Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres
Autor(a) principal: | |
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Data de Publicação: | 2005 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/10621 |
Resumo: | Due to the high chemical versatility of β-keto esters and the β-enamino carbonylic compounds as synthetic precursors, our research group has investigated and developed methodologies for their synthesis and reactivity. In the present work, we aim to establish a methodology for the transesterification of β-keto esters using montmorillonite (K-10) as a support or catalyst by itself or together with microwave irradiation (MW). We used the methodology to evaluate the synthesis and reactivity of β-enamino esters. The cyclic β-keto ester ethyl-2-oxo-1-cyclopentanecarboxilate was synthesized by ethanol esterification followed by Dieckmann Cyclization of adipic acid. To obtain the series of the cyclic β-keto esters derived from ethyl-2-oxo-1-cyclopentanecarboxilate by transesterification reaction with allylic and benzylic alcohol and (1S, 2R, 5S)-(+)-menthol, montmorillonite (K-10) as catalyst with microwaves was used. To validate the methodology chosen for our work, we compared microwave irradiation to the use of reflux in toluene. The use of K-10/MW in the absence of solvent was shown to be more efficient than refluxing in toluene, giving higher yields with a much reduced reaction time. Cyclic β-enamino esters were obtained by condensation of the previously synthesized β-keto esters with primary amines, using the same K-10/MW methodology adapted to a sealed flask. This step gave excellent results. For the study of the β-enamino esters reactivity evaluation we tried several reduction systems for ethyl 2-allylamino-1-cyclopentene-1-carboxylate, without success. For the evaluation of the β-keto esters reactivity we chose ethyl 2-oxo-1-cyclopentanecarboxylate and allyl 2-oxo-1-cyclopentanecarboxylate. They were used in the condensation reaction with secondary amines and also for cyclization using Mn(OAc)3, to give a cyclic amide and a spiro compound, respectively. |
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Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteresUse of K-10 and microwave irradiation for the transesterification and synthesis of β-enamino estersK-10MicroondasTransesterificaçãoβ-cetoésteresβ-enamino ésteresMicrowaveTransesterificationβ-keto estersβ-enamino estersCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICADue to the high chemical versatility of β-keto esters and the β-enamino carbonylic compounds as synthetic precursors, our research group has investigated and developed methodologies for their synthesis and reactivity. In the present work, we aim to establish a methodology for the transesterification of β-keto esters using montmorillonite (K-10) as a support or catalyst by itself or together with microwave irradiation (MW). We used the methodology to evaluate the synthesis and reactivity of β-enamino esters. The cyclic β-keto ester ethyl-2-oxo-1-cyclopentanecarboxilate was synthesized by ethanol esterification followed by Dieckmann Cyclization of adipic acid. To obtain the series of the cyclic β-keto esters derived from ethyl-2-oxo-1-cyclopentanecarboxilate by transesterification reaction with allylic and benzylic alcohol and (1S, 2R, 5S)-(+)-menthol, montmorillonite (K-10) as catalyst with microwaves was used. To validate the methodology chosen for our work, we compared microwave irradiation to the use of reflux in toluene. The use of K-10/MW in the absence of solvent was shown to be more efficient than refluxing in toluene, giving higher yields with a much reduced reaction time. Cyclic β-enamino esters were obtained by condensation of the previously synthesized β-keto esters with primary amines, using the same K-10/MW methodology adapted to a sealed flask. This step gave excellent results. For the study of the β-enamino esters reactivity evaluation we tried several reduction systems for ethyl 2-allylamino-1-cyclopentene-1-carboxylate, without success. For the evaluation of the β-keto esters reactivity we chose ethyl 2-oxo-1-cyclopentanecarboxylate and allyl 2-oxo-1-cyclopentanecarboxylate. They were used in the condensation reaction with secondary amines and also for cyclization using Mn(OAc)3, to give a cyclic amide and a spiro compound, respectively.Conselho Nacional de Desenvolvimento Científico e TecnológicoDevido à grande versatilidade química como precursores sintéticos, os β-cetoésteres e os compostos β-enamino carbonílicos, têm sido alvo de estudos em nosso grupo de pesquisa no desenvolvimento de metodologias para a síntese e reatividade desses compostos. Neste trabalho buscamos estabelecer metodologias para transesterificação de β-cetoésteres, utilizando montmorillonita (K-10), como suporte ou catalisador associado ou não ao uso de energia de microondas e avaliar a obtenção e a reatividade de β-enamino ésteres. Visando tais objetivos, sintetizamos o β-cetoéster cíclico, 2-oxo-1-ciclopentanocarboxilato de etila a partir do ácido adípico, através da esterificação em etanol, seguida de uma Ciclização de Dieckmann. Na obtenção de uma série de β-cetoésteres cíclicos derivados do 2-oxo-1-ciclopentanocarboxilato de etila, pela reação de transesterificação deste frente a álcool alílico, benzílico e (1S, 2R, 5S)-(+)-mentol, elegeu-se a metodologia utilizando montmorillonita (K-10) como catalisador associada a energia de microondas. Para validação desta metodologia, comparou-se a utilização de energia de microondas com o emprego de refluxo em tolueno. A metodologia empregando K-10/MO na ausência de solvente mostrou-se, mais eficiente, pois apresentou melhores rendimentos e tempos reacionais bastante reduzidos em relação à outra metodologia avaliada. Foram obtidos β-enamino ésteres cíclicos pela condensação dos β-cetoésteres sintetizados com aminas primárias empregando a metodologia de suporte sólido (K-10), associada à energia de microondas adaptada para vaso vedado obtendo ótimos resultados. Para a avaliação da reatividade dos β-enamino ésteres, vários sistemas redutores foram empregados para o 2-alilamino-1-ciclopenteno-1-carboxilato de etila, sem sucesso. Para o estudo da reatividade de β-cetoésteres, elegemos o 2-oxo-1-ciclopentanocarboxilato de etila e o 2-oxo-1-ciclopentanocarboxilato de alila, que foram submetidos à reação de condensação frente à amina secundária e à reação de ciclização promovida por Mn(OAc)3, obtendo-se, respectivamente, uma amida cíclica e um composto espiro.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaBraibante, Mara Elisa Forteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788627U5Morel, Ademir Fariashttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8Dalcol, Ionara Irionhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9Brauer, Martin Claudio Nin2017-05-192017-05-192005-05-20info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfapplication/pdfBRAUER, Martin Claudio Nin. Use of K-10 and microwave irradiation for the transesterification and synthesis of β-enamino esters. 2005. 123 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005.http://repositorio.ufsm.br/handle/1/10621porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2017-07-30T04:56:38Zoai:repositorio.ufsm.br:1/10621Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-30T04:56:38Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres Use of K-10 and microwave irradiation for the transesterification and synthesis of β-enamino esters |
title |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
spellingShingle |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres Brauer, Martin Claudio Nin K-10 Microondas Transesterificação β-cetoésteres β-enamino ésteres Microwave Transesterification β-keto esters β-enamino esters CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
title_full |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
title_fullStr |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
title_full_unstemmed |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
title_sort |
Uso de K-10 e irradiação de microondas no estudo da metodologia de transesterificação e na síntese de β-enamino ésteres |
author |
Brauer, Martin Claudio Nin |
author_facet |
Brauer, Martin Claudio Nin |
author_role |
author |
dc.contributor.none.fl_str_mv |
Braibante, Mara Elisa Fortes http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788627U5 Morel, Ademir Farias http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8 Dalcol, Ionara Irion http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9 |
dc.contributor.author.fl_str_mv |
Brauer, Martin Claudio Nin |
dc.subject.por.fl_str_mv |
K-10 Microondas Transesterificação β-cetoésteres β-enamino ésteres Microwave Transesterification β-keto esters β-enamino esters CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
K-10 Microondas Transesterificação β-cetoésteres β-enamino ésteres Microwave Transesterification β-keto esters β-enamino esters CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Due to the high chemical versatility of β-keto esters and the β-enamino carbonylic compounds as synthetic precursors, our research group has investigated and developed methodologies for their synthesis and reactivity. In the present work, we aim to establish a methodology for the transesterification of β-keto esters using montmorillonite (K-10) as a support or catalyst by itself or together with microwave irradiation (MW). We used the methodology to evaluate the synthesis and reactivity of β-enamino esters. The cyclic β-keto ester ethyl-2-oxo-1-cyclopentanecarboxilate was synthesized by ethanol esterification followed by Dieckmann Cyclization of adipic acid. To obtain the series of the cyclic β-keto esters derived from ethyl-2-oxo-1-cyclopentanecarboxilate by transesterification reaction with allylic and benzylic alcohol and (1S, 2R, 5S)-(+)-menthol, montmorillonite (K-10) as catalyst with microwaves was used. To validate the methodology chosen for our work, we compared microwave irradiation to the use of reflux in toluene. The use of K-10/MW in the absence of solvent was shown to be more efficient than refluxing in toluene, giving higher yields with a much reduced reaction time. Cyclic β-enamino esters were obtained by condensation of the previously synthesized β-keto esters with primary amines, using the same K-10/MW methodology adapted to a sealed flask. This step gave excellent results. For the study of the β-enamino esters reactivity evaluation we tried several reduction systems for ethyl 2-allylamino-1-cyclopentene-1-carboxylate, without success. For the evaluation of the β-keto esters reactivity we chose ethyl 2-oxo-1-cyclopentanecarboxylate and allyl 2-oxo-1-cyclopentanecarboxylate. They were used in the condensation reaction with secondary amines and also for cyclization using Mn(OAc)3, to give a cyclic amide and a spiro compound, respectively. |
publishDate |
2005 |
dc.date.none.fl_str_mv |
2005-05-20 2017-05-19 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.uri.fl_str_mv |
BRAUER, Martin Claudio Nin. Use of K-10 and microwave irradiation for the transesterification and synthesis of β-enamino esters. 2005. 123 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005. http://repositorio.ufsm.br/handle/1/10621 |
identifier_str_mv |
BRAUER, Martin Claudio Nin. Use of K-10 and microwave irradiation for the transesterification and synthesis of β-enamino esters. 2005. 123 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005. |
url |
http://repositorio.ufsm.br/handle/1/10621 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805922015874383872 |