Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica
Ano de defesa: | 2017 |
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Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/14256 |
Resumo: | The present dissertation describes the development of a three-step, one-pot methodology, involving the sequential reactions of Sonogashira cross-coupling, deprotection of terminal alkyne (removal of trimethylsilane group), and copper salt catalyzed azide-alkyne cycloaddition (CuAAC) in obtaining a series of fifteen new examples of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles in yields of 29-72%. The present methodology comprises of obtaining, initially, three examples of 3-methyl(aryl)-1-phenyl-5-trifluoromethyl-1H-pyrazoles, where aryl = Ph and 4-FC6H4, in 86 – 92% yields, from cyclocondensation reaction [3+2] between 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones and phenylhydrazine. Subsequently, the 3-substituted-1-phenyl-5-trifluoromethyl-1H-pyrazoles were used for the synthesis of 3-methyl(aryl)-4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazoles, in yields of 92 – 95%, by electrophilic bromination reaction using N-bromosuccinimide (NBS). The heterocycle 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole was obtained from the cyclocondensation [3+2] of 3-bromo-4-ethoxy-1,1,1-trifluoro-3-buten-2-one and phenylhydrazine in 38% yield. The optimization of the stepwise reaction for the synthesis of the 1- alkyl(aryl)-4-(3-methyl(aryl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles series was possible by evaluating the catalytic activity of palladium complexes with five different dialkylaryl phosphines in Sonogashira cross-coupling reaction between 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole and ethynyltrimethylsilane. This step showed that dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Xphos) is the best performance catalyst for the studied coupling, allowing the isolation of 3-methyl-1-phenyl-5-(trifluoromethyl)-4-((trimethylsilyl)ethynyl)-1H-pyrazole in 83% yield. In the final step, a deprotection reaction using CsF followed by a cycloaddition reaction (CuAAC) in the presence of benzyl azide afforded the preparation of 1-benzyl 1-benzyl-4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazole as the final product in 72% yield. After the step by step optimization was carried out a three-step one-pot methodology was used to construct the series of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl) -1H-1,2,3-triazoles (15 examples). |
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Biblioteca Digital de Teses e Dissertações do UFSM |
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2018-09-11T17:28:16Z2018-09-11T17:28:16Z2017-08-11http://repositorio.ufsm.br/handle/1/14256The present dissertation describes the development of a three-step, one-pot methodology, involving the sequential reactions of Sonogashira cross-coupling, deprotection of terminal alkyne (removal of trimethylsilane group), and copper salt catalyzed azide-alkyne cycloaddition (CuAAC) in obtaining a series of fifteen new examples of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles in yields of 29-72%. The present methodology comprises of obtaining, initially, three examples of 3-methyl(aryl)-1-phenyl-5-trifluoromethyl-1H-pyrazoles, where aryl = Ph and 4-FC6H4, in 86 – 92% yields, from cyclocondensation reaction [3+2] between 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones and phenylhydrazine. Subsequently, the 3-substituted-1-phenyl-5-trifluoromethyl-1H-pyrazoles were used for the synthesis of 3-methyl(aryl)-4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazoles, in yields of 92 – 95%, by electrophilic bromination reaction using N-bromosuccinimide (NBS). The heterocycle 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole was obtained from the cyclocondensation [3+2] of 3-bromo-4-ethoxy-1,1,1-trifluoro-3-buten-2-one and phenylhydrazine in 38% yield. The optimization of the stepwise reaction for the synthesis of the 1- alkyl(aryl)-4-(3-methyl(aryl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles series was possible by evaluating the catalytic activity of palladium complexes with five different dialkylaryl phosphines in Sonogashira cross-coupling reaction between 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole and ethynyltrimethylsilane. This step showed that dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Xphos) is the best performance catalyst for the studied coupling, allowing the isolation of 3-methyl-1-phenyl-5-(trifluoromethyl)-4-((trimethylsilyl)ethynyl)-1H-pyrazole in 83% yield. In the final step, a deprotection reaction using CsF followed by a cycloaddition reaction (CuAAC) in the presence of benzyl azide afforded the preparation of 1-benzyl 1-benzyl-4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazole as the final product in 72% yield. After the step by step optimization was carried out a three-step one-pot methodology was used to construct the series of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl) -1H-1,2,3-triazoles (15 examples).A presente dissertação descreve o desenvolvimento de uma metodologia one pot, três etapas, envolvendo sequencialmente as reações de acoplamento cruzado de Sonogashira, desproteção de alcino terminal (remoção de grupo trimetilsilano) e cicloadição azida-alcino catalisada por sal de cobre (CuAAC) na obtenção de uma série de quinze novos exemplos de 4-(5-(trifluormetil)-1H-pirazol-4-il)-1H-1,2,3-triazóis em rendimentos de 29 – 72%. A presente metodologia compreende, inicialmente, na obtenção de três exemplos de 3-metil(aril)-1-fenil-5-trifluormetil-1H-pirazóis, onde aril = Ph e 4-FC6H4, com rendimentos de 86 – 92%, a partir da reação de ciclocondensação [3+2] entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e fenilhidrazina. Subsequentemente, os 1-fenil-5-trifluormetil-1H-pirazóis 3-substituídos foram utilizados para a síntese de 3-metil(aril)-4-bromo-1-fenil-5-trifluormetil-1H-pirazóis, em rendimentos de 92 – 95%, através de reação de bromação eletrofílica usando N-bromo-succinimida (NBS). Um heterociclo 4-bromo-1-fenil-5-trifluormetil-1H-pirazol, não substituído na posição 3, foi obtido a partir da ciclocondensação [3+2] entre 3-bromo-4-etóxi-1,1,1-triflúor-3-buten-2-ona e fenilhidrazina com rendimento de 38%. A otimização da reação em etapas para a síntese da série 1-alquil(aril)-4-(3-metil(aril)-1-fenil-5-(trifluormetil)-1H-pirazol-4-il)-1H-1,2,3-triazóis foi possível avaliando a atividade catalítica de complexos de paládio e cinco diferentes dialquil biaril fosfinas em reação de acoplamento cruzado de Sonogashira entre 4-bromo-1-fenil-5-trifluormetil-1H-pirazol e etinil-trimetilsilano. Esta etapa evidenciou que diciclohexil(2’,4’,6’-tri-isopropil-[1,1’-bifenil]-2-il)fosfina (Xphos) é o catalisador de melhor desempenho para o acoplamento estudado, possibilitando o isolamento de 3-metil-1-fenil-5-(trifluormetil)-4-((trimetilsilil)etinil)-1H-pirazol em rendimento de 83%. Em etapa final, uma reação de desproteção usando CsF seguida de uma reação de cicloadição (CuAAC), na presença de benzil azida, possibilitou a obtenção de 1-benzil-4-(5-(trifluormetil)-1H-pirazol-4-il)-1H-1,2,3-triazol como produto final em rendimento de 72%. Realizada a otimização do processo, passo a passo, foi procedida a metodologia one pot, três etapas, para a construção da série de 4-(5-(trifluormetil)-1H-pirazol-4-il)-1H-1,2,3-triazóis (15 exemplos).Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessAzóisPirazóisTriazóisSonogashira “cross-coupling”“One-pot”Sonogashira "cross-coupling"AzolesPyrazolesTriazoles"One-pot"CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálicaSynthesis of 4-(1-phenyl-5-(trifluoromethyl)-1h-pyrazol-4-yl)-1h-1,2,3-triazoles prometed by dialkyl biaryl phosphines and metal catalysisinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Rodrigues, Oscar Endrigo Dorneleshttp://lattes.cnpq.br/6536519955416085Fantinel, Leonardohttp://lattes.cnpq.br/3934644027018397http://lattes.cnpq.br/2085211576408663Dal Forno, Gean Michel10060000000060006c852ad-d805-43c3-99d6-93a6a86f507c744282af-acf3-4d41-986f-7670d47fc420d315e5ef-8c77-48c9-bc87-e90cab9c43e9079f4612-cd36-4354-af6f-25f7736dccd2reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2017_DAL FORNO_GEAN.pdfDIS_PPGQUIMICA_2017_DAL FORNO_GEAN.pdfDissertação de Mestradoapplication/pdf9061670http://repositorio.ufsm.br/bitstream/1/14256/1/DIS_PPGQUIMICA_2017_DAL%20FORNO_GEAN.pdf82f5f59fb21746c92af96a2cb6e0a41aMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
dc.title.alternative.eng.fl_str_mv |
Synthesis of 4-(1-phenyl-5-(trifluoromethyl)-1h-pyrazol-4-yl)-1h-1,2,3-triazoles prometed by dialkyl biaryl phosphines and metal catalysis |
title |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
spellingShingle |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica Dal Forno, Gean Michel Azóis Pirazóis Triazóis Sonogashira “cross-coupling” “One-pot” Sonogashira "cross-coupling" Azoles Pyrazoles Triazoles "One-pot" CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
title_full |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
title_fullStr |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
title_full_unstemmed |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
title_sort |
Síntese de 4-(1-fenil-5-trifluormetil-1h-pirazol-4-il)-1h-1,2,3-triazóis promovida por dialquil biaril fosfinas e catálise metálica |
author |
Dal Forno, Gean Michel |
author_facet |
Dal Forno, Gean Michel |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/7275608974248322 |
dc.contributor.referee1.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/6536519955416085 |
dc.contributor.referee2.fl_str_mv |
Fantinel, Leonardo |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/3934644027018397 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2085211576408663 |
dc.contributor.author.fl_str_mv |
Dal Forno, Gean Michel |
contributor_str_mv |
Bonacorso, Helio Gauze Rodrigues, Oscar Endrigo Dorneles Fantinel, Leonardo |
dc.subject.por.fl_str_mv |
Azóis Pirazóis Triazóis Sonogashira “cross-coupling” “One-pot” Sonogashira "cross-coupling" |
topic |
Azóis Pirazóis Triazóis Sonogashira “cross-coupling” “One-pot” Sonogashira "cross-coupling" Azoles Pyrazoles Triazoles "One-pot" CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Azoles Pyrazoles Triazoles "One-pot" |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present dissertation describes the development of a three-step, one-pot methodology, involving the sequential reactions of Sonogashira cross-coupling, deprotection of terminal alkyne (removal of trimethylsilane group), and copper salt catalyzed azide-alkyne cycloaddition (CuAAC) in obtaining a series of fifteen new examples of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles in yields of 29-72%. The present methodology comprises of obtaining, initially, three examples of 3-methyl(aryl)-1-phenyl-5-trifluoromethyl-1H-pyrazoles, where aryl = Ph and 4-FC6H4, in 86 – 92% yields, from cyclocondensation reaction [3+2] between 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones and phenylhydrazine. Subsequently, the 3-substituted-1-phenyl-5-trifluoromethyl-1H-pyrazoles were used for the synthesis of 3-methyl(aryl)-4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazoles, in yields of 92 – 95%, by electrophilic bromination reaction using N-bromosuccinimide (NBS). The heterocycle 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole was obtained from the cyclocondensation [3+2] of 3-bromo-4-ethoxy-1,1,1-trifluoro-3-buten-2-one and phenylhydrazine in 38% yield. The optimization of the stepwise reaction for the synthesis of the 1- alkyl(aryl)-4-(3-methyl(aryl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazoles series was possible by evaluating the catalytic activity of palladium complexes with five different dialkylaryl phosphines in Sonogashira cross-coupling reaction between 4-bromo-1-phenyl-5-trifluoromethyl-1H-pyrazole and ethynyltrimethylsilane. This step showed that dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Xphos) is the best performance catalyst for the studied coupling, allowing the isolation of 3-methyl-1-phenyl-5-(trifluoromethyl)-4-((trimethylsilyl)ethynyl)-1H-pyrazole in 83% yield. In the final step, a deprotection reaction using CsF followed by a cycloaddition reaction (CuAAC) in the presence of benzyl azide afforded the preparation of 1-benzyl 1-benzyl-4-(5-(trifluoromethyl)-1H-pyrazol-4-yl)-1H-1,2,3-triazole as the final product in 72% yield. After the step by step optimization was carried out a three-step one-pot methodology was used to construct the series of 4-(5-(trifluoromethyl)-1H-pyrazol-4-yl) -1H-1,2,3-triazoles (15 examples). |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017-08-11 |
dc.date.accessioned.fl_str_mv |
2018-09-11T17:28:16Z |
dc.date.available.fl_str_mv |
2018-09-11T17:28:16Z |
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/1/14256 |
url |
http://repositorio.ufsm.br/handle/1/14256 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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100600000000 |
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600 |
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dc.rights.driver.fl_str_mv |
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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.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações do UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
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Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Biblioteca Digital de Teses e Dissertações do UFSM |
collection |
Biblioteca Digital de Teses e Dissertações do UFSM |
bitstream.url.fl_str_mv |
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Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
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