Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos
Ano de defesa: | 2008 |
---|---|
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: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/10417 |
Resumo: | This work describes, at first, the synthesis of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one by the acylation reaction of 1,1,3,3-tetramethoxybutane, in 65% yields. Afterwards, the synthesis of a new series of 4,5-dihydro-1H-pyrazoles, which contain a ketal-protected aldehyde function as substituent, is described. These compounds are obtained by the reaction of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one with hydrazines (NH2NHR, R= 2-furoyl, C6F5, COOMe, COMe, Nicotinoyl), in 90-97% yields. In a subsequent step, dehydration reactions of 4,5-dihydro-1H-pyrazoles are reported, leading to 1H-pyrazoles. In addition, this work proposes a fluorination methodology of the ketal substituent of the 4,5-diidro-1H-pyrazoles and 1H-pyrazoles using diethylaminosulfur trifluoride (DAST). Finally, this work reports the desprotection of the ketal substituent to obtain the respective carbonyl compound and the subsequent fluorination reaction leading to the difluorinated analogues, in 55-60% yields. The compounds were characterized by 1H and 13C NMR experiments and by Mass Spectrometry, and their purity was confirmed by elemental analysis. |
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2017-05-182017-05-182008-02-01PORTE, Liliane Medianeira Favero. Synthesis de 5-hydroxi-3-(1,1-dimethoxyetan-2-yl)-5-trifluoromethyl-2-pyrazolines e 3-(1,1-difluoroetan-2-yl)-1H-pyrazoles analogues. 2008. 139 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008.http://repositorio.ufsm.br/handle/1/10417This work describes, at first, the synthesis of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one by the acylation reaction of 1,1,3,3-tetramethoxybutane, in 65% yields. Afterwards, the synthesis of a new series of 4,5-dihydro-1H-pyrazoles, which contain a ketal-protected aldehyde function as substituent, is described. These compounds are obtained by the reaction of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one with hydrazines (NH2NHR, R= 2-furoyl, C6F5, COOMe, COMe, Nicotinoyl), in 90-97% yields. In a subsequent step, dehydration reactions of 4,5-dihydro-1H-pyrazoles are reported, leading to 1H-pyrazoles. In addition, this work proposes a fluorination methodology of the ketal substituent of the 4,5-diidro-1H-pyrazoles and 1H-pyrazoles using diethylaminosulfur trifluoride (DAST). Finally, this work reports the desprotection of the ketal substituent to obtain the respective carbonyl compound and the subsequent fluorination reaction leading to the difluorinated analogues, in 55-60% yields. The compounds were characterized by 1H and 13C NMR experiments and by Mass Spectrometry, and their purity was confirmed by elemental analysis.A presente dissertação descreve, inicialmente, a síntese de 4,6,6-trimetoxi-1,1,1-trifluorhex-3-en-2-ona através da reação de acilação do acetal 1,1,3,3-tetrametoxibutano, com rendimento de 65%. Subsequentemente é descrita a síntese de uma nova série de 4,5-diidro-1H-pirazóis, que possuem como substituinte uma função aldeído protegida sob a forma de acetal, obtidos a partir da reação de 4,6,6-trimetoxi-1,1,1-trifluorhex-3-en-2-ona com hidrazinas (NH2NHR, R= 2-furanoil, C6F5, COOMe, COMe, Nicotinoil), com rendimentos de 90-97%. Numa etapa posterior, são descritas as reações de desidratação dos 4,5-diidro-1Hpirazóis, as quais levaram ao isolamento dos respectivos 1H-pirazóis. Além disso, são propostas neste trabalho metodologias para a fluoração do substituinte acetal dos 4,5-diidro-1H-pirazóis e 1H-pirazóis, utilizando Dietilamino Trifluoreto de Enxofre (DAST). Finalmente, é descrito neste trabalho a etapa de desproteção do substituinte acetal para obtenção do composto carbonílico correspondente e posterior reação de fluoração levando ao isolamento dos análogos difluorados com rendimentos de 55-60%. Os compostos foram caracterizados por experimentos de RMN de 1H, RMN de 13C {1H} e por Espectrometria de Massas, e sua pureza comprovada por Análise Elementar.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaDASTFluoraçãoPirazóisCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogosSynthesis de 5-hydroxi-3-(1,1-dimethoxyetan-2-yl)-5-trifluoromethyl-2-pyrazolines e 3-(1,1-difluoroetan-2-yl)-1H-pyrazoles analoguesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Rodrigues, Oscar Endrigo Dorneleshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6Flores, Alex Fabiani Clarohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774Y0http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4713752A4Porte, Liliane Medianeira Favero10060000000040050050050050006c852ad-d805-43c3-99d6-93a6a86f507c1d0c70cc-6b4c-4b99-819e-4ea7e25fa58dd315e5ef-8c77-48c9-bc87-e90cab9c43e917a00027-8984-4561-9228-46697f540c2binfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALLILIANEFAVEROPORTE.pdfapplication/pdf1964213http://repositorio.ufsm.br/bitstream/1/10417/1/LILIANEFAVEROPORTE.pdfb085299dfcfdcc8e7352e4898b49ffc5MD51TEXTLILIANEFAVEROPORTE.pdf.txtLILIANEFAVEROPORTE.pdf.txtExtracted texttext/plain144615http://repositorio.ufsm.br/bitstream/1/10417/2/LILIANEFAVEROPORTE.pdf.txt58c13e3edeadfc424dc498f52256bbf9MD52THUMBNAILLILIANEFAVEROPORTE.pdf.jpgLILIANEFAVEROPORTE.pdf.jpgIM Thumbnailimage/jpeg5240http://repositorio.ufsm.br/bitstream/1/10417/3/LILIANEFAVEROPORTE.pdf.jpge4108e27fc3f3a6b718765db01ee2986MD531/104172017-07-25 12:03:12.779oai:repositorio.ufsm.br:1/10417Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T15:03:12Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
dc.title.alternative.eng.fl_str_mv |
Synthesis de 5-hydroxi-3-(1,1-dimethoxyetan-2-yl)-5-trifluoromethyl-2-pyrazolines e 3-(1,1-difluoroetan-2-yl)-1H-pyrazoles analogues |
title |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
spellingShingle |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos Porte, Liliane Medianeira Favero DAST Fluoração Pirazóis CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
title_full |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
title_fullStr |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
title_full_unstemmed |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
title_sort |
Síntese de 5-hidróxi-3-(1,1-dimetoxietan-2-il)-5-trifluormetil-2-pirazolinas e 3-(1,1-difluoretan-2-il)-1H-pirazóis análogos |
author |
Porte, Liliane Medianeira Favero |
author_facet |
Porte, Liliane Medianeira Favero |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.referee1.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6 |
dc.contributor.referee2.fl_str_mv |
Flores, Alex Fabiani Claro |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774Y0 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4713752A4 |
dc.contributor.author.fl_str_mv |
Porte, Liliane Medianeira Favero |
contributor_str_mv |
Bonacorso, Helio Gauze Rodrigues, Oscar Endrigo Dorneles Flores, Alex Fabiani Claro |
dc.subject.por.fl_str_mv |
DAST Fluoração Pirazóis |
topic |
DAST Fluoração Pirazóis CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes, at first, the synthesis of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one by the acylation reaction of 1,1,3,3-tetramethoxybutane, in 65% yields. Afterwards, the synthesis of a new series of 4,5-dihydro-1H-pyrazoles, which contain a ketal-protected aldehyde function as substituent, is described. These compounds are obtained by the reaction of 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one with hydrazines (NH2NHR, R= 2-furoyl, C6F5, COOMe, COMe, Nicotinoyl), in 90-97% yields. In a subsequent step, dehydration reactions of 4,5-dihydro-1H-pyrazoles are reported, leading to 1H-pyrazoles. In addition, this work proposes a fluorination methodology of the ketal substituent of the 4,5-diidro-1H-pyrazoles and 1H-pyrazoles using diethylaminosulfur trifluoride (DAST). Finally, this work reports the desprotection of the ketal substituent to obtain the respective carbonyl compound and the subsequent fluorination reaction leading to the difluorinated analogues, in 55-60% yields. The compounds were characterized by 1H and 13C NMR experiments and by Mass Spectrometry, and their purity was confirmed by elemental analysis. |
publishDate |
2008 |
dc.date.issued.fl_str_mv |
2008-02-01 |
dc.date.accessioned.fl_str_mv |
2017-05-18 |
dc.date.available.fl_str_mv |
2017-05-18 |
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.citation.fl_str_mv |
PORTE, Liliane Medianeira Favero. Synthesis de 5-hydroxi-3-(1,1-dimethoxyetan-2-yl)-5-trifluoromethyl-2-pyrazolines e 3-(1,1-difluoroetan-2-yl)-1H-pyrazoles analogues. 2008. 139 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10417 |
identifier_str_mv |
PORTE, Liliane Medianeira Favero. Synthesis de 5-hydroxi-3-(1,1-dimethoxyetan-2-yl)-5-trifluoromethyl-2-pyrazolines e 3-(1,1-difluoroetan-2-yl)-1H-pyrazoles analogues. 2008. 139 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008. |
url |
http://repositorio.ufsm.br/handle/1/10417 |
dc.language.iso.fl_str_mv |
por |
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por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
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400 500 500 500 500 |
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openAccess |
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Universidade Federal de Santa Maria |
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UFSM |
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Química |
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Universidade Federal de Santa Maria |
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