Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados
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/1/22959 |
Resumo: | In the present work, it was carried out a study of the reactivity of 5-bromo-1,1,1-trifluoro- 4-methoxypent-3-en-2-one (5-bromo enone) towards primary aliphatic amines, which furnishes as products two novel series of N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles (pyrroles) and 5-(amino(1-amino-5-(trifluoromethyl)-1H-pyrrol-3-yl)amino)-4-(amino)-1,1,1- trifluoropent-3-en-2-ones (enamine pyrroles). The pyrroles were obtained through the reaction of 5-bromo enone with excess of the primary aliphatic amine in refluxing acetonitrile for 2 hours (13 examples, yields 30 – 90%), while the enamine pyrroles were obtained using a molar ratio of 1.0:1.5 of 5-bromo enone/primary amine, respectively, in a solventless-sealed tube procedure at 120 °C for 15 min (7 examples, yields 7 – 78%). In a second part of the work, derivatization reactions were carried out in order to promote further functionalization of the N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles, obtained in the previous step, with different alkylating agents, such as methyl iodide, allyl bromide and propargyl bromide using acetone as solvent, under reflux conditions for 2 hours. Through the N-alkylation reactions, 11 tertiary aliphatic amines bearing three different substituents (one being the pyrrole core), were obtained in yields up to 90%. Following this, the propargylic pyrroles were employed in the synthesis of a series of 1,2,3-triazoles, through the [3+2] cycloaddition reaction using benzylic azides, and, 7 examples with yields 72 – 91% were obtained. In addition, the synthesis of a tri-heterocyclic scaffold containing the pyrrole, 1,2,3- triazole and pyrimidine nuclei, was carried out using the propargylic pyrrole and 4- (azidomethyl)-2-(methylthio)-6-(trifluoromethyl)pyrimidine, at 80% yield, under the same reaction conditions. |
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Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivadosSynthesis of 1-alkyl-4-aminoalkyl-2-trifluormethyl-1H-pyrroids and 1,2,3-derived triazoles5-bromo-1,1,1-trifluor-4-metoxi-3-penten-2-onaTrifluormetil pirróisHeterociclos1,2,3-triazóis4-amino-2-trifluormetil-1H-pirróis N-substituídosAminas terciárias5-bromo-1,1,1-trifluoro-4-methoxy-pent-3-en-2-one5-bromo-4-enaminoketoneN-substituted 4-amino-3-trifluoromethyl-1H-pyrrolesTertiary aminesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAIn the present work, it was carried out a study of the reactivity of 5-bromo-1,1,1-trifluoro- 4-methoxypent-3-en-2-one (5-bromo enone) towards primary aliphatic amines, which furnishes as products two novel series of N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles (pyrroles) and 5-(amino(1-amino-5-(trifluoromethyl)-1H-pyrrol-3-yl)amino)-4-(amino)-1,1,1- trifluoropent-3-en-2-ones (enamine pyrroles). The pyrroles were obtained through the reaction of 5-bromo enone with excess of the primary aliphatic amine in refluxing acetonitrile for 2 hours (13 examples, yields 30 – 90%), while the enamine pyrroles were obtained using a molar ratio of 1.0:1.5 of 5-bromo enone/primary amine, respectively, in a solventless-sealed tube procedure at 120 °C for 15 min (7 examples, yields 7 – 78%). In a second part of the work, derivatization reactions were carried out in order to promote further functionalization of the N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles, obtained in the previous step, with different alkylating agents, such as methyl iodide, allyl bromide and propargyl bromide using acetone as solvent, under reflux conditions for 2 hours. Through the N-alkylation reactions, 11 tertiary aliphatic amines bearing three different substituents (one being the pyrrole core), were obtained in yields up to 90%. Following this, the propargylic pyrroles were employed in the synthesis of a series of 1,2,3-triazoles, through the [3+2] cycloaddition reaction using benzylic azides, and, 7 examples with yields 72 – 91% were obtained. In addition, the synthesis of a tri-heterocyclic scaffold containing the pyrrole, 1,2,3- triazole and pyrimidine nuclei, was carried out using the propargylic pyrrole and 4- (azidomethyl)-2-(methylthio)-6-(trifluoromethyl)pyrimidine, at 80% yield, under the same reaction conditions.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESConselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqNo presente trabalho realizou-se um estudo da reatividade de 5-bromo-1,1,1-trifluor-4- metoxipent-3-en-2-ona (5-bromo enona) frente à aminas primárias alifáticas, fornecendo como produtos duas séries inéditas de 4-amino-2-trifluormetil-1H-pirróis N-substituídos (pirróis) e 5- {amino[1-amino-5-(trifluormetil)-1H-pirrol-3-il]amino}-4-(amino)-1,1,1-trifluorpent-3-en-2- onas (enamino pirróis). Os pirróis foram obtidos através da reação da 5-bromo enona com excesso de aminas primárias em acetonitrila em refluxo por 2 horas (13 exemplos, com rendimentos entre 30 e 90%), enquanto que, os enamino pirróis foram obtidos utilizando uma relação molar de 1,0:1,5 da 5-bromo enona/amina primária, respectivamente, com a reação conduzida em tubo selado, sem solvente, a uma temperatura de 120 °C por 15 minutos (7 exemplos, com rendimentos entre 7 e 78%). Sequencialmente, foram realizadas reações de derivatização para promover uma maior funcionalização dos 4-amino-2-trifluormetil-1H-pirróis N-substituídos, obtidos na etapa anterior, com diferentes agentes alquilantes, como iodeto de metila, brometo de alila e brometo de propargila, utilizando acetona como solvente, sob refluxo, por duas horas. Através das reações de N-alquilação, foram obtidas 11 aminas terciárias alifáticas contendo os três substituintes diferentes (sendo um deles o núcleo pirrólico), em rendimentos de até 90%. Posteriormente, os pirróis propargílicos foram empregados para a síntese de uma série de 1,2,3- triazóis, pela reação de cicloadição [3+2] usando azidas benzílicas e, 7 exemplos com rendimentos entre 72 e 91% foram obtidos. Além disso, foi realizada a síntese de um derivado tri-heterocíclico contendo os núcleos pirrol, 1,2,3-triazol e pirimidina conjugados, com rendimento de 80%, através da reação do pirrol propargílico com com a 4-(azidometil)-2- (metiltio)-6-(trifluormetil)pirimidina, sob as mesmas condições reacionais.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasZanatta, Nilohttp://lattes.cnpq.br/0719465062354576Schneider, Paulo HenriqueAmaral, Simone SchneiderDalcol, Ionara IrionBonacorso, Helio GauzeZachow, Lucimara Lais2021-11-24T16:58:09Z2021-11-24T16:58:09Z2020-12-04info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/22959porAttribution-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:UFSM2022-07-01T13:04:43Zoai:repositorio.ufsm.br:1/22959Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-07-01T13:04:43Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados Synthesis of 1-alkyl-4-aminoalkyl-2-trifluormethyl-1H-pyrroids and 1,2,3-derived triazoles |
title |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
spellingShingle |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados Zachow, Lucimara Lais 5-bromo-1,1,1-trifluor-4-metoxi-3-penten-2-ona Trifluormetil pirróis Heterociclos 1,2,3-triazóis 4-amino-2-trifluormetil-1H-pirróis N-substituídos Aminas terciárias 5-bromo-1,1,1-trifluoro-4-methoxy-pent-3-en-2-one 5-bromo-4-enaminoketone N-substituted 4-amino-3-trifluoromethyl-1H-pyrroles Tertiary amines CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
title_full |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
title_fullStr |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
title_full_unstemmed |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
title_sort |
Síntese de 1-alquil-4-aminoalquil-2-trifluormetil-1H-pirróis e 1,2,3- triazóis derivados |
author |
Zachow, Lucimara Lais |
author_facet |
Zachow, Lucimara Lais |
author_role |
author |
dc.contributor.none.fl_str_mv |
Zanatta, Nilo http://lattes.cnpq.br/0719465062354576 Schneider, Paulo Henrique Amaral, Simone Schneider Dalcol, Ionara Irion Bonacorso, Helio Gauze |
dc.contributor.author.fl_str_mv |
Zachow, Lucimara Lais |
dc.subject.por.fl_str_mv |
5-bromo-1,1,1-trifluor-4-metoxi-3-penten-2-ona Trifluormetil pirróis Heterociclos 1,2,3-triazóis 4-amino-2-trifluormetil-1H-pirróis N-substituídos Aminas terciárias 5-bromo-1,1,1-trifluoro-4-methoxy-pent-3-en-2-one 5-bromo-4-enaminoketone N-substituted 4-amino-3-trifluoromethyl-1H-pyrroles Tertiary amines CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
5-bromo-1,1,1-trifluor-4-metoxi-3-penten-2-ona Trifluormetil pirróis Heterociclos 1,2,3-triazóis 4-amino-2-trifluormetil-1H-pirróis N-substituídos Aminas terciárias 5-bromo-1,1,1-trifluoro-4-methoxy-pent-3-en-2-one 5-bromo-4-enaminoketone N-substituted 4-amino-3-trifluoromethyl-1H-pyrroles Tertiary amines CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In the present work, it was carried out a study of the reactivity of 5-bromo-1,1,1-trifluoro- 4-methoxypent-3-en-2-one (5-bromo enone) towards primary aliphatic amines, which furnishes as products two novel series of N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles (pyrroles) and 5-(amino(1-amino-5-(trifluoromethyl)-1H-pyrrol-3-yl)amino)-4-(amino)-1,1,1- trifluoropent-3-en-2-ones (enamine pyrroles). The pyrroles were obtained through the reaction of 5-bromo enone with excess of the primary aliphatic amine in refluxing acetonitrile for 2 hours (13 examples, yields 30 – 90%), while the enamine pyrroles were obtained using a molar ratio of 1.0:1.5 of 5-bromo enone/primary amine, respectively, in a solventless-sealed tube procedure at 120 °C for 15 min (7 examples, yields 7 – 78%). In a second part of the work, derivatization reactions were carried out in order to promote further functionalization of the N-substituted 4-amino-2-trifluoromethyl-1H-pyrroles, obtained in the previous step, with different alkylating agents, such as methyl iodide, allyl bromide and propargyl bromide using acetone as solvent, under reflux conditions for 2 hours. Through the N-alkylation reactions, 11 tertiary aliphatic amines bearing three different substituents (one being the pyrrole core), were obtained in yields up to 90%. Following this, the propargylic pyrroles were employed in the synthesis of a series of 1,2,3-triazoles, through the [3+2] cycloaddition reaction using benzylic azides, and, 7 examples with yields 72 – 91% were obtained. In addition, the synthesis of a tri-heterocyclic scaffold containing the pyrrole, 1,2,3- triazole and pyrimidine nuclei, was carried out using the propargylic pyrrole and 4- (azidomethyl)-2-(methylthio)-6-(trifluoromethyl)pyrimidine, at 80% yield, under the same reaction conditions. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-12-04 2021-11-24T16:58:09Z 2021-11-24T16:58:09Z |
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/1/22959 |
url |
http://repositorio.ufsm.br/handle/1/22959 |
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 |
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1805922173965041664 |