Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados
Autor(a) principal: | |
---|---|
Data de Publicação: | 2009 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4180 |
Resumo: | Several methods for the regioselective synthesis of trifluoromethylated heterocycles from 4-alcoxy-1,1,1-trifluoro-3-alken-2-ones and hydrazones are described. In the first part of this work, a series of (E)-2-[N -benzyl(1-phenylethyl)idenehydrazino]-4-trifluoromethyl-pyrimidines were obtained in a convergent manner from the cyclocondensation reaction between Nguanidinobenzylimines and 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones in excellent yields (68-99%). Most reactions were highly diastereoselective and the benzyliminic bound presented preferably the E configuration which was determined by single-crystal X-ray analysis of two diastereoisomeric pure benzylidenepyrimidines derivatives. Afterwards, the synthetic versatility of these pyrimidines was demonstrated through the synthesis of 2-(N -enzylhydrazino)-4-trifluoromethyl-pyrimidines and 3-aryl-7-trifluoromethyl[1,2,4]triazolo[4,3- a]pyrimidines. The synthesis of benzylhydrazinopyrimidines were achieved from the selective reduction of the benzyliminic moiety of the benzylidenepyrimidines employing NaBH3CN as reduction agent in an acidic media (pH 3-5). Yields were in the 33-74% range. The 1,2,4-triazolo[4,3-a]pyrimidines were isolated after oxidative heterocyclisation promoted by a copper II catalyst. Those reactions proceeded under mild conditions (DMF, 1.5h, 50-90 °C), were highly chemoselective and yields from 33 and 70%. In the second part of this work, the synthesis of 1-phenyl-3-trifluoromethyl-1H-pyrazoles from 4-alkoxyvinyl trifluoromethyl ketones and phenylhydrazine hydrazones are reported. Those heterocyclisations were highly selective, presented good yields (40-93%) and furnished a series of new enaminones as reaction intermediates. Those reactions that furnished a mixture isomeric pyrazoles, the major isomer was easily isolated through column chromatography. |
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2017-05-252017-05-252009-07-31AMARAL, Simone Schneider. Heterocyclization of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones with hydrazones: selective methods for the synthesis of trifluoromethylated heterocycles. 2009. 288 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2009.http://repositorio.ufsm.br/handle/1/4180Several methods for the regioselective synthesis of trifluoromethylated heterocycles from 4-alcoxy-1,1,1-trifluoro-3-alken-2-ones and hydrazones are described. In the first part of this work, a series of (E)-2-[N -benzyl(1-phenylethyl)idenehydrazino]-4-trifluoromethyl-pyrimidines were obtained in a convergent manner from the cyclocondensation reaction between Nguanidinobenzylimines and 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones in excellent yields (68-99%). Most reactions were highly diastereoselective and the benzyliminic bound presented preferably the E configuration which was determined by single-crystal X-ray analysis of two diastereoisomeric pure benzylidenepyrimidines derivatives. Afterwards, the synthetic versatility of these pyrimidines was demonstrated through the synthesis of 2-(N -enzylhydrazino)-4-trifluoromethyl-pyrimidines and 3-aryl-7-trifluoromethyl[1,2,4]triazolo[4,3- a]pyrimidines. The synthesis of benzylhydrazinopyrimidines were achieved from the selective reduction of the benzyliminic moiety of the benzylidenepyrimidines employing NaBH3CN as reduction agent in an acidic media (pH 3-5). Yields were in the 33-74% range. The 1,2,4-triazolo[4,3-a]pyrimidines were isolated after oxidative heterocyclisation promoted by a copper II catalyst. Those reactions proceeded under mild conditions (DMF, 1.5h, 50-90 °C), were highly chemoselective and yields from 33 and 70%. In the second part of this work, the synthesis of 1-phenyl-3-trifluoromethyl-1H-pyrazoles from 4-alkoxyvinyl trifluoromethyl ketones and phenylhydrazine hydrazones are reported. Those heterocyclisations were highly selective, presented good yields (40-93%) and furnished a series of new enaminones as reaction intermediates. Those reactions that furnished a mixture isomeric pyrazoles, the major isomer was easily isolated through column chromatography.Esta tese descreve diversas metodologias para a síntese regiosseletiva de heterociclos trifluormetilados a partir de 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas. Na primeira parte do trabalho, uma série de (E)-2-[N -benzil(1-feniletil) idenohidrazino]-4-trifluormetilpirimidinas inéditas foi obtida de maneira convergente a partir da ciclocondensação entre N-guanidinobenziliminas e 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas em ótimos rendimentos (68-99%). A maior parte das reações foram altamente diastereosseletivas e a configuração E da ligação benzilimínica foi considerada preferencial após análise por difração de raios X dos monocristais de duas benzilidenopirimidinas diastereoisomericamente puras. Posteriormente, a versatilidade sintética desses heterociclos foi demonstrada através da obtenção das 2-(N - benzilhidrazino)-4-trifluormetilpirimidinas e das 3-aril-7- trifluormetil[1,2,4]triazolo[4,3-a]pirimidinas. As benzilhidrazinopirimidinas foram obtidas a partir da redução seletiva do grupo benzilimínico das benzilidenopirimidinas empregando NaBH3CN como agente redutor em meio ácido (pH 3-5) com rendimentos que variaram entre 33-74%. As 1,2,4-triazolo[4,3-a]pirimidinas, por sua vez, foram sintetizadas a partir do mesmo precursor através de heterociclização oxidativa mediada por cloreto de cobre II. Essas reações empregaram condições reacionais relativamente brandas (DMF, 1,5h, 50-90 °C), foram altamente quimiosseletivas e apresentaram rendimentos entre 33-70%. Na segunda parte deste estudo, a síntese de 1-fenil-3-trifluormetil-1Hpirazóis a partir das 4-alcoxivinil-trifluormetil cetonas e das hidrazonas derivadas da fenilhidrazina foi descrita. Essas heterociclizações foram altamente seletivas, apresentaram bons rendimentos (40-93%) e ainda possibilitaram a obtenção de uma série de enaminonas inéditas como intermediários reacionais. Nas reações em que foram obtidas misturas de pirazóis isoméricos, os isômeros majoritários desejados foram isolados por cromatografia em coluna.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaEnonasHidrazonasRegioquímicaHeterociclos trifluormetiladosEnonesHydrazonesRegiochemistryTrifluoromethylated heterocyclesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAHeterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetiladosHeterocyclization of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones with hydrazones: selective methods for the synthesis of trifluoromethylated heterocyclesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZanatta, Nilohttp://lattes.cnpq.br/0719465062354576Schneider, Paulo Henriquehttp://lattes.cnpq.br/9953361052942820Merlo, Aloir Antoniohttp://lattes.cnpq.br/7385210507816401Bonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Morel, Ademir Fariashttp://lattes.cnpq.br/3554994385525333http://lattes.cnpq.br/3630924725753644Amaral, Simone Schneider100600000000400300300300300300300233dc1de-ab03-4f57-9b85-e40dc01a2d4fcbc76e21-a5e2-4afa-8d9d-8192d63ec28c45261c66-d648-4472-9675-c315a838b768ba299257-7593-404d-a7ba-31a61c67fdec8c234091-0259-4703-a717-5d611977d5f1c3c96b69-2f73-4fc2-8eaa-efa435793c3finfo:eu-repo/semantics/openAccessreponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALAMARAL, SIMONE SCHEIDER.pdfapplication/pdf14061043http://repositorio.ufsm.br/bitstream/1/4180/1/AMARAL%2c%20SIMONE%20SCHEIDER.pdf237a5dd3885858fc697b72f16d086611MD51TEXTAMARAL, SIMONE SCHEIDER.pdf.txtAMARAL, SIMONE SCHEIDER.pdf.txtExtracted texttext/plain265968http://repositorio.ufsm.br/bitstream/1/4180/2/AMARAL%2c%20SIMONE%20SCHEIDER.pdf.txta2a2640945bcec60f8fc11797c77b106MD52THUMBNAILAMARAL, SIMONE SCHEIDER.pdf.jpgAMARAL, SIMONE SCHEIDER.pdf.jpgIM Thumbnailimage/jpeg4566http://repositorio.ufsm.br/bitstream/1/4180/3/AMARAL%2c%20SIMONE%20SCHEIDER.pdf.jpg191d72c976733f9b09c2d62eb3849df4MD531/41802023-05-08 09:10:48.812oai:repositorio.ufsm.br:1/4180Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132023-05-08T12:10:48Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
dc.title.alternative.eng.fl_str_mv |
Heterocyclization of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones with hydrazones: selective methods for the synthesis of trifluoromethylated heterocycles |
title |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
spellingShingle |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados Amaral, Simone Schneider Enonas Hidrazonas Regioquímica Heterociclos trifluormetilados Enones Hydrazones Regiochemistry Trifluoromethylated heterocycles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
title_full |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
title_fullStr |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
title_full_unstemmed |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
title_sort |
Heterociclização entre 4-alcóxi-1,1,1-triflúor-3-alquen-2-onas e hidrazonas: metodologias seletivas para a obtenção de heterociclos trifluormetilados |
author |
Amaral, Simone Schneider |
author_facet |
Amaral, Simone Schneider |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zanatta, Nilo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0719465062354576 |
dc.contributor.referee1.fl_str_mv |
Schneider, Paulo Henrique |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/9953361052942820 |
dc.contributor.referee2.fl_str_mv |
Merlo, Aloir Antonio |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/7385210507816401 |
dc.contributor.referee3.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/7275608974248322 |
dc.contributor.referee4.fl_str_mv |
Morel, Ademir Farias |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/3554994385525333 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/3630924725753644 |
dc.contributor.author.fl_str_mv |
Amaral, Simone Schneider |
contributor_str_mv |
Zanatta, Nilo Schneider, Paulo Henrique Merlo, Aloir Antonio Bonacorso, Helio Gauze Morel, Ademir Farias |
dc.subject.por.fl_str_mv |
Enonas Hidrazonas Regioquímica Heterociclos trifluormetilados |
topic |
Enonas Hidrazonas Regioquímica Heterociclos trifluormetilados Enones Hydrazones Regiochemistry Trifluoromethylated heterocycles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Enones Hydrazones Regiochemistry Trifluoromethylated heterocycles |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Several methods for the regioselective synthesis of trifluoromethylated heterocycles from 4-alcoxy-1,1,1-trifluoro-3-alken-2-ones and hydrazones are described. In the first part of this work, a series of (E)-2-[N -benzyl(1-phenylethyl)idenehydrazino]-4-trifluoromethyl-pyrimidines were obtained in a convergent manner from the cyclocondensation reaction between Nguanidinobenzylimines and 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones in excellent yields (68-99%). Most reactions were highly diastereoselective and the benzyliminic bound presented preferably the E configuration which was determined by single-crystal X-ray analysis of two diastereoisomeric pure benzylidenepyrimidines derivatives. Afterwards, the synthetic versatility of these pyrimidines was demonstrated through the synthesis of 2-(N -enzylhydrazino)-4-trifluoromethyl-pyrimidines and 3-aryl-7-trifluoromethyl[1,2,4]triazolo[4,3- a]pyrimidines. The synthesis of benzylhydrazinopyrimidines were achieved from the selective reduction of the benzyliminic moiety of the benzylidenepyrimidines employing NaBH3CN as reduction agent in an acidic media (pH 3-5). Yields were in the 33-74% range. The 1,2,4-triazolo[4,3-a]pyrimidines were isolated after oxidative heterocyclisation promoted by a copper II catalyst. Those reactions proceeded under mild conditions (DMF, 1.5h, 50-90 °C), were highly chemoselective and yields from 33 and 70%. In the second part of this work, the synthesis of 1-phenyl-3-trifluoromethyl-1H-pyrazoles from 4-alkoxyvinyl trifluoromethyl ketones and phenylhydrazine hydrazones are reported. Those heterocyclisations were highly selective, presented good yields (40-93%) and furnished a series of new enaminones as reaction intermediates. Those reactions that furnished a mixture isomeric pyrazoles, the major isomer was easily isolated through column chromatography. |
publishDate |
2009 |
dc.date.issued.fl_str_mv |
2009-07-31 |
dc.date.accessioned.fl_str_mv |
2017-05-25 |
dc.date.available.fl_str_mv |
2017-05-25 |
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info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
AMARAL, Simone Schneider. Heterocyclization of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones with hydrazones: selective methods for the synthesis of trifluoromethylated heterocycles. 2009. 288 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2009. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4180 |
identifier_str_mv |
AMARAL, Simone Schneider. Heterocyclization of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones with hydrazones: selective methods for the synthesis of trifluoromethylated heterocycles. 2009. 288 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2009. |
url |
http://repositorio.ufsm.br/handle/1/4180 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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400 300 300 300 300 300 300 |
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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 |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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