No presente trabalho investigou-se a utilização de diferentes haletos metálicos hidratados (SnCl2.2H2O, MnCl2.4H2O, SrCl2.6H2O, CrCl2.6H2O, CoCl2.6H2O e CeCl3.7H2O) como catalisadores ácidos de Lewis na alquilação de indóis com olefinas ativadas via reação de Friedel-Crafts. Nas reações entre indóis e cetonas α,β-insaturadas os melhores resultados foram obtidos com o emprego de SnCl2.2H2O (10% em mol) como catalisador. As reações com enonas alifáticas foram realizadas à temperatura ambiente, já a obtenção de adutos indólicos derivados das chalconas só foi possível sob condições de refluxo. Para as reações com nitro-olefinas os melhores resultados foram observados com a utilização de CoCl2.6H2O (10% em mol) como catalisador: seu uso em condições sem solvente, sob aquecimento, permitiu a obtenção de diversos nitroadutos em altos rendimentos e baixos tempos de reação. Dois dos compostos obtidos através desta metodologia foram utilizados com sucesso como materiais de partida na síntese de tetraidro-β-carbolinas, demonstrando a utilidade sintética da metodologia desenvolvida. Um novo líquido iônico imidazólico 1-alquil-éter funcionalizado também foi investigado como promotor na reação de alquilação de indóis, sendo utilizado com sucesso como catalisador nas reações com enonas alifáticas e nitro-olefinas em condições de ausência de solvente. / In the present work, metal halide hydrates (such as SnCl2.2H2O, MnCl2.4H2O, SrCl2.6H2O, CrCl2.6H2O, CoCl2.6H2O and CeCl3.7H2O) were investigated as Lewis acids catalysts for the Friedel-Crafts alkylation reaction between indoles and activated olefins. In the reactions of indoles with α,β-unsaturated ketones the best results were achieved using SnCl2.2H2O as the catalyst. The reactions with aliphatic enones were carried out at room temperature, while reflux conditions were required for the reactions leading to chalcone indolic derivatives. For the reactions with nitroolefins the best results were obtained employing CoCl2.6H2O as the catalyst: its use under heating, in solvent-free reactions, lead to several nitro adducts in high yields and short reaction times. Two of the compounds obtained by this methodology were successfully used as starting reagents for the synthesis of tetrahydro-β-carbolines, illustrating the synthetic utility of the developed methodology. A new 1-alkyl ether functionalized imidazolium ionic liquid was also evaluated as the promoter in the indole alkylation reaction, being successfully employed as the catalyst in reactions with aliphatic enones and nitroolefins under solventless conditions.

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No description available.

The development of the Friedel-Crafts reaction using anhydrous aluminum chloride in the condensation or aromatic hydrocarbons and alkyl or acyl halides has resulted in many new and diversified applications of this reaction, such as the preparation of hydrocarbons, keto acids, acids, ketones, and phenols. Halides of iron, tin, phosphorus, zinc, and other metals, and acids such as phosphoric, sulfuric, and anhydrous hydrofluoric have been found to catalyze a large number of reactions of this type. These same catalysts now find a wide commercial application in the alkylation of paraffins and naphthenes, and other types of reactions, such as isomerization, transfer of radicals, and cracking of petroleum. Although the Friedel-Crafts synthesis is very widely used in organic syntheses because of its high efficiency, very little work has been done toward developing a more economical catalyst. The anhydrous aluminum chloride generally used is wholly or partially consumed in a large number of the reactions, in addition to presenting a difficult corrosion problem. Some work has recently been done by Sachanen and Caesar⁽²⁵⁾ on the catalytic effect of activated clays and the type of silica-alumina catalysts used in the cracking of petroleum, when used in a Friedel-Crafts type reaction. The limited amount of work which has been done so far indicates that it might be economical to use a synthetic silica-alumina type catalyst to replace the anhydrous aluminum chloride in reactions of this type, because it could be used for some time without replacement. The object of this investigation was to determine the feasibility of using different synthetic silica-alumina type catalysts in the condensation of benzene with acetic anhydride to produce acetophenone. / Master of Science

La présente thèse s’articule autour de deux sujets. Le premier concerne la localisation des électrons en présence d’impuretés ou d’interfaces dans le réseau hexagonal. Le deuxième, en revanche, traite de l’accumulation de spin dans un supraconducteur hors-Équilibre de type s.Le graphène est la principale motivation de la première partie. Ce matériau bidimensionnel consiste en un feuillet d’atomes de carbones et peut être décrit comme un réseau hexagonal, c’est-à-dire un réseau de Bravais triangulaire avec un motif diatomique. La structure de bande électronique révèle alors l’existence d’électrons de Dirac sans masse et chiraux à basse énergie.D’une part, il est possible d’annihiler ces fermions chiraux en étirant de façon uni-Axiale le matériau. Pour une valeur seuil de l’étirement, les électrons deviennent massiques et non-Relativistes, ce qui définit une transition de phase dite de Lifshitz. Afin de caractériser cette transition, nous étudions la diffusion des électrons sur des impuretés en fonction de l’étirement. Une impureté localisée induit des interférences quantiques dans la densité électronique, connues sous le nom d’oscillations de Friedel. Etant sensibles à la nature chirale des électrons, nous montrons que ces oscillations décroissent selon des lois de puissances qui permettent de caractériser chacune des phases de la transition. La même étude est réalisée dans le cas limite où le diffuseur est une lacune.D’autre part, le motif diatomique du réseau hexagonal propose aussi une incursion dans le monde des isolants et supraconducteurs topologiques. Pour ces systèmes, la caractérisation topologique de la structure de bande électronique permet de prédire l’existence d’états de bord aux interfaces. Nous développons notamment un modèle de supraconducteur topologique basé sur le réseau hexagonal du graphène, en présence de supraconductivité de type singulet (s ou d). Lorsque la symétrie par renversement du temps est brisée par un champ Zeeman, et en présence de couplage spin-Orbit Rashba, nous donnons une prescription qui permet de caractériser les différentes phases topologiques possibles et de prédire l’apparition d’états de bord (états de Majorana) dans des nano-Rubans de graphène.La seconde partie discute l’accumulation de spin dans un supraconducteur hors-Équilibre, joint à un ferromagnétique. Lorsqu’il est à l’équilibre, le supraconducteur est composé de quasiparticules et d’un condensat. L’injection de particules polarisées en charge et en spin, à savoir des électrons polarisés en spin, induit une accumulation de spin et de charge à l’intérieur du supraconducteur. Si l’injection cesse, les populations de spin et de charge vont relaxer vers l’équilibre, mais pas nécessairement sur des échelles de temps identiques. Récemment, la réalisation d’une expérience a mis en évidence que le la charge pouvait relaxer bien plus rapidement que le spin. Afin de confirmer cet effet, une nouvelle expérience a été réalisée grâce à des mesures établies dans le domaine fréquentiel. Ici, nous adressons un model relatif à cette dernière expérience, dans le but d’extraire le temps caractéristique de relaxation du spin qui s’avère être de l’ordre de quelques nanosecondes. / Two fields of research define the framework in which the present thesis can be apprehended. The first one deals with impurity and boundary modes in the hexagonal lattice. The second one concerns a spin accumulation in an out-Of-Equilibrium superconductor.Two fields of research define the framework in which the present thesis can be apprehended. The first one deals with impurity and boundary modes in the hexagonal lattice. The second one concerns a spin accumulation in an out-Of-Equilibrium superconductor.Graphene is the main motivation of the first part. From a crystallographic perspective, the carbon atoms in graphene, a graphite layer, design a triangular Bravais lattice with a diatomic pattern. This gives rise to an extra degree of freedom in the electronic band structure that crucially reveals chiral massless Dirac electrons at low-Energy. First of all, it is possible to make these chiral fermions annihilate when a uniaxial strain stretches the graphene layer. For a critical value of the strain, all the fermions become massive and nonrelativistic, which defines a Lifshitz transition. We study the impurity scattering as a function of the strain magnitude. A localised impurity yields quantum interferences in the local density of states that are known as Friedel oscillations. Because they are affected by the chiral nature of the electrons, we show that the decaying laws of these oscillations are specific to the phase the system belongs to. Thus, the impurity scattering offers the possibility to fully characterise the transition.Second, the diatomic pattern of the graphene lattice can also be considered as an invitation to the world of topological insulators and superconductors. The existence of edge states in such systems relies on the topological characterization of the band structure. Here we especially introduce a model of topological superconductor based on the honeycomb lattice with induces spin-Singlet superconductivity. When a Zeeman field breaks the time-Reversal invariance, and in the presence of Rashba spin-Orbit interactions, we give a prescription to describe the topological phases of the system and predict the emergence of Majorana modes (edge states) in strained and doped nanoribbons.The second part discusses the study of a spin accumulation in an out-Of-Equilibrium s-Wave superconductor. At the equilibrium, the superconductor is made of particles coupled by a s-Wave pairing, as well as unpaired quasiparticles. Injecting spin-Polarised electrons into the superconductor induces charge and spin imbalances. When the injection stops, it may happen that charge and spin do not relax over the same time-Scale. The first experiment that points out such a spin-Charge decoupling has recently been realised. In order to confirm this chargeless spin-Relaxation time, a new experiment has been developed [96], based on measurements in the frequency domain. Here, we address a model that fits the experimental data and thus enables the extraction of this characteristic time that is of the order of a few nanoseconds.

Neste trabalho, um polímero eletrólito derivado do poli(indeno) (PInd) foi desenvolvido como componente de membranas poliméricas a base de polibenzimidazol (PBI) para célula a combustível de média temperatura. Foi investigado o método de síntese, envolvendo a reação de fosfonação pelo método de Friedel-Crafts assistido por catalisador ácido de Lewis AlCl3. O polímero poli(indeno) fosfonado (PPInd) foi comparado com seu análogo sulfonado, o poli(indeno) sulfonado (SPInd), e usados nas blendas com 5, 7,5 e 10% em peso com o PBI. Os polímeros precursores foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, espectroscopia de energia dispersiva, espectrometria de espalhamento Rutherford, análise termogravimétrica acoplada com espectrometria de massas e calorimetria exploratória diferencial. As blendas PPInd/PBI e SPInd/PBI foram caracterizadas por análise termogravimétrica, grau de dopagem e espectroscopia de impedância eletroquímica. A modificação realizada pelo método de Friedel-Crafts permitiu a obtenção do poli(indeno) fosfonado parcialmente solúvel em solventes orgânicos e água, com grau de modificação de 81%. Houve convergência dos teores de modificação encontrados pelas análises termogravimétrica, espectrometria de espalhamento Rutherford e espectroscopia de energia dispersiva. O polímero PPInd apresentou estabilidade química na temperatura de operação da célula a combustível de média temperatura, passando por processos de degradação típicos de sua estrutura aromática fosfonada. A degradação dos polímeros PInd, PPInd e SPInd ocorreu majoritariamente com cisão de unidades monoméricas de indeno não funcionalizado. A inserção dos polímeros modificados PPInd e SPInd no PBI resultou no aumento da condutividade iônica, tendo a blenda com 10% de PPInd apresentado o maior valor de condutividade protônica (0,015 S.cm-1), a 25 oC. O uso do poli(indeno) modificado com grupos ácido fosfônico visa aumentar a gama de eletrólitos para células a combustível de média temperatura. / In this work a polymer electrolyte derivated from the poly(indene) (PInd) was developed to be used as polymer electrolyte membrane in medium-temperature fuel cells. The modification method, based on the AlCl3 assisted Friedel-Crafts reaction, was investigated as fosfonation strategy. The phosphonated poly(indene) was compared to its similar sulphonated poly(indene) and they were used in blends of 5, 7.5 and 10wt% in polybenzimidazole (PBI). Pristine polymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, energy dispersive spectroscopy, Rutherford backscattering spectrometry, thermogravimetric analysis coupled with mass spectrometry and differential scanning calometry. The PPInd/PBI and SPInd/PBI blends were characterized by thermogravimetric analysis, doping level and electrochemical impedance spectroscopy. The modification by Friedel-Crafts reaction produced phophonated poly(indene) with degree of phosphonation of 81%, partially soluble in organic solvent and water. It was found convergence on the results for degree of phosphonation calculated by thermogravimetric analysis, Rutherford backscattering spectrometry and energy dispersive spectroscopy. PPInd presented chemical and thermal stabilities within the fuel cell operating temperature, passing by typical degradation processes of macromolecules made of phosphonated aromatic structures. The degradation of PPInd and SPInd occurred mainly by cleavage of monomeric units of non-funcionalized indene. Addition of modified polymers PPInd and SPInd resulted in increase of PBI’s ionic conductivity. 10PPInd/PBI blend presented the highest ionic conductivity (0.015 S.cm-1) at 25 oC. The use of phosphonated poly(indene) on PBI membranes enlarges the variety of available polymer electrolyte membranes for medium-temperature fuel cells.

Neste trabalho, um polímero eletrólito derivado do poli(indeno) (PInd) foi desenvolvido como componente de membranas poliméricas a base de polibenzimidazol (PBI) para célula a combustível de média temperatura. Foi investigado o método de síntese, envolvendo a reação de fosfonação pelo método de Friedel-Crafts assistido por catalisador ácido de Lewis AlCl3. O polímero poli(indeno) fosfonado (PPInd) foi comparado com seu análogo sulfonado, o poli(indeno) sulfonado (SPInd), e usados nas blendas com 5, 7,5 e 10% em peso com o PBI. Os polímeros precursores foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, espectroscopia de energia dispersiva, espectrometria de espalhamento Rutherford, análise termogravimétrica acoplada com espectrometria de massas e calorimetria exploratória diferencial. As blendas PPInd/PBI e SPInd/PBI foram caracterizadas por análise termogravimétrica, grau de dopagem e espectroscopia de impedância eletroquímica. A modificação realizada pelo método de Friedel-Crafts permitiu a obtenção do poli(indeno) fosfonado parcialmente solúvel em solventes orgânicos e água, com grau de modificação de 81%. Houve convergência dos teores de modificação encontrados pelas análises termogravimétrica, espectrometria de espalhamento Rutherford e espectroscopia de energia dispersiva. O polímero PPInd apresentou estabilidade química na temperatura de operação da célula a combustível de média temperatura, passando por processos de degradação típicos de sua estrutura aromática fosfonada. A degradação dos polímeros PInd, PPInd e SPInd ocorreu majoritariamente com cisão de unidades monoméricas de indeno não funcionalizado. A inserção dos polímeros modificados PPInd e SPInd no PBI resultou no aumento da condutividade iônica, tendo a blenda com 10% de PPInd apresentado o maior valor de condutividade protônica (0,015 S.cm-1), a 25 oC. O uso do poli(indeno) modificado com grupos ácido fosfônico visa aumentar a gama de eletrólitos para células a combustível de média temperatura. / In this work a polymer electrolyte derivated from the poly(indene) (PInd) was developed to be used as polymer electrolyte membrane in medium-temperature fuel cells. The modification method, based on the AlCl3 assisted Friedel-Crafts reaction, was investigated as fosfonation strategy. The phosphonated poly(indene) was compared to its similar sulphonated poly(indene) and they were used in blends of 5, 7.5 and 10wt% in polybenzimidazole (PBI). Pristine polymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, energy dispersive spectroscopy, Rutherford backscattering spectrometry, thermogravimetric analysis coupled with mass spectrometry and differential scanning calometry. The PPInd/PBI and SPInd/PBI blends were characterized by thermogravimetric analysis, doping level and electrochemical impedance spectroscopy. The modification by Friedel-Crafts reaction produced phophonated poly(indene) with degree of phosphonation of 81%, partially soluble in organic solvent and water. It was found convergence on the results for degree of phosphonation calculated by thermogravimetric analysis, Rutherford backscattering spectrometry and energy dispersive spectroscopy. PPInd presented chemical and thermal stabilities within the fuel cell operating temperature, passing by typical degradation processes of macromolecules made of phosphonated aromatic structures. The degradation of PPInd and SPInd occurred mainly by cleavage of monomeric units of non-funcionalized indene. Addition of modified polymers PPInd and SPInd resulted in increase of PBI’s ionic conductivity. 10PPInd/PBI blend presented the highest ionic conductivity (0.015 S.cm-1) at 25 oC. The use of phosphonated poly(indene) on PBI membranes enlarges the variety of available polymer electrolyte membranes for medium-temperature fuel cells.

Neste trabalho, um polímero eletrólito derivado do poli(indeno) (PInd) foi desenvolvido como componente de membranas poliméricas a base de polibenzimidazol (PBI) para célula a combustível de média temperatura. Foi investigado o método de síntese, envolvendo a reação de fosfonação pelo método de Friedel-Crafts assistido por catalisador ácido de Lewis AlCl3. O polímero poli(indeno) fosfonado (PPInd) foi comparado com seu análogo sulfonado, o poli(indeno) sulfonado (SPInd), e usados nas blendas com 5, 7,5 e 10% em peso com o PBI. Os polímeros precursores foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, espectroscopia de energia dispersiva, espectrometria de espalhamento Rutherford, análise termogravimétrica acoplada com espectrometria de massas e calorimetria exploratória diferencial. As blendas PPInd/PBI e SPInd/PBI foram caracterizadas por análise termogravimétrica, grau de dopagem e espectroscopia de impedância eletroquímica. A modificação realizada pelo método de Friedel-Crafts permitiu a obtenção do poli(indeno) fosfonado parcialmente solúvel em solventes orgânicos e água, com grau de modificação de 81%. Houve convergência dos teores de modificação encontrados pelas análises termogravimétrica, espectrometria de espalhamento Rutherford e espectroscopia de energia dispersiva. O polímero PPInd apresentou estabilidade química na temperatura de operação da célula a combustível de média temperatura, passando por processos de degradação típicos de sua estrutura aromática fosfonada. A degradação dos polímeros PInd, PPInd e SPInd ocorreu majoritariamente com cisão de unidades monoméricas de indeno não funcionalizado. A inserção dos polímeros modificados PPInd e SPInd no PBI resultou no aumento da condutividade iônica, tendo a blenda com 10% de PPInd apresentado o maior valor de condutividade protônica (0,015 S.cm-1), a 25 oC. O uso do poli(indeno) modificado com grupos ácido fosfônico visa aumentar a gama de eletrólitos para células a combustível de média temperatura. / In this work a polymer electrolyte derivated from the poly(indene) (PInd) was developed to be used as polymer electrolyte membrane in medium-temperature fuel cells. The modification method, based on the AlCl3 assisted Friedel-Crafts reaction, was investigated as fosfonation strategy. The phosphonated poly(indene) was compared to its similar sulphonated poly(indene) and they were used in blends of 5, 7.5 and 10wt% in polybenzimidazole (PBI). Pristine polymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, energy dispersive spectroscopy, Rutherford backscattering spectrometry, thermogravimetric analysis coupled with mass spectrometry and differential scanning calometry. The PPInd/PBI and SPInd/PBI blends were characterized by thermogravimetric analysis, doping level and electrochemical impedance spectroscopy. The modification by Friedel-Crafts reaction produced phophonated poly(indene) with degree of phosphonation of 81%, partially soluble in organic solvent and water. It was found convergence on the results for degree of phosphonation calculated by thermogravimetric analysis, Rutherford backscattering spectrometry and energy dispersive spectroscopy. PPInd presented chemical and thermal stabilities within the fuel cell operating temperature, passing by typical degradation processes of macromolecules made of phosphonated aromatic structures. The degradation of PPInd and SPInd occurred mainly by cleavage of monomeric units of non-funcionalized indene. Addition of modified polymers PPInd and SPInd resulted in increase of PBI’s ionic conductivity. 10PPInd/PBI blend presented the highest ionic conductivity (0.015 S.cm-1) at 25 oC. The use of phosphonated poly(indene) on PBI membranes enlarges the variety of available polymer electrolyte membranes for medium-temperature fuel cells.

Cette thèse a pour objectif d'étudier les réactions des alcools en conditions hydrothermales. Dans une phase préliminaire, le phényl-éthanediol a été étudiés. Après aldolisation, cyclisation intramoléculaire et aromatisation sont suivi en formant 1-phénylnaphthalène. L'aldolisation et la cyclisation du type de Friedel et Crafts ont été mise en œuvre.Les transformations de l'éthylène glycol et du 1,2-propanediol sont fortement dépendantes des conditions de réaction (température, durée de réaction et nature du solvant). La réaction de transformation du 1,2-propanediol permet de synthètiser les composés suivants : mésitylène, 2-méthyl-pentènal et 2-éthyl-3,5-diméthyl-cyclopent-2-ènone. Ces produits peuvent être utilisés comme biocarburant ou solvant ou peuvent constituer des matières premières pour des synthèses organiques.Les alkylations du naphthalène et du phénol ont été étudiées en détails en fonction de la nature du solvant. L'emploi d'acide chlorhydrique en concentration de 0.05mol/L à 180°C permet l'alkylation des aromats par l'alcool benzylique. D'autres solvants (acide acétique, acide formique à 1mol/L) permettent d'obtenir ces composés avec des rendements d'alkylation inférieurs. Par ailleurs, le recyclage de ces solvants est réalisable. Notons enfin que l'alcool benzylique peut polymériser et cette polymérisation est fortement influencée par la température utilisée. La polymérisation de l'alcool benzylique a été appliquée avec succès à la séparation des platinoïdes d'une solution modèle d'effluents issue du traitement du combustible nucléaire. / This thesis aims to study and to apply reactions of alcohols under hydrothermal conditions.Studies on 1-phenyl-ethanediol show an aldolisation, followed by an intramolecular Friedel-Crafts type reaction and an aromatisation. Finally, it ends up by as 1-phenyl-naphthalene.Ethylene glycol reacts on itself with a strong dependence on the temperature and the solvent. The conversion of 1,2-propanediol showed similar dependences and obtained even the aromatic compound mesitylene and especially the amount of products proves dependence on the temperature and the duration of the reaction. The main compounds can be used as solvents, as biofuel and for syntheses, whereas the byproducts might be biocarburants after hydrogenation.The Friedel-Crafts type reaction is transferred to an intermolecular one. Naphthalene and phenol are studied in more detail. 0.05mol/L HCl are enough in order to benzylate an aromatic compound at 180°C. HCl can be replaced by acetic acid or formic acid, but even concentrations of 1.0mol/L do not achieve results as good as 0.05mol/L HCl. The recycling of the aqueous phase of these reactions is advantageous. Additionally, benzyl alcohol alkylates benzyl alcohol and thus it can polymerize. Higher temperatures lead to longer polymers. This polymerization can be used in the domain of nuclear fuel recycling in order to separate platinum group metals out of a model solution.

The original purpose of this investigation was to prepare a series of diketones. However, since considerable difficulty was encountered in the preparation of these diketones, attention was shifted to a study of the Friedel-Craft reactions of phenolic ethers and to the reaction between phenolic ethers and dicarboxylic acids with boron trifluoride as a catalyst.