β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/23075 |
Resumo: | This work shows the synthesis, spectroscopic structural characterization, microbiological properties determination, photophysical, and the DNA bonds of the new difluorooraganoboron compounds, wich are BODIPYs derivatives and analogues synthesized from substituted trihalomethyl β-enaminoketones. Furthermore, also presents a study of intramolecular cyclization reactions and the regioselectivity elucidation of ring closure in derivatives aminocoumarinics. So, were obtained two series of β-enaminoketones wich were used with a precursos, alkyl(aryl)amines (5aa-ai, 5be) (61-90%) and, 6-amino-coumarin (9,10a-e) (50-95%), with the substituted alkyl(aryl) trihalomethyl. These substitued trihalomethyl β-enaminoketones were applied with a precursor bloc in the synthesis of new compounds 2,2,-difluoro-3,4-alkyl(heteroaryl)-6-(trichloromethyl)-2H-1,3,2-oxazaborinin-3- ium-2-uides in front of BF3·OEt2 as a source of BF2. The trifluoromethyled β-aminoketones didn’t presented enough reactivity for the synthesis of difluoroorganoboron compounds. Whereas the trichloromethyl β-aminoketones carried out to a synthesis of thirteen unpublished compounds (7aa-ai, 7be, 12a, 12b, 12e) with good yields (50 – 91%) Some compouds showed antimicrobial effects in front of many pathogenic microorganisms in low concentration, lower that presents cytotoxics effects. In analysis of interaction with DNA through spectroscopical methods of absorption and emission, the derivatives 7aa-i e 7be showed strongs interactions with ct-DNA, apresentaram fortes interações com o ct-DNA, wich are attributed to the hydrophobic forces. For the compounds 12a, 12b, 12e were performed spectrocopic tests of absortion and emission that presentes two absortion bands: the first in the region of 270-290 nm and the second in the region of 305-370 nm. All derivatives coumarinics showed fluorescence with low and moderate quantum yields (Φ������������) in dichloromethane when compared to the 9,10-diphenylanthracene (DPA), emission reference. The substracts substituted trihalomethyl β-enaminoketones submitted to thermocyclization under acid catalysis didn’t presented regioselectivity. Only the substituted trifluoromethyl β-enaminocoumarin 9b carried to formation of two products one linear (13b) (15%) and another angular (15b) (10%) being that chlorinated didn’t reacted. Finally was observed that chemical behavior of the nucleophile 4 amino-coumarin in front of the substituted trihalomethyl vinylketones under acid catalysis, carried out the pyrido-coumarins (20a-i) directly, without a intermediate formation, the β- enaminoketones. The methodology cariied to the synthesis of nine compounds trifluoromethyled 1,4-substituted in yield between 25 – 66%. The substituted trichloromethyl vinylketones didn’t reacted. |
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β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramolecularesSubstituted trihalomethyl β-enaminoketones: synthesis, structure and photophysical properties of difluoroorganoboron chelates and intramolecular cyclocondensation rractionsDiflúor-organoboroCumarinaβ-enaminocetonaCromóforosPropriedades fotofísicasMicroorganismosDifluoroorganoboronCoumarinβ-enaminoketoneChromophoresPhotophysical propertiesMicroorganismsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThis work shows the synthesis, spectroscopic structural characterization, microbiological properties determination, photophysical, and the DNA bonds of the new difluorooraganoboron compounds, wich are BODIPYs derivatives and analogues synthesized from substituted trihalomethyl β-enaminoketones. Furthermore, also presents a study of intramolecular cyclization reactions and the regioselectivity elucidation of ring closure in derivatives aminocoumarinics. So, were obtained two series of β-enaminoketones wich were used with a precursos, alkyl(aryl)amines (5aa-ai, 5be) (61-90%) and, 6-amino-coumarin (9,10a-e) (50-95%), with the substituted alkyl(aryl) trihalomethyl. These substitued trihalomethyl β-enaminoketones were applied with a precursor bloc in the synthesis of new compounds 2,2,-difluoro-3,4-alkyl(heteroaryl)-6-(trichloromethyl)-2H-1,3,2-oxazaborinin-3- ium-2-uides in front of BF3·OEt2 as a source of BF2. The trifluoromethyled β-aminoketones didn’t presented enough reactivity for the synthesis of difluoroorganoboron compounds. Whereas the trichloromethyl β-aminoketones carried out to a synthesis of thirteen unpublished compounds (7aa-ai, 7be, 12a, 12b, 12e) with good yields (50 – 91%) Some compouds showed antimicrobial effects in front of many pathogenic microorganisms in low concentration, lower that presents cytotoxics effects. In analysis of interaction with DNA through spectroscopical methods of absorption and emission, the derivatives 7aa-i e 7be showed strongs interactions with ct-DNA, apresentaram fortes interações com o ct-DNA, wich are attributed to the hydrophobic forces. For the compounds 12a, 12b, 12e were performed spectrocopic tests of absortion and emission that presentes two absortion bands: the first in the region of 270-290 nm and the second in the region of 305-370 nm. All derivatives coumarinics showed fluorescence with low and moderate quantum yields (Φ������������) in dichloromethane when compared to the 9,10-diphenylanthracene (DPA), emission reference. The substracts substituted trihalomethyl β-enaminoketones submitted to thermocyclization under acid catalysis didn’t presented regioselectivity. Only the substituted trifluoromethyl β-enaminocoumarin 9b carried to formation of two products one linear (13b) (15%) and another angular (15b) (10%) being that chlorinated didn’t reacted. Finally was observed that chemical behavior of the nucleophile 4 amino-coumarin in front of the substituted trihalomethyl vinylketones under acid catalysis, carried out the pyrido-coumarins (20a-i) directly, without a intermediate formation, the β- enaminoketones. The methodology cariied to the synthesis of nine compounds trifluoromethyled 1,4-substituted in yield between 25 – 66%. The substituted trichloromethyl vinylketones didn’t reacted.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESO trabalho apresenta a síntese, caracterização estrutural espectroscópica, determinação das propriedades microbiológicas, fotofísicas, e de ligação com DNA de novos compostos diflúor-organoboro análogos a BODIPYs derivados de precursores β-enaminocetonas trialometil substituídas. Além disso, apresenta também um estudo das reações de ciclização intramolecular e a elucidação da regiosseletividade de fechamento anelar em derivados aminocumarínicos. Assim, obteve-se duas séries de β-enaminocetonas na qual foram utilizados como precursores, alquil(aril)aminas (5aa-ai, 5be) (61-90%) e, 6-amino-cumarina (9,10a-e) (50- 95%), frente a vinilcetonas alquil(aril) trialometil substituídas. Aplicou-se essas β- enaminocetonas trialometil substituídas como bloco precursor na síntese de novos compostos 2,2-diflúor-3,4-alquil(heteroaril)-6-(triclorometil)-2H-1,3,2-oxazaborinin-3-ium-2-uides frente a BF3 .OEt2 como fonte de BF2. As β-enaminocetonas trifluormetiladas não apresentaram reatividade suficiente para a síntese dos compostos diflúor-organoboro. Já as β-enaminocetonas triclorometil substituídas levaram a síntese de treze compostos (7aa-ai, 7be, 12a, 12b, 12e) inéditos em rendimentos que variaram de 50 – 91%. Alguns compostos apresentaram efeitos antimicrobianos em vários micro-organismos patogênicos em concentrações abaixo daquelas que mostraram efeitos citotóxicos. Na análise de interação com o DNA por métodos espectroscópicos de absorção e emissão, os derivados 7aa-i e 7be apresentaram fortes interações com o ct-DNA, sendo essas, atribuídas a forças hidrofóbicas. Para os compostos 12a, 12b, 12e realizaram-se testes espectroscópicos de absorção e emissão na qual mostraram que a absorção apresenta duas bandas: uma primeira na região de 270-290 nm e a segunda na região de 305-370 nm. Todos os derivados cumarínicos mostraram fluorescência com rendimentos quânticos de moderados a baixos (Φfl) em solução de diclorometano quando comparado com o 9,10-difenilantraceno (DPA), referência de emissão. Os substratos β-enaminocumarínicos trialometil substituídos submetidos a termociclização sob catálise ácida não apresentaram regiosseletividade. Apenas a β-enaminocumarina trifluormetil substituída 9b levou a formação de dois produtos um linear (13b) (15%) e outro angular (15b) (10%) sendo que as cloradas nem reagiram. Finalmente, observou-se que o comportamento químico do nucleófilo 4-aminocumarina frente as vinilcetonas trialometil substituídas sob catálise ácida, leva a obtenção direta de pirido-cumarinas (20a-i) sem passar por nenhum tipo de intermediário β-enamino cetônicos. A metodologia levou a síntese de nove compostos trifluormetilados 1,4-substituídos em rendimentos que variaram de 25 – 66%. As vinilcetonas triclorometil substituídas não reagiram.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Iglesias, Bernardo AlmeidaSchumacher, Ricardo FredericoFantinel, LeonardoRosa, Fernanda Andreia daRosa, Wilian Carvalho da2021-11-30T15:47:50Z2021-11-30T15:47:50Z2020-03-27info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/23075porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2021-12-01T16:01:36Zoai:repositorio.ufsm.br:1/23075Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2021-12-01T16:01:36Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares Substituted trihalomethyl β-enaminoketones: synthesis, structure and photophysical properties of difluoroorganoboron chelates and intramolecular cyclocondensation rractions |
title |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
spellingShingle |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares Rosa, Wilian Carvalho da Diflúor-organoboro Cumarina β-enaminocetona Cromóforos Propriedades fotofísicas Microorganismos Difluoroorganoboron Coumarin β-enaminoketone Chromophores Photophysical properties Microorganisms CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
title_full |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
title_fullStr |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
title_full_unstemmed |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
title_sort |
β-enaminocetonas trialometil substituídas: síntese, estrutura e propriedades fotofísicas de quelatos difluororganoboro e reações de ciclocondensação intramoleculares |
author |
Rosa, Wilian Carvalho da |
author_facet |
Rosa, Wilian Carvalho da |
author_role |
author |
dc.contributor.none.fl_str_mv |
Bonacorso, Helio Gauze http://lattes.cnpq.br/7275608974248322 Iglesias, Bernardo Almeida Schumacher, Ricardo Frederico Fantinel, Leonardo Rosa, Fernanda Andreia da |
dc.contributor.author.fl_str_mv |
Rosa, Wilian Carvalho da |
dc.subject.por.fl_str_mv |
Diflúor-organoboro Cumarina β-enaminocetona Cromóforos Propriedades fotofísicas Microorganismos Difluoroorganoboron Coumarin β-enaminoketone Chromophores Photophysical properties Microorganisms CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Diflúor-organoboro Cumarina β-enaminocetona Cromóforos Propriedades fotofísicas Microorganismos Difluoroorganoboron Coumarin β-enaminoketone Chromophores Photophysical properties Microorganisms CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work shows the synthesis, spectroscopic structural characterization, microbiological properties determination, photophysical, and the DNA bonds of the new difluorooraganoboron compounds, wich are BODIPYs derivatives and analogues synthesized from substituted trihalomethyl β-enaminoketones. Furthermore, also presents a study of intramolecular cyclization reactions and the regioselectivity elucidation of ring closure in derivatives aminocoumarinics. So, were obtained two series of β-enaminoketones wich were used with a precursos, alkyl(aryl)amines (5aa-ai, 5be) (61-90%) and, 6-amino-coumarin (9,10a-e) (50-95%), with the substituted alkyl(aryl) trihalomethyl. These substitued trihalomethyl β-enaminoketones were applied with a precursor bloc in the synthesis of new compounds 2,2,-difluoro-3,4-alkyl(heteroaryl)-6-(trichloromethyl)-2H-1,3,2-oxazaborinin-3- ium-2-uides in front of BF3·OEt2 as a source of BF2. The trifluoromethyled β-aminoketones didn’t presented enough reactivity for the synthesis of difluoroorganoboron compounds. Whereas the trichloromethyl β-aminoketones carried out to a synthesis of thirteen unpublished compounds (7aa-ai, 7be, 12a, 12b, 12e) with good yields (50 – 91%) Some compouds showed antimicrobial effects in front of many pathogenic microorganisms in low concentration, lower that presents cytotoxics effects. In analysis of interaction with DNA through spectroscopical methods of absorption and emission, the derivatives 7aa-i e 7be showed strongs interactions with ct-DNA, apresentaram fortes interações com o ct-DNA, wich are attributed to the hydrophobic forces. For the compounds 12a, 12b, 12e were performed spectrocopic tests of absortion and emission that presentes two absortion bands: the first in the region of 270-290 nm and the second in the region of 305-370 nm. All derivatives coumarinics showed fluorescence with low and moderate quantum yields (Φ������������) in dichloromethane when compared to the 9,10-diphenylanthracene (DPA), emission reference. The substracts substituted trihalomethyl β-enaminoketones submitted to thermocyclization under acid catalysis didn’t presented regioselectivity. Only the substituted trifluoromethyl β-enaminocoumarin 9b carried to formation of two products one linear (13b) (15%) and another angular (15b) (10%) being that chlorinated didn’t reacted. Finally was observed that chemical behavior of the nucleophile 4 amino-coumarin in front of the substituted trihalomethyl vinylketones under acid catalysis, carried out the pyrido-coumarins (20a-i) directly, without a intermediate formation, the β- enaminoketones. The methodology cariied to the synthesis of nine compounds trifluoromethyled 1,4-substituted in yield between 25 – 66%. The substituted trichloromethyl vinylketones didn’t reacted. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-03-27 2021-11-30T15:47:50Z 2021-11-30T15:47:50Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/23075 |
url |
http://repositorio.ufsm.br/handle/1/23075 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
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 |
_version_ |
1805922098096373760 |