Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo
Ano de defesa: | 2018 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de São Carlos
Câmpus São Carlos |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química - PPGQ
|
Departamento: |
Não Informado pela instituição
|
País: |
Não Informado pela instituição
|
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | https://repositorio.ufscar.br/handle/ufscar/10920 |
Resumo: | Heterocyclic compounds containing the 1,2,3-triazole nucleus have received special attention in the field of synthetic chemistry have seen that have a wide field of application in biological and material areas. In this work, a new methodology was developed through a more sustainable approach for the synthesis of 1,2,3-triazoles, employing microwave irradiation as a heating source for the 1,3-dipolar cycloaddition reaction. As dipolarophile, β-dicarbonyl compounds, commercially available and others prepared by means of transesterification reactions between methyl acetoacetate and different alcohols were used. As the dipole species, different organic azides were prepared via a diazonium salt formation reaction. The triazoles were synthesized using nanoparticles of copper oxide II as catalyst under microwave irradiation. This new protocol allowed the preparation of a broad scope of highly functionalized 1,4,5-trisubstituted 1,2,3-triazoles in the short reaction time, in good to excellent yields. At the end of the synthesis, a study was performed on the recovery of the nanocatalyst, being possible its use for up to 3 reactional cycles with good yields of triazoles. Still in the context of more sustainable methodologies, the continuous flow reactors have been successfully applied in the development of new synthetic methodologies, since the efficient transfer of heat and better mixing of the reactants, has implied a smaller amount of byproducts and high conversion rates, among other advantages. In this part of the work, a new methodology for the synthesis of 1,2,3-triazoles 1,4,5-trisubstituted was initiated, via a reaction of 1,3-dipolar cycloaddition between carbonyl substrates, and arylazides, with reactions catalyzed by molecular sieves under continuous flow regime catalysed by molecular sieves, obtaining high conversion rates in the triazoles. |
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Dias, Cássio da SilvaSchwab, Ricardo Samuelhttp://lattes.cnpq.br/6935890756504964http://lattes.cnpq.br/43706948078780742019-02-07T16:42:57Z2019-02-07T16:42:57Z2018-07-05DIAS, Cássio da Silva. Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10920.https://repositorio.ufscar.br/handle/ufscar/10920Heterocyclic compounds containing the 1,2,3-triazole nucleus have received special attention in the field of synthetic chemistry have seen that have a wide field of application in biological and material areas. In this work, a new methodology was developed through a more sustainable approach for the synthesis of 1,2,3-triazoles, employing microwave irradiation as a heating source for the 1,3-dipolar cycloaddition reaction. As dipolarophile, β-dicarbonyl compounds, commercially available and others prepared by means of transesterification reactions between methyl acetoacetate and different alcohols were used. As the dipole species, different organic azides were prepared via a diazonium salt formation reaction. The triazoles were synthesized using nanoparticles of copper oxide II as catalyst under microwave irradiation. This new protocol allowed the preparation of a broad scope of highly functionalized 1,4,5-trisubstituted 1,2,3-triazoles in the short reaction time, in good to excellent yields. At the end of the synthesis, a study was performed on the recovery of the nanocatalyst, being possible its use for up to 3 reactional cycles with good yields of triazoles. Still in the context of more sustainable methodologies, the continuous flow reactors have been successfully applied in the development of new synthetic methodologies, since the efficient transfer of heat and better mixing of the reactants, has implied a smaller amount of byproducts and high conversion rates, among other advantages. In this part of the work, a new methodology for the synthesis of 1,2,3-triazoles 1,4,5-trisubstituted was initiated, via a reaction of 1,3-dipolar cycloaddition between carbonyl substrates, and arylazides, with reactions catalyzed by molecular sieves under continuous flow regime catalysed by molecular sieves, obtaining high conversion rates in the triazoles.Compostos heterocíclicos que apresentam o núcleo 1,2,3-triazol têm recebido uma atenção especial no ramo da química sintética, haja vista que apresentam um vasto campo de aplicação nas áreas biológicas e de materiais. Neste trabalho desenvolveu-se uma nova metodologia, por meio de uma abordagem mais sustentável, para a síntese de 1,2,3-triazóis, empregando a irradiação de micro-ondas como fonte de aquecimento para a reação de cicloadição 1,3-dipolar. Como dipolarófilo foram utilizados compostos β-dicarbonílicos, adquidos comercialmente e outros preparados por meio de reações de transesterificação entre o acetoacetato de metila e diferentes álcoois. Como espécie dipolar foram preparadas diferentes azidas orgânicas, via reação de formação de sal diazônio. Os triazóis foram sintetizados empregando nanopartículas de óxido de cobre II como catalisador, sob irradiação de micro-ondas. Esse novo protocolo permitiu a preparação de um amplo escopo de 1,2,3-triazóis 1,4,5-trissubstituídos altamente funcionalizados em baixo tempo de reação, com bons e excelentes rendimentos. Ao término da síntese, um estudo foi realizado acerca da recuperação do nanocatalisador, sendo possível sua reutilização por até 3 ciclos reacionais levando aos triazóis com bons rendimentos. Ainda no contexto de metodologias mais sustentáveis os reatores em fluxo contínuo têm sido aplicados com sucesso no desenvolvimento de novas metodologias sintéticas, pois a eficiente transferência de calor e melhor mistura dos reagentes, implica em menor quantidade de subprodutos e leva a altas taxas de conversão, dentre outras vantagens. Nessa parte do trabalho, foi dado início ao desenvolvimento de uma nova metodologia de síntese de 1,2,3-triazóis 1,4,5-trissubstituídos 3, via reação de cicloadição 1,3-dipolar entre substratos carbonílicos, e arilazidas, com reações catalisadas por peneira molecular em regime de fluxo, sendo obtidas altas taxas de conversão nos triazóis.OutraIFMA/ProqualisporUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCar1,2,3-triazolesNanoparticlesMicrowaveContinuous flowCIENCIAS EXATAS E DA TERRA::QUIMICASíntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuoSynthesis of 1,2,3-triazoles 1,4,5-trisubstituted via heterogeneous catalysis employing reactions in microwave and continuous flowinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnlineinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese versão final Cássio da Silva Dias.pdfTese versão final Cássio da Silva Dias.pdfTeseapplication/pdf18181289https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10920/3/Tese%20vers%c3%a3o%20final%20C%c3%a1ssio%20da%20Silva%20Dias.pdf4340460b79fd1a088fd1e8c3cbfb3991MD53LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10920/5/license.txtae0398b6f8b235e40ad82cba6c50031dMD55TEXTTese versão final Cássio da Silva Dias.pdf.txtTese versão final Cássio da Silva Dias.pdf.txtExtracted texttext/plain321350https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10920/6/Tese%20vers%c3%a3o%20final%20C%c3%a1ssio%20da%20Silva%20Dias.pdf.txtf0ea93abc3c0eb1af58453d70fde44ceMD56THUMBNAILTese versão final Cássio da Silva Dias.pdf.jpgTese versão final Cássio da Silva Dias.pdf.jpgIM Thumbnailimage/jpeg9138https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10920/7/Tese%20vers%c3%a3o%20final%20C%c3%a1ssio%20da%20Silva%20Dias.pdf.jpg662cf1ef4e06e494fa0755864458f126MD57ufscar/109202019-09-11 03:38:21.889oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-05-25T12:57:02.287235Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
dc.title.alternative.eng.fl_str_mv |
Synthesis of 1,2,3-triazoles 1,4,5-trisubstituted via heterogeneous catalysis employing reactions in microwave and continuous flow |
title |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
spellingShingle |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo Dias, Cássio da Silva 1,2,3-triazoles Nanoparticles Microwave Continuous flow CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
title_full |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
title_fullStr |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
title_full_unstemmed |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
title_sort |
Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo |
author |
Dias, Cássio da Silva |
author_facet |
Dias, Cássio da Silva |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/4370694807878074 |
dc.contributor.author.fl_str_mv |
Dias, Cássio da Silva |
dc.contributor.advisor1.fl_str_mv |
Schwab, Ricardo Samuel |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6935890756504964 |
contributor_str_mv |
Schwab, Ricardo Samuel |
dc.subject.eng.fl_str_mv |
1,2,3-triazoles Nanoparticles Microwave Continuous flow |
topic |
1,2,3-triazoles Nanoparticles Microwave Continuous flow CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Heterocyclic compounds containing the 1,2,3-triazole nucleus have received special attention in the field of synthetic chemistry have seen that have a wide field of application in biological and material areas. In this work, a new methodology was developed through a more sustainable approach for the synthesis of 1,2,3-triazoles, employing microwave irradiation as a heating source for the 1,3-dipolar cycloaddition reaction. As dipolarophile, β-dicarbonyl compounds, commercially available and others prepared by means of transesterification reactions between methyl acetoacetate and different alcohols were used. As the dipole species, different organic azides were prepared via a diazonium salt formation reaction. The triazoles were synthesized using nanoparticles of copper oxide II as catalyst under microwave irradiation. This new protocol allowed the preparation of a broad scope of highly functionalized 1,4,5-trisubstituted 1,2,3-triazoles in the short reaction time, in good to excellent yields. At the end of the synthesis, a study was performed on the recovery of the nanocatalyst, being possible its use for up to 3 reactional cycles with good yields of triazoles. Still in the context of more sustainable methodologies, the continuous flow reactors have been successfully applied in the development of new synthetic methodologies, since the efficient transfer of heat and better mixing of the reactants, has implied a smaller amount of byproducts and high conversion rates, among other advantages. In this part of the work, a new methodology for the synthesis of 1,2,3-triazoles 1,4,5-trisubstituted was initiated, via a reaction of 1,3-dipolar cycloaddition between carbonyl substrates, and arylazides, with reactions catalyzed by molecular sieves under continuous flow regime catalysed by molecular sieves, obtaining high conversion rates in the triazoles. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-07-05 |
dc.date.accessioned.fl_str_mv |
2019-02-07T16:42:57Z |
dc.date.available.fl_str_mv |
2019-02-07T16:42:57Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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publishedVersion |
dc.identifier.citation.fl_str_mv |
DIAS, Cássio da Silva. Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10920. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/10920 |
identifier_str_mv |
DIAS, Cássio da Silva. Síntese de 1,2,3-triazóis 1,4,5-trissubstituídos via catálise heterogênea empregando reações em micro-ondas e fluxo contínuo. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10920. |
url |
https://repositorio.ufscar.br/handle/ufscar/10920 |
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por |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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