Conselho Nacional de Desenvolvimento Científico e Tecnológico / 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. / Nesta 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.
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.ufsm.br:1/4288 |
| Date | 26 August 2016 |
| Creators | Vargas, Pâmela Schütz de |
| Contributors | Martins, Marcos Antonio Pinto, Dornelles, Luciano, Zanatta, Nilo, Rosa, Fernanda Andreia, Fantinel, Leonardo |
| Publisher | Universidade Federal de Santa Maria, Programa de Pós-Graduação em Química, UFSM, BR, Química |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis |
| Format | application/pdf |
| Source | reponame:Repositório Institucional da UFSM, instname:Universidade Federal de Santa Maria, instacron:UFSM |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 100600000000, 400, 300, 300, 300, 300, 300, 300, c28419d9-6027-4f9c-acd2-76e8067a85d1, 7a116aad-38a3-47b2-bbb6-f8fb2ec260f4, 7dfea8f7-fe97-4100-9d09-8f5a40fe2316, 2f7bd6ce-78fa-4968-ac66-2d1407e90f60, 44ffdb62-6636-4c47-9be5-3e29df1aed8d, ddd6f15c-7a34-42fb-b189-fd578d3d33a9 |
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