dc.creator | Malavolta, Juliana Limana | |
dc.date.accessioned | 2019-07-04T18:54:29Z | |
dc.date.available | 2019-07-04T18:54:29Z | |
dc.date.issued | 2014-12-19 | |
dc.identifier.uri | http://repositorio.ufsm.br/handle/1/17319 | |
dc.description.abstract | This study shows strategies to prepare 1,3,4-oxadiazoles and derivatives from 4-oxopentanoic acid is reported. The compounds 4-(2-(5-substituted-1,3,4-oxadiazol-2-yl)ethyl)-2-(methylthio/phenyl)-6-(trifluoromethyl)pyrimidine; 7aa (5-H, 2-SMe); 7ab (5-Me, 2-SMe); 7ac (5-Ph, 2-SMe); 7ba (5-H, 2-Ph); 7bb (5-Me, 2-Ph); 7bc (5-Ph, 2-Ph); and 2-methyl-5-(2-(5-substituted-1,3,4-oxadiazol-2-yl)ethyl)-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidine; 8a (5-H); 8b (5-Me); 8c (5-Ph); were obtained through of reaction between the hydrazides trifluormetilated previously synthesized with orthoesters which lead to obtaining of product in yields of 55-98%. The synthesis of oxadiazoles-2-tiosubstituted through of reaction of hydrazides with carbon disulfide conducted the formation of compounds 5-(2-(methylthio/phenyl-6-(trifluoromethyl)pyrimidin-4-yl)ethyl)-1,3,4-oxadiazole-2-thiol; 9a (2-SMe); 9b (2-Ph); and 5-(2-methyl-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-5-yl)ethyl)-1,3,4-oxadiazole-2-thiol; 10; with yields of 84-97%. This compounds series were reacted with alkylating and acylating agents and derivatized to compounds 1,3,4-oxadiazoles 2-S-alkylated/acylated 5-(2-(methylthio/phenyl)-6-(trifluoromethyl)pyrimidin-4-yl)ethyl)-1,3,4-oxadiazol-2-yl-thiosubstituted; 11aa (2-SMe, 2-S(CO)Me); 11ab (2-SMe, 2-S(CO)CCl3); 11ac (2-SMe, 2-SCH2(CO)Ph); 11ba (2-Ph, 2-S(CO)Me); 11bb (2-Ph, 2-S(CO)CCl3); 11bc (2-Ph, 2-SCH2(CO)Ph); and 5-(2-methyl-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-5-yl)ethyl)-1,3,4-oxadiazol-2-yl-thiosubstituted; 12 (2-S(CO)Me). Series of hydrazones N’-(substituted)-3-(2-
(methylthio/phenyl)-6-(trifluoromethyl)pyrimidin-4-yl)propanehydrazide, 13aa (Ph, 2-SMe); 13ab (2-ClPh, 2-SMe); 13ac (4-(N(Me)2)Ph, 2-SMe); 13ad (4-NO2Ph, 2-SMe); 13ae (furano, 2-SMe); 13ba (Ph, 2-Ph); 13bb (2-ClPh, 2-Ph); 13bc (4-(N(Me)2)Ph, 2-Ph); 13be (furan, 2-Ph); and N’-(substituted)-3-(2-methyl-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-5-yl)propanehydrazide; 14a (Ph); 14b (2-ClPh); 14c (4-(N(Me)2)Ph); 14e (furan); were also synthesized to use as precursors for 2,3-dihydro-1,3,4-oxadiazoles synthesis. N-substituted by reaction with acetic anhydride which led to the formation of N-acetyl-3-(2-(methylthio/phenyl)-6-(trifluoromethyl)pyrimidin-4-yl)propanehydrazide; 15a (2-SMe); 15b (2-Ph) with yields of 51-66%. Finally was investigated the oxadative cyclization of N-acyl hydrazones with trichloroisocyanuric acid to obtain 1,3,4-oxadiazoles it allowed to obtain 2-methyl-5-(3-yl-propanoate ethyl)-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidine and 2-(methylthio/phenyl)-4-(3-propanoate ethyl-yl)-6-(trifluoromethyl)pyrimidine with yields of 64-79%. All the synthesized compounds are new and their structures were confirmed by 1H, 13C NMR data and two-dimensional NMR techniques as well as mass spectrometry data. | eng |
dc.description.sponsorship | Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq | por |
dc.language | por | por |
dc.publisher | Universidade Federal de Santa Maria | por |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 International | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject | Ácido 4-oxopentanóico | por |
dc.subject | Pirimidinas | por |
dc.subject | Pirazolo[1,5-a]pirimidinas hidrazidas | por |
dc.subject | 1,3,4-oxadiazóis | por |
dc.subject | 4-oxopentanoic acid | eng |
dc.subject | Pyrimidines | eng |
dc.subject | Pyrazolo[1,5-a]-pyrimidine | eng |
dc.subject | Hydrazides | eng |
dc.subject | 1,3,4-oxadiazoles | eng |
dc.title | 1,3,4-oxadiazóis: estratégias para síntese e derivatização a partir do ácido 4-oxopentanóico | por |
dc.title.alternative | 1,3,4-oxadiazoles: strategies for synthesis and derivatization from 4-oxopentanoic acid | eng |
dc.type | Tese | por |
dc.description.resumo | Este trabalho descreve um estudo sobre estratégias sintéticas para promover a síntese de 1,3,4-oxadiazóis e seus derivados a partir do ácido 4-oxopentanóico. Os compostos 4-(2-(5-substituído-1,3,4-oxadiazol-2-il)etil)-2-(metiltio/fenil)-6-(trifluormetil)pirimidina; 7aa (5-H, 2-SMe); 7ab (5-Me, 2-SMe); 7ac (5-Ph, 2-SMe); 7ba (5-H, 2-Ph); 7bb (5-Me, 2-Ph); 7bc (5-Ph, 2-Ph); e 2-metil-5-(2-(5-substituído-1,3,4-oxadiazol-2-il)etil)-7-(trifluormetil)pirazolo[1,5-a]pirimidina; 8a (5-H); 8b (5-Me); 8c (5-Ph); foram obtidos através da reação entre hidrazidas trifluormetiladas previamente sintetizadas, com ortoésteres, o que possibilitou a obtenção dos produtos alvo com rendimentos de 55-98%. A síntese de oxadiazóis 2-tiossubstituídos através da reação entre as hidrazidas com dissulfeto de carbono conduziu à formação dos compostos 5-(2-(metiltio/fenil-6-(trifluormetil)pirimidin-4-il)etil)-1,3,4-oxadiazol-2-tiol; 9a (2-SMe); 9b (2-Ph); e 5-(2-metil-7-(trifluormetil)-pirazolo[1,5-a]pirimidin-5-il)etil)-1,3,4-oxadiazol-2-tiol 10; com rendimentos de 84-97%. Esta série de compostos foi levada à reação com agentes alquilantes e acilantes e derivatizadas para os compostos 1,3,4-oxadiazóis 2-S-alquilados/acilados 5-(2-(metiltio/fenil)-6-(trifluormetil)pirimidin-4-il)etil)-1,3,4-oxadiazol-2-il-tiosubstituído; 11aa (2-SMe, 2-S(CO)Me); 11ab (2-SMe, 2-S(CO)CCl3); 11ac (2-SMe, 2-SCH2(CO)Ph); 11ba (2-Ph, 2-S(CO)Me); 11bb (2-Ph, 2-S(CO)CCl3); 11bc (2-Ph, 2-SCH2(CO)Ph); e 5-(2-metil-7-(trifluormetil)pirazolo[1,5-a]pirimidin-5-il)etil)-1,3,4-oxadiazol-2-il-tiosubstituído; 12 (2-S(CO)Me). As séries de hidrazonas
N’-(substituído)-3-(2-(metiltio/fenil)-6-(trifluormetil)pirimidin-4-il)propanoidrazida, 13aa (Ph, 2-SMe); 13ab (2-ClPh, 2-SMe); 13ac (4-(N(Me)2)Ph, 2-SMe); 13ad (4-NO2Ph, 2-SMe); 13ae (furano, 2-SMe); 13ba (Ph, 2-Ph); 13bb (2-ClPh, 2-Ph); 13bc (4-(N(Me)2)Ph, 2-Ph); 13be (furano, 2-Ph); e N’-(substituído)-3-(2-metil-7-(trifluormetil)pirazolo[1,5-a]pirimidin-5-il)propanoidrazida; 14a (Ph); 14b (2-ClPh); 14c (4-(N(Me)2)Ph); 14e (furano); também foram sintetizadas a fim de serem utilizadas como precursores para a síntese de 2,3-diidro-1,3,4-oxadiazóis-N-substituídos através da reação com anidrido acético, as quais promoveram a formação das N-acetil-3-(2-(metiltio/fenil)-6-(trifluormetil)pirimidin-4-il)propanohidrazida; 15a (2-SMe); 15b (2-Ph) com rendimentos de 51-66%. Por fim, foi investigada a ciclização oxiadativa das N-acilidrazonas com ácido tricloroisocianúrico para obtenção dos 1,3,4-oxadiazóis, a qual possibilitou obtenção da 2-metil-5-(propanoato-3-il de etila)-7-(trifluormetil)pirazolo[1,5-a]pirimidina 16 e 2-(metiltio/fenil)-4-(propanoato-3-il de etila)-6-(trifluormetil)pirimidina; 17a (2-SMe); 17b (2-Ph); com rendimentos de 64-79%. Todos os compostos sintetizados são inéditos e tiveram suas estruturas confirmadas por dados de RMN 1H, 13C e técnicas bidimensionais além de dados de espectrometria de massas. | por |
dc.contributor.advisor1 | Flores, Alex Fabiani Claro | |
dc.contributor.advisor1Lattes | http://lattes.cnpq.br/1159954352174167 | por |
dc.contributor.referee1 | Fernandes, Liana da Silva | |
dc.contributor.referee1Lattes | http://lattes.cnpq.br/0573570242395130 | por |
dc.contributor.referee2 | Zanatta, Nilo | |
dc.contributor.referee2Lattes | http://lattes.cnpq.br/0719465062354576 | por |
dc.contributor.referee3 | Machado, Pablo | |
dc.contributor.referee3Lattes | http://lattes.cnpq.br/3319303431365448 | por |
dc.contributor.referee4 | Silva, Sidnei Moura e | |
dc.contributor.referee4Lattes | http://lattes.cnpq.br/3505301292906591 | por |
dc.creator.Lattes | http://lattes.cnpq.br/8371389172266454 | por |
dc.publisher.country | Brasil | por |
dc.publisher.department | Química | por |
dc.publisher.initials | UFSM | por |
dc.publisher.program | Programa de Pós-Graduação em Química | por |
dc.subject.cnpq | CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA | por |
dc.publisher.unidade | Centro de Ciências Naturais e Exatas | por |