Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações do UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/30245 |
Resumo: | In this work a methodology was developed for the synthesis of 4-substituted oxazinoindolones through a nucleophilic cyclization of N-(ethoxicarbonil)alkynylindois produced by electrophiles. Initially, the first studies were carried out using diorganoyl diselenides and transition metal salts (more specifically iron). Due to initial studies in obtaining the cyclized product, a series of detailed studies, involving reaction conditions and stoichiometry of the reagents, was developed to reach the best condition for obtaining the final product. Thus, having established the best reaction condition, a variety of derivatives of 4-organochalcogene [1,3] oxazino[3,4-a] indol-1-one was synthesized. The diversity of synthesized products involved different diselenides, both aryl and alkyl, as well as the change in the groups linked to the N- (ethoxicarbonil)alkynylindois; electron donors and electron withdrawers, alkyl groups, sterically hindered groups. Altogether 15 new compounds were synthesized with yields from 51 to 92%. In order to expand the scope of the work, a second stage of the study made use of molecular iodine as an electrophilic source. Again, a series of reaction studies perfected the best reaction condition, therefore it was possible to achieve the best yield of 90% iodine-cyclized product. The methodology was tested for different substrates, 7 new compounds derived from 4-Iodo[1,3]oxazino[3,4-a]indol-1-one were synthesized with yields from 51 to 90%. The methodology tolerated several groups of different characteristics (takers, donors, bulky, alkyl), similar to the previous study with organochalcogens. They are left to studies in order to investigate the high lability of their Csp2-Se and Csp2-I bonds in the future synthesis of new compounds. Substitution reactions and cross-coupling catalyzed by metals were two methodalloys tested against the synthesized compounds. Finally, the classes of synthesized compounds were submitted to photophysical and electrochemical tests, in order to further study their electrical absorption/emission and redox properties. |
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2023-09-19T18:28:09Z2023-09-19T18:28:09Z2023-08-11http://repositorio.ufsm.br/handle/1/30245In this work a methodology was developed for the synthesis of 4-substituted oxazinoindolones through a nucleophilic cyclization of N-(ethoxicarbonil)alkynylindois produced by electrophiles. Initially, the first studies were carried out using diorganoyl diselenides and transition metal salts (more specifically iron). Due to initial studies in obtaining the cyclized product, a series of detailed studies, involving reaction conditions and stoichiometry of the reagents, was developed to reach the best condition for obtaining the final product. Thus, having established the best reaction condition, a variety of derivatives of 4-organochalcogene [1,3] oxazino[3,4-a] indol-1-one was synthesized. The diversity of synthesized products involved different diselenides, both aryl and alkyl, as well as the change in the groups linked to the N- (ethoxicarbonil)alkynylindois; electron donors and electron withdrawers, alkyl groups, sterically hindered groups. Altogether 15 new compounds were synthesized with yields from 51 to 92%. In order to expand the scope of the work, a second stage of the study made use of molecular iodine as an electrophilic source. Again, a series of reaction studies perfected the best reaction condition, therefore it was possible to achieve the best yield of 90% iodine-cyclized product. The methodology was tested for different substrates, 7 new compounds derived from 4-Iodo[1,3]oxazino[3,4-a]indol-1-one were synthesized with yields from 51 to 90%. The methodology tolerated several groups of different characteristics (takers, donors, bulky, alkyl), similar to the previous study with organochalcogens. They are left to studies in order to investigate the high lability of their Csp2-Se and Csp2-I bonds in the future synthesis of new compounds. Substitution reactions and cross-coupling catalyzed by metals were two methodalloys tested against the synthesized compounds. Finally, the classes of synthesized compounds were submitted to photophysical and electrochemical tests, in order to further study their electrical absorption/emission and redox properties.Neste trabalho foi desenvolvida uma metodologia para a síntese de oxazinoindolonas 4-susbtituído através de uma ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos. Inicialmente, os primeiros estudos foram realizados pelo uso de disselenetos de diorganoíla e sais de metais de transição (mais especificamente ferro). Em virtude de estudos iniciais na obtenção do produto ciclizado, uma série de estudos detalhados, envolvendo condições reacionais e estequiometria dos reagentes, foi desenvolvida para alcançar a melhor condição de obtenção do produto final. Dessa forma, tendo a melhor condição reacional estabelecida, foi sintetizada uma variedade de derivados de 4-organocalcogeno [1,3] oxazino[3,4-a] indol-1-ona. A diversidade de produtos sintetizados envolveu diferentes disselenetos, arílicos e alquílicos, e a mudança nos grupamentos ligados aos N- (etóxicarbonil)alquinilindois, doadores e retiradores de elétrons, grupamentos alquílicos, grupos estericamente impedidos. Ao todo 15 compostos inéditos foram sintetizados com rendimentos de 51 % a 92%. A fim de expandir o escopo do trabalho, uma segunda etapa do estudo fez uso de iodo molecular como fonte eletrofílica. Novamente, uma série de estudos reacionais aperfeiçoou a melhor condição de reação, portanto, foi possível lograr o melhor rendimento do produto ciclizado com iodo em 90%. A metodologia foi testada para diferentes substratos, 7 novos compostos derivados de 4-Iodo [1,3] oxazino[3,4-a] indol-1-ona foram sintetizados com rendimentos de 51 a 90%. A metodologia tolerou vários grupos de diferentes caratcteristicas (retiradores, doadores, volumosos, alquílicos), semelhante ao estudo anterior com organocalcogênios. Os mesmos foram submetidos a estudos a fim de investigar a alta labilidade de suas ligações Csp2 -Se e Csp2 -I na síntese futura de novos compostos. Reações de substituição e acoplamento cruzado catalizada por metais as metodologias testadas frente aos compostos sintetizados. Por fim, as clases de compostos sintetizadas foram submetidas a testes fotofísicos e eletroquímicos, a fim de estudar mais profundadamente suas propriedades eletrônicas de absorção/emissão e redoxConselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessIndolAlquinilindoisOrganocalcogêniosIodoCiclização eletrofílicaIndolesAlkinylindolesOrganochalcogensIodineElectrophilic ciclizationElectrophilic ciclizationCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICACiclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídosinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Santos Neto, José SebastiãoRodrigues, Oscar Endrigo DornelesSchumacher, Ricardo FredericoSilva, Thiago Barcellos dahttp://lattes.cnpq.br/1042388169453183Leonel, Guilherme100600000000600600600600600600600b35c9860-bf5d-4c8a-ab16-02ed6931c067dc489a41-c052-426a-8ab9-4b3ee00acec27a2f445b-1730-4ac1-a60a-5f19ddeed012f0970438-aab7-4bbe-8d26-13140ae7303a5f3bda36-92ea-446e-a7a0-238149706d78b15d8bc3-9be3-4fcc-a89c-53eeee7d7510reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMLICENSElicense.txtlicense.txttext/plain; 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dc.title.por.fl_str_mv |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
title |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
spellingShingle |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos Leonel, Guilherme Indol Alquinilindois Organocalcogênios Iodo Ciclização eletrofílica Indoles Alkinylindoles Organochalcogens Iodine Electrophilic ciclization Electrophilic ciclization CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
title_full |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
title_fullStr |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
title_full_unstemmed |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
title_sort |
Ciclização eletrofílica de N- (etóxicarbonil)alquinilindois promovida por eletrófilos: síntese e caracterização de oxazinoindolonas 4- substituídos |
author |
Leonel, Guilherme |
author_facet |
Leonel, Guilherme |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2355575631197937 |
dc.contributor.referee1.fl_str_mv |
Santos Neto, José Sebastião |
dc.contributor.referee2.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee3.fl_str_mv |
Schumacher, Ricardo Frederico |
dc.contributor.referee4.fl_str_mv |
Silva, Thiago Barcellos da |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/1042388169453183 |
dc.contributor.author.fl_str_mv |
Leonel, Guilherme |
contributor_str_mv |
Zeni, Gilson Rogério Santos Neto, José Sebastião Rodrigues, Oscar Endrigo Dorneles Schumacher, Ricardo Frederico Silva, Thiago Barcellos da |
dc.subject.por.fl_str_mv |
Indol Alquinilindois Organocalcogênios Iodo Ciclização eletrofílica |
topic |
Indol Alquinilindois Organocalcogênios Iodo Ciclização eletrofílica Indoles Alkinylindoles Organochalcogens Iodine Electrophilic ciclization Electrophilic ciclization CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Indoles Alkinylindoles Organochalcogens Iodine Electrophilic ciclization Electrophilic ciclization |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this work a methodology was developed for the synthesis of 4-substituted oxazinoindolones through a nucleophilic cyclization of N-(ethoxicarbonil)alkynylindois produced by electrophiles. Initially, the first studies were carried out using diorganoyl diselenides and transition metal salts (more specifically iron). Due to initial studies in obtaining the cyclized product, a series of detailed studies, involving reaction conditions and stoichiometry of the reagents, was developed to reach the best condition for obtaining the final product. Thus, having established the best reaction condition, a variety of derivatives of 4-organochalcogene [1,3] oxazino[3,4-a] indol-1-one was synthesized. The diversity of synthesized products involved different diselenides, both aryl and alkyl, as well as the change in the groups linked to the N- (ethoxicarbonil)alkynylindois; electron donors and electron withdrawers, alkyl groups, sterically hindered groups. Altogether 15 new compounds were synthesized with yields from 51 to 92%. In order to expand the scope of the work, a second stage of the study made use of molecular iodine as an electrophilic source. Again, a series of reaction studies perfected the best reaction condition, therefore it was possible to achieve the best yield of 90% iodine-cyclized product. The methodology was tested for different substrates, 7 new compounds derived from 4-Iodo[1,3]oxazino[3,4-a]indol-1-one were synthesized with yields from 51 to 90%. The methodology tolerated several groups of different characteristics (takers, donors, bulky, alkyl), similar to the previous study with organochalcogens. They are left to studies in order to investigate the high lability of their Csp2-Se and Csp2-I bonds in the future synthesis of new compounds. Substitution reactions and cross-coupling catalyzed by metals were two methodalloys tested against the synthesized compounds. Finally, the classes of synthesized compounds were submitted to photophysical and electrochemical tests, in order to further study their electrical absorption/emission and redox properties. |
publishDate |
2023 |
dc.date.accessioned.fl_str_mv |
2023-09-19T18:28:09Z |
dc.date.available.fl_str_mv |
2023-09-19T18:28:09Z |
dc.date.issued.fl_str_mv |
2023-08-11 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/30245 |
url |
http://repositorio.ufsm.br/handle/1/30245 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 600 600 |
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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.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
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