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dc.creatorVargas, Pâmela Schütz de
dc.date.accessioned2017-05-22
dc.date.available2017-05-22
dc.date.issued2016-08-26
dc.identifier.citationVARGAS, 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.por
dc.identifier.urihttp://repositorio.ufsm.br/handle/1/4288
dc.description.abstractIn 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.eng
dc.description.sponsorshipConselho Nacional de Desenvolvimento Científico e Tecnológico
dc.formatapplication/pdfpor
dc.languageporpor
dc.publisherUniversidade Federal de Santa Mariapor
dc.rightsAcesso Abertopor
dc.subjectEnaminodicetonapor
dc.subjectCiclocondensaçãopor
dc.subjectPirimidinaspor
dc.subjectPirazolo[1,5-a]pirimidinapor
dc.subjectPirazolo-piridazinonapor
dc.subjectEnamino diketoneeng
dc.subjectCyclocondensationeng
dc.subjectPyrimidineseng
dc.subjectPyrazolo[1,5-a]pyrimidineseng
dc.subjectPyrazolopyridazinoneeng
dc.titleReações de β-enaminodicetonas com ncn dinucleófilos: obtenção de pirimidinas e sistemas heterocíclicos fundidospor
dc.title.alternativeReactions of the β-enamino diketones with ncn bisnucleophiles: getting pyrimidines and fused heterocyclic systemseng
dc.typeTesepor
dc.description.resumoNesta 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.por
dc.contributor.advisor1Martins, Marcos Antonio Pinto
dc.contributor.advisor1Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3por
dc.contributor.referee1Dornelles, Luciano
dc.contributor.referee1Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797177P9por
dc.contributor.referee2Zanatta, Nilo
dc.contributor.referee2Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9por
dc.contributor.referee3Rosa, Fernanda Andreia
dc.contributor.referee3Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4772056D8por
dc.contributor.referee4Fantinel, Leonardo
dc.contributor.referee4Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9por
dc.creator.Latteshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4219984P8por
dc.publisher.countryBRpor
dc.publisher.departmentQuímicapor
dc.publisher.initialsUFSMpor
dc.publisher.programPrograma de Pós-Graduação em Químicapor
dc.subject.cnpqCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICApor


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