Mechanistic studies by mass spectrometry of the Knoevenagel condensation using functionalized ionic liquids

• Grant number: 12/17032-0
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Effective date (Start): November 01, 2013
• Effective date (End): July 31, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Marcos Nogueira Eberlin
• Grantee: Dávila de Souza Zampieri
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 10/51677-2 - Development of new mass spectrometry techniques and their general applications in science: chemistry, biochemistry, material sciences, forensics, medicine, food science, pharmaceutical and veterinary medicine, AP.TEM

Abstract

The Knoevenagel condensation is one of the classical methods for the formation of the C=C bond. Its products are used in the synthesis of biologically active molecules. The application of modern organocatalysis, where the use of chiral catalysts has drawn the attention of researchers, the use of ionic liquids containing primary or secondary amines in their cations has shown promise. Ionic liquids are used as the solvent and co-solvent reactions, in addition, the ionic liquids can be easily recycled, one of the main reasons they are applied in several classical organic processes, reducing the cost of the process as a whole. Currently, there are few reports of the study of reaction mechanisms using functionalized ionic liquids as a catalyst and as the reaction medium. In this context, mass spectrometry has advanced as a powerful tool in understanding and elucidation of mechanisms of reaction, making it possible to detect and study not only of the reactants and reaction products, but also transient intermediates, giving birth to investigations of these mechanisms reactions. And the use of functionalized ionic liquids as labels load avoids the use of additives to protonate and deprotonate intermediates, which can interfere with the reaction procedure since organic reactions often are dependent on the reaction medium. Furthermore, the use of ion mobility spectrometry is used as a complementary tool in the investigation of organic structure, for example, diastereoisomers since separates the ions according to their size, charge and their interactions with the gas mobility. Therefore, this project will carry out a detailed study of Knoevenagel condensation reactions and their catalytic cycle using ionic liquids functionalized with proline, by mass spectrometry.