Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis
Ano de defesa: | 2011 |
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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: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/10546 |
Resumo: | This paper presents a new synthetic route for obtain regioselective 5-alkyl(aryl/heteroaryl)-3-trifluoromethyl-1H-1-phenylpyrazoles (3a-e) (50-85% yields) and 5-alkyl(aryl/heteroaryl)-3-carboxialkyl-1H-1-phenylpyrazoles (4a-e) (51-89% yields) via cyclocondensation reactions of the type [3 + 2], using 1,1,1-trifluoro(chloro)-4-alkyl(aryl/heteroaryl)-4-alkoxy-3-alken-2-ones as 1,3-dielectrophile blocks and 1-phenylsemicarbazide as a new 1,2-dinucleophile. Compounds (3a-e, 4a-e) were synthesized by reactions between 4-alkoxy-1,1,1-trifluoro(chloro)-3-alken-2-ones (1a-e, 2a-e) and 1- phenylsemicarbazide in molar ratio 1:1.5, respectively, conducted in methanol as solvent and sulfuric acid as catalyst, at temperature of 60 °C and with a reaction time of 24 hours. The developed synthetic method enables the achievement of the regioselective 1,3-substituted pyrazole as a single product and/or majority in a single step reaction through the hydrolysis of the amide group. Also, the conversion of the trichloromethyl substituent, present in the precursors (2a-e), in a carboxyalkyl group was successful overcome. Finally, two series of 5-(alkyl/aryl)-4-bromo-3-(carboxyl/trifluoromethyl)-1H-1-phenylpyrazoles (7a-c, 8a-c) were obtained starting from the reactions of synthesized pyrazoles (3a-b,3e, 4a-b,4d) with N-bromosuccinimide in N,N-dimethylformamide (DMF) as solvent, in a temperature of 80 °C and with a reaction time of 2 hours (35-82% yields). |
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2017-05-192017-05-192011-05-19CORREA, Michele Stach. Regioselective obtain of 5-alkyl(aryl/heteroaryl)-3-(carboxyl/trifluoromethyl)-1h-1-phenylpyrazoles. 2011. 167 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011.http://repositorio.ufsm.br/handle/1/10546This paper presents a new synthetic route for obtain regioselective 5-alkyl(aryl/heteroaryl)-3-trifluoromethyl-1H-1-phenylpyrazoles (3a-e) (50-85% yields) and 5-alkyl(aryl/heteroaryl)-3-carboxialkyl-1H-1-phenylpyrazoles (4a-e) (51-89% yields) via cyclocondensation reactions of the type [3 + 2], using 1,1,1-trifluoro(chloro)-4-alkyl(aryl/heteroaryl)-4-alkoxy-3-alken-2-ones as 1,3-dielectrophile blocks and 1-phenylsemicarbazide as a new 1,2-dinucleophile. Compounds (3a-e, 4a-e) were synthesized by reactions between 4-alkoxy-1,1,1-trifluoro(chloro)-3-alken-2-ones (1a-e, 2a-e) and 1- phenylsemicarbazide in molar ratio 1:1.5, respectively, conducted in methanol as solvent and sulfuric acid as catalyst, at temperature of 60 °C and with a reaction time of 24 hours. The developed synthetic method enables the achievement of the regioselective 1,3-substituted pyrazole as a single product and/or majority in a single step reaction through the hydrolysis of the amide group. Also, the conversion of the trichloromethyl substituent, present in the precursors (2a-e), in a carboxyalkyl group was successful overcome. Finally, two series of 5-(alkyl/aryl)-4-bromo-3-(carboxyl/trifluoromethyl)-1H-1-phenylpyrazoles (7a-c, 8a-c) were obtained starting from the reactions of synthesized pyrazoles (3a-b,3e, 4a-b,4d) with N-bromosuccinimide in N,N-dimethylformamide (DMF) as solvent, in a temperature of 80 °C and with a reaction time of 2 hours (35-82% yields).Este trabalho apresenta uma nova rota sintética para a obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3-trifluormetil-1H-1-fenilpirazóis (3a-e) (50-85%) e 5-alquil(aril/heteroaril)-3-carboxialquil-1H-1-fenilpirazóis (4a-e) (51-89%) via reações de ciclocondensação do tipo [3 + 2], utilizando 1,1,1-trifluor(cloro)-4-alquil(aril/heteroaril)-4-alcóxi-3-alquen-2-onas e 1-fenilsemicarbazida, a qual é um novo 1,2-dinucleófilo. Os compostos (3a-e, 4a-e) foram sintetizados através de reações entre as 1,1,1-trifluor(cloro)-4-alquil(aril/heteroaril)-4-alcóxi-3-alquen-2-onas (1a-e, 2a-e) e 1-fenilsemicarbazida em relação molar 1:1,5, respectivamente, conduzidas em metanol como solvente e ácido sulfúrico como catalisador, a temperatura de 60 °C e tempo reacional de 24 horas. O método sintético desenvolvido permite a obtenção regiosseletiva do pirazol 1,3-substituído como produto único e/ou majoritário, em uma única etapa reacional, através da hidrólise do grupamento amídico. Além de permitir a conversão do substituinte triclorometila, presente nos precursores (2a-e), em carboxialquil. Finalmente, uma série de 5-(alquil/aril)-4-bromo-3-(carboxil/trifluormetil)-1H-1-fenilpirazóis (7a-c, 8a-c) (35-82%) foi obtida apartir de reações entre os pirazóis sintetizados (3a-b, 3e, 4a-b, 4d) e N-bromosuccinimida em N, N-dimetilformamida como solvente, a temperatura de 80 °C e tempo reacional de 2 horas.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaPirazóisFenilsemicarbazidaDinucleófiloRegiosseletividadeCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAObtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóisRegioselective obtain of 5-alkyl(aryl/heteroaryl)-3-(carboxyl/trifluoromethyl)-1h-1-phenylpyrazolesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Flores, Alex Fabiani Clarohttp://lattes.cnpq.br/1159954352174167Dornelles, Lucianohttp://lattes.cnpq.br/7629319262073140http://lattes.cnpq.br/2872123356659944Correa, Michele Stach10060000000040050030050050006c852ad-d805-43c3-99d6-93a6a86f507cc245bf86-b283-43a7-89ad-74f11f743c764d308e51-3866-4274-9e77-03644c9383df4a671e0c-bfb0-436b-bd8f-ab5645f4229einfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALCORREA, MICHELE STACH.pdfapplication/pdf6131391http://repositorio.ufsm.br/bitstream/1/10546/1/CORREA%2c%20MICHELE%20STACH.pdf372430d524dbbe6d24d3a4a14cc8b657MD51TEXTCORREA, MICHELE STACH.pdf.txtCORREA, MICHELE STACH.pdf.txtExtracted texttext/plain167217http://repositorio.ufsm.br/bitstream/1/10546/2/CORREA%2c%20MICHELE%20STACH.pdf.txt66e6427aea7141ca7ac24169bdc58ef7MD52THUMBNAILCORREA, MICHELE STACH.pdf.jpgCORREA, MICHELE STACH.pdf.jpgIM Thumbnailimage/jpeg6149http://repositorio.ufsm.br/bitstream/1/10546/3/CORREA%2c%20MICHELE%20STACH.pdf.jpgcbb7c1c03034b69c6889a619c1e99547MD531/105462022-08-29 14:35:35.892oai:repositorio.ufsm.br:1/10546Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132022-08-29T17:35:35Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
dc.title.alternative.eng.fl_str_mv |
Regioselective obtain of 5-alkyl(aryl/heteroaryl)-3-(carboxyl/trifluoromethyl)-1h-1-phenylpyrazoles |
title |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
spellingShingle |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis Correa, Michele Stach Química Pirazóis Fenilsemicarbazida Dinucleófilo Regiosseletividade CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
title_full |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
title_fullStr |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
title_full_unstemmed |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
title_sort |
Obtenção regiosseletiva de 5-alquil(aril/heteroaril)-3- (carboxil/trifluormetil)-1h-1-fenilpirazóis |
author |
Correa, Michele Stach |
author_facet |
Correa, Michele Stach |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/7275608974248322 |
dc.contributor.referee1.fl_str_mv |
Flores, Alex Fabiani Claro |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/1159954352174167 |
dc.contributor.referee2.fl_str_mv |
Dornelles, Luciano |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/7629319262073140 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2872123356659944 |
dc.contributor.author.fl_str_mv |
Correa, Michele Stach |
contributor_str_mv |
Bonacorso, Helio Gauze Flores, Alex Fabiani Claro Dornelles, Luciano |
dc.subject.por.fl_str_mv |
Química Pirazóis Fenilsemicarbazida Dinucleófilo Regiosseletividade |
topic |
Química Pirazóis Fenilsemicarbazida Dinucleófilo Regiosseletividade CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This paper presents a new synthetic route for obtain regioselective 5-alkyl(aryl/heteroaryl)-3-trifluoromethyl-1H-1-phenylpyrazoles (3a-e) (50-85% yields) and 5-alkyl(aryl/heteroaryl)-3-carboxialkyl-1H-1-phenylpyrazoles (4a-e) (51-89% yields) via cyclocondensation reactions of the type [3 + 2], using 1,1,1-trifluoro(chloro)-4-alkyl(aryl/heteroaryl)-4-alkoxy-3-alken-2-ones as 1,3-dielectrophile blocks and 1-phenylsemicarbazide as a new 1,2-dinucleophile. Compounds (3a-e, 4a-e) were synthesized by reactions between 4-alkoxy-1,1,1-trifluoro(chloro)-3-alken-2-ones (1a-e, 2a-e) and 1- phenylsemicarbazide in molar ratio 1:1.5, respectively, conducted in methanol as solvent and sulfuric acid as catalyst, at temperature of 60 °C and with a reaction time of 24 hours. The developed synthetic method enables the achievement of the regioselective 1,3-substituted pyrazole as a single product and/or majority in a single step reaction through the hydrolysis of the amide group. Also, the conversion of the trichloromethyl substituent, present in the precursors (2a-e), in a carboxyalkyl group was successful overcome. Finally, two series of 5-(alkyl/aryl)-4-bromo-3-(carboxyl/trifluoromethyl)-1H-1-phenylpyrazoles (7a-c, 8a-c) were obtained starting from the reactions of synthesized pyrazoles (3a-b,3e, 4a-b,4d) with N-bromosuccinimide in N,N-dimethylformamide (DMF) as solvent, in a temperature of 80 °C and with a reaction time of 2 hours (35-82% yields). |
publishDate |
2011 |
dc.date.issued.fl_str_mv |
2011-05-19 |
dc.date.accessioned.fl_str_mv |
2017-05-19 |
dc.date.available.fl_str_mv |
2017-05-19 |
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 |
CORREA, Michele Stach. Regioselective obtain of 5-alkyl(aryl/heteroaryl)-3-(carboxyl/trifluoromethyl)-1h-1-phenylpyrazoles. 2011. 167 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10546 |
identifier_str_mv |
CORREA, Michele Stach. Regioselective obtain of 5-alkyl(aryl/heteroaryl)-3-(carboxyl/trifluoromethyl)-1h-1-phenylpyrazoles. 2011. 167 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011. |
url |
http://repositorio.ufsm.br/handle/1/10546 |
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100600000000 |
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400 500 300 500 500 |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
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BR |
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Química |
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Universidade Federal de Santa Maria |
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