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.

No description available.

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

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.

Des complexes NHC du gallium(III) et de l’indium(III) ont été préparés. Ces composés, simples à synthétiser, se sont révélés être beaucoup plus stables que les sels commerciaux de type MX₃ (M = Ga, In ; X = Cl, Br, I). Ces complexes, une fois activés par AgSbF₆, présentent un fort caractère acide de Lewis. [IPr-GaCl₂][SbF₆] s’est ainsi montré très actif en tant qu’acide de Lewis π et a été utilisé comme catalyseur dans différentes réactions impliquant l’activation de fonctions carbonées insaturées. Il a ainsi permis d’effectuer des hydroarylations inter- et intramoléculaires d’alcynes, d’alcènes et d’allènes. La généralité de cette transformation a pu être démontrée dans une réaction tandem de cycloisomérisation/Friedel-Crafts entre un arényne et un nucléophile aromatique. La capacité des complexes cationiques de gallium et d’indium à activer des alcènes a également pu être mise à profit pour la réduction de dérivés styréniques en présence de cyclohexa-1,4-diène comme source d’hydrogène. Et parce que ces complexes permettent la génération de dérivés du styrène par hydroarylation d’alcynes, une cyclisation réductrice d’arénynes sans précédent a pu être développée. Enfin le complexe [IPr-GaCl₂][SbF₆] a été utilisé dans des réaction impliquant l’eau en tant que réactif. Quelques alcynes ont ainsi pu être hydratés et des esters γ,δ-insaturés ont été transformés en lactones. En résumé, nos complexes cationiques de gallium et d’indium peuvent être utilisés dans des réactions généralement considérées comme relevant du domaine des métaux de transition nobles (Au, Pt, Ru…). / NHC complexes of gallium(III) and indium(III) have been prepared. These compounds, easy to synthesize, proved to be much more stable than the commercially-available salts MX₃ (M = Ga, In ; X = Cl, Br, I). These complexes, once activated by AgSbF₆, show a strong Lewis acid character. For instance, [IPr-GaCl₂][SbF₆] showed a high activity as π-Lewis acid and was used as catalyst in several reactions triggered by the activation of unsaturated C-C bonds such as inter- and intramolecular hydroarylations of alkynes, alkenes and allenes. The versatility of this transformation was demonstrated in a cycloisomerization/Friedel-Crafts tandem reaction between an arenyne and an aromatic nucleophile. The ability of cationic complexes of gallium and indium to activate alkenes was also used for the reduction of styrene derivatives with 1,4-cyclohexadiene as hydrogen source. Also, because these complexes are able to generate styrene derivatives by hydroarylation of alkynes, an unprecedented reductive cyclization of arenynes could be developped. Moreover, [IPr-GaCl₂][SbF₆] was used in reactions involving water as reagent. Several alkynes were hydrated and γ,δ-unsaturated esters were transformed into lactones. In summary, our cationic complexes of gallium and indium can be used in reactions generally catalyzed by noble metals (Au, Pt, Ru…).

A variety of organometallic-fused heterocycles and acene quinones were prepared and characterized. This work was divided into three parts: first, the synthesis of 5,5-fused heterocyclic complexes of tricarbonylmanganese and (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium; second, the synthesis of 1,2-diacylcyclopentadienyl p-cymene complexes of ruthenium(II); and third, synthesis of cyclopentadienyl-fused polyacenequinone complexes of ruthenium, iron and manganese. The first examples of the convenient, versatile and symmetric cyclopentadienyl-fused heterocycle complexes of (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium(II) and tricarbonylmanganese(I) were synthesized starting from (1,2-dicarbophenoxycyclopentadienyl)sodium. The sodium salt was transmetalated using [MnBr(CO)5] and 1/4 [Ru(μ3-Cl)(Cp*)]4 to give [Mn(CO)3{η5-C5H3(CO2Ph)2-1,2}] and [Ru{η5-C5H3(CO2Ph)2-1,2}(Cp*)]. The diester complexes were saponified under basic conditions to obtain the corresponding dicarboxylic acids. The dicarboxylic acids were used to synthesize unique cyclopentadienylmetal complexes including diacyl chlorides, anhydrides, thioanhydrides and p-tolyl imides of ruthenium and manganese. Similarly, a series of 1,2-diacylcyclopentadienyl-p-cymene cationic complexes of ruthenium were synthesized using thallium salt of 2-acyl-6-hydroxyfulvene and [Ru(η6-p-cymene)(μ-Cl)Cl]2 in a 2:1 ratio with an intension of converting them into heterocycle-fused cationic sandwich complexes. However, our attempts of ring closing on 1,4-diketons with sulfur or selenium were unsuccessful. A methodology involving the synthesis of metallocene-fused quinone complexes was employed starting from pentamethylruthenocene-1,2-dicarboxylic acids. The diacyl chloride was prepared in situ from the dicarboxylic acids and used for Friedel-Crafts acylation. We observed single-step room-temperature diacylation of aromatics, including benzene, o-xylene, toluene, 1,4-dimethoxybenzene and ferrocene with pentamethylruthenocene-1,2-diacyl chloride to obtain the corresponding quinone complexes. Similarly, we synthesized mononuclear and binuclear γ-quinones by aldol condensation of 1,2-diformylcyclopentadienylmetal complexes with cyclohexane-1,4-dione or 1,4-dihydroxyarenes. The third methodology involves the Friedel-Crafts acylation of ferrocene with 2-carbomethoxyaroyl chlorides followed by saponification, carbonyl reduction, and ring closing by second Friedel-Crafts acylation to give Ferrocene-capped anthrone-like tricyclic and tetracyclic ketones. The oxidation of the ketones gave [3,4-c]-fused α-quinone complexes of iron. The oxidative and reductive coupling, enolization and C-alkylation of the anthrone complex were studied. Solvolysis of α-carbinol gave α-ferrocenylcarbenium salt, which underwent dimerization on treatment with non-nucleophilic base. We were successful to trap the in situ generated trimethylsilylenol ether of ferrocene-anthrone using dienophiles like N-phenylmaleimide or dimethylacetylenedicarboxylate under Diels-Alder conditions.

No description available.