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Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors

The Knoevenagel reaction is a classic reaction in organic chemistry for the formation of C-C bonds. In this study, various catalytic monomers for Knoevenagel reactions were synthesized and polymerized via photolithography to form polymeric gel dots with a composition of 90% catalyst, 9% gelling agen...

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Autores principales: Killi, Naresh, Bartenbach, Julian, Kuckling, Dirk
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10048661/
https://www.ncbi.nlm.nih.gov/pubmed/36975620
http://dx.doi.org/10.3390/gels9030171
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author Killi, Naresh
Bartenbach, Julian
Kuckling, Dirk
author_facet Killi, Naresh
Bartenbach, Julian
Kuckling, Dirk
author_sort Killi, Naresh
collection PubMed
description The Knoevenagel reaction is a classic reaction in organic chemistry for the formation of C-C bonds. In this study, various catalytic monomers for Knoevenagel reactions were synthesized and polymerized via photolithography to form polymeric gel dots with a composition of 90% catalyst, 9% gelling agent and 1% crosslinker. Furthermore, these gel dots were inserted into a microfluidic reactor (MFR) and the conversion of the reaction using gel dots as catalysts in the MFR for 8 h at room temperature was studied. The gel dots containing primary amines showed a better conversion of about 83–90% with aliphatic aldehyde and 86–100% with aromatic aldehyde, compared to the tertiary amines (52–59% with aliphatic aldehyde and 77–93% with aromatic aldehydes) which resembles the reactivity of the amines. Moreover, the addition of polar solvent (water) in the reaction mixture and the swelling properties of the gel dots by altering the polymer backbone showed a significant enhancement in the conversion of the reaction, due to the increased accessibility of the catalytic sites in the polymeric network. These results suggested the primary-amine-based catalysts facilitate better conversion compared to tertiary amines and the reaction solvent had a significant influence on organocatalysis to improve the efficiency of MFR.
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spelling pubmed-100486612023-03-29 Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors Killi, Naresh Bartenbach, Julian Kuckling, Dirk Gels Article The Knoevenagel reaction is a classic reaction in organic chemistry for the formation of C-C bonds. In this study, various catalytic monomers for Knoevenagel reactions were synthesized and polymerized via photolithography to form polymeric gel dots with a composition of 90% catalyst, 9% gelling agent and 1% crosslinker. Furthermore, these gel dots were inserted into a microfluidic reactor (MFR) and the conversion of the reaction using gel dots as catalysts in the MFR for 8 h at room temperature was studied. The gel dots containing primary amines showed a better conversion of about 83–90% with aliphatic aldehyde and 86–100% with aromatic aldehyde, compared to the tertiary amines (52–59% with aliphatic aldehyde and 77–93% with aromatic aldehydes) which resembles the reactivity of the amines. Moreover, the addition of polar solvent (water) in the reaction mixture and the swelling properties of the gel dots by altering the polymer backbone showed a significant enhancement in the conversion of the reaction, due to the increased accessibility of the catalytic sites in the polymeric network. These results suggested the primary-amine-based catalysts facilitate better conversion compared to tertiary amines and the reaction solvent had a significant influence on organocatalysis to improve the efficiency of MFR. MDPI 2023-02-21 /pmc/articles/PMC10048661/ /pubmed/36975620 http://dx.doi.org/10.3390/gels9030171 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Killi, Naresh
Bartenbach, Julian
Kuckling, Dirk
Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title_full Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title_fullStr Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title_full_unstemmed Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title_short Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors
title_sort polymeric networks containing amine derivatives as organocatalysts for knoevenagel reaction within continuously driven microfluidic reactors
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10048661/
https://www.ncbi.nlm.nih.gov/pubmed/36975620
http://dx.doi.org/10.3390/gels9030171
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AT kucklingdirk polymericnetworkscontainingaminederivativesasorganocatalystsforknoevenagelreactionwithincontinuouslydrivenmicrofluidicreactors