Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados
Ano de defesa: | 2013 |
---|---|
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/1/10564 |
Resumo: | This work describes firstly an efficient and regioselective method for the synthesis of a new series of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones from the Kabbe adducts (spiro[chroman-2,1 -cycloalkan]-4-ones). Yields of 38 % to 61 % were obtained when trifluoroacetylation reactions of mixtures of enolethers and/or acetals derived from four spiro ketones (Kabbe adducts) were performed at a temperature of 45 oC and employing anhydrous chloroform as the solvent. Subsequently, when the respective trifluoroacetylated Kabbe adducts reacted with phenylhydrazine and methylhydrazine at a 1:1 molar ratio in refluxing ethanol for 24 hours, a new series of seven examples of a novel spiro-condensed heterocyclic system, namely 1(2)-methyl(phenyl)-3-(trifluoromethyl)-1,4(2,4)-dihydro-spiro(chromen[4,3-c]pyrazole-4,n -cycloalkanes) where cycloalkanes are cyclopentane, cyclohexane and cycloheptane (n = 1) and tetrahydro-2H-pyran (n = 2) were isolated at yields of between 35 % and 51 %. NMR and X-ray diffraction techniques demonstrated clearly that reactions from methylhydrazine and phenylhydrazine were regioselective and allowed to isolate separately the 1,3- and 2,3-trifluoromethylated isomers, respectively. Subsequently, two examples of new 3-hydroxy-3-(trifluoromethyl)-3,3a-dihydro-4H-spiro(chromen[4,3-c]isoxazole-4,1 -cycloalkanes), derivated from cyclopentanone and cyclopentanone, were obtained from the reaction of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones with hydroxylamine hydrochloride in yields of 42% and 58%, respectively. Finally, the structures of new spiro heterocycles were determined with the aid and simultaneous application of 1H-, 13C{1H}- and 19F-NMR, X-ray monocrystal diffraction, Mass Spectrometry and DFT calculation techniques and their purity were proved by elemental analysis or High Resolution Mass Spectrometry (HRMS). |
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2017-05-152017-05-152013-12-03GARCIA, Fábio Dutra. New Spirochromenyl-Trifluoroethanones from Trifluoroacetylation Reactions of Kabbe Adducts and their Spiro[dihydrochromeno-cycloalcan]pyrazoles and Isoxazoles Derivatives. 2013. 142 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/10564This work describes firstly an efficient and regioselective method for the synthesis of a new series of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones from the Kabbe adducts (spiro[chroman-2,1 -cycloalkan]-4-ones). Yields of 38 % to 61 % were obtained when trifluoroacetylation reactions of mixtures of enolethers and/or acetals derived from four spiro ketones (Kabbe adducts) were performed at a temperature of 45 oC and employing anhydrous chloroform as the solvent. Subsequently, when the respective trifluoroacetylated Kabbe adducts reacted with phenylhydrazine and methylhydrazine at a 1:1 molar ratio in refluxing ethanol for 24 hours, a new series of seven examples of a novel spiro-condensed heterocyclic system, namely 1(2)-methyl(phenyl)-3-(trifluoromethyl)-1,4(2,4)-dihydro-spiro(chromen[4,3-c]pyrazole-4,n -cycloalkanes) where cycloalkanes are cyclopentane, cyclohexane and cycloheptane (n = 1) and tetrahydro-2H-pyran (n = 2) were isolated at yields of between 35 % and 51 %. NMR and X-ray diffraction techniques demonstrated clearly that reactions from methylhydrazine and phenylhydrazine were regioselective and allowed to isolate separately the 1,3- and 2,3-trifluoromethylated isomers, respectively. Subsequently, two examples of new 3-hydroxy-3-(trifluoromethyl)-3,3a-dihydro-4H-spiro(chromen[4,3-c]isoxazole-4,1 -cycloalkanes), derivated from cyclopentanone and cyclopentanone, were obtained from the reaction of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones with hydroxylamine hydrochloride in yields of 42% and 58%, respectively. Finally, the structures of new spiro heterocycles were determined with the aid and simultaneous application of 1H-, 13C{1H}- and 19F-NMR, X-ray monocrystal diffraction, Mass Spectrometry and DFT calculation techniques and their purity were proved by elemental analysis or High Resolution Mass Spectrometry (HRMS).O presente trabalho descreve inicialmente um método eficiente e regiosseletivo para a síntese de uma nova série de 2,2,2-triflúor-1-[4-metóxi-espiro(2H-cromen-2,1 -cicloalcan)-3-il]etanonas a partir de adutos de Kabbe (espiro[croman-2,1 -cicloalcan]-4-onas). Rendimentos de 38% a 61% foram obtidos quando reações de trifluoracetilação de misturas de enoléteres e/ou acetais derivados de quatro espiro cetonas (adutos de Kabbe) foram realizadas a 45 ºC usando clorofórmio anidro como solvente. Subsequentemente, quando os respectivos adutos de Kabbe trifluoracetilados foram reagidos com fenilhidrazina ou metilhidrazina, em relação molar de 1:1, sob refluxo de etanol por 24 horas, uma série de sete exemplares de um novo sistema heterocíclico espiro-condensado, denominado 1(2)-metil(fenil)-3-(trifluormetil)-1,4(2,4)-diidro-espiro(chromen[4,3-c]pirazol-4,n -cicloalcanos) onde os cicloalcanos são ciclopentano, ciclohexano e cicloheptano (n = 1) e tetraidro-2H-pirano (n = 2), foi isolada em rendimentos entre 35 % e 51 %. Técnicas de RMN e de difração de raios-X demonstraram claramente que as reações a partir da metilhidrazina e da fenilhidrazina foram regiosseletivas e permitiram isolar separadamente os isômeros trifluormetilados 1,3 e 2,3, respectivamente. Em sequência, dois exemplares de novas 3-hidróxi-3-(trifluormetil)-3,3a-diidro-4H-espiro(cromen[4,3-c]isoxazol-4,1 -cicloalcanos), derivados da ciclopentanona e ciclohexanona, foram obtidos a partir da reação de 2,2,2-triflúor-1-[4-metóxi-espiro(2H-cromen-2,1 -cicloalcan)-3-il]etanonas com cloridrato de hidroxilamina em rendimentos de 42% e 58%, respectivamente. Finalmente, as estruturas dos novos espiro heterociclos foram determinadas com o auxílio e aplicação simultânea de experimentos de RMN de 1H, 13C{1H}, 19F, difração de raios-X em monocristais, Espectrometria de Massas e cálculos DFT e, a sua pureza comprovada por Análise Elementar ou por Espectrometria de Massas de Alta Resolução (HRMS).Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaPirazóisCompostos espiroIsoxazóisTrifluormetil cetonasReação de KabbePyrazolesSpiro-compoundsIsoxazolesTrifluoromethyl ketonesKabbe reactionCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICANovos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis DerivadosNew Spirochromenyl-Trifluoroethanones from Trifluoroacetylation Reactions of Kabbe Adducts and their Spiro[dihydrochromeno-cycloalcan]pyrazoles and Isoxazoles Derivativesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Dornelles, Lucianohttp://lattes.cnpq.br/7629319262073140Costa, Michelle Budkehttp://lattes.cnpq.br/8752647892614261http://lattes.cnpq.br/6515346350624787Garcia, Fábio Dutra10060000000040050030050030006c852ad-d805-43c3-99d6-93a6a86f507c98d3a25d-c852-4a5a-b35e-4da08a2103d67dfea8f7-fe97-4100-9d09-8f5a40fe2316244ee975-1b0f-4c57-b99d-009b75caf0afinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALGARCIA, FABIO DUTRA.pdfapplication/pdf3357510http://repositorio.ufsm.br/bitstream/1/10564/1/GARCIA%2c%20FABIO%20DUTRA.pdfd7b74c7e5e68adf618b828b0f8604ca5MD51TEXTGARCIA, FABIO DUTRA.pdf.txtGARCIA, FABIO DUTRA.pdf.txtExtracted texttext/plain191013http://repositorio.ufsm.br/bitstream/1/10564/2/GARCIA%2c%20FABIO%20DUTRA.pdf.txt2cd62ccef23c7c5cc5d3d4be776b5a58MD52THUMBNAILGARCIA, FABIO DUTRA.pdf.jpgGARCIA, FABIO DUTRA.pdf.jpgIM Thumbnailimage/jpeg5632http://repositorio.ufsm.br/bitstream/1/10564/3/GARCIA%2c%20FABIO%20DUTRA.pdf.jpg50226eea6476e514d50a031636ee788cMD531/105642022-06-01 11:26:42.048oai:repositorio.ufsm.br:1/10564Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132022-06-01T14:26:42Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
dc.title.alternative.eng.fl_str_mv |
New Spirochromenyl-Trifluoroethanones from Trifluoroacetylation Reactions of Kabbe Adducts and their Spiro[dihydrochromeno-cycloalcan]pyrazoles and Isoxazoles Derivatives |
title |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
spellingShingle |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados Garcia, Fábio Dutra Pirazóis Compostos espiro Isoxazóis Trifluormetil cetonas Reação de Kabbe Pyrazoles Spiro-compounds Isoxazoles Trifluoromethyl ketones Kabbe reaction CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
title_full |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
title_fullStr |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
title_full_unstemmed |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
title_sort |
Novos Espirocromenil-Trifluoretanonas a partir de Reações de Trifluoracetilação de Adutos de Kabbe e seus Espiro[diidrocromeno-cicloalcan]pirazóis e Isoxazóis Derivados |
author |
Garcia, Fábio Dutra |
author_facet |
Garcia, Fábio Dutra |
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 |
Dornelles, Luciano |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/7629319262073140 |
dc.contributor.referee2.fl_str_mv |
Costa, Michelle Budke |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/8752647892614261 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/6515346350624787 |
dc.contributor.author.fl_str_mv |
Garcia, Fábio Dutra |
contributor_str_mv |
Bonacorso, Helio Gauze Dornelles, Luciano Costa, Michelle Budke |
dc.subject.por.fl_str_mv |
Pirazóis Compostos espiro Isoxazóis Trifluormetil cetonas Reação de Kabbe |
topic |
Pirazóis Compostos espiro Isoxazóis Trifluormetil cetonas Reação de Kabbe Pyrazoles Spiro-compounds Isoxazoles Trifluoromethyl ketones Kabbe reaction CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Pyrazoles Spiro-compounds Isoxazoles Trifluoromethyl ketones Kabbe reaction |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes firstly an efficient and regioselective method for the synthesis of a new series of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones from the Kabbe adducts (spiro[chroman-2,1 -cycloalkan]-4-ones). Yields of 38 % to 61 % were obtained when trifluoroacetylation reactions of mixtures of enolethers and/or acetals derived from four spiro ketones (Kabbe adducts) were performed at a temperature of 45 oC and employing anhydrous chloroform as the solvent. Subsequently, when the respective trifluoroacetylated Kabbe adducts reacted with phenylhydrazine and methylhydrazine at a 1:1 molar ratio in refluxing ethanol for 24 hours, a new series of seven examples of a novel spiro-condensed heterocyclic system, namely 1(2)-methyl(phenyl)-3-(trifluoromethyl)-1,4(2,4)-dihydro-spiro(chromen[4,3-c]pyrazole-4,n -cycloalkanes) where cycloalkanes are cyclopentane, cyclohexane and cycloheptane (n = 1) and tetrahydro-2H-pyran (n = 2) were isolated at yields of between 35 % and 51 %. NMR and X-ray diffraction techniques demonstrated clearly that reactions from methylhydrazine and phenylhydrazine were regioselective and allowed to isolate separately the 1,3- and 2,3-trifluoromethylated isomers, respectively. Subsequently, two examples of new 3-hydroxy-3-(trifluoromethyl)-3,3a-dihydro-4H-spiro(chromen[4,3-c]isoxazole-4,1 -cycloalkanes), derivated from cyclopentanone and cyclopentanone, were obtained from the reaction of 2,2,2-trifluoro-1-[4-methoxy-spiro(2H-chromen-2,1 -cycloalkan)-3-yl]ethanones with hydroxylamine hydrochloride in yields of 42% and 58%, respectively. Finally, the structures of new spiro heterocycles were determined with the aid and simultaneous application of 1H-, 13C{1H}- and 19F-NMR, X-ray monocrystal diffraction, Mass Spectrometry and DFT calculation techniques and their purity were proved by elemental analysis or High Resolution Mass Spectrometry (HRMS). |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-12-03 |
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/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
GARCIA, Fábio Dutra. New Spirochromenyl-Trifluoroethanones from Trifluoroacetylation Reactions of Kabbe Adducts and their Spiro[dihydrochromeno-cycloalcan]pyrazoles and Isoxazoles Derivatives. 2013. 142 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10564 |
identifier_str_mv |
GARCIA, Fábio Dutra. New Spirochromenyl-Trifluoroethanones from Trifluoroacetylation Reactions of Kabbe Adducts and their Spiro[dihydrochromeno-cycloalcan]pyrazoles and Isoxazoles Derivatives. 2013. 142 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/10564 |
dc.language.iso.fl_str_mv |
por |
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100600000000 |
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400 500 300 500 300 |
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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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Universidade Federal de Santa Maria |
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