Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular
Autor(a) principal: | |
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Data de Publicação: | 2013 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4254 |
Resumo: | In the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields. |
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2014-10-292014-10-292013-11-26STEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/4254In the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields.Este trabalho relata a síntese de uma série de heterociclos através da ciclização intramolecular de substratos alquinílicos com dicalcogenetos de diorganoíla mediados por sais de cobre ou sais de ferro. Primeiramente, relatamos a síntese de selenofenos e telurofenos 2 através da ciclização intramolecular de (Z)-selenoeninos e (Z)-teluroeninos 1 com dicalcogenetos de diorganoíla mediados por FeCl3. Essa metodologia permitiu a obtenção de novos derivados de calcogenofenos de moderados a bons rendimentos com a adicional inserção de uma molécula orgânica de calcogênio na posição 3 do anel formado. Com a finalidade de avaliar o potencial reatividade dos compostos obtidos 2, o composto 2,5-difenil-3-(selenofenil)-selenofeno foi submetido a uma reação de bromação do anel aromático resultando na formação do selenofeno substituído com bromo, nas posições 3 e 4 do anel heterocíclico, em 86% de rendimento. Adicionalmente, o composto 2,5-difenil-3-(selenobutil)selenofeno foi selecionado como material de partida para uma reação de troca selênio-lítio com a subsequente reação com aldeídos levando a formação dos álcoois secundários, na posição 3 do anel do selenofeno, em rendimentos de 68-73%. Posteriormente, desenvolvemos uma metodologia para síntese de 4-organocalcogeno-isoquinolinas 4, partindo-se dos substratos o-alquinil benzaldiminas 3. A combinação de quantidades catalíticas de CuI com dicalcogenetos de diorganoíla mostrou-se eficiente para obtenção das isoquinolinas em bons rendimentos A fim de avaliar a versatilidade das 4-organocalcogeno isoquinolinas obtidas, como precursores para síntese de isoquinolinas com diferentes funcionalizações, o composto 4-(telurobutil)-3-fenilisoquinolina foi submetido a reações de acoplamento cruzado do tipo Suzuki e do tipo Sonogashira, catalizados por sais de paládio. Também, foram realizadas as reações de troca telúrio-lítio com a subsequente reação com diferentes aldeídos levando aos alcoóis derivados em bons rendimentos.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaHeterociclosCalcogenofenosDicalcogenetosQuímica orgânicaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização IntramolecularSynthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactionsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZeni, Gilson Rogériohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6Cunha, Rodrigo Luiz Oliveira Rodrigueshttp://lattes.cnpq.br/1982300219137583Perin, Gelsonhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797983H8Morel, Ademir Fariashttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8Lenardao, Eder Joaohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723709P2http://lattes.cnpq.br/9602558013154418Stein, André Luiz Agnes100600000000400300300300300300300b21a898a-0ab0-4f33-b980-2b55ef590b94d1a7a1e6-1d83-4fc4-8703-5118e5980e5dc116e12f-6c33-444e-be98-e7ead6394ed71fdc0f55-b165-4805-8083-0d6d98ff1a2593fa7550-c825-4f7a-a899-13bde347653c01d01235-8115-49df-be39-1ad96c2be5ddinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALSTEIN, ANDRE LUIZ AGNES.pdfapplication/pdf29661187http://repositorio.ufsm.br/bitstream/1/4254/1/STEIN%2c%20ANDRE%20LUIZ%20AGNES.pdf0bbda273a05f0fb55bddc5fa44dce116MD51TEXTSTEIN, ANDRE LUIZ AGNES.pdf.txtSTEIN, ANDRE LUIZ AGNES.pdf.txtExtracted texttext/plain211567http://repositorio.ufsm.br/bitstream/1/4254/2/STEIN%2c%20ANDRE%20LUIZ%20AGNES.pdf.txt3331a5a3fda0b35a203ceff39ab17238MD52THUMBNAILSTEIN, ANDRE LUIZ AGNES.pdf.jpgSTEIN, ANDRE LUIZ AGNES.pdf.jpgIM Thumbnailimage/jpeg5359http://repositorio.ufsm.br/bitstream/1/4254/3/STEIN%2c%20ANDRE%20LUIZ%20AGNES.pdf.jpge38defaeabf75b5a15827b0541f7e8e7MD531/42542017-07-25 11:05:10.263oai:repositorio.ufsm.br:1/4254Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132017-07-25T14:05:10Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
dc.title.alternative.eng.fl_str_mv |
Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions |
title |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
spellingShingle |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular Stein, André Luiz Agnes Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_full |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_fullStr |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_full_unstemmed |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_sort |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
author |
Stein, André Luiz Agnes |
author_facet |
Stein, André Luiz Agnes |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6 |
dc.contributor.referee1.fl_str_mv |
Cunha, Rodrigo Luiz Oliveira Rodrigues |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/1982300219137583 |
dc.contributor.referee2.fl_str_mv |
Perin, Gelson |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797983H8 |
dc.contributor.referee3.fl_str_mv |
Morel, Ademir Farias |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8 |
dc.contributor.referee4.fl_str_mv |
Lenardao, Eder Joao |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723709P2 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/9602558013154418 |
dc.contributor.author.fl_str_mv |
Stein, André Luiz Agnes |
contributor_str_mv |
Zeni, Gilson Rogério Cunha, Rodrigo Luiz Oliveira Rodrigues Perin, Gelson Morel, Ademir Farias Lenardao, Eder Joao |
dc.subject.por.fl_str_mv |
Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica |
topic |
Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields. |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-11-26 |
dc.date.accessioned.fl_str_mv |
2014-10-29 |
dc.date.available.fl_str_mv |
2014-10-29 |
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 |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
STEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4254 |
identifier_str_mv |
STEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/4254 |
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