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Les nanoparticules métalliques (MNPs) ont un grand succès dans les dernières décennies dû à la variété d'applications dans différents domaines (microélectronique, matériaux, catalyse). Mis à part les solvants organiques, les liquides ioniques, l'eau, le CO2 supercritique et les polyols, en particulier le glycérol, ont démontré leur capacité à stabiliser et immobiliser les nanoparticules métalliques. Ces milieux évitent l'agglomération des MNPs et facilitent leur recyclage. Des nanoparticules de Pd(0) et Ni(0) dans le glycérol, sphériques, petites en taille et bien dispersées, ont été synthétisées avec succès à partir d'une méthodologie simple sous pression d'hydrogène, en présence de différents stabilisants (alkaloïdes, phosphine, polymer). La caractérisation complète de ces matériaux en solution et à l'état solide, ainsi que la possibilité de faire des synthèses à grande échelle et de stocker les solutions catalytiques longtemps, montrent la grande stabilité de ces solutions colloïdales. Les nanoparticules dans le glycérol ont été impliquées dans une large variété de transformations : hydrogénations, hydrodéhalogénations, couplages de Hiyama, additions conjuguées et hydrosilylations. De plus, nous avons étudié l'effet du stabilisant sur la réactivité catalytique, nous permettant de contrôler l'état de surface des nanoparticules et moduler ainsi leur réactivité. Nous avons montré, de même, la capacité du glycérol pour immobiliser les catalyseurs, ce qui s'est traduit par la possibilité de recycler la phase catalytique entre 4 et 10 fois sans perte de metal. En parallèle, nous avons évalué le comportement du Ni(OAc)2 libre de ligands dans le glycérol, en tant que catalyseur alternatif pour des couplages C-C et C-hétéroélément. Nous présentons aussi une étude en flux continu, en collaboration avec la Maison Européenne des Procédés Innovants (MEPI), pour l'hydrogénation de différents groupes fonctionnels, en utilisant les PdNPs dans le glycérol synthétisées préalablement. / Metal nanoparticles (MNPs) have been largely studied in the last decades due to their interesting properties which found applications in several fields (microelectronics, materials and catalysis, among others). In contrast to common organic solvents, ionic liquids, water, supercritical CO2, polyols such as glycerol, represent innovative solvents for the immobilization of MNPs, avoiding their agglomeration and facilitating their recycling. Small, spherical, and well-dispersed Pd(0) and Ni(0) nanoparticles were synthesized under hydrogen pressure in glycerol, in the presence of different kinds of stabilizers (cinchona-based alkaloids, phosphine, polymer). The high stability of these colloidal solutions permitted the full characterization both in solution and at solid state, large-scale synthesis, and stocking the solutions for months. These colloidal catalysts were applied in a large variety of transformations including hydrogenations, hydrodehalogenations, Hiyama C-C couplings, hydrosilylation reactions, and Michael conjugate additions. Furthermore, we conducted a comparative study exhibiting the differences in catalytic reactivity by effect of the stabilizer, allowing us tuning the surface-state of the nanoparticles. Moreover, we showed the ability of glycerol to immobilize metal nanoparticles permitting the recycle of the catalytic phase between 4 and 10 times, without metal leaching. Additionally, we studied the behavior of ligand-free Ni(OAc)2 in glycerol as an alternative catalyst for C-C and C-heteroatom couplings. Also, we developped a continuous flow study, in collaboration with the Maison Européenne des Procédés Innovants (MEPI), for the hydrogenation of different functional groups, using PdNPs in glycerol

La nécessité grandissante de disposer d’une large librairie de diverses petites molécules pour le screening biologique constitue une puissante force motrice pour les chimistes organiciens et requiert en amont le développement de méthodologies rapides et efficaces. Dans ce cadre, nous nous sommes plus particulièrement intéressés à la fonctionnalisation d’énamides qui représentent des blocs moléculaires intéressants permettant d’introduire des fonctionnalités aminées dans des systèmes variés. Notre objectif a été de synthétiser des petites bibliothèques de molécules azotées à partir de substrats communs tout en mettant en oeuvre les différentes stratégies de la synthèse orientée vers la diversité et en s’attachant à respecter les règles suivantes : économie d’atomes, processus catalysés, synthèses rapides en peu d’étapes et contrôle de la stéréoselectivité. Dans un premier temps, nous avons principalement synthétisé divers énamides, nous permettant par la suite de développer des méthodologies innovantes et d’accéder à des « structures privilégiées » ou des fragments clés présents dans des produits naturels ou dans des substances potentiellement biologiquement actives en mettant en jeu des processus variés telles que des réactions d’aza-Michael, d’oxyamidation ou en cascade et la chimie du palladium avec de la CH insertion, des dioxoazoborocanes ou encore l’utilisation de l’auxiliaire chiral SAMP. / The continuing demand to synthesize new and original collections of small molecules for the biological screening is an attractive subject for organic chemists and requires upstream the development of fast and easy synthetic methods. In this context, we decided to focus particularly on the functionalization of enamides which represent valuable building blocks in order to introduce nitrogen based functionality into various organic systems. Our objective was to synthesize new nitrogen containing compound libraries starting from common substrates by applying Diversity-Oriented Synthesis strategy and following these rules: atom economy, catalyzed reactions, fast synthesis in few steps and control of stereoselectivity. Firstly we mainly synthesized enamides. Thereafter, we developped efficient methodologies giving access to motifs frequently found in “privileged structures” or key scaffolds present in natural products or potential bioactive compounds thanks to various processes like aza-Michael, oxyamidation or cascade reactions, palladium chemistry with CH activation, dioxoazoborocanes or chiral auxiliary SAMP.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-21T16:28:43Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-21T16:28:43Z (GMT). No. of bitstreams: 0 / O titanato de estrôncio (SrTiO3) possui estrutura cristalina do tipo perovsquita. Materiais com este tipo de estrutura são utilizados para diversas aplicações, tais como, sensores, atuadores, em células a combustível de óxido sólido, entre outros. Devido as suas interessantes propriedades físicas, o SrTiO3 vem sendo intensamente estudado, em especial com a introdução de dopantes. Portanto, neste trabalho foi investigada a influência de diferentes teores de Ca (1; 2,5 e 5% mol) e Pr (0,025; 0,050; 0,075 e 1% mol) na microestrutura e propriedades elétricas e dielétricas do SrTiO3, assim como o material sem aditivos (puro). Os resultados mostram que após a sinterização do SrTiO3 puro, a microestrutura consiste de grãos poligonais com tamanho médio micrométrico, além de texturas lisas e rugosas. A condutividade elétrica das amostras sintetizadas sinterizadas a 1450 e 1500ºC é máxima para 2 horas de patamar. Apenas as amostras de SrTiO3 contendo 1% em mol de Ca apresentam fase única. O tamanho médio de grãos das amostras contendo 1% em mol de Ca é 10,65 ± 0,28 µm e para teores acima deste valor ocorre crescimento significativo dos grãos. As medidas de condutividade elétrica mostraram que as amostras contendo a adição de 1% em mol de Ca possuem maior condutividade dos grãos em relação ao material puro. Para as amostras contendo teores de até 0,075% mol de Pr, pode-se observar alguns grãos lisos e outros rugosos e não há variação considerável do tamanho médio de grãos. As amostras contendo menor teor de Pr (0,025% mol) apresentam maior condutividade dos grãos e contornos de grãos. As amostras de SrTiO3 sintetizado sinterizadas a 1450ºC/10 h apresentaram permissividade elétrica colossal em temperatura ambiente em altas frequências. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Nucleophilic additions are an important class of reactions in the preparation of several organic compounds. Metals facilitate nucleophilic additions in many cases. The present work Mechanistic Investigation of Metal Promoted Nucleophilic additions is an attempt to understand the mechanism of nucleophilic additions to imines and carbonyl compounds mediated by the transition metal complexes. Understanding the mechanism of metal promoted nucleophilic additions can facilitate the design and synthesis of more efficient catalysts. Chapter 1 provides a brief introduction to nucleophilic addition. A few named reactions that involve nucleophilic addition are described. An overview of the metal promoted nucleophilic addition reactions and their mechanisms are presented. A short note on the importance of understanding the mechanism of metal promoted nucleophilic addition is included. This section ends with the scope of the present work. Chapter 2 “Mechanistic Investigation of Titanium Mediated Reactions of Imines” deals with two reactions. The first reaction is the formation of reduced amines on reduction of imines. Amines and diamines are synthesized often from imines. A convenient route to such nitrogen containing compounds is through reduction of imines and through reductive coupling of imines respectively. Since both reactions occur in a parallel fashion, during the synthesis of diamines, amines are obtained as side products and vice versa. This problem is acute in the case of titanium based reducing agents. These reducing agents are called low valent titanium reagents because low valent titanium species are generated in situ either from titanium(IV) or titanium(III) reagents. There is no clear understanding of the nature of the low valent titanium involved in the reaction. To rectify this, a mechanistic understanding of this reaction is essential. An attempt was made to probe the mechanism of formation of amines using low valent titanium formed by using two different reducing agents namely phenylsilane and zinc. With the help of isotopic labelling studies, it was found that the mechanism of formation of an amine with phenylsilane involves a direct hydrogen transfer from phenylsilane to an imine. This was verified using deuterium labelled phenylsilane. With zinc, it follows a traditional titanacycle pathway which was verified by quenching with the deuterium oxide. A second reaction that has been probed is the alkylation of imines by Grignard reagents using chiral titanium complexes. Alkylation of imines is one of the suitable routes to prepare chiral amines. Alkylation of imines employing a Grignard reagent with Ti(OiPr)4 can proceed through two different pathways depending on the amount of the Grignard reagent used. Alkylation reaction with one equivalent of Grignard reagent can proceed through a Ti(IV) species and the alkylation reaction with two equivalents of the Grignard reagent can proceed through a Ti(II) species. The reaction proceeding through Ti(IV) is less wasteful as it only requires one equivalent of the Grignard reagent. The two pathways differ from each other in the nature of the transition state where the C-C bond is formed. To verify the favourable pathway, chiral titanium complexes were prepared and alkylation carried out. The alkylation results suggest that one equivalent of Grignard is sufficient to give good yields of the alkylated product and the reaction may proceed through a Ti(IV) promoted path. It was reported in the literature that at least three equivalents of Grignard reagent are required to get good yields of the alkylated product with zirconium complexes. This work suggests a greener alternate to alkylation of imines. Chapter 3 “Asymmetric Transfer Hydrogenation Reaction of Ketones in Water” deals with the synthesis of chiral ruthenium half-sandwich complexes employing a proline diamine ligand which has phenyl, ethyl, benzyl, or hydrogen as a substituent. These complexes were characterized by X-ray diffraction. In addition, all these complexes were obtained as single diastereoisomers. These complexes were used as catalysts for the reduction of a variety of ketones to chiral alcohols in water using sodium formate as a hydride source. Stoichiometric reaction between sodium formate and the catalysts showed the formation of hydride complexes as the active species. Based on the electronic effects observed, the key step is found to be a nucleophilic attack of hydride on the carbonyl carbon of ketones. In the transfer hydrogenation reaction with DCOONa, more of 1-phenylethanol- 1-2H1 was observed with all the ruthenium catalysts suggesting that the hydrogen from sodium formate is transformed into a metal hydride which is subsequently transferred to the ketones to form chiral alcohols. The catalysts were optimized with acetophenone as a model substrate. Only in the case of a catalyst which has a phenyl substituent, silver nitrate was found to enhance the formation of aqua complex which in turn resulted in good yields of the chiral alcohols. Among all the complexes studied, the catalyst bearing a phenyl group induces greatest enantioselectivity. It can also be recycled. Chapter 4 “On the Formation of a Ruthenium-PPh2H Complex Using 1- Phenylethane-1,2-diol” deals with the mechanism of formation of PPh2H from PPh2Cl. This unique transformation involves a ruthenium-cymene dimer, PPh2Cl and 1-phenylethane-1,2- diol. In the attempted synthesis of a ruthenium bisphosphinite complex, using the ruthenium-cymene dimer, chlorodiphenylphosphine and 1-phenylethane-1,2-diol, the formation of [Ru(η6-cymene)Cl2PPh2H] was observed in good yield. Formation of the expected ruthenium bisphosphinite complex was not observed. The reaction was carried out in the absence of 1-phenylethane-1,2-diol resulted in the formation of [Ru(η6- cymene)Cl2PPh2Cl] suggests that the diol acts as a reducing agent. To verify the source of hydrogen in the 1-phenylethane-1,2-diol, deuterated diols were prepared. The reactions with the deuterated diols revealed several interesting aspects of the formation of the Ru-PPh2H complex. Chapter 5 “Mechanistic Studies on the Diazo Transfer Reaction” deals with the synthesis of labelled azides and the labelled azidating reagent to probe the mechanism of the diazo transfer reaction. Azides are important precursors used for a variety of chemical transformations including the celebrated Cu(I) catalyzed click reaction. Azides are also used as protecting groups for amines as they can be conveniently reduced to amines. Azidation of amines usually yield azides, with retention of stereochemistry. There is a possibility that the azide formation can occur through the SNi mechanism with retention of configuration where nitrogen in the starting material will not be retained after forming an azide. The reaction was carried out with 13C and 15N labelled L-valine and L-isoleucine to probe this possibility. The resultant labelled azide has 15N retained in its position. This excluded the SNi pathway. To show where the nucleophilic amine group is attacking the azide, labelled imidazole-1¬sulfonyl azide was synthesized from NaN215N. Reactions were carried out with L-valine (labelled and unlabelled) in the presence of a metal catalyst and with unlabelled L-valine in the absence of catalyst. These results confirm the postulated pathways described in the literature.

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Il est possible de modifier la composition des bétons utilisés dans le domaine de la construction pour réduire sensiblement le dégagement de CO2 associé à leur fabrication. Ceci est obtenu en réduisant significativement la quantité de clinker et en incorporant des matériaux de substitution appelés additions. Elles sont généralement moins réactives et demandent, pour maintenir un niveau acceptable de performances mécaniques et de durabilité, une réduction importante du dosage en eau. C'est le cas des bétons à faible impact environnemental. L'utilisation de superplastifiant dans ces bétons permet d'augmenter leur fluidité mais leur viscosité plastique reste toujours élevée ce qui induit des problèmes de mise en œuvre. La maîtrise de la viscosité plastique de ce type de béton est donc cruciale pour le développement de ces produits.Avec cet objectif fixé, dans la première partie de cette étude, un rhéomètre à béton, adapté aux spécificités des bétons à faible impact environnemental, a été développé. Associé à un protocole d'essai pertinent cet appareil permet de caractériser le comportement rhéologique non seulement des bétons courants mais également des bétons à faible impact environnemental.Ensuite, l'utilisation de ce rhéomètre dans un programme expérimental a permis de mettre en évidence l'effet des paramètres de compositions et notamment le taux de substitution et la nature des additions sur leur comportement rhéologique.Les résultats obtenus à partir de ce programme ont permis de proposer et valider un modèle de calcul de la viscosité plastique en considérant que le béton est constitué de deux échelles : pâte et granulats. Le modèle est applicable pour les bétons ordinaires et pour les bétons à faible impact environnemental. Une méthode d'optimisation de la viscosité a été proposée à l'aide du modèle. / It is possible to modify the composition of conventional concrete used in the building field in order to reduce the emission of CO2 associated with their manufacture, particularly in the production of their constituents. This is can be achieved by significantly reducing the amount of clinker and incorporating alternative materials (mineral and chemical additions), which are generally have a lower reactivity and require a low quantity of water, with an adequate level of mechanical performance and durability. This is the case of concrete with low environmental impact. The use superplasticizer in the production of concrete allows increasing their flowability, despite the using of low content of water, but their plastic viscosity remains high and may cause problems of implementation. Controlling the plastic viscosity of this type of concrete is crucial to ensure the development of these products.Within this objective, a rheometer for concrete was developed. The relevant test protocol used for this apparatus enables to characterize the rheological behavior not only for conventional concrete, but also for concrete with low environmental impact.The use of the developed rheometer within an experimental program permits then to highlight the effect of the parameters of concrete compositions, and in particular the used additions (type and rate of substitution) on their rheological behavior.The obtained results from this program propose and validate a mathematical model for assessing the plastic viscosity, which is applicable for ordinary concrete and concrete with low environmental impact. An optimization method for calculating the plastic viscosity of the concrete has been proposed using this model.

O aproveitamento de fibras naturais como materiais de reforço em compósitos cimentícios é uma alternativa que apresenta potencial técnico, econômico, social e ambiental. Porém seu uso é limitado pela baixa durabilidade e estabilidade dimensional, refletidas na perda da capacidade de reforço das fibras em consequência da sua rápida degradação dentro da matriz de cimento. Para abordar esta situação, estudos ao redor do mundo mostraram que é possível aplicar tratamentos sobre as fibras e/ou matriz, modificando seu comportamento e obtendo resultados positivos. Dentro deste contexto, o presente estudo teve por objetivo aplicar e avaliar o efeito do tratamento de hornificação sobre polpas vegetais de eucalipto e pinus (não branqueadas) e do tratamento de carbonatação acelerada ou uso de adições pozolânicas sobre a matriz de cimento, alterando sua alcalinidade, buscando assim, maior durabilidade do material de reforço e otimizando o desempenho geral do compósito. Para atingir os objetivos propostos foram determinadas e analisadas propriedades físicas, morfologias e microestruturais das polpas antes e após do processo de hornificação. Posteriormente, em uma segunda etapa do trabalho, foram produzidos compósitos cimentícios com vistas em determinar o teor de reforço ótimo (6%, 8% e 10%) de polpas celulósicas (tratadas e não tratadas), curados por cura térmica sendo avaliados por meio da determinação de propriedades físico-mecânicas, microestruturais e de durabilidade. Seguidamente, em uma terceira etapa do trabalho, foram produzidos compósitos cimentícios com polpas celulósicas (tratadas e não tratadas) curados por carbonatação acelerada, sendo avaliados por meio da determinação de propriedades físico-mecânicas, microestruturais e de durabilidade. Na última etapa, foram avaliadas formulações de compósitos cimentícios reforçados com a polpa celulósica (tratada e não tratada) de melhor desempenho com adição de cinzas de casca de arroz ou resíduo de carvão ativado como material pozolânico, sendo avaliadas suas propriedades físico-mecânicas, microestruturais e de durabilidade. Os resultados obtidos permitem identificar que a hornificação gera modificações na estrutura interna das polpas reduzindo sua capacidade de absorção de água, estabilidade dimensiona, colapso do lúmen e incremento da rugosidade superficial sem ocasionar deterioração da sua estrutura ou componentes. No que concerne à influência da porcentagem de polpa de reforço aplicada, o desempenho das propriedades físico-mecânicas caiu proporcionalmente com o incremento da porcentagem de reforço, sendo este fenômeno acompanhado pela formação de aglomerações de polpas. Assim, os compósitos com 6% de reforço de polpas de eucalipto ou pinus se destacaram pelo desempenho. Em relação ao reforço com fibras hornificadas, foram obtidas melhoras no desempenho do módulo de ruptura e energia específica, com destacável conservação após do material ser envelhecido. Ao ser aplicada a cura por carbonatação acelerada sobre as matrizes, se obtiveram melhoras destacáveis na durabilidade das fibras e no desempenho mecânico antes e após do envelhecimento acelerado em relação aos compósitos curados por cura térmica. Estas melhoras foram mais representativas com o reforço de polpas hornificadas. O uso de substituição parcial do cimento por CCA mostrou o pior desempenho físico-mecânico. Por sua vez, a substituição de 25% de RCA permitiu alcançar melhoras no comportamento das propriedades físico-mecânicas das matrizes, especialmente com o reforço com a polpa hornificada. / The use of natural fibers as reinforcement materials in cement composites is an alternative that offers technical, economic, social and environmental potential. But their use is limited by its low durability and dimensional stability, reflected in a building capacity loss as result of its rapid degradation within the cement matrix. To address this situation, studies around the world show that it is possible to apply treatments on the fibers and/or the matrix, thus, modifying their behavior and obtaining positive results. Within this context, this study aimed to implement and evaluate the effect an hornification treatment on eucalyptus and pine kraft pulps (unbleached); and an accelerated carbonation treatment or use pozzolanic additions on the cement matrix that changes its alkalinity, seeking thus, greater durability of the reinforcing material, optimizing the overall performance of the composite. To achieve the proposed objectives, the physical, and microstructural morphologies of the pulps were determined and analyzed before and after the hornification process. Then, in a second stage of the work, cementitious composites were produced with a view to determining the optimal reinforcement content (6%, 8% and 10%) of cellulosic pulps (treated and untreated), cured by thermal curing, being evaluated by the determination of its durability, physical-mechanical and microstructure properties. Subsequently, in a third stage of the work, cementitious composites were developed with cellulose pulps (treated and untreated) and cured by accelerated carbonation, being evaluated by the determination of its durability, physical-mechanical and microstructure properties. In the last stage, formulations of cementitious composites reinforced with cellulose pulps (treated and untreated) of better performance were evaluated with the addition of rice husk ash (CCA) or activated coal mining waste (RCA) as pozzolanic material, being evaluated their physicomechanical, microstructural and durability properties. Therefore, we expected to obtain a cement matrix of low alkalinity and a reinforcing fiber with lower capacity for water absorption and higher dimensional stability, which acting together would achieve a superior mechanical performance as well as a longer durability over time. The obtained results allow to identify that the hornification generates modifications in the internal structure of the pulps reducing its capacity of water absorption, stability, lumen collapse and increase surface roughness without causing deterioration of its structure or components. Regarding the influence of the percentage of reinforcing pulp applied, the performance of the physical-mechanical properties fell proportionally with the increment of the reinforcement percentage, being this phenomenon accompanied by formation of agglomerations of pulps. Thus, the composites with 6% reinforcement of pulps of eucalyptus or pinus stood out by the performance. In relation to the reinforcement with hornificated fibers, the performance of the modulus of rupture and specific energy were obtained, with detachable conservation after the material was aged. When accelerated carbonatation curing was applied to the matrices, the durability of the fibers and the mechanical performance before and after the accelerated aging were obtained in relation to the heat curing composites. These improvements were more representative with the reinforcement of hornified pulps. The use of partial cement substitution by CCA showed the worst physicomechanical performance. On the other hand, the substitution of 25% or RCA allowed to achieve improvements in the behavior of the physical-mechanical properties of the matrices, especially with the reinforcement with the hornified pulp.