Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos
Autor(a) principal: | |
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Data de Publicação: | 2016 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4288 |
Resumo: | In this study the reactivity of β-enamino diketones [RC(O)C(=CHNMe2)C(O)CO2Et, R = C6H5, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Br-C6H4, 4-NO2-C6H4, tien-2-il] with NCN bisnucleophiles as amidine and guanidine was investigated. The tiopirimidines ethyl 2-benzylthio-pyrimidine-4-carboxylates, (65-91 %) and Ethyl 2-metiltiopirimidine-4-carboxylates (69-91 %) were obtained in a highly regioselective manner by cyclocondensation reaction of β-enamino diketones with benzylisothiourea hydrochloride and methylisothiourea sulfate, respectively. Following the studies, was also investigated the reactivity of β-enamino diketones with guanidine hydrochloride and was possible to synthesize 2-aminopyrimidines that were obtained in a regioisomeric mixture of compounds with yields of 64-89 % and the reaction of β-enamino diketones with 2-acethylguanidine led to a highly regioselective synthesis of 2-acethylaminopyrimidines-4-carboxylates in yields (74-88 %). Ethyl 2-benzylthio-pyrimidine-4-carboxylates obtained were cyclized with hydrazine monohydrate and pyrimidopyridazinones were obtained in 52-95 % yields. Finally, were β-enamino diketones were cyclocondensed with 3(5)-amino-5(3)methylpyrazole leading to pyrazolo[1,5-a]pyrimidines of highly regioselective manner. These, in turn, are cyclized with an equivalent amount of hydrazine monohydrate to form a series of pyrazolo-pyrimido-pyridazinone (43-68%) and when using excess hydrazine monohydrate pyrazole-pyridazinone were formed by ANRORC (Addition of Nucleophile followed by Ring-Opening and Ring-Closure)mechanism yields 62-84%. The reactions for the synthesis of these heterocyclic systems involving simple steps, mild conditions and short reaction times. |
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Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidosReactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systemsEnaminodicetonaCiclocondensaçãoPirimidinasPirazolo[1,5-a]pirimidinaPirazolo-piridazinonaEnamino diketoneCyclocondensationPyrimidinesPyrazolo[1,5-a]pyrimidinesPyrazolopyridazinoneCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAIn this study the reactivity of β-enamino diketones [RC(O)C(=CHNMe2)C(O)CO2Et, R = C6H5, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Br-C6H4, 4-NO2-C6H4, tien-2-il] with NCN bisnucleophiles as amidine and guanidine was investigated. The tiopirimidines ethyl 2-benzylthio-pyrimidine-4-carboxylates, (65-91 %) and Ethyl 2-metiltiopirimidine-4-carboxylates (69-91 %) were obtained in a highly regioselective manner by cyclocondensation reaction of β-enamino diketones with benzylisothiourea hydrochloride and methylisothiourea sulfate, respectively. Following the studies, was also investigated the reactivity of β-enamino diketones with guanidine hydrochloride and was possible to synthesize 2-aminopyrimidines that were obtained in a regioisomeric mixture of compounds with yields of 64-89 % and the reaction of β-enamino diketones with 2-acethylguanidine led to a highly regioselective synthesis of 2-acethylaminopyrimidines-4-carboxylates in yields (74-88 %). Ethyl 2-benzylthio-pyrimidine-4-carboxylates obtained were cyclized with hydrazine monohydrate and pyrimidopyridazinones were obtained in 52-95 % yields. Finally, were β-enamino diketones were cyclocondensed with 3(5)-amino-5(3)methylpyrazole leading to pyrazolo[1,5-a]pyrimidines of highly regioselective manner. These, in turn, are cyclized with an equivalent amount of hydrazine monohydrate to form a series of pyrazolo-pyrimido-pyridazinone (43-68%) and when using excess hydrazine monohydrate pyrazole-pyridazinone were formed by ANRORC (Addition of Nucleophile followed by Ring-Opening and Ring-Closure)mechanism yields 62-84%. The reactions for the synthesis of these heterocyclic systems involving simple steps, mild conditions and short reaction times.Conselho Nacional de Desenvolvimento Científico e TecnológicoNesta tese foi investigada a reatividade de β-enaminodicetonas [RC(O)C(=CHNMe2)C(O)CO2Et, em que R = C6H5, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Br-C6H4, 4-NO2-C6H4, tien-2-il] frente NCN dinucleófilos como amidinas e guanidina. As tiopirimidinas 2-benziltio-pirimidinas-4-carboxilato de etila (65-91 %) e 2-metiltiopirimidinas-4-carboxilatos de etila (69-91 %) foram obtidas de maneira altamente regiosseletiva através da reação de ciclocondensação das β-enaminodicetonas com cloreto de benzilisotioureia e sulfato de 2-metilisotioureia, respectivamente. Já nas reações com cloridrato de guanidina foram obtidas 2-aminopirimidinas numa mistura regioisomérica de compostos com rendimentos de 64-89 % e a reação de β-enaminodicetonas com 2-acetilguanidina conduziu a uma síntese altamente regiosseletiva das 2-acetoamidopirimidinas-4-carboxilatos de etila em rendimentos de (74-87%). As 2- benziltio-pirimidinas-4-carboxilato de etila foram escolhidas para verificar o potencial sintético das pirimidinas sintetizadas, e, através da reação de ciclização destas com monoidrato de hidrazina foram obtidas as pirimido-piridazinonas, (52-95 %). Por fim, as β-enaminodicetonas foram ciclocondensadas com 3-(5)-amino-5(3)metilpirazol formando pirazolo[1,5-a]pirimidinas de maneira altamente regiosseletiva. Essas, por sua vez, foram ciclizadas com quantidade equivalente de monoidrato de hidrazina formando uma série de pirazolo-pirimido-piridazinona (43-68 %) e quando cilcizadas utilizando excesso de monoidrato de hidrazina formaram pirazolo-piridazinona através do mecanismo ANRORC (Addition of Nucleophile followed by Ring-Opening and Ring-Closure) com rendimentos de 62-84 %. As reações para a síntese desses sistemas heterocíclicos envolveram etapas simples, condições brandas e curtos tempos de reação.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaMartins, Marcos Antonio Pintohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3Dornelles, Lucianohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797177P9Zanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9Rosa, Fernanda Andreiahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4772056D8Fantinel, Leonardohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9Vargas, Pâmela Schütz de2017-05-222017-05-222016-08-26info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfVARGAS, Pâmela Schütz de. Reactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systems. 2016. 238 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016.http://repositorio.ufsm.br/handle/1/4288porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2017-07-25T14:05:03Zoai:repositorio.ufsm.br:1/4288Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:03Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos Reactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systems |
title |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
spellingShingle |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos Vargas, Pâmela Schütz de Enaminodicetona Ciclocondensação Pirimidinas Pirazolo[1,5-a]pirimidina Pirazolo-piridazinona Enamino diketone Cyclocondensation Pyrimidines Pyrazolo[1,5-a]pyrimidines Pyrazolopyridazinone CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
title_full |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
title_fullStr |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
title_full_unstemmed |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
title_sort |
Reações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidos |
author |
Vargas, Pâmela Schütz de |
author_facet |
Vargas, Pâmela Schütz de |
author_role |
author |
dc.contributor.none.fl_str_mv |
Martins, Marcos Antonio Pinto http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3 Dornelles, Luciano http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797177P9 Zanatta, Nilo http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9 Rosa, Fernanda Andreia http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4772056D8 Fantinel, Leonardo http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9 |
dc.contributor.author.fl_str_mv |
Vargas, Pâmela Schütz de |
dc.subject.por.fl_str_mv |
Enaminodicetona Ciclocondensação Pirimidinas Pirazolo[1,5-a]pirimidina Pirazolo-piridazinona Enamino diketone Cyclocondensation Pyrimidines Pyrazolo[1,5-a]pyrimidines Pyrazolopyridazinone CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Enaminodicetona Ciclocondensação Pirimidinas Pirazolo[1,5-a]pirimidina Pirazolo-piridazinona Enamino diketone Cyclocondensation Pyrimidines Pyrazolo[1,5-a]pyrimidines Pyrazolopyridazinone CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this study the reactivity of β-enamino diketones [RC(O)C(=CHNMe2)C(O)CO2Et, R = C6H5, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Br-C6H4, 4-NO2-C6H4, tien-2-il] with NCN bisnucleophiles as amidine and guanidine was investigated. The tiopirimidines ethyl 2-benzylthio-pyrimidine-4-carboxylates, (65-91 %) and Ethyl 2-metiltiopirimidine-4-carboxylates (69-91 %) were obtained in a highly regioselective manner by cyclocondensation reaction of β-enamino diketones with benzylisothiourea hydrochloride and methylisothiourea sulfate, respectively. Following the studies, was also investigated the reactivity of β-enamino diketones with guanidine hydrochloride and was possible to synthesize 2-aminopyrimidines that were obtained in a regioisomeric mixture of compounds with yields of 64-89 % and the reaction of β-enamino diketones with 2-acethylguanidine led to a highly regioselective synthesis of 2-acethylaminopyrimidines-4-carboxylates in yields (74-88 %). Ethyl 2-benzylthio-pyrimidine-4-carboxylates obtained were cyclized with hydrazine monohydrate and pyrimidopyridazinones were obtained in 52-95 % yields. Finally, were β-enamino diketones were cyclocondensed with 3(5)-amino-5(3)methylpyrazole leading to pyrazolo[1,5-a]pyrimidines of highly regioselective manner. These, in turn, are cyclized with an equivalent amount of hydrazine monohydrate to form a series of pyrazolo-pyrimido-pyridazinone (43-68%) and when using excess hydrazine monohydrate pyrazole-pyridazinone were formed by ANRORC (Addition of Nucleophile followed by Ring-Opening and Ring-Closure)mechanism yields 62-84%. The reactions for the synthesis of these heterocyclic systems involving simple steps, mild conditions and short reaction times. |
publishDate |
2016 |
dc.date.none.fl_str_mv |
2016-08-26 2017-05-22 2017-05-22 |
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.uri.fl_str_mv |
VARGAS, Pâmela Schütz de. Reactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systems. 2016. 238 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. http://repositorio.ufsm.br/handle/1/4288 |
identifier_str_mv |
VARGAS, Pâmela Schütz de. Reactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systems. 2016. 238 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
url |
http://repositorio.ufsm.br/handle/1/4288 |
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 |
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1805922107889025024 |