The syntheses and catalytic properties of four new 1,2-acenaphthenyl N-heterocyclic carbene-supported palladium(II) catalysts are presented. The acenaphthenyl carbene can be prepared using either mesityl or 2,6-diisopropyl N-aryl substituents. In addition, two new heterogeneous analogs were synthesized with 2,6-diisopropyl N-aryl substituents that were anchored through the backbone to an insoluble silica-support. Comprehensive catalytic studies of the Suzuki coupling of aryl halides with aryl boronic acids were carried out. In general, the homogeneous diisopropyl-functionalized catalyst was found to exhibit superior selectivity and reactivity. A comparison of the performances of the aforementioned catalysts in toluene, dichloromethane and aqueous solutions are also presented. In organic solvents, the catalysts were found to be proficient for the homogeneous Suzuki coupling of aryl iodides, bromides and chlorides with boronic acids at low temperatures (35‒40 °C). Similar reactions that were carried out in aqueous media resulted in the formation of insoluble colloidal catalytic species. Nevertheless, these species still retained high activities in terms of in the Suzuki reaction with aryl chlorides. Moreover, the heterogeneous Pd precipitates can be easily recovered for subsequent use by means of filtration. The activation energies that were determined for the aryl bromide-based Suzuki reactions were found to fall in the range, 159.2‒171.2 kJ mol⁻¹ in organic solvents and 111.3‒115.9 kJ mol⁻¹ in water. The corresponding activation energy for the aryl chloride was found to be 321.8 kJ mol⁻¹ in aqueous media using the homogeneous diisopropyl-functionalized carbene catalyst. Conversely, the heterogeneous catalyst exhibited reactivity toward aryl iodides and bromides exclusively, and required significantly higher temperatures and catalyst loadings in both toluene and water. Additional experimental trials that were performed in tetrahydrofuran solution at lower temperatures resulted in substantially larger catalytic conversions. The heterogeneous catalyst allowed for easy separation and recovery. However, the catalyst exhibited a significant decrease in reactivity toward the aryl halides after two consecutive trials. / text

O biodiesel é definido como um mono alquil éster de ácidos graxos de cadeia longa derivado de fontes renováveis tais como óleos vegetais e gorduras animais. Sua importância está associada ao uso como um combustível alternativo para motores do ciclo Diesel. É obtido através da reação de transesterificação nas quais os triacilglicerídeos (óleo ou gordura) reagem com o álcool, em presença de um catalisador ácido ou básico, produzindo ésteres de ácidos graxos e glicerol. Esta transesterificação pode ser por catálise homogênea ou heterogênea, dependendo do tipo de catalisador. O grande desafio da indústria é encontrar os parâmetros ideais desse processo a fim de alcançar um produto e uma rota de produção tecnologicamente eficiente e que seja ambientalmente correta. Nesta dissertação, estudou-se a síntese do biodiesel a partir da transesterificação do óleo de soja por catálises homogênea e heterogênea. Foram realizadas reações de transesterificação por rotas metílica e etílica, empregando os catalisadores homogêneos (hidróxido de potássio e ácido sulfúrico) e heterogêneos [resinas comerciais de troca iônica (Amberlyst 15, Amberlyst 26 e Lewatit VPOC 1800)]. Estudou-se o efeito da variação do tipo e da percentagem de catalisador, razão molar álcool/óleo, temperatura e tempo de reação. As reações foram conduzidas em um reator de vidro, a pressão atmosférica e a conversão foi avaliada pela massa do produto, análises de espectrometria na região do infra-vermelho (FTIR) e de espectrometria de ressonância magnética nuclear de 1H (RMN1H). Na catálise homogênea, observaram-se rendimentos acima de 95 % com 1 % de KOH em todas as proporções metanol/óleo à temperatura ambiente. Com etanol, o máximo atingindo foi de 82 % de ésteres na razão molar 6:1. Na catálise ácida homogênea, os rendimentos foram menores, atingindo o máximo de 81 % de conversão, com 3 % de ácido sulfúrico, razão metanol/óleo 12/1, 50 C, por 3h. Nas reações aplicando as resinas de troca iônica, a melhor condição de reação encontrada foi com a utilização da Amberlyst 26, percentagem molar de 12,5 % (de grupos funcionais da resina em relação ao óleo), obtendo-se 100 % de conversão em ésteres com metanol, por 8 h de reação, a 65 C e agitação 300 rpm. Com a Amberlyst 15, o máximo atingido foi de 13 % de rendimento, utilizando metanol, 50 % de resina, a 65 C e por 8 h. Com a VPOC, não foram obtidos resultados significativos. Estes testes provam a viabilidade do uso da resina de troca iônica básica como um potencial catalisador para a produção de biodiesel. / Biodiesel is defined as a mono alkyl ester of fatty acids of long chain derived from renewable sources such as vegetable oils and animal fats. Its importance is related to the use as an alternative fuel for diesel cycle engines. The biodiesel could be obtained by the transesterification reaction in which triacylglycerides (oil or grease) react with alcohol in the presence of an acid or base catalyst to produce esters of fatty acids and glycerol. Such transesterification can be carried out by homogeneous or heterogeneous catalysis, depending on the type of catalyst. The major challenge is to find the ideal parameters of this process in order to achieve a technologically efficient product and route of production environmentally friendly. In this work, we studied the synthesis of biodiesel from transesterification of soybean oil employing homogeneous or heterogeneous catalyses. Transesterification reactions by methanol and ethanol routes were carried out using the homogeneous catalysts (potassium hydroxide and sulfuric acid) and heterogeneous [ion-exchange commercial resins (Amberlyst 15, Amberlyst 26 and Lewatit VPOC 1800)]. We studied the effect of varying the type and percentage of catalyst, molar ratio alcohol/oil, temperature and reaction time. The reactions were conducted in a glass reactor, atmospheric pressure and the conversion was evaluated by the product mass, analysis of spectrometry in the infrared region (FTIR), and 1H nuclear magnetic resonance spectroscopy (1H NMR). In homogeneous catalysis, yields above 95% with 1% KOH at any ratio methanol/oil at room temperature were achieved. With ethanol, the maximum conversion achieved was 82% ester at a molar ratio of 6:1. In homogeneous acid catalysis, the yields were lower, reaching a maximum of 81% conversion, with 3% sulfuric acid, methanol/oil ratio of 12/1, at 50 C for 3 h. In the reactions where ion exchange resins were applied, the best reaction condition was found with the use of Amberlyst 26, molar percentage of 12.5% (functional groups of the resin in relation to oil), obtaining 100% conversion esters with methanol for 8h-reaction at 65C and agitation at 300 rpm. With Amberlyst 15, the maximum reached was 13% yield, using methanol, 50% resin at 65 C for 8 h. No significant results were obtained with VPOC resin. These results prove the feasibility of using basic ion-exchange resin as a potential catalyst for the production of biodiesel.

O biodiesel é definido como um mono alquil éster de ácidos graxos de cadeia longa derivado de fontes renováveis tais como óleos vegetais e gorduras animais. Sua importância está associada ao uso como um combustível alternativo para motores do ciclo Diesel. É obtido através da reação de transesterificação nas quais os triacilglicerídeos (óleo ou gordura) reagem com o álcool, em presença de um catalisador ácido ou básico, produzindo ésteres de ácidos graxos e glicerol. Esta transesterificação pode ser por catálise homogênea ou heterogênea, dependendo do tipo de catalisador. O grande desafio da indústria é encontrar os parâmetros ideais desse processo a fim de alcançar um produto e uma rota de produção tecnologicamente eficiente e que seja ambientalmente correta. Nesta dissertação, estudou-se a síntese do biodiesel a partir da transesterificação do óleo de soja por catálises homogênea e heterogênea. Foram realizadas reações de transesterificação por rotas metílica e etílica, empregando os catalisadores homogêneos (hidróxido de potássio e ácido sulfúrico) e heterogêneos [resinas comerciais de troca iônica (Amberlyst 15, Amberlyst 26 e Lewatit VPOC 1800)]. Estudou-se o efeito da variação do tipo e da percentagem de catalisador, razão molar álcool/óleo, temperatura e tempo de reação. As reações foram conduzidas em um reator de vidro, a pressão atmosférica e a conversão foi avaliada pela massa do produto, análises de espectrometria na região do infra-vermelho (FTIR) e de espectrometria de ressonância magnética nuclear de 1H (RMN1H). Na catálise homogênea, observaram-se rendimentos acima de 95 % com 1 % de KOH em todas as proporções metanol/óleo à temperatura ambiente. Com etanol, o máximo atingindo foi de 82 % de ésteres na razão molar 6:1. Na catálise ácida homogênea, os rendimentos foram menores, atingindo o máximo de 81 % de conversão, com 3 % de ácido sulfúrico, razão metanol/óleo 12/1, 50 C, por 3h. Nas reações aplicando as resinas de troca iônica, a melhor condição de reação encontrada foi com a utilização da Amberlyst 26, percentagem molar de 12,5 % (de grupos funcionais da resina em relação ao óleo), obtendo-se 100 % de conversão em ésteres com metanol, por 8 h de reação, a 65 C e agitação 300 rpm. Com a Amberlyst 15, o máximo atingido foi de 13 % de rendimento, utilizando metanol, 50 % de resina, a 65 C e por 8 h. Com a VPOC, não foram obtidos resultados significativos. Estes testes provam a viabilidade do uso da resina de troca iônica básica como um potencial catalisador para a produção de biodiesel. / Biodiesel is defined as a mono alkyl ester of fatty acids of long chain derived from renewable sources such as vegetable oils and animal fats. Its importance is related to the use as an alternative fuel for diesel cycle engines. The biodiesel could be obtained by the transesterification reaction in which triacylglycerides (oil or grease) react with alcohol in the presence of an acid or base catalyst to produce esters of fatty acids and glycerol. Such transesterification can be carried out by homogeneous or heterogeneous catalysis, depending on the type of catalyst. The major challenge is to find the ideal parameters of this process in order to achieve a technologically efficient product and route of production environmentally friendly. In this work, we studied the synthesis of biodiesel from transesterification of soybean oil employing homogeneous or heterogeneous catalyses. Transesterification reactions by methanol and ethanol routes were carried out using the homogeneous catalysts (potassium hydroxide and sulfuric acid) and heterogeneous [ion-exchange commercial resins (Amberlyst 15, Amberlyst 26 and Lewatit VPOC 1800)]. We studied the effect of varying the type and percentage of catalyst, molar ratio alcohol/oil, temperature and reaction time. The reactions were conducted in a glass reactor, atmospheric pressure and the conversion was evaluated by the product mass, analysis of spectrometry in the infrared region (FTIR), and 1H nuclear magnetic resonance spectroscopy (1H NMR). In homogeneous catalysis, yields above 95% with 1% KOH at any ratio methanol/oil at room temperature were achieved. With ethanol, the maximum conversion achieved was 82% ester at a molar ratio of 6:1. In homogeneous acid catalysis, the yields were lower, reaching a maximum of 81% conversion, with 3% sulfuric acid, methanol/oil ratio of 12/1, at 50 C for 3 h. In the reactions where ion exchange resins were applied, the best reaction condition was found with the use of Amberlyst 26, molar percentage of 12.5% (functional groups of the resin in relation to oil), obtaining 100% conversion esters with methanol for 8h-reaction at 65C and agitation at 300 rpm. With Amberlyst 15, the maximum reached was 13% yield, using methanol, 50% resin at 65 C for 8 h. No significant results were obtained with VPOC resin. These results prove the feasibility of using basic ion-exchange resin as a potential catalyst for the production of biodiesel.

Depuis le début des années 1990, l'hétéroannélation de Larock est apparue comme une méthode de choix pour obtenir, en une seule étape, des indoles 2,3-disubstitués. Cependant, bien qu'efficace, certains inconvénients restaient associés à cette stratégie comme l'utilisation d'un système catalytique homogène associé à l'emploi de sels. Pour cette raison, nous avons développé une nouvelle méthodologie sans sels ou additifs par catalyse hétérogène. Différents catalyseurs commerciaux ou faciles d'accès (Pd/C ou [Pd]/NaY) ainsi que de nouveaux complexes au palladium immobilisés sur SBA-15 ont été testés. De façon surprenante, ces nouvelles conditions ont permis une activation de 2-bromoanilines et ce, sans l'emploi d'additifs. Une autre méthode d'obtention de ces hétérocycles a émergé ces dernières années et se pose comme une alternative aux couplages traditionnels : l'arylation d'indoles. Malgré de nombreuses améliorations, aucun travail ne décrivait une procédure permettant une arylation complémentaire C2 ou C3 d'indoles libres avec un système catalytique unique. Nous avons développé un tel système, basé sur une pallado-catalyse dans l'eau. Cette stratégie permet d'atteindre des sélectivités C2/C3 ou C3/C2 élevées avec de bons rendements isolés par un simple contrôle du couple (base/halogénure d’aryle).Enfin, dans le cadre de nos travaux visant la synthèse par catalyse hétérogène de produits à haute valeur ajoutée, nous avons initié des études sur l'obtention de pyrroloiminoquinones. La méthode consistant en une catalyse hétérogène monotope en seulement deux grandes étapes devrait permettre un accès rapide à de nombreux dérivés bioactifs isolés d'organismes marins. / Since the beginning of the 90's, the Larock heteroannulation became a method of choice to afford, in a single step, 2,3-disubstituted indoles. While effective, this methodology suffered of drawbacks lied to the use of salts, additives and homogeneous catalyst. Thus, we developed the first ligand and salt free heterogeneous Larock heteroannulation. Different commercially available, home made catalysts (Pd/C or [Pd]/NaY) or new palladium complexes immobilised onto mesoporous silica SBA-15 were evaluated. Surprisingly, this methodology allowed an activation of the 2-bromoanilines without using additives. Another procedure to obtain indole nucleus emerged over the past few years as an outstanding alternative to traditional cross-coupling reactions: namely the “direct arylation”. Despite major improvements, no report focuses on complementary C2 and C3-arylation procedures by means of a unique catalytic system. Herein, we describe an innovative “on water” palladium-catalyzed C–H arylation of (NH)-indoles that is site-selective through a base/halide-controlled using cheap reagents. This methodology allows the preparation of either C2- or C3-arylindoles with high isolated yields. Finally, as part of our project related to syntheses of high added value products by heterogeneous catalysis, we investigated studies in order to obtain pyrroloiminoquinones. This new methodology using only two steps will permit an access to numerous bioactive analogues.

La recherche de nouvelles méthodes pour l’acquisition de données physiques et chimiques de réactions en limitant les effet néfastes sur l’Homme est d’une grande importance pour la chimie moderne. L’utilisation de nouveaux outils miniaturisés permet de limiter les quantités de produits chimiques utilisées tout en augmentant la productivité de la recherche. En effet, l’étude de différents paramètres contrôlés simultanément permet d’augmenter le nombre d’expériences pour un temps donné. Malgré tout, cette étape doit être réalisée après détermination au préalable des paramètres clés de la réaction par l’utilisation d’outils haut débit tels que la robotique. Cesdifférents outils sont utilisés pour l’optimisation et la recherche d’une nouvelle voie de synthèse d’une réaction d’intérêt industriel.De plus, pour répondre à l’intérêt de la catalyse hétérogène dans l’industrie pour la séparation facilitée et le recyclage de ces catalyseurs, nous avons développé deux outils miniaturisés. Cesderniers permettent l’étude et l’acquisition de données de réactions chimiques catalysées par des solides. Le développement s’est inscrit en deux étapes : une caractérisation physique des outils puis l’étude d’une réaction modèle industrielle, l’acylation de l’anisole par des catalyseurs de type zéolite. / The search for new methods for the acquisition of physical and chemical reactions by limiting the effect on humans is of great importance for modern chemistry. The use of new miniaturized tools can limit the quantities of chemicals used while increasing research productivity. Indeed, the study of the various parameters monitored simultaneously increases the number of experimentsfor a given time. Nevertheless, this step must be performed after prior determination ofthe key parameters of the reaction by the use of high flow tools such as robotics. These tools are used for optimization and the search for new synthetic pathway of a reaction of industrial interest. In addition, to meet the interests of heterogeneous catalysis in industry for easier separation and recycling of these catalysts, we have developed two miniaturized tools. These allow the study and data acquisition of chemical reactions catalyzed by solid. Development was registeredin two stages : a physical characterization tools and the study of an industrial model reaction, the acylation of anisole with zeolite catalysts.