Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3
Ano de defesa: | 2015 |
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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/1/22431 |
Resumo: | The present study reported the synthesis of a series of chalcogenophenes through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. First, selenophenes 2 were synthesized through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. A similar protocol was used to prepare thiophenes 3 using dialkyldichalcogenides, FeCl3 and iodine as additive. In order to evaluate the potential reactivity of compounds 2, the compound 2,5-diphenyl-3,4-(selenephenyl)-selenophene was submitted to a bromation reaction in the aromatic ring resulting in the formation of selenophene 4 substituted with bromine, in 65% yield, in positions 3 and 4 in the heterocyclic ring. Further, the compound 2,5 diphenyl-3,4 (methilthio)thiophene was selected as the starting material for an oxidation reaction using glacial acetic acid and hydrogen peroxide. Subsequent cyclization reaction using triflic acid led to the formation of a sulfur polycyclic 5 in 83% yield. After this, the compound 3-bromo-4-(methylthio)-2,5-diphenylthiophene 6 was selected as the starting material for the cross coupling reaction with a terminal alkyne, 1- ethynylcyclohexanol, 7 to give compound 3(cyclohexylethynyl)-4-(methylthio)-2,5- diphenylthiophene 8 in 63% yield. Moreover, compound 8 was selected as the starting material for a cyclization reaction using iodine, to give as a product 1-(3-iodo-4,6- diphenylthieno[3,4-b]thiophen-2-yl)cyclohexanol, 9 in 40% yield. |
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network_name_str |
Biblioteca Digital de Teses e Dissertações do UFSM |
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2021-10-18T12:31:40Z2021-10-18T12:31:40Z2015-02-27http://repositorio.ufsm.br/handle/1/22431The present study reported the synthesis of a series of chalcogenophenes through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. First, selenophenes 2 were synthesized through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. A similar protocol was used to prepare thiophenes 3 using dialkyldichalcogenides, FeCl3 and iodine as additive. In order to evaluate the potential reactivity of compounds 2, the compound 2,5-diphenyl-3,4-(selenephenyl)-selenophene was submitted to a bromation reaction in the aromatic ring resulting in the formation of selenophene 4 substituted with bromine, in 65% yield, in positions 3 and 4 in the heterocyclic ring. Further, the compound 2,5 diphenyl-3,4 (methilthio)thiophene was selected as the starting material for an oxidation reaction using glacial acetic acid and hydrogen peroxide. Subsequent cyclization reaction using triflic acid led to the formation of a sulfur polycyclic 5 in 83% yield. After this, the compound 3-bromo-4-(methylthio)-2,5-diphenylthiophene 6 was selected as the starting material for the cross coupling reaction with a terminal alkyne, 1- ethynylcyclohexanol, 7 to give compound 3(cyclohexylethynyl)-4-(methylthio)-2,5- diphenylthiophene 8 in 63% yield. Moreover, compound 8 was selected as the starting material for a cyclization reaction using iodine, to give as a product 1-(3-iodo-4,6- diphenylthieno[3,4-b]thiophen-2-yl)cyclohexanol, 9 in 40% yield.Este trabalho relata a síntese de calcogenofenos através da ciclização de 1,3 diinos 1 com dicalcogenetos de diorganoíla mediados por cloreto férrico. Inicialmente, os selenofenos 2 foram sintetizados através da ciclização de 1,3 diinos 1 com dicalcogenetos de diorganoíla mediados por FeCl3. Um protocolo semelhante foi aplicado para a síntese de tiofenos 3 utilizando dicalcogenetos de diorganoíla, FeCl3 e iodo molecular como aditivo. Com a finalidade de avaliar a potencial reatividade dos compostos 2 obtidos, o composto 2,5-difenil- 3,4-(selenofenil)-selenofeno foi submetido a uma reação de bromação do anel aromático resultando na formação do selenofeno 4 substituído com bromo, nas posições 3 e 4 do anel heterocíclico, em 65% de rendimento. Adicionalmente, o composto 2,5-difenil-3,4 bis- (metiltio)tiofeno foi selecionado como material de partida para uma reação de oxidação com ácido acético glacial e peróxido de hidrogênio e subsequente reação de ciclização com ácido tríflico levando à formação de um policiclo de enxofre 5 em 83% de rendimento. Posteriormente, selecionou-se o composto 3-bromo-2,5difenil-4(metiltio)-tiofeno 6 como material de partida para uma reação de acoplamento do tipo Sonogashira com o alcino terminal etinil-ciclohexanol 7 para levar ao 2,5-difenil-1((4-metiltio)-tiofen-3il)etinil)-ciclohexanol 8 em 63% de rendimento. O composto 8 obtido foi utilizado como material de partida para uma reação de ciclização com iodo molecular, o que levou a formação do composto 1- 4,6-difenil-3-iodo-tieno[3,4-b]tiofen-2-il)-ciclo-hexanol 9 em 40% de rendimento.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/openAccessCiclizaçãoFerroDicalcogenetos de diorganoílaSelenofenoTiofenoCyclizationIronDiorganoyl dichalcogenidesSelenopheneThiopheneCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3Synthesis of chalcogenophenes via cyclization of 1,3-diynes promoted by iron(III) chloride and dialkyl dichalcogenidesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Godoi, Marcelo deSilva, Paulo Henrique Menezes dahttp://lattes.cnpq.br/5984881997839617Bilheri, Filipe Neimaier100600000000600600600b21a898a-0ab0-4f33-b980-2b55ef590b94ef18907d-e564-45db-b9d1-c5439c3a6129b7fa9a3b-3ef6-4dd5-a68d-00c7947af7045ba48325-1e6f-415e-aa9e-956ae547209dreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2015_BILHERI_FILIPE.pdfDIS_PPGQUIMICA_2015_BILHERI_FILIPE.pdfDissertação de Mestradoapplication/pdf9819672http://repositorio.ufsm.br/bitstream/1/22431/1/DIS_PPGQUIMICA_2015_BILHERI_FILIPE.pdf53e832c201b2e832ca8e9f6fd8b8e2bbMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
dc.title.alternative.eng.fl_str_mv |
Synthesis of chalcogenophenes via cyclization of 1,3-diynes promoted by iron(III) chloride and dialkyl dichalcogenides |
title |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
spellingShingle |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 Bilheri, Filipe Neimaier Ciclização Ferro Dicalcogenetos de diorganoíla Selenofeno Tiofeno Cyclization Iron Diorganoyl dichalcogenides Selenophene Thiophene CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
title_full |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
title_fullStr |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
title_full_unstemmed |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
title_sort |
Síntese de calcogenofenos via reações de ciclização de diinos com dicalcogenetos de diorganoíla promovida por FeCl3 |
author |
Bilheri, Filipe Neimaier |
author_facet |
Bilheri, Filipe Neimaier |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2355575631197937 |
dc.contributor.referee1.fl_str_mv |
Godoi, Marcelo de |
dc.contributor.referee2.fl_str_mv |
Silva, Paulo Henrique Menezes da |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5984881997839617 |
dc.contributor.author.fl_str_mv |
Bilheri, Filipe Neimaier |
contributor_str_mv |
Zeni, Gilson Rogério Godoi, Marcelo de Silva, Paulo Henrique Menezes da |
dc.subject.por.fl_str_mv |
Ciclização Ferro Dicalcogenetos de diorganoíla Selenofeno Tiofeno |
topic |
Ciclização Ferro Dicalcogenetos de diorganoíla Selenofeno Tiofeno Cyclization Iron Diorganoyl dichalcogenides Selenophene Thiophene CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Cyclization Iron Diorganoyl dichalcogenides Selenophene Thiophene |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present study reported the synthesis of a series of chalcogenophenes through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. First, selenophenes 2 were synthesized through the cyclization of 1,3-diynes 1 mediated by FeCl3 and dialkyldichalcogenides. A similar protocol was used to prepare thiophenes 3 using dialkyldichalcogenides, FeCl3 and iodine as additive. In order to evaluate the potential reactivity of compounds 2, the compound 2,5-diphenyl-3,4-(selenephenyl)-selenophene was submitted to a bromation reaction in the aromatic ring resulting in the formation of selenophene 4 substituted with bromine, in 65% yield, in positions 3 and 4 in the heterocyclic ring. Further, the compound 2,5 diphenyl-3,4 (methilthio)thiophene was selected as the starting material for an oxidation reaction using glacial acetic acid and hydrogen peroxide. Subsequent cyclization reaction using triflic acid led to the formation of a sulfur polycyclic 5 in 83% yield. After this, the compound 3-bromo-4-(methylthio)-2,5-diphenylthiophene 6 was selected as the starting material for the cross coupling reaction with a terminal alkyne, 1- ethynylcyclohexanol, 7 to give compound 3(cyclohexylethynyl)-4-(methylthio)-2,5- diphenylthiophene 8 in 63% yield. Moreover, compound 8 was selected as the starting material for a cyclization reaction using iodine, to give as a product 1-(3-iodo-4,6- diphenylthieno[3,4-b]thiophen-2-yl)cyclohexanol, 9 in 40% yield. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-02-27 |
dc.date.accessioned.fl_str_mv |
2021-10-18T12:31:40Z |
dc.date.available.fl_str_mv |
2021-10-18T12:31:40Z |
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/1/22431 |
url |
http://repositorio.ufsm.br/handle/1/22431 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 |
dc.relation.authority.fl_str_mv |
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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.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 |
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UFSM |
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UFSM |
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Biblioteca Digital de Teses e Dissertações do UFSM |
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