Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos

Detalhes bibliográficos
Autor(a) principal: Wiethan, Carson Wanderley
Data de Publicação: 2013
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Manancial - Repositório Digital da UFSM
dARK ID: ark:/26339/0013000009rdd
Texto Completo: 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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spelling Comportamento 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 alcoholsAzóis trialoacetil/trifluormetil substituídosReagentes alilalumínioÁlcooils homoalílicosTrihaloacetyl/trifluoromethyl substituted azolesAllylaluminum reagentsHomoallylic alcoholsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe 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%).Conselho Nacional de Desenvolvimento Científico e TecnológicoO 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%).Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Porte, Liliane Medianeira Faverohttp://lattes.cnpq.br/3554882420821307Severo Filho, Wolmar Alípiohttp://lattes.cnpq.br/1999826579939679Wiethan, Carson Wanderley2014-06-112014-06-112013-03-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfapplication/pdfWIETHAN, 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/1/10539ark:/26339/0013000009rddporinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2022-03-17T16:50:39Zoai: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:2022-03-17T16:50:39Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.none.fl_str_mv Comportamento químico de azóis trialoacetil/trifluormetil substituídos em reações de alilação: síntese de álcoois trialometil heteroaril homoalílicos
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.none.fl_str_mv Bonacorso, Helio Gauze
http://lattes.cnpq.br/7275608974248322
Porte, Liliane Medianeira Favero
http://lattes.cnpq.br/3554882420821307
Severo Filho, Wolmar Alípio
http://lattes.cnpq.br/1999826579939679
dc.contributor.author.fl_str_mv Wiethan, Carson Wanderley
dc.subject.por.fl_str_mv Azóis trialoacetil/trifluormetil substituídos
Reagentes alilalumínio
Álcooils homoalílicos
Trihaloacetyl/trifluoromethyl substituted azoles
Allylaluminum reagents
Homoallylic alcohols
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic Azóis trialoacetil/trifluormetil substituídos
Reagentes alilalumínio
Álcooils homoalílicos
Trihaloacetyl/trifluoromethyl substituted azoles
Allylaluminum reagents
Homoallylic alcohols
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.none.fl_str_mv 2013-03-01
2014-06-11
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
format masterThesis
status_str publishedVersion
dc.identifier.uri.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.
http://repositorio.ufsm.br/handle/1/10539
dc.identifier.dark.fl_str_mv ark:/26339/0013000009rdd
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.
ark:/26339/0013000009rdd
url http://repositorio.ufsm.br/handle/1/10539
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Santa Maria
BR
Química
UFSM
Programa de Pós-Graduação em Química
publisher.none.fl_str_mv Universidade Federal de Santa Maria
BR
Química
UFSM
Programa de Pós-Graduação em Química
dc.source.none.fl_str_mv reponame:Manancial - Repositório Digital da UFSM
instname:Universidade Federal de Santa Maria (UFSM)
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instname_str Universidade Federal de Santa Maria (UFSM)
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institution UFSM
reponame_str Manancial - Repositório Digital da UFSM
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repository.name.fl_str_mv Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)
repository.mail.fl_str_mv atendimento.sib@ufsm.br||tedebc@gmail.com
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