Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida
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/1/10538 |
Resumo: | The present dissertation describes a chemical methodology for the synthesis of three series containing fourteen new molecules of trifluoro(chloro)methyl substituted 1H-1,2,3-triazoles, which are structural analogues to the antiepileptic drug Rufinamide. The protocol used consisted in reactions of 1,3-dipolar cycloaddition of 2,6-difluorobenzyl azide and 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoro(chloro)-3-alken-2-ones, where the 4-substituents are H, Me, Ph, 4-OMeC6H4, 4-NO2C6H4,4-FC6H4,2-Thienyle 4,4 -Biphenyl. The optimized reactios were carried-out in absense of solvente, in reaction times of 48 to 96 hours at 100-150°C and in yields of 30-75%. The reactions employing the 4-alkoxy-4-aryl(heteroaryl)-1,1,1-trifluoro-3-alken-2-ones 1and 2,6-difluorobenzyl azidedemonstrated a 4-substituent dependency of the enones precursors (above mentioned) and conducted to the formation of isomeric mixtures of 4-trifluoroacetyl substituted and/or 5-trifluoromethyl substituted triazoles in varying proportions, which were separated and purified by chromatographic columns. On the other hand, the reactions employing the 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trichloro-3-alken-2-ones and the same 2,6-difluorobenzyl azide produced exclusively a series of 4- trichloroacetyl substituted triazoles without the detection of the respective 5-trichloromethyl substituted regioisomer. The synthesized triazoles were characterized by 1H, 13C, uni- and two-dimensional NMR Spectroscopy techniques as HMQC, gas chromatography coupled to mass spectrometry (GC-MS), mono-crystal X-ray diffraction, high resolution mass spectrometry (HRMS) and their purity determined by CHN Elemental Analysis. |
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2017-05-182017-05-182013-02-15MORAES, Maiara Correa de. Synthesis of the trihaloacetil substituted 1h-1,2,3-triazoles structural analoguesof rufinamide. 2013. 146 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/10538The present dissertation describes a chemical methodology for the synthesis of three series containing fourteen new molecules of trifluoro(chloro)methyl substituted 1H-1,2,3-triazoles, which are structural analogues to the antiepileptic drug Rufinamide. The protocol used consisted in reactions of 1,3-dipolar cycloaddition of 2,6-difluorobenzyl azide and 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoro(chloro)-3-alken-2-ones, where the 4-substituents are H, Me, Ph, 4-OMeC6H4, 4-NO2C6H4,4-FC6H4,2-Thienyle 4,4 -Biphenyl. The optimized reactios were carried-out in absense of solvente, in reaction times of 48 to 96 hours at 100-150°C and in yields of 30-75%. The reactions employing the 4-alkoxy-4-aryl(heteroaryl)-1,1,1-trifluoro-3-alken-2-ones 1and 2,6-difluorobenzyl azidedemonstrated a 4-substituent dependency of the enones precursors (above mentioned) and conducted to the formation of isomeric mixtures of 4-trifluoroacetyl substituted and/or 5-trifluoromethyl substituted triazoles in varying proportions, which were separated and purified by chromatographic columns. On the other hand, the reactions employing the 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trichloro-3-alken-2-ones and the same 2,6-difluorobenzyl azide produced exclusively a series of 4- trichloroacetyl substituted triazoles without the detection of the respective 5-trichloromethyl substituted regioisomer. The synthesized triazoles were characterized by 1H, 13C, uni- and two-dimensional NMR Spectroscopy techniques as HMQC, gas chromatography coupled to mass spectrometry (GC-MS), mono-crystal X-ray diffraction, high resolution mass spectrometry (HRMS) and their purity determined by CHN Elemental Analysis.A presente dissertação descreve uma metodologia química para a síntese de três séries de 1H-1,2,3-triazóis trifluor(cloro)metil substituídos, totalizando quatorze moléculas inéditas, as quais são análogas estruturais do fármaco antiepiléptico Rufinamida. O protocolo consistiu na realização de reações de cicloadição 1,3-dipolares envolvendo 2,6-difluorbenzil azida e 4-alcóxi-4-alquil(aril/heteroaril)-1,1,1-trifluor(cloro)-3-alquen-2-onas, sendo os substituintes 4-alquila(arila/heteroarila) iguais a H, Me, Ph, 4-OMeC6H4, 4-NO2C6H4,4-FC6H4,2-Tienila e 4,4 -Bifenila. As reações otimizadas se processaram na ausência de solvente, em tempos reacionais de 48 a 96 horas a 100-150°C e levaram a rendimentos na faixa de 30-75%. As reações que utilizaram 4-alcóxi-4-aril(heteroaril)-1,1,1-triflúor-3-alquen-2-onase 2,6-difluorbenzil azida apresentaram uma dependência quanto a substituição da posição 4 das enonas precursoras (acima descritos) e conduziram à formação de misturas isoméricas de triazóis 4-trifluoracetil substituídos e/ou 5-trifluormetil substituídos em proporções variadas, as quais foram passíveis de separação e purificação por cromatografia em coluna. Por outro lado, as reações empregando 4-alcóxi-4-alquil(aril/heteroaril)-1,1,1-tricloro-3-alquen-2-onas e a mesma 2,6-difluorbenzil azida produziram, exclusivamente, uma série de triazóis 4-tricloroacetil substituídos sem a detecção dos respectivos regioisômeros 5-triclorometil substituídos. Os triazóis sintetizados foram caracterizados por espectroscopia de RMN de 1H, 13C por técnicas uni- e bidimensionais (HMQC), cromatografia a gás acoplada à espectrometria de massas (GC-MS), difração de raios-X em mono-cristal, espectrometria de massas de alta resolução (HRMS) e a sua pureza determinada através de análise elementar CHN.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímica1H-1,2,3-triazóisCicloadição 1,3-dipolarRufinamida1H-1,2,3-triazoles1,3-dipolar cycloadditionRufinamideCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamidaSynthesis of the trihaloacetil substituted 1h-1,2,3-triazoles structural analoguesof rufinamideinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Braibante, Mara Elisa Forteshttp://lattes.cnpq.br/0685197822607977Campos, Patrick Teixeirahttp://lattes.cnpq.br/9549998755426589http://lattes.cnpq.br/4640105595488964Moraes, Maiara Correa de10060000000040050030030030006c852ad-d805-43c3-99d6-93a6a86f507cad0da548-7212-43a4-899a-d881b672929f2c128d4d-5411-4956-940a-6ba1d883805d89e21349-4fbd-4166-b4c7-8536cd59e133info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALMORAES, MAIARA CORREA DE.pdfapplication/pdf4644880http://repositorio.ufsm.br/bitstream/1/10538/1/MORAES%2c%20MAIARA%20CORREA%20DE.pdf0744789615173e52f95b8d4e15eaf71fMD51TEXTMORAES, MAIARA CORREA DE.pdf.txtMORAES, MAIARA CORREA DE.pdf.txtExtracted texttext/plain177886http://repositorio.ufsm.br/bitstream/1/10538/2/MORAES%2c%20MAIARA%20CORREA%20DE.pdf.txtcaead5d724bac051bddc4b4337d27290MD52THUMBNAILMORAES, MAIARA CORREA DE.pdf.jpgMORAES, MAIARA CORREA DE.pdf.jpgIM Thumbnailimage/jpeg5025http://repositorio.ufsm.br/bitstream/1/10538/3/MORAES%2c%20MAIARA%20CORREA%20DE.pdf.jpg37034fb7e9913af2883446186cf96a19MD531/105382023-06-13 14:34:48.189oai:repositorio.ufsm.br:1/10538Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132023-06-13T17:34:48Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
dc.title.alternative.eng.fl_str_mv |
Synthesis of the trihaloacetil substituted 1h-1,2,3-triazoles structural analoguesof rufinamide |
title |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
spellingShingle |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida Moraes, Maiara Correa de 1H-1,2,3-triazóis Cicloadição 1,3-dipolar Rufinamida 1H-1,2,3-triazoles 1,3-dipolar cycloaddition Rufinamide CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
title_full |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
title_fullStr |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
title_full_unstemmed |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
title_sort |
Síntese de 1h-1,2,3-triazóis trialoacetil substituídos análogos estruturais da rufinamida |
author |
Moraes, Maiara Correa de |
author_facet |
Moraes, Maiara Correa de |
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 |
Braibante, Mara Elisa Fortes |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/0685197822607977 |
dc.contributor.referee2.fl_str_mv |
Campos, Patrick Teixeira |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/9549998755426589 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4640105595488964 |
dc.contributor.author.fl_str_mv |
Moraes, Maiara Correa de |
contributor_str_mv |
Bonacorso, Helio Gauze Braibante, Mara Elisa Fortes Campos, Patrick Teixeira |
dc.subject.por.fl_str_mv |
1H-1,2,3-triazóis Cicloadição 1,3-dipolar Rufinamida |
topic |
1H-1,2,3-triazóis Cicloadição 1,3-dipolar Rufinamida 1H-1,2,3-triazoles 1,3-dipolar cycloaddition Rufinamide CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
1H-1,2,3-triazoles 1,3-dipolar cycloaddition Rufinamide |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present dissertation describes a chemical methodology for the synthesis of three series containing fourteen new molecules of trifluoro(chloro)methyl substituted 1H-1,2,3-triazoles, which are structural analogues to the antiepileptic drug Rufinamide. The protocol used consisted in reactions of 1,3-dipolar cycloaddition of 2,6-difluorobenzyl azide and 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoro(chloro)-3-alken-2-ones, where the 4-substituents are H, Me, Ph, 4-OMeC6H4, 4-NO2C6H4,4-FC6H4,2-Thienyle 4,4 -Biphenyl. The optimized reactios were carried-out in absense of solvente, in reaction times of 48 to 96 hours at 100-150°C and in yields of 30-75%. The reactions employing the 4-alkoxy-4-aryl(heteroaryl)-1,1,1-trifluoro-3-alken-2-ones 1and 2,6-difluorobenzyl azidedemonstrated a 4-substituent dependency of the enones precursors (above mentioned) and conducted to the formation of isomeric mixtures of 4-trifluoroacetyl substituted and/or 5-trifluoromethyl substituted triazoles in varying proportions, which were separated and purified by chromatographic columns. On the other hand, the reactions employing the 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trichloro-3-alken-2-ones and the same 2,6-difluorobenzyl azide produced exclusively a series of 4- trichloroacetyl substituted triazoles without the detection of the respective 5-trichloromethyl substituted regioisomer. The synthesized triazoles were characterized by 1H, 13C, uni- and two-dimensional NMR Spectroscopy techniques as HMQC, gas chromatography coupled to mass spectrometry (GC-MS), mono-crystal X-ray diffraction, high resolution mass spectrometry (HRMS) and their purity determined by CHN Elemental Analysis. |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-02-15 |
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 |
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masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
MORAES, Maiara Correa de. Synthesis of the trihaloacetil substituted 1h-1,2,3-triazoles structural analoguesof rufinamide. 2013. 146 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10538 |
identifier_str_mv |
MORAES, Maiara Correa de. Synthesis of the trihaloacetil substituted 1h-1,2,3-triazoles structural analoguesof rufinamide. 2013. 146 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/10538 |
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por |
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100600000000 |
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UFSM |
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BR |
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Química |
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Universidade Federal de Santa Maria |
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