Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila
Ano de defesa: | 2010 |
---|---|
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: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4192 |
Resumo: | The present work describes the synthesis of novel 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines, aza-condensed tetrahydropyridines and ethyl-1H-pyrazoles-3(5)-carboxylate from the use of cyclic enones as precursors. The 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different primary amines in 55 96% yield, under basic catalysis, whereas the aza-condensed tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different diamines, leading to the desired products in 81 96% yield. The acylation of 2,3-dihydrofuran, 3,4-dihydropyran and 2-alkoxy-3,4-dihydro-2H-pyran with ethyloxallyl chloride furnished esterified enones (4-(2-ethyl-oxoacetate)2,3-dihydrofuran, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran and 2-methoxy-5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) in 47 81% yield. Finally, the cyclocondensation reaction between enones (4-(2-ethyl-oxoacetate)-2,3-dihydrofuran-2-oxoacetate, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) with different hydrazines led to the synthesis of 1H-pyrazole-3(5)-carboxylate ethyl ester in 62 96% yield. The N1 H substituted ethyl-1H-pyrazole-3(5)-carboxylate esters were N-alkylated with alkyl , allyl , and benzyl halides leading to the desired N-substituted pyrazoles in 48 96% yield. |
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2017-05-182017-05-182010-07-15FERNANDES, Liana da Silva. Application of cyclic enones as precursors for the synthesis of trifluoroacetyltetrahydropyridines and ethyl 1H-pyrazoles-3(5)-carboxylate . 2010. 260 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010.http://repositorio.ufsm.br/handle/1/4192The present work describes the synthesis of novel 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines, aza-condensed tetrahydropyridines and ethyl-1H-pyrazoles-3(5)-carboxylate from the use of cyclic enones as precursors. The 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different primary amines in 55 96% yield, under basic catalysis, whereas the aza-condensed tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different diamines, leading to the desired products in 81 96% yield. The acylation of 2,3-dihydrofuran, 3,4-dihydropyran and 2-alkoxy-3,4-dihydro-2H-pyran with ethyloxallyl chloride furnished esterified enones (4-(2-ethyl-oxoacetate)2,3-dihydrofuran, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran and 2-methoxy-5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) in 47 81% yield. Finally, the cyclocondensation reaction between enones (4-(2-ethyl-oxoacetate)-2,3-dihydrofuran-2-oxoacetate, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) with different hydrazines led to the synthesis of 1H-pyrazole-3(5)-carboxylate ethyl ester in 62 96% yield. The N1 H substituted ethyl-1H-pyrazole-3(5)-carboxylate esters were N-alkylated with alkyl , allyl , and benzyl halides leading to the desired N-substituted pyrazoles in 48 96% yield.Este trabalho apresenta a síntese de três séries de compostos inéditos: 1-alquil(aril)-2-alcóxi-5-trifluoracetil-1,2,3,4-tetraidropiridinas, hexaidroimidazopiridinas e heterociclos análogos aza-condensados e 1H-pirazóis-3(5)-carboxilato de etila a partir da utilização de enonas cíclicas como precursores. As 1-alquil(aril)-2-alcóxi-5-trifluoracetil-1,2,3,4-tetraidropiridinas, foram obtidas com rendimentos entre 55 e 96%, utilizando-se quantidades estequiométricas dos 2-alcóxi-5-trifluoracetil-3,4-diidro-2H-piranos com diferentes aminas primárias, sob catálise básica de piridina, enquanto que, as hexaidroimidazopiridinas e heterociclos aza-condensados foram sintetizados através da reação entre os mesmos precursores, em relação estequiométrica, frente a diaminas conduzindo a formação dos produtos desejados em rendimentos de 81 e 96%. A acilação entre o 2,3-diidrofurano, 3,4-diidropirano e 2-alcóxi-3,4-diidro-2H-pirano com o cloreto de etiloxalila promoveu a obtenção das enonas esterificadas (4-(etil-2-oxoacetato)-2,3-diidrofurano, 5-(etil-2-oxoacetato)-3,4-diidro-2H-pirano e 2-metóxi-5-(etil-2-oxoacetato)-3,4-diidro-2H-pirano) com rendimentos de 47 e 81%. A reação de ciclocondensação entre as enonas (4-(etil-2-oxoacetato)-2,3-diidrofurano, 5-(etil-2-oxoacetato)-3,4-diidro-2H-pirano) com diferentes hidrazinas conduziu à síntese dos 1H-pirazóis-3(5)-carboxilato de etila com rendimentos entre 62 e 96%, sendo que os 1H-pirazóis-3(5)-carboxilato de etila que apresentam hidrogênio como substituinte na posição-1, foram submetidos à posterior reação de N-alquilação conduzindo aos produtos desejados com rendimentos entre 48 e 96%.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaEnonas cíclicasTetraidropiridinasHexaidroimidazopiridinasPirazóisCyclic enonesTetrahydropyridinesAza-condensaded tetrahydropyridinesPyrazolesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila Application of cyclic enones as precursors for the synthesis of trifluoroacetyltetrahydropyridines and ethyl 1H-pyrazoles-3(5)-carboxylate info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9Schneider, Paulo Henriquehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760508Y4Caro, Miguel Soriano Balpardahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537Y2Dalcol, Ionara Irionhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9Bonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4730845T9Fernandes, Liana da Silva100600000000400300300300300500300233dc1de-ab03-4f57-9b85-e40dc01a2d4f46d16ce1-77e3-4208-ba26-c794fbcbae7d45261c66-d648-4472-9675-c315a838b7683209cb7e-bf46-45b7-9ec0-d81b856e6a0711b367fb-0eed-426e-9ab5-e42e52a8d09848e895f9-11c1-4820-af8e-776681d2fe26info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALFERNANDES, LIANA DA SILVA.pdfapplication/pdf8616017http://repositorio.ufsm.br/bitstream/1/4192/1/FERNANDES%2c%20LIANA%20DA%20SILVA.pdf02554c66a0f094ad98a68b9418e51fb1MD51TEXTFERNANDES, LIANA DA SILVA.pdf.txtFERNANDES, LIANA DA SILVA.pdf.txtExtracted texttext/plain300451http://repositorio.ufsm.br/bitstream/1/4192/2/FERNANDES%2c%20LIANA%20DA%20SILVA.pdf.txt1393f87f8c51be6aae55860c07147f95MD52THUMBNAILFERNANDES, LIANA DA SILVA.pdf.jpgFERNANDES, LIANA DA SILVA.pdf.jpgIM Thumbnailimage/jpeg6741http://repositorio.ufsm.br/bitstream/1/4192/3/FERNANDES%2c%20LIANA%20DA%20SILVA.pdf.jpg0b5d969a36bd2c5913c205f7ea0b646fMD531/41922017-07-25 11:05:04.584oai:repositorio.ufsm.br:1/4192Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:04Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
dc.title.alternative.eng.fl_str_mv |
Application of cyclic enones as precursors for the synthesis of trifluoroacetyltetrahydropyridines and ethyl 1H-pyrazoles-3(5)-carboxylate |
title |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
spellingShingle |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila Fernandes, Liana da Silva Enonas cíclicas Tetraidropiridinas Hexaidroimidazopiridinas Pirazóis Cyclic enones Tetrahydropyridines Aza-condensaded tetrahydropyridines Pyrazoles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
title_full |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
title_fullStr |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
title_full_unstemmed |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
title_sort |
Aplicação de enonas cíclicas como precursores para síntese de trifluoracetiltetraidropiridinas e 1H-pirazóis-3(5)-carboxilato de etila |
author |
Fernandes, Liana da Silva |
author_facet |
Fernandes, Liana da Silva |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zanatta, Nilo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9 |
dc.contributor.referee1.fl_str_mv |
Schneider, Paulo Henrique |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760508Y4 |
dc.contributor.referee2.fl_str_mv |
Caro, Miguel Soriano Balparda |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537Y2 |
dc.contributor.referee3.fl_str_mv |
Dalcol, Ionara Irion |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9 |
dc.contributor.referee4.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4730845T9 |
dc.contributor.author.fl_str_mv |
Fernandes, Liana da Silva |
contributor_str_mv |
Zanatta, Nilo Schneider, Paulo Henrique Caro, Miguel Soriano Balparda Dalcol, Ionara Irion Bonacorso, Helio Gauze |
dc.subject.por.fl_str_mv |
Enonas cíclicas Tetraidropiridinas Hexaidroimidazopiridinas Pirazóis |
topic |
Enonas cíclicas Tetraidropiridinas Hexaidroimidazopiridinas Pirazóis Cyclic enones Tetrahydropyridines Aza-condensaded tetrahydropyridines Pyrazoles CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Cyclic enones Tetrahydropyridines Aza-condensaded tetrahydropyridines Pyrazoles |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present work describes the synthesis of novel 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines, aza-condensed tetrahydropyridines and ethyl-1H-pyrazoles-3(5)-carboxylate from the use of cyclic enones as precursors. The 1-alkyl(aryl)-2-alkoxy-5-trifluoroacetyl-1,2,3,4-tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different primary amines in 55 96% yield, under basic catalysis, whereas the aza-condensed tetrahydropyridines were synthesized using stoichiometric amounts of trifluoroacetyl dihydropyranes and different diamines, leading to the desired products in 81 96% yield. The acylation of 2,3-dihydrofuran, 3,4-dihydropyran and 2-alkoxy-3,4-dihydro-2H-pyran with ethyloxallyl chloride furnished esterified enones (4-(2-ethyl-oxoacetate)2,3-dihydrofuran, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran and 2-methoxy-5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) in 47 81% yield. Finally, the cyclocondensation reaction between enones (4-(2-ethyl-oxoacetate)-2,3-dihydrofuran-2-oxoacetate, 5-(2-ethyl-oxoacetate)-3,4-dihydro-2H-pyran) with different hydrazines led to the synthesis of 1H-pyrazole-3(5)-carboxylate ethyl ester in 62 96% yield. The N1 H substituted ethyl-1H-pyrazole-3(5)-carboxylate esters were N-alkylated with alkyl , allyl , and benzyl halides leading to the desired N-substituted pyrazoles in 48 96% yield. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-07-15 |
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 |
FERNANDES, Liana da Silva. Application of cyclic enones as precursors for the synthesis of trifluoroacetyltetrahydropyridines and ethyl 1H-pyrazoles-3(5)-carboxylate . 2010. 260 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4192 |
identifier_str_mv |
FERNANDES, Liana da Silva. Application of cyclic enones as precursors for the synthesis of trifluoroacetyltetrahydropyridines and ethyl 1H-pyrazoles-3(5)-carboxylate . 2010. 260 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
url |
http://repositorio.ufsm.br/handle/1/4192 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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100600000000 |
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400 300 300 300 300 500 300 |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
dc.publisher.country.fl_str_mv |
BR |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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