N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas
Ano de defesa: | 2016 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/10628 |
Resumo: | This work presents the synthesis of three new series of nitrogen-heterocycles containing the substituent trifluoromethyl, exploiting the synthetic versatility and regioselectivity of 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones and 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones in reactions with compounds containing nucleophilic nitrogen. Two series of 1-(3-alkoxy-5-trifluoromethyl-2,3-dihydrofuran-3-yl)-4,5-alkyl-3-(trifluoromethyl)-1H-pyrazoles were synthesized by the N-functionalization reaction of pyrazoles with 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones, by Michael s nucleophilic addition. In the first step, there is a nucleophilic addition of the pyrazol molecule to the beta position of enones (Cβ), followed by an intramolecular cyclization reaction, where the furan ring is formed by replacement of the bromine atom by the carbonyl oxygen of enone, resulting in thirteen novel compounds with yields between 55-86%. The other compounds series, (E)-4-(amino)-1,1,1-trifluoro-5-(5-methyl-3- (trifluoromethyl)-1H-pyrazol-1-yl)pent-3-en-2-ones, was synthesized by N-alkylation reaction, through a bimolecular nucleophilic substitution (SN2) mechanism, with replament of the bromine atom, at five position (Cγ) of 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones, by the nucleophilic nitrogen of the pyrazoline ring. Seven N-alkylated products were obtained, with yields among 65-85%. In addition, the regioselectivity study of N-functionalized pyrazoles reactions is described, including the evaluation of reaction conditions and how substituents present in the pyrazole structure can influence the product formation, because many different steric and electronic factors. The obtained compounds were characterized by nuclear magnetic resonance 1H and 13C, mass spectrometry, elementary analysis and X-ray diffractometry. |
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2017-05-222017-05-222016-08-19MORAES, Paulo Alexandre de. Regioselective N-alkylation of pyrazoles using 4-alkoxy(amino)-5-bromo-1,1,1-trifluoropent-3-en-2-ones". 2016. 144 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016.http://repositorio.ufsm.br/handle/1/10628This work presents the synthesis of three new series of nitrogen-heterocycles containing the substituent trifluoromethyl, exploiting the synthetic versatility and regioselectivity of 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones and 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones in reactions with compounds containing nucleophilic nitrogen. Two series of 1-(3-alkoxy-5-trifluoromethyl-2,3-dihydrofuran-3-yl)-4,5-alkyl-3-(trifluoromethyl)-1H-pyrazoles were synthesized by the N-functionalization reaction of pyrazoles with 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones, by Michael s nucleophilic addition. In the first step, there is a nucleophilic addition of the pyrazol molecule to the beta position of enones (Cβ), followed by an intramolecular cyclization reaction, where the furan ring is formed by replacement of the bromine atom by the carbonyl oxygen of enone, resulting in thirteen novel compounds with yields between 55-86%. The other compounds series, (E)-4-(amino)-1,1,1-trifluoro-5-(5-methyl-3- (trifluoromethyl)-1H-pyrazol-1-yl)pent-3-en-2-ones, was synthesized by N-alkylation reaction, through a bimolecular nucleophilic substitution (SN2) mechanism, with replament of the bromine atom, at five position (Cγ) of 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones, by the nucleophilic nitrogen of the pyrazoline ring. Seven N-alkylated products were obtained, with yields among 65-85%. In addition, the regioselectivity study of N-functionalized pyrazoles reactions is described, including the evaluation of reaction conditions and how substituents present in the pyrazole structure can influence the product formation, because many different steric and electronic factors. The obtained compounds were characterized by nuclear magnetic resonance 1H and 13C, mass spectrometry, elementary analysis and X-ray diffractometry.A presente dissertação relata a síntese de três séries inéditas de heterociclos nitrogenados trifluormetil substituídos, que exploram a versatilidade sintética e a regiosseletividade das 4-alcóxi-5-bromo-1,1,1-trifluorpent-3-en-2-onas e das 4-amino-5-bromo-1,1,1-trifluorpent-3-en-2-onas, em reações com nucleófilos nitrogenados. As primeiras duas séries dos compostos 1-(3-alcóxi-5-trifluorometil-2,3-diidrofuran-3-il)-4,5-alquil-3-(trifluorometil)-1H-pirazóis, foram sintetizadas através do processo de N-funcionalização de pirazóis, a partir da reação com as 4-alcóxi-5-bromo-1,1,1-trifluorpent-3-en-2-onas, cujo o caminho mecanístico se deu através de uma reação de adição nucleofílica de Michael. Inicialmente, ocorre a adição do pirazol nucleofílico na posição beta (Cβ) das enonas bromadas, seguida de uma reação de ciclocondensação intramolecular formando o anel furano, com a substituição átomo de bromo pelo oxigênio enólico, resultando na formação de treze compostos inéditos, com rendimentos entre 55 e 86%. Outra série de compostos (E)-4-(amino)1,1,1-triflúor-5-(5-metil-3-(trifluormetil)-1H-pirazóis-1-il)pent-3-en-2-onas, foi sintetizada através da reação de N-alquilacão, via substituição nucleofílica bimolecular (SN2), onde o átomo de bromo na posição cinco (Cγ), das 4-amino-5-bromo-1,1,1-trifluorpent-3-en-2-onas, foi substituído pelo nitrogênio nucleofílico do anel pirazolínico, promovendo a formação de sete produtos N-alquilados, com rendimentos que variam entre 65 e 85%. Além disso, um estudo de regiosseletividade das reações N-funcionalizadas de pirazóis está descrito, onde a avaliação das condições reacionais e também de fatores estéricos e eletrônicos dos substituintes presentes nos substratos, foram determinantes para formação do produto formado. Os produtos obtidos neste trabalho foram caracterizados por ressonância magnética nuclear de 1H e 13C, espectrometria de massas de baixa e alta resolução, análise elementar e difratometria de Raio X.application/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaPirazolTrifluormetilFuranoEnonasEnaminonasBromoAdição de MichaelN-alquilacãoPyrazole trifluoromethylFuranEnonesEnaminonesBromineMichael additionN-alkylationCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas Regioselective N-alkylation of pyrazoles using 4-alkoxy(amino)-5-bromo-1,1,1-trifluoropent-3-en-2-ones"info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisZanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9Lüdtke, Diogo Seiberthttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706332Z7Bonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Moraes, Paulo Alexandre de100600000000400500300300500233dc1de-ab03-4f57-9b85-e40dc01a2d4f2dba95c4-e357-4e3f-83e0-fafb12ebf232a2ac0343-9b3c-4004-96b1-41b889220f936112c8ea-0206-4324-bf67-465ff831088finfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALMORAES, PAULO ALEXANDRE DE.pdfapplication/pdf7580725http://repositorio.ufsm.br/bitstream/1/10628/1/MORAES%2c%20PAULO%20ALEXANDRE%20DE.pdf011c8f925b237c53238b06a81d22d05cMD51TEXTMORAES, PAULO ALEXANDRE DE.pdf.txtMORAES, PAULO ALEXANDRE DE.pdf.txtExtracted texttext/plain179417http://repositorio.ufsm.br/bitstream/1/10628/2/MORAES%2c%20PAULO%20ALEXANDRE%20DE.pdf.txtcfe8dd334dcf999634909712379af131MD52THUMBNAILMORAES, PAULO ALEXANDRE DE.pdf.jpgMORAES, PAULO ALEXANDRE DE.pdf.jpgIM Thumbnailimage/jpeg5543http://repositorio.ufsm.br/bitstream/1/10628/3/MORAES%2c%20PAULO%20ALEXANDRE%20DE.pdf.jpg80a97c5082bd2d13c509fcfe19b53afeMD531/106282017-07-25 12:05:13.804oai:repositorio.ufsm.br:1/10628Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T15:05:13Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
dc.title.alternative.eng.fl_str_mv |
Regioselective N-alkylation of pyrazoles using 4-alkoxy(amino)-5-bromo-1,1,1-trifluoropent-3-en-2-ones" |
title |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
spellingShingle |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas Moraes, Paulo Alexandre de Pirazol Trifluormetil Furano Enonas Enaminonas Bromo Adição de Michael N-alquilacão Pyrazole trifluoromethyl Furan Enones Enaminones Bromine Michael addition N-alkylation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
title_full |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
title_fullStr |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
title_full_unstemmed |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
title_sort |
N-alquilação regiosseletiva de pirazóis empregando 4-alcóxi(amino)-5-bromo-1,1,1-trifluorpent-3-en-2-onas |
author |
Moraes, Paulo Alexandre de |
author_facet |
Moraes, Paulo Alexandre de |
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 |
Lüdtke, Diogo Seibert |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706332Z7 |
dc.contributor.referee2.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.author.fl_str_mv |
Moraes, Paulo Alexandre de |
contributor_str_mv |
Zanatta, Nilo Lüdtke, Diogo Seibert Bonacorso, Helio Gauze |
dc.subject.por.fl_str_mv |
Pirazol Trifluormetil Furano Enonas Enaminonas Bromo Adição de Michael N-alquilacão |
topic |
Pirazol Trifluormetil Furano Enonas Enaminonas Bromo Adição de Michael N-alquilacão Pyrazole trifluoromethyl Furan Enones Enaminones Bromine Michael addition N-alkylation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Pyrazole trifluoromethyl Furan Enones Enaminones Bromine Michael addition N-alkylation |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the synthesis of three new series of nitrogen-heterocycles containing the substituent trifluoromethyl, exploiting the synthetic versatility and regioselectivity of 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones and 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones in reactions with compounds containing nucleophilic nitrogen. Two series of 1-(3-alkoxy-5-trifluoromethyl-2,3-dihydrofuran-3-yl)-4,5-alkyl-3-(trifluoromethyl)-1H-pyrazoles were synthesized by the N-functionalization reaction of pyrazoles with 4-alkoxy-5-bromo-1,1,1-trifluorpent-3-en-2-ones, by Michael s nucleophilic addition. In the first step, there is a nucleophilic addition of the pyrazol molecule to the beta position of enones (Cβ), followed by an intramolecular cyclization reaction, where the furan ring is formed by replacement of the bromine atom by the carbonyl oxygen of enone, resulting in thirteen novel compounds with yields between 55-86%. The other compounds series, (E)-4-(amino)-1,1,1-trifluoro-5-(5-methyl-3- (trifluoromethyl)-1H-pyrazol-1-yl)pent-3-en-2-ones, was synthesized by N-alkylation reaction, through a bimolecular nucleophilic substitution (SN2) mechanism, with replament of the bromine atom, at five position (Cγ) of 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-ones, by the nucleophilic nitrogen of the pyrazoline ring. Seven N-alkylated products were obtained, with yields among 65-85%. In addition, the regioselectivity study of N-functionalized pyrazoles reactions is described, including the evaluation of reaction conditions and how substituents present in the pyrazole structure can influence the product formation, because many different steric and electronic factors. The obtained compounds were characterized by nuclear magnetic resonance 1H and 13C, mass spectrometry, elementary analysis and X-ray diffractometry. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-08-19 |
dc.date.accessioned.fl_str_mv |
2017-05-22 |
dc.date.available.fl_str_mv |
2017-05-22 |
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 |
MORAES, Paulo Alexandre de. Regioselective N-alkylation of pyrazoles using 4-alkoxy(amino)-5-bromo-1,1,1-trifluoropent-3-en-2-ones". 2016. 144 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10628 |
identifier_str_mv |
MORAES, Paulo Alexandre de. Regioselective N-alkylation of pyrazoles using 4-alkoxy(amino)-5-bromo-1,1,1-trifluoropent-3-en-2-ones". 2016. 144 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
url |
http://repositorio.ufsm.br/handle/1/10628 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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100600000000 |
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400 500 300 300 500 |
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openAccess |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
dc.publisher.country.fl_str_mv |
BR |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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