Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2018-07-10T12:56:00Z No. of bitstreams: 2 Dissertação - Achiles Silva Ferreira - 2018.pdf: 3183279 bytes, checksum: 59976d2d13952581ed03b3a3f2983a22 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-07-11T10:40:15Z (GMT) No. of bitstreams: 2 Dissertação - Achiles Silva Ferreira - 2018.pdf: 3183279 bytes, checksum: 59976d2d13952581ed03b3a3f2983a22 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-07-11T10:40:15Z (GMT). No. of bitstreams: 2 Dissertação - Achiles Silva Ferreira - 2018.pdf: 3183279 bytes, checksum: 59976d2d13952581ed03b3a3f2983a22 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-04-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present work describes the development of a simple and efficient methodology for the synthesis of 2-aminoheteroazoic compounds using the solvent PEG 400 as an alternative to toxic and flammable organic solvents. Several media and reactional conditions were compared. A series of substituted 2-aminothiazoic compounds was obtained in good yields (60 to 96%) by a 3 hour reaction procedure using PEG 400 at room temperature and without the need for additives or catalysts. A selenium analogue and a 2-imino-1,3-thiazoline were also obtained by this method. The products were characterized by 1H and 13C NMR and infrared spectroscopies and mass spectrometry. The method covers some points of Green Chemistry, such as: safe synthesis, prevention in the formation of residues or derivatives, development of products that do not harm the environment, energy efficiency and accident prevention. / O presente trabalho descreve o desenvolvimento de uma metodologia simples e eficiente para a síntese de compostos 2-amino-heteroazóicos, utilizando o solvente PEG 400 como alternativa a solventes orgânicos tóxicos e inflamáveis. Diversos meios e condições reacionais foram comparados. Uma série de compostos 2-amino-tioazóicos substituídos foi obtida, em bons rendimentos (60 a 96%), através de procedimento reacional com 3 horas de duração, utilizando PEG 400 à temperatura ambiente e sem a necessidade de aditivos ou catalisadores. Um análogo de selênio e uma 2-imino-1,3-tiazolina também foram obtidos através desse método. Os produtos foram caracterizados por espectroscopias de RMN de 1H e 13C e infravermelho e espectrometria de massas. O método abrange alguns pontos da Química Verde, como: síntese segura, prevenção na formação de resíduos ou derivados, desenvolvimento de produtos que não agridem o meio ambiente, eficiência energética e prevenção de acidentes.

Orientador: Rosangela da Silva de Laurentiz / Resumo: As lignanas apresentam grande variedade estrutural e diversidade de propriedades biológicas, desta forma ocupam um papel de destaque na busca por moléculas bioativas. A introdução de nitrogênio no esqueleto químicos de lignanas ariltetralínicas e arilnaftalênicas fornece compostos azo-heterocíclicos que contém o núcleo quinolínico e o anel lactônico e, portanto, são lactonas dihidroquinolinicas e quinolínicas. Essas estruturas podem ser potenciais alvos na pesquisa por novas moléculas para o desenvolvimento de fármacos para uma série de enfermidades. Desta forma, o objetivo deste trabalho foi sintetizar azo-análogos de lignanas ariltetralínicas, de estruturas conhecidas e inéditas, a fim de determinar suas propriedades leishmanicida, esquistossomicida, antimicrobiana e citotóxica contra células tumorais. A síntese dos azo-ariltetralinicos foi realizada a partir da reação multicomponente assistida por micro-ondas entre ácido tetrônico, anilinas substituídas e aldeídos aromáticos. O uso de reação multicomponente assistida por micro-ondas tem a finalidade a obtenção desses compostos de uma forma mais rápida e eficiente em relação às metodologias tradicionais de síntese. Foram obtidos 39 derivados azo-ariltetralínicos, pela variação dos substituintes dos aldeídos e anilinas, em rendimentos que variaram de 70 a 94%. Dentre os ensaios biológicos aos quais esses compostos foram submetidos, deve-se destacar a atividade leishmanicida e atividade antimicrobiana com valores de CI50, par... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Lignans have a great variety of structure and diversity of biological properties, thus they play a prominent role in the search for new bioactive molecules. The introduction of nitrogen into the chemical skeleton of aryltetralin and arylnaphthalene lignans provides azo-heterocyclic compounds containing the quinolinic nucleus and the lactonic ring and thus are dihydroquinolinic and quinolinic lactones. These structures may be potential targets in the search for novel molecules for the development of drugs for a range of diseases. Thus, the aim of this work was to synthesize azo-analogues of aryltetralin lignans of known and novel structures in order to determine their leishmanicidal, schistosomicidal, antimicrobial and cytotoxic properties against tumor cells. The synthesis of azo-aryltetralinics was carried out from the microwave-assisted multicomponent reaction between tetronic acid, substituted anilines and aromatic aldehydes. The use of microwave-assisted multicomponent reaction has the purpose of obtaining these compounds more quickly and efficiently than traditional synthetic methodologies. Thirty-nine azo-aryltetralin derivatives were obtained by varying the aldehyde and aniline substituents in yields ranging from 70 to 94%. Among the biological assays to which these compounds were submitted, the leishmanicidal activity and antimicrobial activity with IC50 values varying of 1.07-3.57 μg/mL and 12.5-100 μg/mL, respectively, for the most active compounds, should be highli... (Complete abstract click electronic access below) / Doutor

Ce manuscrit décrit la synthèse et la caractérisation de nouveaux systèmes moléculaires à base de phosphore : dans la première partie sont étudiés des dérivés π-conjugués du cycle phosphole et la seconde partie fait état d'assemblages supramoléculaires à ligands phosphines. Tout d'abord, une introduction à la chimie du phosphole (historique, méthodes de synthèse, insertion dans des systèmes π-conjugués) est présentée. Le premier chapitre décrit la synthèse et l'étude physico-chimique de dérivés phospholes possédant un système π étendu afin de les utiliser en tant qu'émetteurs oranges-rouges dans des diodes électroluminescentes organiques (OLEDs). Différentes modifications chimiques de la triple liaison sont ensuite mises en place pour modifier les propriétés optiques des dérivés synthétisés en déplaçant leurs maximas d'absorption et/ou d'émission vers les plus grandes longueurs d'onde. Le chapitre II décrit la synthèse et l'étude de complexes utilisant une brique phosphole acétylénique comme connecteur conjugué entre deux centres métalliques. De nouveaux complexes de Fe(II), Pt(II) et d'Au(I) ont ainsi été développés et la communication électronique entre les métaux est étudiée. La deuxième partie de ces travaux de thèse commence avec un historique sur les complexes de Cu(I) luminescents, qu'ils soient mono- ou polynucléaires, qu'ils possèdent une structure de forme cubane ou autres. Dans le chapitre III, sont présentées les synthèses, les études structurales et optiques de nouveaux assemblages supramoléculaires émissifs à l'état solide synthétisés à partir de clips moléculaires de Cu(I) préassemblés et stabilisés par des ligands phosphines (dppm ou dpmp) avec des ligands connecteurs de type cyano CN-. Ensuite, le dernier chapitre utilise cette même stratégie de synthèse en utilisant des ligands connecteurs organiques à fonctions nitriles terminales et de nouveaux complexes de Cu(I) discrets ou étendus sont caractérisés. Tout au long de cette deuxième partie, les propriétés de luminescence des dérivés de Cu(I) sont étudiées en fonction de leur environnement extérieur et des phénomènes de thermochromisme, de vapochromisme et de mécanochromisme sont mis en évidence chez certains d'entre eux. / This manuscript describes the synthesis and characterization of new molecular systems based on phosphorus atom: we developed and studied π-conjugated systems based on phosphole and secondly supramolecular assemblies with phosphine ligand have been studied. Firstly, an introduction to the phosphole chemistry (history, synthesis methods, integration into π-conjugated systems) is presented. The first chapter describes the synthesis and physico-chemical study of phospholes derivatives having an extended π-system for the development of orange-red emitters in organic light-emitting diodes (OLEDs). Different molecular engineering involving the triple bond leads to modifications of the optical properties of the synthesized compounds by red-shifting their absorption and/or emission maxima. Chapter II describes the synthesis and the physical properties of complexes using phosphole based π-systems as linkers between two metal centers. New Fe (II), Pt (II) and Au (I) complexes have been developed and the electronic communication between the two metals is studied. The second part of the thesis work starts with a review on the emissive Cu(I) complexes. In Chapter III, are presented the syntheses, the structural and optical studies of new solid-state emissive supramolecular assemblies synthesized from pre-assembled Cu(I) molecular clips and stabilized by phosphine ligands (dppm or dpmp) with cyano ligands as linkers. Then in the final chapter new Cu(I) complexes are synthesized by using organic ligands with terminal nitrile functions as linkers. The solid-state luminescence properties of these new Cu(I) derivatives are studied according to their external environment and thermochromism, vapochromism and mechanochromism phenomena have been demonstrated for some of them.