Abordagens sintéticas para a funcionalização de novas porfirinas
Autor(a) principal: | |
---|---|
Data de Publicação: | 2016 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/8417 |
Resumo: | Herein, we optimized some conditions in the synthesis of a β-octasubstitued porphyrin with electron withdrawing groups (1). This system was used to study the bromination of the meso position aiming at subsequent cross-coupling reactions and meso-functionalization of these porphyrin systems (Scheme 3). The main goal was to obtain porphyrin derivatives with modulations in the UV-visible spectra with potential application as photosensitizers for photodynamic therapy treatments (PDT). We found better conditions for the preparation of the porphyrin 1 changing the formaldehyde precursor from trioxane to dimethoxymethane, and reducing the time of second step in the reaction (oxidation of the porphyrinogen). The yield was increased to 13%. After the optimization of 1, different bromination methodologies were tested in order to obtain the meso-bromoporphyrins 2 or 3; but unsuccessfully. In this perspective, we also proposed the synthesis of β-fused porphyrins with imide moieties (Scheme 4), being the functionalized pyrrole 8 the starting material. Porphyrins 9 and 11 might be alternatives for the preparation of new substituted derivatives via cross-coupling reactions, leading to compounds with different photophysical properties. The synthesis of porphyrin 9 was not succeeded by the approaches adopted here, showing only complex mixtures or total degradation of 8. Furthermore, experiments for the formation of dipyrrolmethane 10 were made without any success, precluding the construction of the porphyrin 11. Certain intermediates of interest could be isolated with relative success, and future explorations will be considered. |
id |
SCAR_76004f7fccb342ed1fcf92c99d1bad47 |
---|---|
oai_identifier_str |
oai:repositorio.ufscar.br:ufscar/8417 |
network_acronym_str |
SCAR |
network_name_str |
Repositório Institucional da UFSCAR |
repository_id_str |
4322 |
spelling |
Barona Castaño, Juan CamiloThiago de Oliveira, Kleberhttp://lattes.cnpq.br/3759761373942891http://lattes.cnpq.br/196901463385980613be22ae-7f9a-4aa8-ab9d-fac42bbee33b2017-01-16T17:35:49Z2017-01-16T17:35:49Z2016-09-30BARONA CASTAÑO, Juan Camilo. Abordagens sintéticas para a funcionalização de novas porfirinas. 2016. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8417.https://repositorio.ufscar.br/handle/ufscar/8417Herein, we optimized some conditions in the synthesis of a β-octasubstitued porphyrin with electron withdrawing groups (1). This system was used to study the bromination of the meso position aiming at subsequent cross-coupling reactions and meso-functionalization of these porphyrin systems (Scheme 3). The main goal was to obtain porphyrin derivatives with modulations in the UV-visible spectra with potential application as photosensitizers for photodynamic therapy treatments (PDT). We found better conditions for the preparation of the porphyrin 1 changing the formaldehyde precursor from trioxane to dimethoxymethane, and reducing the time of second step in the reaction (oxidation of the porphyrinogen). The yield was increased to 13%. After the optimization of 1, different bromination methodologies were tested in order to obtain the meso-bromoporphyrins 2 or 3; but unsuccessfully. In this perspective, we also proposed the synthesis of β-fused porphyrins with imide moieties (Scheme 4), being the functionalized pyrrole 8 the starting material. Porphyrins 9 and 11 might be alternatives for the preparation of new substituted derivatives via cross-coupling reactions, leading to compounds with different photophysical properties. The synthesis of porphyrin 9 was not succeeded by the approaches adopted here, showing only complex mixtures or total degradation of 8. Furthermore, experiments for the formation of dipyrrolmethane 10 were made without any success, precluding the construction of the porphyrin 11. Certain intermediates of interest could be isolated with relative success, and future explorations will be considered.Neste trabalho foram otimizadas algumas condições de síntese de uma porfirina β-octasubstituída com grupos retiradores de elétrons (1). Em seguida, estudos sobre bromações nas posições meso deste sistema foram realizados objetivando posteriores reações de acoplamento cruzado e meso-funcionalizações destes sistemas porfirínicos (Esquema 1). O objetivo fundamental foi obter derivados porfirínicos com modulações no espectro de UV-visível e posteriores aplicações como fotossensibilizadores em tratamentos por terapia fotodinâmica (PDT). Encontramos melhores condições reacionais para a formação da porfirina 1 mudando o precursor do formaldeído para dimetoximetano e diminuindo o tempo da segunda etapa de reação (oxidação do porfirinogênio). O rendimento obtido neste trabalho foi de 13%. Após a preparação da porfirina 1 iniciamos os testes reacionais visando a meso-bromação e assim, foram testadas várias metodologias, entretanto, em nenhuma das tentativas foi possível obter os compostos desejados 2 ou 3. Ainda neste contexto, propusemos a síntese de porfirinas β-fundidas com unidades imida (Esquema 2), partindo-se do pirrol contendo este grupo funcional. As porfirinas 9 e 11 poderiam ser submetidas à reações de acoplamento similares às anteriores, permitindo a preparação de novos derivados substituídos e, então, a compostos com diferentes propriedades fotofísicas a ser estudadas. A síntese da porfirina 9 não pôde ser realizada pelas abordagens adotadas, mostrando apenas misturas complexas ou degradação total de 8. Ainda, testes de formação do dipirrolometano 10 foram realizados sem sucesso, impossibilitando então, a construção da porfirina 11. Alguns intermediários de interesse puderam ser isolados com relativo sucesso deixando algumas possibilidades de exploração futuras de alguns resultados aqui obtidos.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarPorfirinasMeso-bromaçõesDioxopirroloporfirinasAnéis fundidosDeslocamentos batocrômicosCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICAAbordagens sintéticas para a funcionalização de novas porfirinasinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisOnline600600bf21d211-1b2d-4683-aa21-2ba8d114d937info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissJCBC.pdfDissJCBC.pdfapplication/pdf5997390https://repositorio.ufscar.br/bitstream/ufscar/8417/1/DissJCBC.pdf80e19d348ed8c7141a681d299fed21d7MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/8417/2/license.txtae0398b6f8b235e40ad82cba6c50031dMD52TEXTDissJCBC.pdf.txtDissJCBC.pdf.txtExtracted texttext/plain151605https://repositorio.ufscar.br/bitstream/ufscar/8417/3/DissJCBC.pdf.txtafe94ab578fcef8828531284f4012f10MD53THUMBNAILDissJCBC.pdf.jpgDissJCBC.pdf.jpgIM Thumbnailimage/jpeg9367https://repositorio.ufscar.br/bitstream/ufscar/8417/4/DissJCBC.pdf.jpg66caf63cbb25629be8d7a699b9fd4b5cMD54ufscar/84172023-09-18 18:31:04.585oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:04Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Abordagens sintéticas para a funcionalização de novas porfirinas |
title |
Abordagens sintéticas para a funcionalização de novas porfirinas |
spellingShingle |
Abordagens sintéticas para a funcionalização de novas porfirinas Barona Castaño, Juan Camilo Porfirinas Meso-bromações Dioxopirroloporfirinas Anéis fundidos Deslocamentos batocrômicos CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
title_short |
Abordagens sintéticas para a funcionalização de novas porfirinas |
title_full |
Abordagens sintéticas para a funcionalização de novas porfirinas |
title_fullStr |
Abordagens sintéticas para a funcionalização de novas porfirinas |
title_full_unstemmed |
Abordagens sintéticas para a funcionalização de novas porfirinas |
title_sort |
Abordagens sintéticas para a funcionalização de novas porfirinas |
author |
Barona Castaño, Juan Camilo |
author_facet |
Barona Castaño, Juan Camilo |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/1969014633859806 |
dc.contributor.author.fl_str_mv |
Barona Castaño, Juan Camilo |
dc.contributor.advisor1.fl_str_mv |
Thiago de Oliveira, Kleber |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3759761373942891 |
dc.contributor.authorID.fl_str_mv |
13be22ae-7f9a-4aa8-ab9d-fac42bbee33b |
contributor_str_mv |
Thiago de Oliveira, Kleber |
dc.subject.por.fl_str_mv |
Porfirinas Meso-bromações Dioxopirroloporfirinas Anéis fundidos Deslocamentos batocrômicos |
topic |
Porfirinas Meso-bromações Dioxopirroloporfirinas Anéis fundidos Deslocamentos batocrômicos CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
description |
Herein, we optimized some conditions in the synthesis of a β-octasubstitued porphyrin with electron withdrawing groups (1). This system was used to study the bromination of the meso position aiming at subsequent cross-coupling reactions and meso-functionalization of these porphyrin systems (Scheme 3). The main goal was to obtain porphyrin derivatives with modulations in the UV-visible spectra with potential application as photosensitizers for photodynamic therapy treatments (PDT). We found better conditions for the preparation of the porphyrin 1 changing the formaldehyde precursor from trioxane to dimethoxymethane, and reducing the time of second step in the reaction (oxidation of the porphyrinogen). The yield was increased to 13%. After the optimization of 1, different bromination methodologies were tested in order to obtain the meso-bromoporphyrins 2 or 3; but unsuccessfully. In this perspective, we also proposed the synthesis of β-fused porphyrins with imide moieties (Scheme 4), being the functionalized pyrrole 8 the starting material. Porphyrins 9 and 11 might be alternatives for the preparation of new substituted derivatives via cross-coupling reactions, leading to compounds with different photophysical properties. The synthesis of porphyrin 9 was not succeeded by the approaches adopted here, showing only complex mixtures or total degradation of 8. Furthermore, experiments for the formation of dipyrrolmethane 10 were made without any success, precluding the construction of the porphyrin 11. Certain intermediates of interest could be isolated with relative success, and future explorations will be considered. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-09-30 |
dc.date.accessioned.fl_str_mv |
2017-01-16T17:35:49Z |
dc.date.available.fl_str_mv |
2017-01-16T17:35:49Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
BARONA CASTAÑO, Juan Camilo. Abordagens sintéticas para a funcionalização de novas porfirinas. 2016. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8417. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/8417 |
identifier_str_mv |
BARONA CASTAÑO, Juan Camilo. Abordagens sintéticas para a funcionalização de novas porfirinas. 2016. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8417. |
url |
https://repositorio.ufscar.br/handle/ufscar/8417 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.confidence.fl_str_mv |
600 600 |
dc.relation.authority.fl_str_mv |
bf21d211-1b2d-4683-aa21-2ba8d114d937 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química - PPGQ |
dc.publisher.initials.fl_str_mv |
UFSCar |
publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFSCAR instname:Universidade Federal de São Carlos (UFSCAR) instacron:UFSCAR |
instname_str |
Universidade Federal de São Carlos (UFSCAR) |
instacron_str |
UFSCAR |
institution |
UFSCAR |
reponame_str |
Repositório Institucional da UFSCAR |
collection |
Repositório Institucional da UFSCAR |
bitstream.url.fl_str_mv |
https://repositorio.ufscar.br/bitstream/ufscar/8417/1/DissJCBC.pdf https://repositorio.ufscar.br/bitstream/ufscar/8417/2/license.txt https://repositorio.ufscar.br/bitstream/ufscar/8417/3/DissJCBC.pdf.txt https://repositorio.ufscar.br/bitstream/ufscar/8417/4/DissJCBC.pdf.jpg |
bitstream.checksum.fl_str_mv |
80e19d348ed8c7141a681d299fed21d7 ae0398b6f8b235e40ad82cba6c50031d afe94ab578fcef8828531284f4012f10 66caf63cbb25629be8d7a699b9fd4b5c |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR) |
repository.mail.fl_str_mv |
|
_version_ |
1802136317922902016 |