(O)CH(Na)CO2Et + H2 :CH3C(O)CH(Na)CO2Et + BuLi → LiCH2C(O)CH(Na)CO2Et + BuH

The dianion (i.e., LiCH2C(O)CH(Na)CO2Et) adds electrophile to the terminal carbon as depicted in the following simplified form: :LiCH2C(O)CH(Na)CO2Et + RX → RCH2C(O)CH(Na)CO2Et + LiX

References

References

  1. Smith, Janice Gorzynski. ''Organic Chemistry: Second Ed''. 2008. pp 905–906
  2. [https://pharmaxchange.info/press/2011/02/acetoacetic-ester-synthesis-alkylation-of-enolates/ Acetoacetic Ester Synthesis – Alkylation of Enolates. PharmaXChange.info]
  3. (2007). "Stereoselective Isoprenoid Chain Extension with Acetoacetate Dianion: [(''E, E, E'')-Geranylgeraniol from (''E, E'')-Farnesol". Organic Syntheses.
Info: Wikipedia Source

This article was imported from Wikipedia and is available under the Creative Commons Attribution-ShareAlike 4.0 License. Content has been adapted to SurfDoc format. Original contributors can be found on the article history page.

carbon-carbon-bond-forming-reactions
Want to explore this topic further?

Ask Mako anything about Acetoacetic ester synthesis — get instant answers, deeper analysis, and related topics.

Research with Mako

Free with your Surf account

Content sourced from Wikipedia, available under CC BY-SA 4.0.

This content may have been generated or modified by AI. CloudSurf Software LLC is not responsible for the accuracy, completeness, or reliability of AI-generated content. Always verify important information from primary sources.

Report