Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/24590 |
Resumo: | The following work presents the synthesis of molecular thread and molecules of rotaxanes containing two stations, succinamide and oxoalkyl-triazole. The synthetic process of the molecular thread was carried out by “click” reactions involving cycloaddition [3+2] of azides and terminal alkynes copper catalyzed (CuAAC), resulting in yields of 55–83%. The formation of rotaxanes molecules was based on the clipping methodology, consisting in a multicomponent reaction with isolated product yields ranging from 8–25%. The synthesized molecules were identified and characterized by 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy in one- and two-dimensional experiments, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), liquid chromatography/tandem mass spectrometry (LC-MS/MS), high resolution mass spectroscopy (HRMS), melting point and single crystal X-ray diffraction (SC-XRD), when possible. The [2]rotaxanes molecules were studied by 1H NMR experiments at variable temperatures. Studies carried out with temperatures variations between -20 to 40 °C revealed the position of the macrocycle over the succinamide station at low temperatures is favored and showing a possible shuttling to the oxoalkyl-triazole station with increasing temperature. This event was observed through variations in chemical displacement of the hydrogens present in the molecular thread station, which suffer a shielding effect due to the formation of hydrogen bonds with the macrocycle. The formation of [3]rotaxanes molecules was not observed for the proposed models. Therefore, alteration in the spacer chain of the oxoalkyl-triazole station is not enough to favor the synthesis of [3]rotaxanes molecules. |
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Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazolSynthesis and characterization of [2]rotaxanes: use of molecular threads with succinamide and oxoalkyl-triazoles stations[2]rotaxanosMáquinas molecularesReações do tipo clickReação multicomponente[2]rotaxanesMolecular machinesClick reactionMulticomponent reactionCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe following work presents the synthesis of molecular thread and molecules of rotaxanes containing two stations, succinamide and oxoalkyl-triazole. The synthetic process of the molecular thread was carried out by “click” reactions involving cycloaddition [3+2] of azides and terminal alkynes copper catalyzed (CuAAC), resulting in yields of 55–83%. The formation of rotaxanes molecules was based on the clipping methodology, consisting in a multicomponent reaction with isolated product yields ranging from 8–25%. The synthesized molecules were identified and characterized by 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy in one- and two-dimensional experiments, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), liquid chromatography/tandem mass spectrometry (LC-MS/MS), high resolution mass spectroscopy (HRMS), melting point and single crystal X-ray diffraction (SC-XRD), when possible. The [2]rotaxanes molecules were studied by 1H NMR experiments at variable temperatures. Studies carried out with temperatures variations between -20 to 40 °C revealed the position of the macrocycle over the succinamide station at low temperatures is favored and showing a possible shuttling to the oxoalkyl-triazole station with increasing temperature. This event was observed through variations in chemical displacement of the hydrogens present in the molecular thread station, which suffer a shielding effect due to the formation of hydrogen bonds with the macrocycle. The formation of [3]rotaxanes molecules was not observed for the proposed models. Therefore, alteration in the spacer chain of the oxoalkyl-triazole station is not enough to favor the synthesis of [3]rotaxanes molecules.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqO presente trabalho apresenta a síntese de eixos moleculares e moléculas de rotaxanos contendo duas estações, succinamida e oxoalquil-triazol. O processo sintético dos eixos moleculares foi realizado por reações do tipo click, envolvendo a cicloadição [3+2] de azidas com alcinos terminais catalisados por cobre, resultando em rendimentos de 55–83%. A formação das moléculas de rotaxanos baseou-se na metodologia de clipping, consistindo em uma reação multicomponente com rendimentos dos produtos isolados variando de 8–25%. As moléculas sintetizadas foram identificadas e caracterizadas por espectroscopia de Ressonância Magnética Nuclear (RMN) de 1H e 13C utilizando experimentos uni e bidimensionais, espectroscopia de infravermelho (IV), análise termogravimétrica (TGA), cromatográfica líquida acomplada a espectroscopia de massas (LC-MS/MS), espectroscopia de massas de alta resolução (HRMS), ponto de fusão e difração de raios X em monocristal (SC-XRD), quando possível. As moléculas de [2]rotaxanos foram estudados por experimentos de RMN de 1H em temperaturas variáveis. Estudos realizados com variação de temperaturas entre -20 a 40 °C evidenciaram que posicionamento do macrociclo sobre a estação succinamida a baixas temperaturas é favorecido e apresentando um possível deslocamento para a estação oxoalquil-triazol com o aumento de temperatura. Este fenômeno foi estudado através de variações de deslocamento químico dos hidrogênios presentes nas estações do eixo molecular, que sofrem efeito de blindagem decorrente da formação das ligações de hidrogênio com o macrociclo. A formação de moléculas de [3]rotaxanos não foi observada para os modelos propostos. Logo, alteração na cadeia espaçadora da estação oxoalquil-triazol não é suficiente para favorecer a síntese de moléculas de [3]rotaxanos.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasMartins, Marcos Antonio Pintohttp://lattes.cnpq.br/6457412713967642Frizzo, Clarissa PiccininBonacorso, Helio GauzeSalbego, Paulo Roberto dos SantosWeimer, Gustavo Henrique2022-05-30T19:09:21Z2022-05-30T19:09:21Z2022-03-04info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/24590porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2022-05-30T19:09:21Zoai:repositorio.ufsm.br:1/24590Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-05-30T19:09:21Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol Synthesis and characterization of [2]rotaxanes: use of molecular threads with succinamide and oxoalkyl-triazoles stations |
title |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
spellingShingle |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol Weimer, Gustavo Henrique [2]rotaxanos Máquinas moleculares Reações do tipo click Reação multicomponente [2]rotaxanes Molecular machines Click reaction Multicomponent reaction CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
title_full |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
title_fullStr |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
title_full_unstemmed |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
title_sort |
Síntese e caracterização de [2]rotaxanos: uso de eixos moleculares com estações succinamida e oxoalquil-triazol |
author |
Weimer, Gustavo Henrique |
author_facet |
Weimer, Gustavo Henrique |
author_role |
author |
dc.contributor.none.fl_str_mv |
Martins, Marcos Antonio Pinto http://lattes.cnpq.br/6457412713967642 Frizzo, Clarissa Piccinin Bonacorso, Helio Gauze Salbego, Paulo Roberto dos Santos |
dc.contributor.author.fl_str_mv |
Weimer, Gustavo Henrique |
dc.subject.por.fl_str_mv |
[2]rotaxanos Máquinas moleculares Reações do tipo click Reação multicomponente [2]rotaxanes Molecular machines Click reaction Multicomponent reaction CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
[2]rotaxanos Máquinas moleculares Reações do tipo click Reação multicomponente [2]rotaxanes Molecular machines Click reaction Multicomponent reaction CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The following work presents the synthesis of molecular thread and molecules of rotaxanes containing two stations, succinamide and oxoalkyl-triazole. The synthetic process of the molecular thread was carried out by “click” reactions involving cycloaddition [3+2] of azides and terminal alkynes copper catalyzed (CuAAC), resulting in yields of 55–83%. The formation of rotaxanes molecules was based on the clipping methodology, consisting in a multicomponent reaction with isolated product yields ranging from 8–25%. The synthesized molecules were identified and characterized by 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy in one- and two-dimensional experiments, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), liquid chromatography/tandem mass spectrometry (LC-MS/MS), high resolution mass spectroscopy (HRMS), melting point and single crystal X-ray diffraction (SC-XRD), when possible. The [2]rotaxanes molecules were studied by 1H NMR experiments at variable temperatures. Studies carried out with temperatures variations between -20 to 40 °C revealed the position of the macrocycle over the succinamide station at low temperatures is favored and showing a possible shuttling to the oxoalkyl-triazole station with increasing temperature. This event was observed through variations in chemical displacement of the hydrogens present in the molecular thread station, which suffer a shielding effect due to the formation of hydrogen bonds with the macrocycle. The formation of [3]rotaxanes molecules was not observed for the proposed models. Therefore, alteration in the spacer chain of the oxoalkyl-triazole station is not enough to favor the synthesis of [3]rotaxanes molecules. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-05-30T19:09:21Z 2022-05-30T19:09:21Z 2022-03-04 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/24590 |
url |
http://repositorio.ufsm.br/handle/1/24590 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805922095658434560 |