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dc.creatorRodrigues, Melissa Budke
dc.date.accessioned2018-11-09T20:40:24Z
dc.date.available2018-11-09T20:40:24Z
dc.date.issued2018-03-23
dc.identifier.urihttp://repositorio.ufsm.br/handle/1/14794
dc.description.abstractIn this thesis, methodologies were developed in order to obtain novel trifluormethyl substituted quinolines through intramolecular cyclocondensation reactions with subsequent C-C and C-N cross coupling of the Sonogashira, Buchwald-Hartwig and Ullmann type using phenylacetylene, morpholine, pyrrolidine and indole as precursors. Its electronic and structural properties were investigated by mass spectrometry, absorption and emission spectroscopy (photoluminescence), nuclear magnetic resonance of 1H and 13C, besides studies involving interaction with DNA and evaluation of possible antimicrobial properties. Initially, a series of 1-(1-((3-chloro-4-fluorophenyl)amino)-3,4-dihydronaphthalen-2-yl)-2,2,2-trifluoroethan-1-one (2a), (Z)-4-((3-chloro-4-fluorophenyl)amino)-1,1,1-trifluoro-3-alken-2-ones (2b-g) and (Z)-4-((4-bromophenyl)amino)-1,1,1-trifluoro-3-alken-2-ones (3b-j) were obtained utilizing the precursors 3-chloro-4-fluoro-aniline, 4-bromo-aniline and 4-alkoxi-4-alkil[aryl(heteroaryl)]-1,1,1-trifluoro-3-alken-2-ones (1a-j) (R = CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-furyl, 2-thienyl). Lastly, the enaminoketones compounds 2 and 3 were subjected to regiosselective intramolecular cyclization in sulfuric acid, resulting in 7-chloro-6-fluoro-4-(trifluoromethyl)quinolines (4) and 6-bromo-4-(trifluoromethyl)quinolines (5) in good yields (65 – 90%). Subsequently, C-C coupling reactions were performed in the quinolinic systems 4 and 5, where it was possible to obtain novel compounds 6-fluoro-7-(phenylethynyl)-4-(trifluoromethyl)quinolines (6) and 6-(phenylethynyl)-4-(trifluoromethyl)quinolines (7) in good yields (25 – 88%) through the Sonogashira coupling reaction using phenylacethylene as one of the precursors. Using the quinolines 5 together, as precursors, with the morpholine and pyrrolidine, it was possible to perform Buchwald-Hartwig coupling reactions, promoting the formation of new C-N bond. Thus, novel compounds 4-(4-(trifluoromethyl)quinolin-6-yl)morpholine (8) and 6-(pyrrolidin-1-yl)-4-(trifluoromethyl)quinolines (9) substituted with R = C6H5, 4-FC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-thienyl were obtained in yields of 60 – 88%. Subsequently, the Ullmann coupling reaction catalyzed for CuI and DMEDA from the 6-bromo-quinolines (5) and indole, led in to obtaining a new series of five compounds 6-(1H-indol-1-yl)-4-(trifluoromethyl)quinolines (10) (R = C6H5, 4-FC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-thienyl) with yields of 57 – 84%. The evaluation of photoluminescent properties of the quinolines 8 and 9 demonstrated that the compounds showed fuorescence in the region of blue for cyan, with moderated quantum yields in the 400 – 700 nm regions. In DNA interaction studies, the compounds showed strong ct-DNA bonding, especially the compounds substituted with morpholine at the 6-position of the quinolinic ring. The compounds 4-10 were evaluated against four types of bacterias and six types of fungi, but these were not active against the microorganism used. Further tests involving other types of bacterias and fungi should be performed to better evaluate the micro- and micobiologic properties of these novel 4-trifluoromethyl-quinolines.eng
dc.description.sponsorshipConselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqpor
dc.languageporpor
dc.publisherUniversidade Federal de Santa Mariapor
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subject4-(trifluormetil)haloquinolinaspor
dc.subjectReações de acoplamento C-C e C-Npor
dc.subjectPropriedades fotoluminescentespor
dc.subject4-(trifluoromethyl)haloquinolineseng
dc.subjectC-C and C-N coupling reactionseng
dc.subjectPhotoluminescent propertieseng
dc.title4-(trifluormetil)haloquinolinas: síntese, reações de acoplamento cruzado c-c e c-n, propriedades fotoluminescentes e antimicrobianaspor
dc.title.alternative4-(trifluoromethyl)haloquinolines: synthesis, c-c and c-n cross coupling reactions, photoluminescent and antimicrobial propertieseng
dc.typeTesepor
dc.description.resumoNesta tese foram desenvolvidas metodologias para a obtenção de novas quinolinas trifluormetil substituídas através de reações de ciclocondensação intramoleculares com posteriores acoplamentos cruzados C-C e C-N do tipo Sonogashira, Buchwald-Hartwig e Ullmann utilizando fenilacetileno, morfolina, pirrolidina e indol como precursores. Suas propriedades estruturais e eletrônicas foram investigadas por espectrometria de massas, espectroscopia eletrônica de absorção e emissão (fotoluminescência), ressonância magnética nuclear de 1H e 13C, além de estudos envolvendo interação com o DNA e avaliação de possíveis propriedades antimicrobianas. Inicialmente foram obtidas uma série de 1-(1-((3-cloro-4-fluorfenil)amino)-3,4-diidronaftalen-2-il)-2,2,2-trifluoretan-1-ona (2a), (Z)-4-((3-cloro-4-fluorfenil)amino)-1,1,1-triflúor-3-alquen-2-onas (2b-g) e (Z)-4-((4-bromofenil)amino)-1,1,1-triflúor-3-alquen-2-onas (3b-j) utilizando os precursores 3-cloro-4-flúor-anilina, 4-bromo-anilina e 4-alcóxi-4-alquila[arila(heteroarila)]-1,1,1-triflúor-3-alquen-2-onas (1a-j) (R = CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-furila, 2-tienila). Após, os compostos enamino cetônicos 2 e 3 foram submetidos à reação regiosseletiva de ciclização intramolecular em ácido sulfúrico, resultando em 7-cloro-6-flúor-4-(trifluormetil)quinolinas (4) e 6-bromo-4-(trifluormetil)quinolinas (5) com bons rendimentos (65 – 90%). Posteriormente, reações de acoplamento C-C foram realizadas nos sistemas quinolínicos 4 e 5, sendo possível obter sistemas inéditos 6-flúor-7-(feniletinil)-4-(trifluormetil)quinolinas (6) e 6-(feniletinil)-4-(trifluormetil)quinolinas (7) com bons rendimentos (25 – 88%) através da reação de acoplamento de Sonogashira utilizando fenilacetileno como um dos precursores. Utilizando como precursores as quinolinas 5 juntamente com as aminas morfolina e pirrolidina, foi possível realizar reações de acoplamento de Buchwald-Hartwig, promovendo a formação de novas ligações C-N. Desta forma, novos compostos 4-(4-(trifluormetil)quinolin-6-il)morfolina (8) e 6-(pirrolidin-1-il)-4-(trifluormetil)quinolinas (9) substituídos com R = C6H5, 4-FC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-tienila foram obtidos com rendimentos de 60 – 88%. Em sequência, as reações de acoplamento de Ullmann catalisadas por CuI e DMEDA a partir das 6-bromo-quinolinas (5) e indol, conduziram à obtenção de uma série inédita de cinco compostos 6-(1H-indol-1-il)-4-(trifluormetil)quinolinas (10) (R = C6H5, 4-FC6H4, 4-CH3C6H4, 4-CF3C6H4, 2-tienila) com rendimentos de 57 – 84%. A avaliação das propriedades fotoluminescentes das quinolinas 8 e 9 demonstrou que os compostos apresentaram fluorescência na região do azul para ciano, com moderados rendimentos quânticos na região de 400 – 700 nm. Nos estudos de interação com o DNA, os compostos apresentaram ligação com ct-DNA, principalmente os compostos substituídos com morfolina na posição 6 do anel quinolínico. Os compostos 4-10 foram avaliados frente a quatro tipos de bactérias e seis tipos de leveduras, mas estes não se mostraram ativos frente aos microrganismos utilizados. Mais testes envolvendo outros tipos de bactérias e leveduras devem ser realizados para melhor avaliar as propriedades micro- e micobiológicas destas novas 4-trifluormetil-quinolinas.por
dc.contributor.advisor1Bonacorso, Helio Gauze
dc.contributor.advisor1Latteshttp://lattes.cnpq.br/7275608974248322por
dc.contributor.referee1Iglesias, Bernardo Almeida
dc.contributor.referee1Latteshttp://lattes.cnpq.br/4402375533322977por
dc.contributor.referee2Zanatta, Nilo
dc.contributor.referee2Latteshttp://lattes.cnpq.br/0719465062354576por
dc.contributor.referee3Andrighetto, Rosália
dc.contributor.referee3Latteshttp://lattes.cnpq.br/9569995843681336por
dc.contributor.referee4Merlo, Aloir Antonio
dc.contributor.referee4Latteshttp://lattes.cnpq.br/7385210507816401por
dc.creator.Latteshttp://lattes.cnpq.br/5087148127700008por
dc.publisher.countryBrasilpor
dc.publisher.departmentQuímicapor
dc.publisher.initialsUFSMpor
dc.publisher.programPrograma de Pós-Graduação em Químicapor
dc.subject.cnpqCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICApor
dc.publisher.unidadeCentro de Ciências Naturais e Exataspor


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