In the work undertaken here, NMR has been used to ascertain the structure of some 1,2,4-triazoles. The investigation provides information concerning the structure of potentially tautomeric triazoles such as hydroxy- and aminotriazole. Connected with this aspect of triazole chemistry is the larger problem of mesohydric tautomerism. The present study also yields information for a comparison of substituent effects in triazoles, N-heteroaromatic substances and benzene.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-09T12:17:20Z No. of bitstreams: 1 gilsonrodriguesferreira.pdf: 5148853 bytes, checksum: 05b9d7e4c0fed65676449cf1f4319a45 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T14:05:39Z (GMT) No. of bitstreams: 1 gilsonrodriguesferreira.pdf: 5148853 bytes, checksum: 05b9d7e4c0fed65676449cf1f4319a45 (MD5) / Made available in DSpace on 2017-05-17T14:05:39Z (GMT). No. of bitstreams: 1 gilsonrodriguesferreira.pdf: 5148853 bytes, checksum: 05b9d7e4c0fed65676449cf1f4319a45 (MD5) Previous issue date: 2014-08-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta tese apresenta o estudo espectroscópico teórico e experimental sobre o equilíbrio tautomérico em corantes derivados do 1-fenil-azo-2-naftol conhecido como Sudan I. O estudo envolveu os azocorantes (Sudan I, Sudan II, Para Red e Sudan Red G) além de dois diazocorantes (Sudan III e Sudan IV) e foi fundamentado em técnicas espectroscópicas; Raman, Infravermelho e UV/vis além de RMN de 13C e 1H. Todo o estudo envolveu a aplicação de metodologias teóricas B3LYP/6-311++G(d,p) na elucidação estrutural e espectroscópica das espécies azo (OH) e hidrazo (NH) para esta família de azocorantes. Foi possível determinar através dos resultados experimentais baseados em evidências teóricas que o tautômero NH é a forma predominante em fase gás, em solução e em estado sólido. Azocorantes derivados do fenil-1-azo-2-naftol também foram usados com sucesso na síntese de novos compostos de coordenação envolvendo íons de metais de transição Ni2+, Cu2+ e Co3+ e seis novos complexos foram completamente caracterizados sendo estes: bis-1-(fenil-azo)-2-naftolatoniquel(II) (1), bis-1-fenil-azo-2-naftolatocobre(II) (2) e tris-1-(fenil-azo)-2-naftolatocobalto(III) (3), bis-1-(2,4-Xylyl-azo)-2-naftolatoniquel(II) (4) e bis-1-(2,4-Xylyl-azo)-2-naftolatocobre(II) (5) e bis-1-(2-metoxi-fenil-azo)-2naftolatocobalto(III).etanol (6). Através dos dados de difração de raios X, associados à química computacional e aos dados espectroscópicos, foi possível sugerir que nos sistemas sintetizados, as forças intermoleculares responsáveis pelo empacotamento supramolecular são de fraca intensidade. Sendo que nos complexos (1), (2) e (3) prevalece às interações do tipo π-stacking, nos complexos (4) e (5) interações de do tipo CH...π não convencionais e no complexo (6) ocorre ligação de hidrogênio. A análise espectroscópica foi utilizada como uma importante ferramenta para a caracterização e confirmação da coordenação dos blocos construtores, sobretudo pela intensidade de muitas bandas que foram alteradas pela perda do próton (NH) para formação dos compostos de coordenação. / This thesis presents the theoretical and experimental spectroscopic study on the tautomeric equilibrium in azo dyes derivatives from 1-phenyl-azo-2-naphthol known as Sudan I. The study involved azo dyes (Sudan I, Sudan II, Para Red and Sudan Red G) besides two diazodyes (Sudan III and Sudan IV) and was based on spectroscopic techniques; Raman, IR and UV/vis also 1H and 13C NMR. All study involved the application of theoretical methods B3LYP/6-311++G (d,p) in the elucidation structural and spectroscopic of the species azo (OH) and (NH) hidrazo for this family of azo dyes. Experimental results based on theoretical evidence pointed the NH tautomer as predominant form in the gas phase, in solution and in solid state. Azo derivatives from phenyl-1-azo-2-naphthol also been successfully used in the synthesis of new coordination compounds involving ions of transition metals Ni2+, Cu2+ and Co3+ and six new compounds were fully characterized these being: bis-1-(phenyl-azo)-2-naftolatoniquel (II) (1), bis-1-phenyl-azo-2-naftolatocobre (II) (2), 1 tris-(phenyl-azo)-2-naftolatocobalto (III) (3), bis-1-(2,4-xylylazo)-2-naftolatoniquel (II) (4), bis-1-(2,4-xylyl-azo)-2-naftolatocobre (II) (5) and bis-1-(2methoxy-phenyl azo)-2-naftolatocobalto (III). ethanol (6). Through the association between crystallographic data, of the computational chemistry and spectroscopic data, we can suggest that the intermolecular forces responsible for the supramolecular packing are of the low intensity. Since the complexes (1), (2) and (3) prevails interaction type π-stacking, in the complexes (4) and (5) interactions of the type CH ... π unconventional and complex (6) occurs hydrogen bond. Spectroscopic analysis was used as an important tool for the characterization and confirmation of the coordination of builder blocks, particularly by the intensity of many bands that were altered by the loss of the proton (NH) for the formation of coordination compounds.

Cette étude considère des systèmes où non seulement la structure moléculaire, mais les conditions expérimentales sont impliquées. Les structures chimiques ont été codées par des descripteurs locaux ISIDA MA ou ISIDA CGR, ciblant spécifiquement les centres actifs et leur environnement le plus proche. Les descripteurs locaux ont été combinés avec les paramètres spécifiques des conditions expérimentales, codant ainsi un objet chimique particulier. La méthodologie a été appliquée avec succès pour la modélisation QSPR des paramètres thermodynamiques et cinétiques des interactions intermoléculaires (liaisons halogène et hydrogène), des équilibres tautomères et des réactions chimiques (cycloaddition et SN1). La méthode GTM a été appliquée pour la première fois pour la modélisation et la visualisation de données chimiques mixtes. La méthode sépare avec succès les groupes de données à la fois en raison des structures et des conditions. / This work describes original approaches for predictive chemoinformatics modeling of molecular interactions and reactions as a function of the structures of interacting partners and of the chemical environment (experimental conditions). Chemical structures have been encoded by local ISIDA MA-based or CGR-based descriptors, specifically targeting the active centers and their closest environment. The local descriptors have been combined with the specific parameters of experimental conditions, thereby encoding a particular chemical object. The methodology has been successfully applied for QSPR modeling of thermodynamic and kinetic parameters of intermolecular interactions (halogen and hydrogen bonds), tautomeric equilibria and chemical reactions (cycloaddition and SN1). GTM method has been applied for the first time for QSPR modeling and visualization of mixed chemical data. This method successfully separates data clusters on account of both chemical structures and experimental conditions.

Ce travail est consacré à la modélisation QSPR des propriétés cinétiques et thermodynamiques des réactions chimiques à l'aide de l'approche Graphe Condensé de Réaction (CGR). Le CGR permet de coder des structures de réactifs et de produits en un seul graphe moléculaire pour lequel des descripteurs moléculaires peuvent être générés.Une base de données contenant plus de 11000 réactions collectées manuellement a été développée puis utilisée dans la modélisation. Les modèles prédictifs ont été construits pour les constantes de vitesse de réactions Diels-Alder, SN2 et E2 ainsi que pour les constantes d'équilibre des transformations tautomères. Ils sont rendus publics via un portail WEB. Une partie de la thèse concerne une étude de mécanique quantique des réactions entre des sydnones et des alcynes contraints pour lesquels la taille du jeux de données n'était pas suffisante pour produire des modèles statistiquement significatifs. / This work is devoted to QSPR modeling of kinetic and thermodynamic properties of chemical reactions using the Condensed Graph of Reaction (CGR) approach. CGR allows encoding structures of reactants and products into one sole molecular graph for which molecular descriptors can be generated. A comprehensive database containing some 11000 manually collected reactions has been developed then used in the modeling. Predictive models were built for rate constants of Diels-Alder, SN2 and E2 reaction as well as for equilibrium constants of tautomeric transformations. They are available for the users via WEB portal. A part of the thesis concerned quantum mechanics studies of reactions between sydnones and strained alkynes for which the size of the dataset was not sufficient to produce statistically meaningful models.