Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações
Ano de defesa: | 2012 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
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/1/4234 |
Resumo: | This work describes firstly the synthesis of a new series of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2H-chromen-5(6H)-ones (4) (thirty-four examples) through the methodology of multicomponent reactions involving 1,3-ciclohexadione (1), six aryl aldehydes (2) and six 4-alkoxy-4-alkyl(aryl/heteroaryl)1,1,1-trifluoro-3-alquen-2-ones (3) in the presence of triethylamine (30 mol%) in ethanol, with yields of 15-75%. In a subsequent step, were carried out derivatization reactions of trifluoromethyl substituted chromenones since their structures have several reactive sites possible to chemical modification, ie a hemi-acetal function at C2, endo and exocyclic carbonyl, C3 and C5, respectively, and an olefinic double bond conjugaste between C8a and C4a. The chemical derivatizations in chromenones (4) were initiated by partial oxidative aromatization involving iodine and alcohol solvent reaction by using conventional methods and heating via microwave irradiation. These procedures led to a series of 3-acyl-2-hydroxy-4-aryl-5-alkoxy-2-(trifluoromethyl)chromans (eleven examples) in 50-89%yield. Subsequently, reduction reactions of 2-hydroxy-2H-chromenones (4) and chromenes (5) using NaBH4 in ethanol as solvent allowed to obtain of 3-acyl-8a-hydroxy-4-aryl-2-(trifluoromethyl)-octaidrochromen-5-ones (8) (nine examples) and 4-phenyl-2-(trifluoromethyl)-2-hydroxy-3-(1-hydroxyethyl)-5-methoxychroman (9) in 25-63% and 83% yield, respectively. Finally, rearrangement reactions between chromenone ring (4) and hydrazine monohydrate resulted in a new series of 2-[(3(5)-trifluormethyl-5(3)-alkyl/aryl-1H-pyrazole-4-il)-aryl]-3-hydroxyciclohex-2-en-1-one (10) (six examples) to yield 63-90%. An example of the series 10 was subjected to reactions of partial oxidative aromatization and N-alkylation, where aryl = phenyl, and 4-MeOC6H4 and alkyl= Me. The partial aromatization reaction, in the presence of iodine/methanol, conducted to formation of 4-(2,6-dimethoxyphenyl-4-methoxyphenyl)phenylmethyl-5(3)-methyl-3(5)-trifluoromethyl-1H-pyrazole (11) in 72% yield. The N-alkylation reaction of 11 employing benzyl chloride, NaH in DMF at room temperature led to the regioselective (isomer 1,5) and allowed the isolation of 2-[(1-benzyl-5-trifluoromethyl-3-methyl-1H-pyrazole-4-yl)phenylmethyl]-3-hydroxyciclohexen-2-en-1-one (12) with 69% yield. The compounds were characterized by 1H and 13C {1H}, 19F, e 2D HSQC NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography (LC-ESI). Their purity was determined by CHN Elemental Analysis and High-resolution Mass Spectrometry (HRMS). |
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2017-05-182017-05-182012-08-20NAVARINI, Jussara. Synthesis of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2h-chromen-5(6h)-ones via multicomponent reactions and derivatizations. 2012. 269 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012.http://repositorio.ufsm.br/handle/1/4234This work describes firstly the synthesis of a new series of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2H-chromen-5(6H)-ones (4) (thirty-four examples) through the methodology of multicomponent reactions involving 1,3-ciclohexadione (1), six aryl aldehydes (2) and six 4-alkoxy-4-alkyl(aryl/heteroaryl)1,1,1-trifluoro-3-alquen-2-ones (3) in the presence of triethylamine (30 mol%) in ethanol, with yields of 15-75%. In a subsequent step, were carried out derivatization reactions of trifluoromethyl substituted chromenones since their structures have several reactive sites possible to chemical modification, ie a hemi-acetal function at C2, endo and exocyclic carbonyl, C3 and C5, respectively, and an olefinic double bond conjugaste between C8a and C4a. The chemical derivatizations in chromenones (4) were initiated by partial oxidative aromatization involving iodine and alcohol solvent reaction by using conventional methods and heating via microwave irradiation. These procedures led to a series of 3-acyl-2-hydroxy-4-aryl-5-alkoxy-2-(trifluoromethyl)chromans (eleven examples) in 50-89%yield. Subsequently, reduction reactions of 2-hydroxy-2H-chromenones (4) and chromenes (5) using NaBH4 in ethanol as solvent allowed to obtain of 3-acyl-8a-hydroxy-4-aryl-2-(trifluoromethyl)-octaidrochromen-5-ones (8) (nine examples) and 4-phenyl-2-(trifluoromethyl)-2-hydroxy-3-(1-hydroxyethyl)-5-methoxychroman (9) in 25-63% and 83% yield, respectively. Finally, rearrangement reactions between chromenone ring (4) and hydrazine monohydrate resulted in a new series of 2-[(3(5)-trifluormethyl-5(3)-alkyl/aryl-1H-pyrazole-4-il)-aryl]-3-hydroxyciclohex-2-en-1-one (10) (six examples) to yield 63-90%. An example of the series 10 was subjected to reactions of partial oxidative aromatization and N-alkylation, where aryl = phenyl, and 4-MeOC6H4 and alkyl= Me. The partial aromatization reaction, in the presence of iodine/methanol, conducted to formation of 4-(2,6-dimethoxyphenyl-4-methoxyphenyl)phenylmethyl-5(3)-methyl-3(5)-trifluoromethyl-1H-pyrazole (11) in 72% yield. The N-alkylation reaction of 11 employing benzyl chloride, NaH in DMF at room temperature led to the regioselective (isomer 1,5) and allowed the isolation of 2-[(1-benzyl-5-trifluoromethyl-3-methyl-1H-pyrazole-4-yl)phenylmethyl]-3-hydroxyciclohexen-2-en-1-one (12) with 69% yield. The compounds were characterized by 1H and 13C {1H}, 19F, e 2D HSQC NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography (LC-ESI). Their purity was determined by CHN Elemental Analysis and High-resolution Mass Spectrometry (HRMS).O presente trabalho descreve, inicialmente, a síntese de uma nova série de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2H-cromen-5(6H)-onas (4) (34 exemplos), através da metodologia de Reações Multicomponentes (RMCs) envolvendo 1,3-cicloexadiona (1), seis aril aldeídos (2) e seis 4-alcóxi-4-alquil(aril/heteroaril)-1,1,1-triflúor-3-alquen-2-onas (3), na presença de trietilamina (25 mol%) em etanol, com rendimentos de 15 a 75%. Numa etapa posterior, realizaram-se reações de derivatização de cromenonas trifluormetil substituídas (4), visto que suas estruturas possuem vários sítios reativos passíveis de modificações químicas, ou seja, uma função hemi-acetal, carbonilas endo e exocíclica e uma dupla olefínica conjugada entre C4a e C8a. As derivatizações químicas nas cromenonas (4) foram iniciadas pela aromatização oxidativa parcial envolvendo 4 em meio reacional iodo/álcool, utilizando métodos de aquecimento convencional e via irradiação por micro-ondas. Estes procedimentos conduziram a uma série de 3-acil-5-alcóxi-4-aril-2-(trifluormetil)-2-hidróxicromanos (onze exemplos) com rendimento de 50 a 89%. Subsequentemente, reações de redução de 2-hidróxi-2H-cromenonas (4) e cromanos (5) empregando NaBH4 em etanol como solvente permitiram a obtenção de 3-acil-4-aril-2-(trifluormetil)-8a-hidroxioctaidrocromen-5-onas (8) (9 exemplos) e 4-fenil-2-(trifluormetil)-2-hidróxi-3-(1-hidroxietil)-5-metoxicromano (9aa) com rendimentos de 25 a 63% e 83%, respectivamente. Finalmente, reações de rearranjo anelar entre cromenonas (4) e hidrazina mono hidratada, resultou em uma nova série de 2-[3(5)-(alquil/aril)-5(3)-trifluormetil-1H-pirazol-4-il)arilmetil]-3-hidroxicicloex-2-en-1-ona (10) (seis exemplos) com rendimentos de 63 a 90 %. Um exemplar da série 10 foi submetido a reações de aromatização oxidativa parcial e de N-alquilação, onde Arila = Fenila e 4-MeOC6H4 e Alquila = Me. A reação de aromatização parcial, realizada na presença de iodo/metanol, conduziu à formação de 3(5)-trifluorometil-5(3)-metil-4-[(2,6-dimetoxifenil)-(4-metoxifenil)metil]-1H-pirazol (11) em 72 % de rendimento. A reação de N-alquilação em 10, empregando cloreto de benzila, NaH em DMF à tempertura ambiente levou regioseletivamente ao isômero 1,5 e possibilitou o isolamento de 2-[(1-benzil-5-trifluormetil-3-metil-1H-pirazol-4-il)fenilmetil]-3-hidroxicicloexen-2-en-1-ona (12) com 69 % de rendimento. Os compostos foram caracterizados por Espectroscopia de RMN de 1H,13C{1H},19F, e 2D HSQC, Espectroscopia de Infravermelho, Cromatografia Gasosa Acoplada à Espectrometria de Massas (CG-EM), Cromatografia Líquida (CL-IES-), Difração de Raios-X e sua pureza determinada via Análise Elementar CHN e Espectrometria de Massas de Alta Resolução (HRMS).Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaCetonas trifluormetilCromononasReações multicomponentesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizaçõesSynthesis of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2h-chromen-5(6h)-ones via multicomponent reactions and derivatizationsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Merlo, Aloir Antoniohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784263J5Siqueira, Geonir Machadohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774H9Morel, Ademir Fariashttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8Zanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4717476U2Navarini, Jussara10060000000040030030030030030030006c852ad-d805-43c3-99d6-93a6a86f507cb2f5a0e3-a336-4863-940b-4874569e988dfa2e7141-9b4f-43d6-a7af-6718960f91a739dc23ab-ef8b-429d-9c37-d1efcde74a4c93fa7550-c825-4f7a-a899-13bde347653cdb72aa79-2ac0-4a18-90a9-823ea140938ainfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALNAVARINI, JUSSARA.pdfapplication/pdf14725040http://repositorio.ufsm.br/bitstream/1/4234/1/NAVARINI%2c%20JUSSARA.pdff986d829a3b67c23124da96a1268271cMD51TEXTNAVARINI, JUSSARA.pdf.txtNAVARINI, JUSSARA.pdf.txtExtracted texttext/plain357401http://repositorio.ufsm.br/bitstream/1/4234/2/NAVARINI%2c%20JUSSARA.pdf.txt9c5e403bd5282d0c85cea9da94486471MD52THUMBNAILNAVARINI, JUSSARA.pdf.jpgNAVARINI, JUSSARA.pdf.jpgIM Thumbnailimage/jpeg5334http://repositorio.ufsm.br/bitstream/1/4234/3/NAVARINI%2c%20JUSSARA.pdf.jpg6f6988b06c45242b5a8d3d34e8df7a7fMD531/42342017-07-25 11:05:09.364oai:repositorio.ufsm.br:1/4234Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:09Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
dc.title.alternative.eng.fl_str_mv |
Synthesis of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2h-chromen-5(6h)-ones via multicomponent reactions and derivatizations |
title |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
spellingShingle |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações Navarini, Jussara Cetonas trifluormetil Cromononas Reações multicomponentes CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
title_full |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
title_fullStr |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
title_full_unstemmed |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
title_sort |
Síntese de 3-acil-4-aril-2-(trifluormetil)-2-hidróxi-3,4,7,8-tetraidro-2h-cromen-5(6h)-onas via reações multicomponentes e derivatizações |
author |
Navarini, Jussara |
author_facet |
Navarini, Jussara |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.referee1.fl_str_mv |
Merlo, Aloir Antonio |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784263J5 |
dc.contributor.referee2.fl_str_mv |
Siqueira, Geonir Machado |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774H9 |
dc.contributor.referee3.fl_str_mv |
Morel, Ademir Farias |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8 |
dc.contributor.referee4.fl_str_mv |
Zanatta, Nilo |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4717476U2 |
dc.contributor.author.fl_str_mv |
Navarini, Jussara |
contributor_str_mv |
Bonacorso, Helio Gauze Merlo, Aloir Antonio Siqueira, Geonir Machado Morel, Ademir Farias Zanatta, Nilo |
dc.subject.por.fl_str_mv |
Cetonas trifluormetil Cromononas Reações multicomponentes |
topic |
Cetonas trifluormetil Cromononas Reações multicomponentes CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes firstly the synthesis of a new series of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2H-chromen-5(6H)-ones (4) (thirty-four examples) through the methodology of multicomponent reactions involving 1,3-ciclohexadione (1), six aryl aldehydes (2) and six 4-alkoxy-4-alkyl(aryl/heteroaryl)1,1,1-trifluoro-3-alquen-2-ones (3) in the presence of triethylamine (30 mol%) in ethanol, with yields of 15-75%. In a subsequent step, were carried out derivatization reactions of trifluoromethyl substituted chromenones since their structures have several reactive sites possible to chemical modification, ie a hemi-acetal function at C2, endo and exocyclic carbonyl, C3 and C5, respectively, and an olefinic double bond conjugaste between C8a and C4a. The chemical derivatizations in chromenones (4) were initiated by partial oxidative aromatization involving iodine and alcohol solvent reaction by using conventional methods and heating via microwave irradiation. These procedures led to a series of 3-acyl-2-hydroxy-4-aryl-5-alkoxy-2-(trifluoromethyl)chromans (eleven examples) in 50-89%yield. Subsequently, reduction reactions of 2-hydroxy-2H-chromenones (4) and chromenes (5) using NaBH4 in ethanol as solvent allowed to obtain of 3-acyl-8a-hydroxy-4-aryl-2-(trifluoromethyl)-octaidrochromen-5-ones (8) (nine examples) and 4-phenyl-2-(trifluoromethyl)-2-hydroxy-3-(1-hydroxyethyl)-5-methoxychroman (9) in 25-63% and 83% yield, respectively. Finally, rearrangement reactions between chromenone ring (4) and hydrazine monohydrate resulted in a new series of 2-[(3(5)-trifluormethyl-5(3)-alkyl/aryl-1H-pyrazole-4-il)-aryl]-3-hydroxyciclohex-2-en-1-one (10) (six examples) to yield 63-90%. An example of the series 10 was subjected to reactions of partial oxidative aromatization and N-alkylation, where aryl = phenyl, and 4-MeOC6H4 and alkyl= Me. The partial aromatization reaction, in the presence of iodine/methanol, conducted to formation of 4-(2,6-dimethoxyphenyl-4-methoxyphenyl)phenylmethyl-5(3)-methyl-3(5)-trifluoromethyl-1H-pyrazole (11) in 72% yield. The N-alkylation reaction of 11 employing benzyl chloride, NaH in DMF at room temperature led to the regioselective (isomer 1,5) and allowed the isolation of 2-[(1-benzyl-5-trifluoromethyl-3-methyl-1H-pyrazole-4-yl)phenylmethyl]-3-hydroxyciclohexen-2-en-1-one (12) with 69% yield. The compounds were characterized by 1H and 13C {1H}, 19F, e 2D HSQC NMR Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GC-MS), Liquid Chromatography (LC-ESI). Their purity was determined by CHN Elemental Analysis and High-resolution Mass Spectrometry (HRMS). |
publishDate |
2012 |
dc.date.issued.fl_str_mv |
2012-08-20 |
dc.date.accessioned.fl_str_mv |
2017-05-18 |
dc.date.available.fl_str_mv |
2017-05-18 |
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 |
NAVARINI, Jussara. Synthesis of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2h-chromen-5(6h)-ones via multicomponent reactions and derivatizations. 2012. 269 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4234 |
identifier_str_mv |
NAVARINI, Jussara. Synthesis of 3-acyl-4-aryl-2-(trifluoromethyl)-2-hydroxy-3,4,7,8-tetrahydro-2h-chromen-5(6h)-ones via multicomponent reactions and derivatizations. 2012. 269 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
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http://repositorio.ufsm.br/handle/1/4234 |
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