CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE

Detalhes bibliográficos
Autor(a) principal: MARTINHO JOSÉ ALVES DE SOUSA
Data de Publicação: 2023
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da UFMS
Texto Completo: https://repositorio.ufms.br/handle/123456789/5707
Resumo: In this work, a method for the functionalization of C(sp2)-H from activated arenes under heavy and transition metal-free conditions was developed. The most sustainable approach followed the Principles of Green Chemistry, following topics such as atomic economy, not using chlorinated solvents and formation of secondary products. The first stage of the project was to find ideal reaction conditions, using diphenyl diselenide and N,N dimethylaniline as standard substrates. Thus, the optimized reaction condition consisted of using 0.5 molar equivalent of PhICl2 as oxidizing agent, 1.4 Dioxane as solvent, at room temperature, in open atmosphere, for 30 minutes. Thus, N,N-Dimethyl-4-(phenylselenyl)aniline was arrived at in an isolated yield of 90%. Subsequently, a series of diorganoyl dichalcogenides (S, Se) were reacted with (hetero)arenes reaching a scope that revealed excellent results. The varied substituents having different electronic and steric effects tolerate the optimized reaction conditions well. In general, the conditions employed with diselenides indicated better yields when compared to disulfides. The influence of substituted groups on the participation in the formation of the C-Se and C-S connection was also notable, where donor groups demonstrated a better performance than withdrawers. The regioselectivity is seen from the greater coupling occurring in the –para position to anilines and phenols, and –ortho, when in the occurrence of substituents that weaken the ring resonance, or that present a steric effect. In order to demonstrate the effectiveness of the regioselective coupling, a gram-scale reaction was carried out where the proposed idea was validated, due to the good result found. As an outcome of the work, based on literature studies and control experiments, a mechanism was proposed, where there is the formation of the electrophilic species RYCl in situ, indicating an ionic pathway. Thus, it was possible to develop a greener effective synthetic route for the chalcogenation of C(sp2)-H.
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spelling 2023-03-23T15:37:06Z2023-03-23T15:37:06Z2023https://repositorio.ufms.br/handle/123456789/5707In this work, a method for the functionalization of C(sp2)-H from activated arenes under heavy and transition metal-free conditions was developed. The most sustainable approach followed the Principles of Green Chemistry, following topics such as atomic economy, not using chlorinated solvents and formation of secondary products. The first stage of the project was to find ideal reaction conditions, using diphenyl diselenide and N,N dimethylaniline as standard substrates. Thus, the optimized reaction condition consisted of using 0.5 molar equivalent of PhICl2 as oxidizing agent, 1.4 Dioxane as solvent, at room temperature, in open atmosphere, for 30 minutes. Thus, N,N-Dimethyl-4-(phenylselenyl)aniline was arrived at in an isolated yield of 90%. Subsequently, a series of diorganoyl dichalcogenides (S, Se) were reacted with (hetero)arenes reaching a scope that revealed excellent results. The varied substituents having different electronic and steric effects tolerate the optimized reaction conditions well. In general, the conditions employed with diselenides indicated better yields when compared to disulfides. The influence of substituted groups on the participation in the formation of the C-Se and C-S connection was also notable, where donor groups demonstrated a better performance than withdrawers. The regioselectivity is seen from the greater coupling occurring in the –para position to anilines and phenols, and –ortho, when in the occurrence of substituents that weaken the ring resonance, or that present a steric effect. In order to demonstrate the effectiveness of the regioselective coupling, a gram-scale reaction was carried out where the proposed idea was validated, due to the good result found. As an outcome of the work, based on literature studies and control experiments, a mechanism was proposed, where there is the formation of the electrophilic species RYCl in situ, indicating an ionic pathway. Thus, it was possible to develop a greener effective synthetic route for the chalcogenation of C(sp2)-H.Neste trabalho foi desenvolvido um método para a funcionalização do C(sp2)-H de arenos ativados sob condições livre de metais pesados e de transição. A abordagem mais sustentável seguiu os Princípios de Química Verde, seguindo tópicos como economia atômica, o não uso de solventes clorados e formação de produtos secindários. A primeira etapa da pesquisa foi encontrar condições ideais de reação, empregando o disseleneto de difenila e a N,N dimetilanilina como substratos padrão. Dessa forma, a condição reacional otimizada consistiu na utilização de 0,5 equivalente molar de PhICl2 como agente oxidante, 1,4 Dioxano como solvente, a uma temperatura ambiente, em atmosfera aberta, por tempo de 30 minutos. Com isso, chegou-se a N,N-Dimetil-4-(fenilselenil)anilina com um rendimento isolado de 90%. Posteriormente, foram reagidos uma séria de dicalcogenetos de diorganoíla (S, Se) com (hetero)arenos chegando a um escopo que revelou excelentes resultados. Os variados substituintes contendo diferentes efeitos eletrônicos e estéricos toleram bem as condições reacionais otimizadas. Em geral, as condições empregadas com disselenetos indicaram rendimentos melhores quando comparadas com os dissulfetos. Também foi notável a influência dos grupos substituídos na participação da formação da ligação C-Se e C-S, onde grupos doadores demonstraram uma melhor atuação do que os retiradores. A regiosseletividade é vista a partir do maior acoplamento ocorrido na posição –para às anilinas e fenóis, e –orto, quando na ocorrência de substituintes que enfraquecem a ressonância do anel, ou que apresentem efeito estérico. Com o intuito de demonstrar a eficácia do acoplamento regiosseletivo, foi feita uma reação em escala de grama onde validou-se a ideia proposta, por conta do bom resultado encontrado. Como desfecho do trabalho, a partir de estudos da literatura e experimentos de controle feito, foi proposto um mecanismo, onde o há a formação da espécie eletrofílica RYCl in situ, indicando uma via iônica. Assim, foi possível o desenvolvimento de uma rota sintética eficaz mais verde para a calcogenação do C(sp2)-H.Fundação Universidade Federal de Mato Grosso do SulUFMSBrasilQuímica Verde(hetero)arenos ativadosdicalcogentetos de diorganoílaregiosseletividadecalcogenação da ligação C(sp2 )-H.CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDEinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisJamal Rafique KhanMARTINHO JOSÉ ALVES DE SOUSAinfo:eu-repo/semantics/openAccessporreponame:Repositório Institucional da UFMSinstname:Universidade Federal de Mato Grosso do Sul (UFMS)instacron:UFMSORIGINALDISSERTAÇÕ MESTRADO M.J. final-CORRIGIDA.pdfDISSERTAÇÕ MESTRADO M.J. final-CORRIGIDA.pdfapplication/pdf5684805https://repositorio.ufms.br/bitstream/123456789/5707/-1/DISSERTA%c3%87%c3%95%20MESTRADO%20M.J.%20final-CORRIGIDA.pdf17581686c76284e2f54dfe48d0de5e6cMD5-1123456789/57072023-03-23 11:37:09.741oai:repositorio.ufms.br:123456789/5707Repositório InstitucionalPUBhttps://repositorio.ufms.br/oai/requestri.prograd@ufms.bropendoar:21242023-03-23T15:37:09Repositório Institucional da UFMS - Universidade Federal de Mato Grosso do Sul (UFMS)false
dc.title.pt_BR.fl_str_mv CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
title CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
spellingShingle CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
MARTINHO JOSÉ ALVES DE SOUSA
Química Verde
(hetero)arenos ativados
dicalcogentetos de diorganoíla
regiosseletividade
calcogenação da ligação C(sp2 )-H.
title_short CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
title_full CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
title_fullStr CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
title_full_unstemmed CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
title_sort CALCOGENÇÃO DE ARENOS ATIVADOS POR UMA ROTA SINTÉTICA MAIS VERDE
author MARTINHO JOSÉ ALVES DE SOUSA
author_facet MARTINHO JOSÉ ALVES DE SOUSA
author_role author
dc.contributor.advisor1.fl_str_mv Jamal Rafique Khan
dc.contributor.author.fl_str_mv MARTINHO JOSÉ ALVES DE SOUSA
contributor_str_mv Jamal Rafique Khan
dc.subject.por.fl_str_mv Química Verde
(hetero)arenos ativados
dicalcogentetos de diorganoíla
regiosseletividade
calcogenação da ligação C(sp2 )-H.
topic Química Verde
(hetero)arenos ativados
dicalcogentetos de diorganoíla
regiosseletividade
calcogenação da ligação C(sp2 )-H.
description In this work, a method for the functionalization of C(sp2)-H from activated arenes under heavy and transition metal-free conditions was developed. The most sustainable approach followed the Principles of Green Chemistry, following topics such as atomic economy, not using chlorinated solvents and formation of secondary products. The first stage of the project was to find ideal reaction conditions, using diphenyl diselenide and N,N dimethylaniline as standard substrates. Thus, the optimized reaction condition consisted of using 0.5 molar equivalent of PhICl2 as oxidizing agent, 1.4 Dioxane as solvent, at room temperature, in open atmosphere, for 30 minutes. Thus, N,N-Dimethyl-4-(phenylselenyl)aniline was arrived at in an isolated yield of 90%. Subsequently, a series of diorganoyl dichalcogenides (S, Se) were reacted with (hetero)arenes reaching a scope that revealed excellent results. The varied substituents having different electronic and steric effects tolerate the optimized reaction conditions well. In general, the conditions employed with diselenides indicated better yields when compared to disulfides. The influence of substituted groups on the participation in the formation of the C-Se and C-S connection was also notable, where donor groups demonstrated a better performance than withdrawers. The regioselectivity is seen from the greater coupling occurring in the –para position to anilines and phenols, and –ortho, when in the occurrence of substituents that weaken the ring resonance, or that present a steric effect. In order to demonstrate the effectiveness of the regioselective coupling, a gram-scale reaction was carried out where the proposed idea was validated, due to the good result found. As an outcome of the work, based on literature studies and control experiments, a mechanism was proposed, where there is the formation of the electrophilic species RYCl in situ, indicating an ionic pathway. Thus, it was possible to develop a greener effective synthetic route for the chalcogenation of C(sp2)-H.
publishDate 2023
dc.date.accessioned.fl_str_mv 2023-03-23T15:37:06Z
dc.date.available.fl_str_mv 2023-03-23T15:37:06Z
dc.date.issued.fl_str_mv 2023
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dc.publisher.country.fl_str_mv Brasil
publisher.none.fl_str_mv Fundação Universidade Federal de Mato Grosso do Sul
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFMS
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reponame_str Repositório Institucional da UFMS
collection Repositório Institucional da UFMS
bitstream.url.fl_str_mv https://repositorio.ufms.br/bitstream/123456789/5707/-1/DISSERTA%c3%87%c3%95%20MESTRADO%20M.J.%20final-CORRIGIDA.pdf
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