Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis
Autor(a) principal: | |
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Data de Publicação: | 2015 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4275 |
Resumo: | This thesis reports the synthesis of various series of trifluoromethyl substituted nitrogenated heterocycles, such as pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles, exploiting the synthetic versatility of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in reactions with nitrogenated nucleophiles. In this way, synthesis of a novel series of 4-amino-3-trifluoromethyl-1H-N-substituted pyrroles was performed through two reaction steps. In the first stage is an addition reaction of primary or secondary amine in the 4-position of 5-bromo-1,1,1-trifluoro-4-methoxy-3-penten-2-one furnishing 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-one. The second stage is a nucleophilic substitution of the bromine by a primary amine followed by an intramolecular cyclocondensation reaction resulting in the formation of pyrroles with yields from 50 to 98%. Through the reaction of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one with sodium azide, 5-azido-1,1,1-trifluoro-4-methoxypent-3-en-2-one was obtained. This compound was subjected to cycloaddition reaction [3 + 2] with terminal alkynes, allowing the synthesis of a novel series of 1,1,1-trifluoro-4-methoxy-5-(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)-pent-3-en-2-one (I) in good yields (74-90%). Through this reaction a wide range of bi-heterocycle compounds was obtained. For example, the reaction of compound I with 2-methylisothiourea sulfate gave a series of 4-(1H-1,2,3-triazol-1-yl)-methyl-6-trifluoromethyl pyrimidine (72-79%). In a second step, the SCH3 group of these pyrimidines was oxidized to SO2CH3 and subsequently substituted by primary and secondary amines to give a series of 2-aminopyrimidines derivatives in yields of 70-93%. Furthermore, the reaction with N1-substituted 2-methylisothiourea sulphates furnished two products: a 4-pyrimidinone and 1,4-dihydropyrimidine derivatives, depending on the reaction conditions employed. From the reaction of compound I with hydrazines and hydrazides a series of 4-[(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)methyl]-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazole, in yields of 77-90%, was obtained. The products obtained in this study were characterized by 1H- and 13C- NMR, mass spectrometry, high resolution mass spectrometry, elemental analysis, and X-ray diffraction. Keywords: 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one, 5-bromo-4-enaminoketone, 4-amino-3-trifluoromethyl-1H-pyrroles N-substituted, 1,2,3-triazole, pyrimidine, pyrazolines, bi-heterocycles. |
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2017-05-152017-05-152015-10-30AQUINO, Estefania da Costa. Application of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in the synthesis of pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles. 2015. 278 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015.http://repositorio.ufsm.br/handle/1/4275This thesis reports the synthesis of various series of trifluoromethyl substituted nitrogenated heterocycles, such as pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles, exploiting the synthetic versatility of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in reactions with nitrogenated nucleophiles. In this way, synthesis of a novel series of 4-amino-3-trifluoromethyl-1H-N-substituted pyrroles was performed through two reaction steps. In the first stage is an addition reaction of primary or secondary amine in the 4-position of 5-bromo-1,1,1-trifluoro-4-methoxy-3-penten-2-one furnishing 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-one. The second stage is a nucleophilic substitution of the bromine by a primary amine followed by an intramolecular cyclocondensation reaction resulting in the formation of pyrroles with yields from 50 to 98%. Through the reaction of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one with sodium azide, 5-azido-1,1,1-trifluoro-4-methoxypent-3-en-2-one was obtained. This compound was subjected to cycloaddition reaction [3 + 2] with terminal alkynes, allowing the synthesis of a novel series of 1,1,1-trifluoro-4-methoxy-5-(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)-pent-3-en-2-one (I) in good yields (74-90%). Through this reaction a wide range of bi-heterocycle compounds was obtained. For example, the reaction of compound I with 2-methylisothiourea sulfate gave a series of 4-(1H-1,2,3-triazol-1-yl)-methyl-6-trifluoromethyl pyrimidine (72-79%). In a second step, the SCH3 group of these pyrimidines was oxidized to SO2CH3 and subsequently substituted by primary and secondary amines to give a series of 2-aminopyrimidines derivatives in yields of 70-93%. Furthermore, the reaction with N1-substituted 2-methylisothiourea sulphates furnished two products: a 4-pyrimidinone and 1,4-dihydropyrimidine derivatives, depending on the reaction conditions employed. From the reaction of compound I with hydrazines and hydrazides a series of 4-[(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)methyl]-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazole, in yields of 77-90%, was obtained. The products obtained in this study were characterized by 1H- and 13C- NMR, mass spectrometry, high resolution mass spectrometry, elemental analysis, and X-ray diffraction. Keywords: 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one, 5-bromo-4-enaminoketone, 4-amino-3-trifluoromethyl-1H-pyrroles N-substituted, 1,2,3-triazole, pyrimidine, pyrazolines, bi-heterocycles.Esta tese apresenta a síntese de várias séries de heterociclos nitrogenados trifluormetil substituidos, tais como pirróis, pirazóis, pirimidinas e 1,2,3-triazóis, explorando-se a versatilidade sintética de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona em reações com nucleófilos nitrogenados. Dessa forma, a síntese de uma série inédita de 4-amino-3-trifluormetil-1H-pirróis N-substituídos foi realizada através de duas etapas reacionais. Na primeira etapa ocorre uma reação de adição de amina primária ou secundária na posição-4 da 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona para a formação de 4-amino-5-bromo-1,1,1-trifluorpent-3-en-2-ona. Na segunda etapa ocorre a substituição nucleofílica do bromo por uma amina primária e consequente ciclocondensação intramolecular para a formação dos pirróis com rendimentos entre 50 a 98%. Através da reação da 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona com azida de sódio, obteve-se a 5-azido-1,1,1-trifluor-4-metoxipent-3-en-2-ona, a qual, pela reação de cicloadição [3+2] com alcinos terminais possibilitou a síntese de uma série inédita de 1,1,1-trifluor-4-metóxi-5-(4-alquil/aril-1H-1,2,3-triazol-1-il)-pent-3-en-2-ona (I), com bons rendimentos (74-90%). Por intermédio destes compostos foi obtida uma vasta gama de bi-heterociclos. Por exemplo, a reação do composto I com sulfato de 2-metilisotioureias possibilitou a obtenção da série de 4-(1H-1,2,3-triazol-1-il)metil-6-trifluormetil pirimidinas (72-79%). Em uma segunda etapa, o grupamento SCH3 destas pirimidinas foi oxidado a SO2CH3 e, posteriormente substituído por aminas primárias e secundárias, obtendo-se, assim, uma série de 2-aminopirimidinas derivadas com rendimentos de 70-93%. Além disso, a reação com os sulfatos de 2-metilisotioureia N1-substituídos levou a obtenção de dois produtos: uma 4-pirimidinona e uma 1,4-diidropirimidina, dependendo da condição reacional empregada. A partir da reação do composto I com hidrazinas e hidrazidas proporcionou a obtenção de uma série de 4-[(4-alquil/aril-1H-1,2,3-triazol-1-il)metil]-5-hidróxi-5-trifluormetil-4,5-diidro-1H-pirazol com rendimentos de 77-90%. Os produtos obtidos neste trabalho foram caracterizados por Ressonância Magnética Nuclear de Hidrogênio e Carbono-13, Espectrometria de Massas, Espectrometria de Massas de Alta Resolução, Análise Elementar e Difratometria de Raio-X.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímica5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona5-bromo-4-enaminocetona4-amino-3-trifluormetil-1H-pirróis N-substituídos1,2,3-triazolPirimidinaPirazolinasBi-heterociclos5-bromo-1,1,1-trifluor-4-methoxipent-3-en-2-one5-bromo-4-enaminoketone4-amino-3-trifluormethil-1H-pyrroles N-substitutedPyrimidinePyrazolinesBi-heterocyclesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóisApplication of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in the synthesis of pyrroles, pyrazoles, pyrimidines and 1,2,3-triazolesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9Frizzo, Clarissa Piccininhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4757171J0Fantinel, Leonardohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9Mostardeiro, Marco Aureliohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785681E6http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4276542T2Aquino, Estefania da Costa100600000000400300300300300300233dc1de-ab03-4f57-9b85-e40dc01a2d4f25499672-5f06-46f7-b231-41f22614e868bf4338e5-e87c-4326-93b7-60f8f505f466079f4612-cd36-4354-af6f-25f7736dccd21ec253ee-25dd-4b17-801e-c4bf7312a9d8info:eu-repo/semantics/openAccessreponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALAQUINO, ESTEFANIA DA COSTA.pdfapplication/pdf15317436http://repositorio.ufsm.br/bitstream/1/4275/1/AQUINO%2c%20ESTEFANIA%20DA%20COSTA.pdf2618b87c388bdfbbffd2cdccfcdfb430MD51TEXTAQUINO, ESTEFANIA DA COSTA.pdf.txtAQUINO, ESTEFANIA DA COSTA.pdf.txtExtracted texttext/plain339400http://repositorio.ufsm.br/bitstream/1/4275/2/AQUINO%2c%20ESTEFANIA%20DA%20COSTA.pdf.txt47f87b6ad129e1021f2dc0d6255eeb37MD52THUMBNAILAQUINO, ESTEFANIA DA COSTA.pdf.jpgAQUINO, ESTEFANIA DA COSTA.pdf.jpgIM Thumbnailimage/jpeg5340http://repositorio.ufsm.br/bitstream/1/4275/3/AQUINO%2c%20ESTEFANIA%20DA%20COSTA.pdf.jpgc9b2a3c027eae7196622e05c159fa9f9MD531/42752017-07-26 23:18:53.843oai:repositorio.ufsm.br:1/4275Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132017-07-27T02:18:53Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
dc.title.alternative.eng.fl_str_mv |
Application of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in the synthesis of pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles |
title |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
spellingShingle |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis Aquino, Estefania da Costa 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona 5-bromo-4-enaminocetona 4-amino-3-trifluormetil-1H-pirróis N-substituídos 1,2,3-triazol Pirimidina Pirazolinas Bi-heterociclos 5-bromo-1,1,1-trifluor-4-methoxipent-3-en-2-one 5-bromo-4-enaminoketone 4-amino-3-trifluormethil-1H-pyrroles N-substituted Pyrimidine Pyrazolines Bi-heterocycles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
title_full |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
title_fullStr |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
title_full_unstemmed |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
title_sort |
Aplicação de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona na síntese de pirróis, pirazóis, pirimidinas e 1,2,3-triazóis |
author |
Aquino, Estefania da Costa |
author_facet |
Aquino, Estefania da Costa |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zanatta, Nilo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9 |
dc.contributor.referee1.fl_str_mv |
Frizzo, Clarissa Piccinin |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4757171J0 |
dc.contributor.referee2.fl_str_mv |
Fantinel, Leonardo |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9 |
dc.contributor.referee3.fl_str_mv |
Mostardeiro, Marco Aurelio |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785681E6 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4276542T2 |
dc.contributor.author.fl_str_mv |
Aquino, Estefania da Costa |
contributor_str_mv |
Zanatta, Nilo Frizzo, Clarissa Piccinin Fantinel, Leonardo Mostardeiro, Marco Aurelio |
dc.subject.por.fl_str_mv |
5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona 5-bromo-4-enaminocetona 4-amino-3-trifluormetil-1H-pirróis N-substituídos 1,2,3-triazol Pirimidina Pirazolinas Bi-heterociclos |
topic |
5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona 5-bromo-4-enaminocetona 4-amino-3-trifluormetil-1H-pirróis N-substituídos 1,2,3-triazol Pirimidina Pirazolinas Bi-heterociclos 5-bromo-1,1,1-trifluor-4-methoxipent-3-en-2-one 5-bromo-4-enaminoketone 4-amino-3-trifluormethil-1H-pyrroles N-substituted Pyrimidine Pyrazolines Bi-heterocycles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
5-bromo-1,1,1-trifluor-4-methoxipent-3-en-2-one 5-bromo-4-enaminoketone 4-amino-3-trifluormethil-1H-pyrroles N-substituted Pyrimidine Pyrazolines Bi-heterocycles |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This thesis reports the synthesis of various series of trifluoromethyl substituted nitrogenated heterocycles, such as pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles, exploiting the synthetic versatility of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in reactions with nitrogenated nucleophiles. In this way, synthesis of a novel series of 4-amino-3-trifluoromethyl-1H-N-substituted pyrroles was performed through two reaction steps. In the first stage is an addition reaction of primary or secondary amine in the 4-position of 5-bromo-1,1,1-trifluoro-4-methoxy-3-penten-2-one furnishing 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-one. The second stage is a nucleophilic substitution of the bromine by a primary amine followed by an intramolecular cyclocondensation reaction resulting in the formation of pyrroles with yields from 50 to 98%. Through the reaction of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one with sodium azide, 5-azido-1,1,1-trifluoro-4-methoxypent-3-en-2-one was obtained. This compound was subjected to cycloaddition reaction [3 + 2] with terminal alkynes, allowing the synthesis of a novel series of 1,1,1-trifluoro-4-methoxy-5-(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)-pent-3-en-2-one (I) in good yields (74-90%). Through this reaction a wide range of bi-heterocycle compounds was obtained. For example, the reaction of compound I with 2-methylisothiourea sulfate gave a series of 4-(1H-1,2,3-triazol-1-yl)-methyl-6-trifluoromethyl pyrimidine (72-79%). In a second step, the SCH3 group of these pyrimidines was oxidized to SO2CH3 and subsequently substituted by primary and secondary amines to give a series of 2-aminopyrimidines derivatives in yields of 70-93%. Furthermore, the reaction with N1-substituted 2-methylisothiourea sulphates furnished two products: a 4-pyrimidinone and 1,4-dihydropyrimidine derivatives, depending on the reaction conditions employed. From the reaction of compound I with hydrazines and hydrazides a series of 4-[(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)methyl]-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazole, in yields of 77-90%, was obtained. The products obtained in this study were characterized by 1H- and 13C- NMR, mass spectrometry, high resolution mass spectrometry, elemental analysis, and X-ray diffraction. Keywords: 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one, 5-bromo-4-enaminoketone, 4-amino-3-trifluoromethyl-1H-pyrroles N-substituted, 1,2,3-triazole, pyrimidine, pyrazolines, bi-heterocycles. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-10-30 |
dc.date.accessioned.fl_str_mv |
2017-05-15 |
dc.date.available.fl_str_mv |
2017-05-15 |
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.citation.fl_str_mv |
AQUINO, Estefania da Costa. Application of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in the synthesis of pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles. 2015. 278 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4275 |
identifier_str_mv |
AQUINO, Estefania da Costa. Application of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in the synthesis of pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles. 2015. 278 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
url |
http://repositorio.ufsm.br/handle/1/4275 |
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Universidade Federal de Santa Maria |
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