Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

Geert J. Noordzij, Carolus H. R. M. Wilsens*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

14 Citations (Web of Science)

Abstract

Although the aza-Michael addition reaction on various unsaturated (di-)carboxylic acids and esters of, for example, itaconic acid, is well-known, the consecutive cyclization reaction has not received much attention in literature. The products of this aza-Michael cascade reaction, being mono- or di-carboxylic acid or ester functionalized N-alkyl-pyrrolidone structures, prove interesting for melt-polycondensation reactions as they exhibit excellent stability at elevated temperatures. In other words, this reaction is a toolbox for the generation of renewable monomers and, in turn, polymers with tunable physiological properties. Therefore, this work provides an overview of the state-of-the-art of the cascade aza-Michael addition-cyclization reactions on biobased unsaturated acids and esters, and their use in polymerization reactions. Furthermore, we extend this overview with the cascade aza-Michael addition-cyclization reaction of trans-trimethyl aconitate with di-amines to form a tetra-functional N-alkyl-bis-(pyrrolidone dimethylcarboxylate), which exhibits excellent thermal stability and could effectively be used as monomer in polycondensation reactions. Importantly, the aza-Michael addition reaction between primary amines and trans-trimethyl aconitate can be considered a click-reaction; it proceeds quantitatively within minutes under ambient conditions and follows the principles of green chemistry.

Original languageEnglish
Article number729
Number of pages14
JournalFrontiers in Chemistry
Volume7
DOIs
Publication statusPublished - 14 Nov 2019

Keywords

  • aza-Michael addition-cyclization
  • N-alkyl-pyrrolidone methylcarboxylate
  • itaconic acid
  • aconitic acid
  • renewable monomers
  • polycondensation
  • POST-POLYMERIZATION MODIFICATION
  • ITACONIC ACID
  • ELECTROCHEMICAL CONVERSION
  • UNSATURATED COPOLYESTERS
  • DICARBOXYLIC-ACIDS
  • BUILDING-BLOCK
  • CATALYST-FREE
  • MUCONIC ACID
  • SOLVENT-FREE
  • POLYMERS

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