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Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups

New enantiomerically pure C(16)-alkyl diamides derived from trihydroxy cyclohexane-1,2-dicarboxylic acid have been synthesized from (−)-shikimic acid. The hydroxyl groups in these compounds are free or, alternatively, they present full or partial protection. Their gelling abilities towards several s...

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Autores principales: Pi-Boleda, Bernat, Campos, María, Sans, Marta, Basavilbaso, Antonio, Illa, Ona, Branchadell, Vicenç, Estévez, Juan Carlos, Ortuño, Rosa M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6358840/
https://www.ncbi.nlm.nih.gov/pubmed/30669453
http://dx.doi.org/10.3390/molecules24020352
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author Pi-Boleda, Bernat
Campos, María
Sans, Marta
Basavilbaso, Antonio
Illa, Ona
Branchadell, Vicenç
Estévez, Juan Carlos
Ortuño, Rosa M.
author_facet Pi-Boleda, Bernat
Campos, María
Sans, Marta
Basavilbaso, Antonio
Illa, Ona
Branchadell, Vicenç
Estévez, Juan Carlos
Ortuño, Rosa M.
author_sort Pi-Boleda, Bernat
collection PubMed
description New enantiomerically pure C(16)-alkyl diamides derived from trihydroxy cyclohexane-1,2-dicarboxylic acid have been synthesized from (−)-shikimic acid. The hydroxyl groups in these compounds are free or, alternatively, they present full or partial protection. Their gelling abilities towards several solvents have been tested and rationalized by means of the combined use of Hansen solubility parameters, scanning electron microscopy (SEM), and circular dichroism (CD), as well as computational calculations. All the results allowed us to account for the capability of each type of organogelator to interact with different solvents and for the main mode of aggregation. Thus, compounds with fully protected hydroxyl groups are good organogelators for methanol and ethanol. In contrast, a related compound bearing three free hydroxyl groups is insoluble in water and polar solvents including alcohols but it is able to gelate some low-polarity solvents. This last behavior can be justified by strong hydrogen bonding between molecules of organogelator, which competes advantageously with polar solvent interactions. As an intermediate case, an organogelator with two free hydroxyl groups presents an ambivalent ability to gelate both apolar and polar solvents by means of two aggregation patterns. These involve hydrogen bonding interactions of the unprotected hydroxyl groups in apolar solvents and intermolecular interactions between amide groups in polar ones.
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spelling pubmed-63588402019-02-06 Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups Pi-Boleda, Bernat Campos, María Sans, Marta Basavilbaso, Antonio Illa, Ona Branchadell, Vicenç Estévez, Juan Carlos Ortuño, Rosa M. Molecules Article New enantiomerically pure C(16)-alkyl diamides derived from trihydroxy cyclohexane-1,2-dicarboxylic acid have been synthesized from (−)-shikimic acid. The hydroxyl groups in these compounds are free or, alternatively, they present full or partial protection. Their gelling abilities towards several solvents have been tested and rationalized by means of the combined use of Hansen solubility parameters, scanning electron microscopy (SEM), and circular dichroism (CD), as well as computational calculations. All the results allowed us to account for the capability of each type of organogelator to interact with different solvents and for the main mode of aggregation. Thus, compounds with fully protected hydroxyl groups are good organogelators for methanol and ethanol. In contrast, a related compound bearing three free hydroxyl groups is insoluble in water and polar solvents including alcohols but it is able to gelate some low-polarity solvents. This last behavior can be justified by strong hydrogen bonding between molecules of organogelator, which competes advantageously with polar solvent interactions. As an intermediate case, an organogelator with two free hydroxyl groups presents an ambivalent ability to gelate both apolar and polar solvents by means of two aggregation patterns. These involve hydrogen bonding interactions of the unprotected hydroxyl groups in apolar solvents and intermolecular interactions between amide groups in polar ones. MDPI 2019-01-19 /pmc/articles/PMC6358840/ /pubmed/30669453 http://dx.doi.org/10.3390/molecules24020352 Text en © 2019 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Pi-Boleda, Bernat
Campos, María
Sans, Marta
Basavilbaso, Antonio
Illa, Ona
Branchadell, Vicenç
Estévez, Juan Carlos
Ortuño, Rosa M.
Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title_full Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title_fullStr Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title_full_unstemmed Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title_short Synthesis and Gelling Abilities of Polyfunctional Cyclohexane-1,2-dicarboxylic Acid Bisamides: Influence of the Hydroxyl Groups
title_sort synthesis and gelling abilities of polyfunctional cyclohexane-1,2-dicarboxylic acid bisamides: influence of the hydroxyl groups
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6358840/
https://www.ncbi.nlm.nih.gov/pubmed/30669453
http://dx.doi.org/10.3390/molecules24020352
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