Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos
Ano de defesa: | 2013 |
---|---|
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
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/10539 |
Resumo: | The present work reports the synthesis of homoallylic alcohols derived from trihaloacetyl/trifluormethyl substituted azoles employing a simple methodology, with excellent cost benefit and able to furnish the desired products with satisfactory yields. The synthetic approach involved the increase of the scope of a previous work of the research group NUQUIMHE, where three new pyrazoles containing a dimethyl acetal aldehyde function bonded to the carbon 3 of the heterocycle (5a-c) were synthetized from cyclocondensation reactions between methyl, phenyl and tert-butyl hydrazine and the 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one (3f) in alcoholic medium. The compounds were obtained like oils, with yields in the range of 89 98 %. In a next step, was performed the deprotection of the acetal moiety of the pyrazoles (5a-c), in order to obtain the corresponding aldehydes (6a-c). To this, it was employed a solution of CHCl3 and aqueous trifluoroacetic acid under reflux for a reactional time of 4 hours. This methodology allowed isolating the desired products with yields in the range of 68 87 %. These compounds were employed to optimize the reactional conditions used in the synthesis of the homoallylic alcohols described in this dissertation. The allylation reaction of pyrazoles 6a-c was performed using allylaluminum reagents generated in situ from the catalytic insertion of aluminum to allyl bromides. The methodology was effective to synthetize the allylic alcohols 7a-c, which were obtained like oils, in the range of 84 90%. Of an analogue way, were realized the allylations of trihaloacetyl substituted 1,2,3-triazoles (4a-f). These precursors, obtained from 1,3 dipolar cycloadditions between the 2,6-difluorobenzyl azide (1) and trihalomethyl substituted enones (3a-f), were reacted with allylaluminum nucleophiles derived from allyl and crotyl bromides, furnishing the corresponding homoallylic alcohols with yields in the range of 85 94 %. In view of accessible price and exquisite chemical reactivity, the employed allylaluminum reagents proved to be an excellent choice for the allylations reactions of the azole 4 and 6, furnishing the desired products in good yield (85 94%). |
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2014-06-112014-06-112013-03-01WIETHAN, Carson Wanderley. Chemical behavior of trihaloacetyl/trifluoromethyl substituted azoles in allylations reactions: synthesis of trihalomethyl heteroaryl homoallylic alcohols. 2013. 157 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/10539The present work reports the synthesis of homoallylic alcohols derived from trihaloacetyl/trifluormethyl substituted azoles employing a simple methodology, with excellent cost benefit and able to furnish the desired products with satisfactory yields. The synthetic approach involved the increase of the scope of a previous work of the research group NUQUIMHE, where three new pyrazoles containing a dimethyl acetal aldehyde function bonded to the carbon 3 of the heterocycle (5a-c) were synthetized from cyclocondensation reactions between methyl, phenyl and tert-butyl hydrazine and the 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one (3f) in alcoholic medium. The compounds were obtained like oils, with yields in the range of 89 98 %. In a next step, was performed the deprotection of the acetal moiety of the pyrazoles (5a-c), in order to obtain the corresponding aldehydes (6a-c). To this, it was employed a solution of CHCl3 and aqueous trifluoroacetic acid under reflux for a reactional time of 4 hours. This methodology allowed isolating the desired products with yields in the range of 68 87 %. These compounds were employed to optimize the reactional conditions used in the synthesis of the homoallylic alcohols described in this dissertation. The allylation reaction of pyrazoles 6a-c was performed using allylaluminum reagents generated in situ from the catalytic insertion of aluminum to allyl bromides. The methodology was effective to synthetize the allylic alcohols 7a-c, which were obtained like oils, in the range of 84 90%. Of an analogue way, were realized the allylations of trihaloacetyl substituted 1,2,3-triazoles (4a-f). These precursors, obtained from 1,3 dipolar cycloadditions between the 2,6-difluorobenzyl azide (1) and trihalomethyl substituted enones (3a-f), were reacted with allylaluminum nucleophiles derived from allyl and crotyl bromides, furnishing the corresponding homoallylic alcohols with yields in the range of 85 94 %. In view of accessible price and exquisite chemical reactivity, the employed allylaluminum reagents proved to be an excellent choice for the allylations reactions of the azole 4 and 6, furnishing the desired products in good yield (85 94%).O presente trabalho teve como objetivo a síntese de álcoois homoalílico derivados de azóis trialoacetil/trifluormetil substituídos empregando uma metodologia simples, com considerável custo benefício e capaz de fornecer rendimentos satisfatórios. A metodologia empregada envolveu a ampliação de um estudo prévio do grupo de pesquisa NUQUIMHE, onde três pirazóis inéditos contendo uma função acetal ligada ao carbono 3 do heterociclo (5a-c) foram sintetizados através de reações de ciclocondensação entre metil, fenil e tert-butil hidrazina e a 4,6,6-trimetoxi-1,1,1-trifluorhex-3-em-2-ona (3g) em meio alcoólico. Os compostos foram obtidos sob a forma de óleos, com rendimentos de 89 98 %. Em uma etapa posterior, foi realizado a desproteção da função acetal presente nos pirazóis (5a-c), visando à obtenção dos aldeídos correspondentes (6a-c). Para isto, empregou-se uma solução de CHCl3 e ácido trifluoroacético aquoso sob refluxo, por um tempo reacional de 4 horas, metodologia que possibilitou a obtenção dos produtos desejados com rendimentos na faixa de 68 87 %. Estes compostos foram empregados na otimização da metodologia reacional utilizada para a síntese dos álcoois homoalílicos descritos nesta dissertação. As alilações dos pirazóis 6a-c foram realizadas empregando reagentes alilalumínio gerados in situ a partir da inserção catalítica de alumínio a brometos alílicos. A metodologia mostrou-se eficiente para a obtenção dos álcoois homoalílicos 7a-c, os quais foram obtidos como óleos com rendimentos na faixa de 84 90%. De forma análoga, foram realizadas as alilações de 1,2,3-triazóis trialoacetil substituídos (4a-f). Estes precursores, obtidos a partir de cicloadições 1,3 dipolares entre a 2,6-difluorbenzil azida (1) e enonas trialometil substituídas (3a-f), foram submetidos a reação com alilalumínio derivados de brometos de alila e crotila, fornecendo os álcoois correspondentes com rendimentos de 85 94 %. Tendo em vista o preço acessível e a ótima reatividade química, os alílalumínios empregados mostraram-se uma excelente escolha para a realização das alilações dos azóis 4 e 6, fornecendo os produtos desejados em bons rendimentos (85 94%).Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaAzóis trialoacetil/trifluormetil substituídosReagentes alilalumínioÁlcooils homoalílicosTrihaloacetyl/trifluoromethyl substituted azolesAllylaluminum reagentsHomoallylic alcoholsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAComportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicosChemical behavior of trihaloacetyl/trifluoromethyl substituted azoles in allylations reactions: synthesis of trihalomethyl heteroaryl homoallylic alcoholsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Porte, Liliane Medianeira Faverohttp://lattes.cnpq.br/3554882420821307Severo Filho, Wolmar Alípiohttp://lattes.cnpq.br/1999826579939679http://lattes.cnpq.br/5311350037734576Wiethan, Carson Wanderley10060000000040050030030050006c852ad-d805-43c3-99d6-93a6a86f507c1775199a-9caa-4da9-8ecc-d713f3b30567feedb2ff-e217-4d69-b48c-c4975696fb55a07c475c-60f3-4ff9-bff8-2a4f54329a61info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALWIETHAN, CARSON WANDERLEY.pdfapplication/pdf5159512http://repositorio.ufsm.br/bitstream/1/10539/1/WIETHAN%2c%20CARSON%20WANDERLEY.pdf5acb97398c39210a0d8398e5eca0db18MD51TEXTWIETHAN, CARSON WANDERLEY.pdf.txtWIETHAN, CARSON WANDERLEY.pdf.txtExtracted texttext/plain170445http://repositorio.ufsm.br/bitstream/1/10539/2/WIETHAN%2c%20CARSON%20WANDERLEY.pdf.txt52da5f45535fdd0aa2e5ff46cfff8f66MD52THUMBNAILWIETHAN, CARSON WANDERLEY.pdf.jpgWIETHAN, CARSON WANDERLEY.pdf.jpgIM Thumbnailimage/jpeg5678http://repositorio.ufsm.br/bitstream/1/10539/3/WIETHAN%2c%20CARSON%20WANDERLEY.pdf.jpgf9b00993362c7040f8a710bbd11bc8bbMD531/105392022-03-17 13:50:39.698oai:repositorio.ufsm.br:1/10539Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-03-17T16:50:39Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
dc.title.alternative.eng.fl_str_mv |
Chemical behavior of trihaloacetyl/trifluoromethyl substituted azoles in allylations reactions: synthesis of trihalomethyl heteroaryl homoallylic alcohols |
title |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
spellingShingle |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos Wiethan, Carson Wanderley Azóis trialoacetil/trifluormetil substituídos Reagentes alilalumínio Álcooils homoalílicos Trihaloacetyl/trifluoromethyl substituted azoles Allylaluminum reagents Homoallylic alcohols CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
title_full |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
title_fullStr |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
title_full_unstemmed |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
title_sort |
Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos |
author |
Wiethan, Carson Wanderley |
author_facet |
Wiethan, Carson Wanderley |
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 |
Porte, Liliane Medianeira Favero |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/3554882420821307 |
dc.contributor.referee2.fl_str_mv |
Severo Filho, Wolmar Alípio |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/1999826579939679 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5311350037734576 |
dc.contributor.author.fl_str_mv |
Wiethan, Carson Wanderley |
contributor_str_mv |
Bonacorso, Helio Gauze Porte, Liliane Medianeira Favero Severo Filho, Wolmar Alípio |
dc.subject.por.fl_str_mv |
Azóis trialoacetil/trifluormetil substituídos Reagentes alilalumínio Álcooils homoalílicos |
topic |
Azóis trialoacetil/trifluormetil substituídos Reagentes alilalumínio Álcooils homoalílicos Trihaloacetyl/trifluoromethyl substituted azoles Allylaluminum reagents Homoallylic alcohols CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Trihaloacetyl/trifluoromethyl substituted azoles Allylaluminum reagents Homoallylic alcohols |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present work reports the synthesis of homoallylic alcohols derived from trihaloacetyl/trifluormethyl substituted azoles employing a simple methodology, with excellent cost benefit and able to furnish the desired products with satisfactory yields. The synthetic approach involved the increase of the scope of a previous work of the research group NUQUIMHE, where three new pyrazoles containing a dimethyl acetal aldehyde function bonded to the carbon 3 of the heterocycle (5a-c) were synthetized from cyclocondensation reactions between methyl, phenyl and tert-butyl hydrazine and the 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one (3f) in alcoholic medium. The compounds were obtained like oils, with yields in the range of 89 98 %. In a next step, was performed the deprotection of the acetal moiety of the pyrazoles (5a-c), in order to obtain the corresponding aldehydes (6a-c). To this, it was employed a solution of CHCl3 and aqueous trifluoroacetic acid under reflux for a reactional time of 4 hours. This methodology allowed isolating the desired products with yields in the range of 68 87 %. These compounds were employed to optimize the reactional conditions used in the synthesis of the homoallylic alcohols described in this dissertation. The allylation reaction of pyrazoles 6a-c was performed using allylaluminum reagents generated in situ from the catalytic insertion of aluminum to allyl bromides. The methodology was effective to synthetize the allylic alcohols 7a-c, which were obtained like oils, in the range of 84 90%. Of an analogue way, were realized the allylations of trihaloacetyl substituted 1,2,3-triazoles (4a-f). These precursors, obtained from 1,3 dipolar cycloadditions between the 2,6-difluorobenzyl azide (1) and trihalomethyl substituted enones (3a-f), were reacted with allylaluminum nucleophiles derived from allyl and crotyl bromides, furnishing the corresponding homoallylic alcohols with yields in the range of 85 94 %. In view of accessible price and exquisite chemical reactivity, the employed allylaluminum reagents proved to be an excellent choice for the allylations reactions of the azole 4 and 6, furnishing the desired products in good yield (85 94%). |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-03-01 |
dc.date.accessioned.fl_str_mv |
2014-06-11 |
dc.date.available.fl_str_mv |
2014-06-11 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
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masterThesis |
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publishedVersion |
dc.identifier.citation.fl_str_mv |
WIETHAN, Carson Wanderley. Chemical behavior of trihaloacetyl/trifluoromethyl substituted azoles in allylations reactions: synthesis of trihalomethyl heteroaryl homoallylic alcohols. 2013. 157 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10539 |
identifier_str_mv |
WIETHAN, Carson Wanderley. Chemical behavior of trihaloacetyl/trifluoromethyl substituted azoles in allylations reactions: synthesis of trihalomethyl heteroaryl homoallylic alcohols. 2013. 157 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/10539 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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400 500 300 300 500 |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
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Química |
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Universidade Federal de Santa Maria |
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