Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos
Autor(a) principal: | |
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Data de Publicação: | 2016 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/22848 |
Resumo: | This thesis describes studies about the use of azido vinylesters in the development of new selective synthetic processes for the obtainment of tetrasubstituted pyrroles, first fused to a pyridazinone ring, generating pyrrolo[3,4-d]pyridazinones and, second, involving organometallic substituents. It was explored the reaction regioselectivity induced by the presence of certain substituents from the azido vinylesters moiety, and the use of alternative methodologies – such as cascade reactions and microwave irradiation – in the generation of new synthetic procedures, faster, with fewer steps and without the use of catalysts. Initially, we designed the starting materials for the cycloaddition reactions [3+2], resulting in a series of azido vinylesters aril/heteroaryl/metallocenyl substituted, obtained in good yields by Knoevenagel condensation reaction between various aldehydes and methyl azidoacetate. Subsequently, we conducted evaluations on the tetrasubstituted pyrroles regioisomers formation, by cycloaddition reaction between substituted methyl azidoacrylates and 1,3- dicarbonyl compounds and analogous, symmetrical and non-symmetrical, noting that for the aryl/heteroaryl substituted azido vinylesters were obtained pyrroles with only one substitution pattern. Posteriorly, we developed a new methodology for the pyrrolo[3,4-d]pyridazinones formation through a one pot procedure and using a cascade reactions protocol, starting with azido vinylesters and diketones for the in situ generation of the corresponding pyrroles and, after reaction with substituted hydrazines, were synthesized the novel pyrrolo[3,4- d]pyridazinones. In continuation, we studied the chemical behavior of substrates containing an organometallic group for the generation of a novel series of ferrocenyl substituted pyrroles, and in adaptation to the specific characteristics of the organometallic, it was developed a new methodology using a microwave irradiation process, dramatically reducing the reaction time. Also, it was observed the peculiarity of the ferrocenyl moiety, which has acted as a radical ix catalyst in the regioinversion of pyrroles, inverting the substituents positions 2 and 3, differently of the previous results for the synthesis of pyrrolo[3,4-d]pyridazinones. Finally, it was performed the structural characterization of the new compounds by combined techniques of ¹H , ¹³C {¹H}, NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography coupled to Mass Spectrometry (LCESI- MS/MS), Infrared Spectroscopy (IR) and X-Ray Diffraction. |
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Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídosRegiochemistry of ciclocondensation reactions of azido vinylesters in the synthesis of pyrrolo[3,4-d]pyridazinones and ferrocenyl substituted pyrrolesAzido vinilésteresPirróisFerrocenoPirrolo[3,4-d]piridazinonasAzido vinylestersPyrrolesFerrocenePyrrolo[3,4-d]pyridazinonesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThis thesis describes studies about the use of azido vinylesters in the development of new selective synthetic processes for the obtainment of tetrasubstituted pyrroles, first fused to a pyridazinone ring, generating pyrrolo[3,4-d]pyridazinones and, second, involving organometallic substituents. It was explored the reaction regioselectivity induced by the presence of certain substituents from the azido vinylesters moiety, and the use of alternative methodologies – such as cascade reactions and microwave irradiation – in the generation of new synthetic procedures, faster, with fewer steps and without the use of catalysts. Initially, we designed the starting materials for the cycloaddition reactions [3+2], resulting in a series of azido vinylesters aril/heteroaryl/metallocenyl substituted, obtained in good yields by Knoevenagel condensation reaction between various aldehydes and methyl azidoacetate. Subsequently, we conducted evaluations on the tetrasubstituted pyrroles regioisomers formation, by cycloaddition reaction between substituted methyl azidoacrylates and 1,3- dicarbonyl compounds and analogous, symmetrical and non-symmetrical, noting that for the aryl/heteroaryl substituted azido vinylesters were obtained pyrroles with only one substitution pattern. Posteriorly, we developed a new methodology for the pyrrolo[3,4-d]pyridazinones formation through a one pot procedure and using a cascade reactions protocol, starting with azido vinylesters and diketones for the in situ generation of the corresponding pyrroles and, after reaction with substituted hydrazines, were synthesized the novel pyrrolo[3,4- d]pyridazinones. In continuation, we studied the chemical behavior of substrates containing an organometallic group for the generation of a novel series of ferrocenyl substituted pyrroles, and in adaptation to the specific characteristics of the organometallic, it was developed a new methodology using a microwave irradiation process, dramatically reducing the reaction time. Also, it was observed the peculiarity of the ferrocenyl moiety, which has acted as a radical ix catalyst in the regioinversion of pyrroles, inverting the substituents positions 2 and 3, differently of the previous results for the synthesis of pyrrolo[3,4-d]pyridazinones. Finally, it was performed the structural characterization of the new compounds by combined techniques of ¹H , ¹³C {¹H}, NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography coupled to Mass Spectrometry (LCESI- MS/MS), Infrared Spectroscopy (IR) and X-Ray Diffraction.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqCoordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESFundação de Apoio à Tecnologia e Ciência - FATECA presente tese descreve os estudos realizados acerca do uso de azido vinilésteres no desenvolvimento seletivo de novos processos sintéticos para obtenção de pirróis tetrassubstituídos, primeiramente fundidos a um anel piridazinônico, gerando pirrolo[3,4- d]piridazinonas e, num segundo momento, envolvendo substituintes organometálicos. Foi explorada a regiosseletividade reacional induzida pela presença de determinados substituíntes provenientes dos azido vinilésteres, além do uso de metodologias alternativas – como reações em cascata e irradiação de micro-ondas – na geração de novos procedimentos sintéticos, mais rápidos, com menor número de etapas e sem o uso de catalisadores. Inicialmente, projetamos os materiais de partida adequados para as reações de cicloadição [3+2], resultando em uma série de azido vinilésteres aril/heteroaril/metalocenil substituídos, obtidos em bons rendimentos através da reação de condensação de Knoevenagel entre diversos aldeídos e azido acetato de metila. Subsequentemente, realizamos avaliações sobre a formação de pirróis tetrassubstituídos e regioisômeros através da reação de cicloadição entre azido acrilatos de metila substituídos e compostos 1,3-dicarbonílicos e análogos, simétricos e não simétricos, observando que, para os substituíntes aril/heteroaril presentes nos azido vinilésteres, foram obtidos pirróis com um único padrão de substituição. Posteriormente, foi desenvolvida uma nova metodologia para a formação de pirrolo[3,4-d]piridazinonas inéditas de maneira one pot e usando o protocolo de reações em cascata, partindo de azido vinilésteres e dicetonas para a geração in situ dos respectivos pirróis e, após reação com hidrazinas substituídas, foram sintetizadas as moléculas de interesse. Em continuação, efetuamos avaliações sobre o comportamento químico de substratos contendo um grupo organometálico para geração de série inédita de pirróis ferrocenil substituídos e, em adequação às características específicas do organometálico, foi desenvolvida uma nova metodologia utilizando irradiação de micro-ondas e reduzindo vii drasticamente os tempos de reação. Ainda, foi observada a peculiaridade da porção ferrocênica como catalisador radicalar na geração de pirróis com regioinversão dos substituintes nas posições 2 e 3, diferentemente dos resultados obtidos na síntese de pirrolo[3,4-d]piridazinonas. Finalmente, foi efetuada a caracterização estrutural dos compostos por técnicas de Espectroscopia de RMN de ¹H, ¹³C {¹H}, Cromatografia Gasosa acoplada à Espectrometria de Massas (CG-EM), Cromatografia Líquida acoplada à Espectrometria de Massas (LC-ESIMS/ MS), Espectrometria de Massas de Alta Resolução (HMRS), Espectroscopia de Infravermelho (IV) e Difração de Raios-X.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Zanatta, NiloFrizzo, Clarissa PiccininMendes, Samuel RodriguesCunico Filho, Wilson JoãoLibero, Francieli Maria2021-11-19T13:30:47Z2021-11-19T13:30:47Z2016-02-17info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/22848porAttribution-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:UFSM2021-11-20T06:04:24Zoai:repositorio.ufsm.br:1/22848Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2021-11-20T06:04:24Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos Regiochemistry of ciclocondensation reactions of azido vinylesters in the synthesis of pyrrolo[3,4-d]pyridazinones and ferrocenyl substituted pyrroles |
title |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
spellingShingle |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos Libero, Francieli Maria Azido vinilésteres Pirróis Ferroceno Pirrolo[3,4-d]piridazinonas Azido vinylesters Pyrroles Ferrocene Pyrrolo[3,4-d]pyridazinones CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
title_full |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
title_fullStr |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
title_full_unstemmed |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
title_sort |
Regioquímica das reações de ciclocondensação de azido vinilésteres na síntese de pirrolo[3,4-d]piridazinonas e pirróis ferrocenil substituídos |
author |
Libero, Francieli Maria |
author_facet |
Libero, Francieli Maria |
author_role |
author |
dc.contributor.none.fl_str_mv |
Bonacorso, Helio Gauze http://lattes.cnpq.br/7275608974248322 Zanatta, Nilo Frizzo, Clarissa Piccinin Mendes, Samuel Rodrigues Cunico Filho, Wilson João |
dc.contributor.author.fl_str_mv |
Libero, Francieli Maria |
dc.subject.por.fl_str_mv |
Azido vinilésteres Pirróis Ferroceno Pirrolo[3,4-d]piridazinonas Azido vinylesters Pyrroles Ferrocene Pyrrolo[3,4-d]pyridazinones CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Azido vinilésteres Pirróis Ferroceno Pirrolo[3,4-d]piridazinonas Azido vinylesters Pyrroles Ferrocene Pyrrolo[3,4-d]pyridazinones CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This thesis describes studies about the use of azido vinylesters in the development of new selective synthetic processes for the obtainment of tetrasubstituted pyrroles, first fused to a pyridazinone ring, generating pyrrolo[3,4-d]pyridazinones and, second, involving organometallic substituents. It was explored the reaction regioselectivity induced by the presence of certain substituents from the azido vinylesters moiety, and the use of alternative methodologies – such as cascade reactions and microwave irradiation – in the generation of new synthetic procedures, faster, with fewer steps and without the use of catalysts. Initially, we designed the starting materials for the cycloaddition reactions [3+2], resulting in a series of azido vinylesters aril/heteroaryl/metallocenyl substituted, obtained in good yields by Knoevenagel condensation reaction between various aldehydes and methyl azidoacetate. Subsequently, we conducted evaluations on the tetrasubstituted pyrroles regioisomers formation, by cycloaddition reaction between substituted methyl azidoacrylates and 1,3- dicarbonyl compounds and analogous, symmetrical and non-symmetrical, noting that for the aryl/heteroaryl substituted azido vinylesters were obtained pyrroles with only one substitution pattern. Posteriorly, we developed a new methodology for the pyrrolo[3,4-d]pyridazinones formation through a one pot procedure and using a cascade reactions protocol, starting with azido vinylesters and diketones for the in situ generation of the corresponding pyrroles and, after reaction with substituted hydrazines, were synthesized the novel pyrrolo[3,4- d]pyridazinones. In continuation, we studied the chemical behavior of substrates containing an organometallic group for the generation of a novel series of ferrocenyl substituted pyrroles, and in adaptation to the specific characteristics of the organometallic, it was developed a new methodology using a microwave irradiation process, dramatically reducing the reaction time. Also, it was observed the peculiarity of the ferrocenyl moiety, which has acted as a radical ix catalyst in the regioinversion of pyrroles, inverting the substituents positions 2 and 3, differently of the previous results for the synthesis of pyrrolo[3,4-d]pyridazinones. Finally, it was performed the structural characterization of the new compounds by combined techniques of ¹H , ¹³C {¹H}, NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography coupled to Mass Spectrometry (LCESI- MS/MS), Infrared Spectroscopy (IR) and X-Ray Diffraction. |
publishDate |
2016 |
dc.date.none.fl_str_mv |
2016-02-17 2021-11-19T13:30:47Z 2021-11-19T13:30:47Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/22848 |
url |
http://repositorio.ufsm.br/handle/1/22848 |
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 |
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1805922143498665984 |