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Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study
A theoretical study of urethane formation through the reaction of phenyl isocyanate and butan-1-ol was carried out, without and in the presence of morpholine, and 4-methylmorpholine catalysts. The reaction with and without catalysts was studied at BHandHLYP/6-31G(d) and G3MP2BHandHLYP levels of theo...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10589236/ https://www.ncbi.nlm.nih.gov/pubmed/37863884 http://dx.doi.org/10.1038/s41598-023-44492-x |
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author | Waleed, Hadeer Q. Hadjadj, Rachid Viskolcz, Béla Fiser, Béla |
author_facet | Waleed, Hadeer Q. Hadjadj, Rachid Viskolcz, Béla Fiser, Béla |
author_sort | Waleed, Hadeer Q. |
collection | PubMed |
description | A theoretical study of urethane formation through the reaction of phenyl isocyanate and butan-1-ol was carried out, without and in the presence of morpholine, and 4-methylmorpholine catalysts. The reaction with and without catalysts was studied at BHandHLYP/6-31G(d) and G3MP2BHandHLYP levels of theories. The reaction mechanism in the presence of catalysts differs significantly from the catalyst-free case and includes seven steps. The catalyst-free system was investigated along with the catalytic process, the geometries were optimized, and the corresponding thermodynamic properties were calculated. Calculated reactant complexes were compared with crystal structures of morpholine, and 4-methylmorpholine complexed with diols found in the literature. The structures were strikingly similar and thus, the validity of the proposed and studied general organocatalytic reaction mechanism was partially verified. Meanwhile, an irregularity in the energy profile occurred due to the zwitterionic nature of an intermediate. To handle the irregularity, a correction was implemented which handles the appearance of a zwitterionic structure and the corresponding energetic properties. The results showed that morpholine is less effective catalyst compared to 4-methylmorpholine, which can be associated with the difference in their PA (1523.95 and 963.07 kJ/mol, respectively). The current results prove the important role of amine catalysts in urethane synthesis which can be applied in polyurethane catalyst design and development. |
format | Online Article Text |
id | pubmed-10589236 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-105892362023-10-22 Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study Waleed, Hadeer Q. Hadjadj, Rachid Viskolcz, Béla Fiser, Béla Sci Rep Article A theoretical study of urethane formation through the reaction of phenyl isocyanate and butan-1-ol was carried out, without and in the presence of morpholine, and 4-methylmorpholine catalysts. The reaction with and without catalysts was studied at BHandHLYP/6-31G(d) and G3MP2BHandHLYP levels of theories. The reaction mechanism in the presence of catalysts differs significantly from the catalyst-free case and includes seven steps. The catalyst-free system was investigated along with the catalytic process, the geometries were optimized, and the corresponding thermodynamic properties were calculated. Calculated reactant complexes were compared with crystal structures of morpholine, and 4-methylmorpholine complexed with diols found in the literature. The structures were strikingly similar and thus, the validity of the proposed and studied general organocatalytic reaction mechanism was partially verified. Meanwhile, an irregularity in the energy profile occurred due to the zwitterionic nature of an intermediate. To handle the irregularity, a correction was implemented which handles the appearance of a zwitterionic structure and the corresponding energetic properties. The results showed that morpholine is less effective catalyst compared to 4-methylmorpholine, which can be associated with the difference in their PA (1523.95 and 963.07 kJ/mol, respectively). The current results prove the important role of amine catalysts in urethane synthesis which can be applied in polyurethane catalyst design and development. Nature Publishing Group UK 2023-10-20 /pmc/articles/PMC10589236/ /pubmed/37863884 http://dx.doi.org/10.1038/s41598-023-44492-x Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Waleed, Hadeer Q. Hadjadj, Rachid Viskolcz, Béla Fiser, Béla Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title | Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title_full | Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title_fullStr | Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title_full_unstemmed | Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title_short | Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
title_sort | effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10589236/ https://www.ncbi.nlm.nih.gov/pubmed/37863884 http://dx.doi.org/10.1038/s41598-023-44492-x |
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