Les ressources minérales s’épuisent inexorablement, les minerais riches sont de plus en plus difficilement accessibles, et le traitement des minerais implique d’importants impacts environnementaux. En Nouvelle-Calédonie, l’extraction du nickel nécessite la destruction de l’horizon fertile supérieur des sols, et les mines se présentent comme des carrières à ciel ouvert, soumises à l’érosion et menaçant la biodiversité du territoire. Bien que l’exploitation du nickel soit au cœur de l’économie locale, la réhabilitation écologique des sites miniers, et la réintroduction durable d’un couvert végétal sont une nécessité.Le laboratoire ChimEco a démontré qu’il était possible de revégétaliser les sites miniers en réintroduisant des espèces végétales pionnières, résistantes et accumulatrices de manganèse. Ces plantes accumulatrices sont capables d’extraire le manganèse naturellement présent dans le sol et de l’accumuler dans leurs parties aériennes : on parle de phytoextraction. Le laboratoire ChimEco propose en outre une valorisation scientifique et à terme économique des efforts de réhabilitation engagés sur le terrain. En effet, à partir de la biomasse riche en manganèse des plantes accumulatrices, le laboratoire ChimEco a développé un procédé innovant de recyclage des éléments métalliques d’origine végétale en catalyseurs polymétalliques pour la chimie. Il s’agit de l’Ecocatalyse. Ces écocatalyseurs riches en Mn, notés Eco-Mn, ont montré une activité catalytique intéressante dans plusieurs synthèses organiques.Les résultats obtenus en écologie et en chimie par le laboratoire ChimEco prouvent la nécessité d’étudier finement la structure des écocatalyseurs en les considérant comme des matériaux innovants, afin de comprendre et d’améliorer leur activité en synthèse organique, et d’exploiter au mieux les possibilités du procédé. C’est précisément dans ce contexte que s’inscrivent ces travaux de thèse.Plusieurs techniques d’analyse ont été utilisées. Les analyses ICP-MS ont permis de déterminer la composition élémentaire des Eco-Mn. La DRX a permis de mettre en évidence la présence de sels mixtes originaux tels que K3NaMnCl6 sous forme cristalline dans les Eco-Mn. Enfin l’absorption des rayons X a permis de déterminer la nature des espèces présentes dans les catalyseurs, ainsi que le degré d’oxydation du manganèse et du fer. En outre, l’étude du réarrangement d’un acétal cyclique, ainsi que le suivi de la désorption de la pyridine à la surface des Eco-Mn, ont été utilisés pour étudier les propriétés acides des écocatalyseurs. Ces analyses ont permis de répondre à deux objectifs précis : d’une part déterminer la nature des complexes qui composent les Eco-Mn, et d’autre part, mieux comprendre les propriétés physico-chimiques de ces catalyseurs, leur degré d’oxydation et leurs propriétés acides. Ces analyses ont également permis de mieux appréhender les deux étapes du procédé de synthèse des Eco-Mn. Enfin, des catalyseurs synthétiques et témoins ont également été produits et étudiés dans les mêmes conditions d’analyse que les Eco-Mn, dans le but de déterminer si les Eco-Mn ont une spécificité et une empreinte végétale. / Mineral resources are running out, ores are hardly accessible, and ores processing damage the environment. In New-Caledonia, nickel ores mining requires to remove all the upper layers of the ground, leading to open-cast mines subjected to erosion, which threaten the environment and the biodiversity of the archipelago. Although mining ores exploitation is important for the economy of New-Caledonia, the ecological remediation of mining areas through the restoration of a vegetation cover, are necessary.ChimEco laboratory has demonstrated that it is possible to reintroduce pioneering endemic plant species, which are resistant to climate conditions and accumulate manganese, to restore New-Caledonian mining sites. These accumulating plants extract Mn from the ground to their aerial parts: it is called phytoextraction. Besides, ChimEco laboratory puts forward a new scientific and economic valorisation of phytoremediation efforts in New-Caledonia. Indeed, an innovative process has been developed to recycle metallic elements from manganese enriched biomass into innovative and polymetallic catalysts for organic synthesis. This new process is called Ecocatalysis. Ecocatalysts enriched in manganese, Eco-Mn, have demonstrated interesting and promising catalytic activities in several reactions.Regarding the good results achieved by ChimEco in ecology and in chemistry with accumulating plants and resulting Eco-Mn, it is necessary to better and precisely characterise Eco-Mn catalysts, by considering them as innovative materials, in order to understand and foresee their catalytic activity. This PhD work belongs within this context.Several analyses have been performed to characterise Eco-Mn catalysts. First, ICP-MS enables to identify metallic composition of Eco-Mn. Besides, XRD analyses highlight the presence of complex crystallized manganese salts, like K3NaMnCl6. Finally, X-ray absorption spectroscopy enables us to study the nature of manganese species which compose Eco-Mn catalysts, and to understand the oxidation states of Mn and Fe. Moreover, acid properties of Eco-Mn were demonstrated thanks to the study of a cyclic acetal rearrangement and infra-red spectroscopy of adsorbed pyridine. All these analyses were performed in order to determine first the composition of Eco-Mn catalysts, and secondly to highlight their physico-chemical properties, their oxidation state and their acid properties. Furthermore, this study also enable us to better understand the different steps of the ecocatalysts production process. Finally, synthetic catalysts were also produced and analysed in the same conditions as Eco-Mn, in order to bring out the specificities of Eco-Mn.

Disponibiliza??o do conte?do parcial, conforme Termo de Autoriza??o no trabalho. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2016-12-21T19:05:57Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-01-31T14:19:01Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) / Made available in DSpace on 2017-01-31T14:19:01Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) Previous issue date: 2016 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Funda??o de Amparo ? Pesquisa do Estado de Minas Gerais (FAPEMIG) / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Neste trabalho foi estudado o comportamento de extra??o do lant?nio em sistemas aquosos bif?sicos (SAB) e foi desenvolvido um novo m?todo hidrometal?rgico ambientalmente seguro para a extra??o seletiva de La a partir de lixiviado de baterias NiMH. O comportamento de extra??o do La foi avaliado verificando a influ?ncia dos seguintes par?metros: presen?a e concentra??o de diversos agentes extratantes (Alaranjado de xilenol, 1-(2-piridilazo)-2-naftol, Ditizona, 8-hidroxiquinolina, e 1,10-fenantrolina); pH (3,00, 6,00 e 9,00); eletr?lito (Li2SO4, Na2SO4, MgSO4, Na2C4H4O6 e Na3C6H5O7 ) e pol?mero (L64 e PEO1500) formadores do sistema. A efici?ncia de recupera??o foi avaliada atrav?s da an?lise da porcentagem de extra??o (% E) e as melhores condi??es de extra??o do analito foram obtidas no SAB formado por PEO1500 + Li2SO4 + H2O, pH = 6,00; empregando o extratante 1,10-fenantrolina, atingindo um valor m?ximo de %E = 74,1 %. Na sequencia o m?todo foi aplicado a um lixiviado de bateria NiMH. Os terras raras foram precipitados mediante ajuste de pH (2,50) e posteriormente solubilizado em solu??o de H2SO4 0,1 M. Ap?s 3 etapas sucessivas de extra??o foram obtidos altos valores de fator de separa??o (S) entre o analito e os concomitantes met?licos (SLa,Co = 6.3 x 103, SLa,Ni= 2,55 x 104, SLa,Fe= 1,15 x 103 and SLa,Ce= 30,9). Al?m disso, foi realizado um ensaio de stripping no qual 88,5% de La, em uma ?nica etapa, foi redisponibilizado sob a forma i?nica na FI para uma poss?vel etapa posterior de eletrodeposi??o. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / In this work was investigated the extraction behavior of lanthanum in the aqueous two-phase system (ATPS) and new environmentally safe hydrometallurgical method was developed for the selective extraction of La from NiMH battery leachate. The extraction behavior of La was evaluated verifying the influence of the following parameters on the metals extraction: presence and concentration of the several extractants 1-(2-piridil-azo)-2-naphtol, dithizone, 8-hydroxyquinoline, 1-10 phenanthroline and xylenol oragne; pH (3.00, 6.00 and 9.0); ATPS-forming electrolyte ((Li2SO4, Na2SO4, MgSO4, Na2C4H4O6 e Na3C6H5O7); ATPS-forming polymer (L64 or PEO1500). The recovery efficiency was evaluated through analyzing the extraction percentage (%E) and the best conditions for analyte extraction were achieved for the PEO1500 + Li2SO4 ATPS, pH = 6.00, using 1-10 phenanthroline as extractant agente (%E = 74,1 %). In the following section, the method was applied to a real NiMH battery leachate. The rare earths were precipitated by pH adjustment (2.50), which was solubilized in 0,1 M H2SO4 solution. After 3 steps of successive extractions it was possible to obtain high separation factor (S) values between the analyte and mettalic concomitant (SLa,Co = 6.3 x 103, SLa,Ni = 2,55 x 104, SLa,Fe = 1,15 x 103 and SLa,Ce = 30,9). Moreover, a stripping assay was carried out and after one single step, 88.5% of lanthanum was available to a possible electro winning step.

Cette thèse porte sur la modélisation multi-échelle des réactions en catalyse hétérogène de polyols sur une surface de platine 111, en phase aqueuse. Ce travail s’inscrit dans l’utilisation de la biomasse lignocellulosique. Les réseaux réactionnels issus du traitement de cette matière première sont très grands en taille, et en complexité. D’autre part, la nature même des molécules la composant impose une chimie en phase aqueuse. Il n’est donc pas possible de cartographier l’ensemble des ces chemins réactionnels avec des méthodes de calcul ab initio, tant les conditions aqueuses et le grand nombre de simulations que cela impliquerai demanderaient d’effort computationnel. Le changement d’échelle de simulation peut répondre à ce problème. Nous avons ainsi développé un modèle d’additivité par groupes permettant la prédiction des propriétés thermodynamiques de réactions de polyols sur platine 111 en phase aqueuse, à partir de la seule structure topologique des réactifs. Ce modèle a été construit sur un jeu de données issus de calculs en théorie de la fonctionnelle de la densité. Nous avons également étudié la cinétique de réactions de mêmes types, afin d’en prédire l’énergie d’activation à partir de leur thermodynamique. En parallèle, nous avons décrit l’influence de la micro-solvatation par rapport à un modèle de solvant implicite sur la réactivité d’alcools sur platine 111, ce qui couplé avec le modèle d’additivité par groupe permettra des simulations micro cinétiques complètes. Enfin, la réactivité des isomères du butanediol a été traitée afin de comprendre l’influence de l’espacement des fonctions alcools sur la réactivité d’un polyol. / This thesis focuses on multi scale simulations heterogeneous catalysis reactions of polyols on platinum (111) in aqueous phase. This work is about lignocellulosic biomass valorisation. The reaction networks raising from these materials are extremely large and complex. Also, the properties of the molecules forming this biomass make aqueous conditions mandatory. Ab initio methods as we know them forbids us to treat entire networks at the finest calculation level, the computational cost would be way beyond feasibility. Changing the simulation scale can tackle this problem. Thus, we developed a group additivity model assessing for thermochemical properties of polyols at a platinum (111) surface under aqueous conditions, with a topology as the only input. This model was built upon a density functional theory set. Kinetics of reactions was also covered, and the difference in terms of impact was investigated between implicit and explicit micro solvation models, in order to predict reaction barriers. The two models might be used together in order to feed a micro kinetic simulation, allowing a drastic decrease of reaction networks complexity. Finally, the influence on reactivity and selectivity, of hydroxyl groups on butanediol isomers was investigated.

Neste trabalho, fracionou-se e tratou-se a argila Brasgel. Esta argila foi pilarizada em vários estágios de facionamento e/ou tratamento com 5 meq de Al / g de argila: (i) Al-PILC, a argila passou por todos os estágios de fracionamento e tratamento (ARG), (ii) Al-PILCFe, a argila não passou pela etapa de retirada de Fe livre (ARGFe) e (iii) Al-PILCFe/silte, a argila não passou pelas etapas de retirada de silte e Fe livre (ARGFE/silte). Em análise por DRX observou-se que as Al-PILCs apresentaram uma distância basal maior que as argilas de partida. A análise textural indicou que as argilas Al-PILCs e ARGs são materiais mesoporosos, com poros do tipo fenda estreita e do tipo fenda, respectivamente. Além disso, as Al-PILCs apresentaram área superficial razoavelmente maior que as ARGs correspondentes. Outras análises feitas nas argilas foram: teor de Si, Fe e Al; CTC; FTIR; TGA e TGD. As argilas Brasgel pilarizadas foram usadas como catalisador na reação de isomerização do óxido de estireno em hexano sob refluxo. A reação foi seletiva na formação de fenilacetaldeído. As argilas Al-PILCFe e Al-PILCFe/silte apresentaram melhor desempenho catalítico (100 % de conversão em 20 min de reação). Assim, as argilas Brasgel pilarizadas se apresentaram como uma Tecnologia Limpa na reação de isomerização do óxido de estireno ao fenilacetaldeído. Palavras-chave: Desenvolvimento Sustentável. Tecnologia Limpa. Química Verde. Argilas Pilarizadas. Isomerização de Epóxidos. / This work, the Brasgel clay was fractionated and treated. The clay was pillared in several stages of fractionation and / or treatment with Al 5 meq / g of clay: (i) Al- PILC, the clay has passed through all stages of treatment and fractionation (ARG), (ii) Al-PILCFe, the clay would not pass the step of removal of free Fe (ARGFe) and (iii) Al-PILCFe/silt, clay has not gone through the steps of removing silt and free Fe (ARGFE/silt). XRD analysis showed that the Al-PILCs showed a basal spacing greater than the starting clays. The textural analysis indicated that the Al-PILCs and ARGs are mesoporous materials, with pore narrow slit type and slit type, respectively. Moreover, the Al-PILCs showed reasonable surface area greater than the corresponding ARGs. Other analyzes were made on clays: the content of Si, Fe and Al; CEC, FTIR, TGA and TGD. Brasgel pillared clays have been used as catalyst in the isomerization reaction of the styrene oxide in refluxing. The reaction was selective for the formation of phenylacetaldehyde. Al-PILCFe and Al-PILCFe/silt clays showed better catalytic performance (100% conversion in 20 min of reaction). Thus, the pillared clays Brasgel presented as a Clean Technology in the isomerization reaction of styrene oxide to phenylacetaldehyde. Keywords: Sustainable Development. Clean Technology. Green Chemistry. Pillared Clays. Isomerization of Epoxides.

Une bibliothèque de nouveaux catalyseurs bifonctionnels combinant à la fois l’aminocatalyse et l’activation acide par un acide phosphonique sur une même structure peptidique a été développée. Des variations structurales ont été apportées afin d’optimiser la géométrie du site catalytique. Le potentiel de ces catalyseurs a été testé sur la réaction d’addition de Michael stéréosélective d’aldéhydes sur divers nitroalcènes aromatiques. Dans des conditions optimisées, de très bonnes sélectivités (r.d. < 95:5 / r.e. < 93:7) ont été atteintes. Grâce à leur forte solubilité dans l’eau, ces catalyseurs ont été facilement extraits et réutilisés sur 10 cycles sans perte significative de sélectivité. Enfin, des études mécanistiques ont été menées afin de connaitre le mode d’action exact de ces catalyseurs. Tant l’énamine que l’activation acide se sont avérées essentielles pour que la réaction ait lieu. L’enchainement peptidique permet une réaction intramoléculaire et stéréosélective. / A novel bifunctional organocatalyst library combining both aminocatalysis and phosphonic acid activation on a peptide structure was developed. Some structural variations allowed the optimization of the catalytic site. The potential of these catalysts was evaluated on the stereoselective Michael addition of aldehydes with several aromatic nitroalkenes. In optimized conditions, very good selectivities (up to 95:5 d.r. and 93:7 e.r) were achieved. Due to their high water-solubility, the catalysts were easily recyclable and reused over several cycles without any significant loss of selectivities. Mechanistic investigations were carried out to understand the exact mode of action of the catalysts. Both enamine formation and acid activation were essential for the reaction to occur. The peptide structure allows an intramolecular and stereoselective reaction.

L'objectif de cette thèse est d'étudier la valorisation de la liqueur noire non soufrée par deux procédés hydrothermaux : la gazéification en eau supercritique et la liquéfaction hydrothermale. Ceux-ci seront comparés au procédé actuel de valorisation (évaporation puis combustion dans chaudière Tomlinson) selon 3 critères : le rendement énergétique, la récupération du sodium et la production de molécules aromatiques biosourcées.Lors de la gazéification, il a été montré que la formation de gaz est compétitive à celle de char. Une chauffe rapide et des températures élevées vont favoriser le rendement gaz et donc le rendement énergétique. Cependant les rendements énergétiques sont plus faibles que le procédé actuel car la conversion des composés aromatiques provenant de la lignine est faible dans la gamme de température étudiée. Lors d'un procédé en continu, à plus haute température (700°C) avec une chauffe rapide, le rendement énergétique peut être le double au procédé actuel (simulé à l'équilibre thermodynamique). La préhydrolyse du bois et l'utilisation de bois de résineux vont défavoriser la conversion de la liqueur noire en gaz.La liquéfaction quant-à-elle permet la formation composés phénoliques et d'un biocrude dont la combustion permettant de meilleur rendements énergétique que le procédé actuel. En effet, la lignine de la liqueur noire est hydrolysée en fragments réactifs, pouvant être soit dégradés soit se recombiner pour former le biocrude. Cette dernière est favorisée par la présence des carbohydrates. L'utilisation de bois de feuillus et la préhydrolyse vont améliorer le rendement énergétique.La récupération du sodium est satisfaisante pour les deux procédés, validant la faisabilité de la substitution de la chaudière par ces procédés hydrothermaux. / This thesis aims to study sulfur free black liquor valorization through two hydrothermal processes: supercritical water gasification and hydrothermal liquefaction. These processes will be compared to the industrial process (evaporation and Tomlinson boiler) with 3 mains criteria: energetic yield, sodium recovery and phenolic molecules production.In supercritical conditions, gas formation is competitive with char formation. Fast heating and high temperature permit to increase gas yield, thus energetic yield. However, conversion of phenolic compounds from lignin is low below 500°C, leading to a lower energetic yield than reference. In a continuous process, at high temperatures (700°C) and fast heating, energetic yield should be 2 times higher than industrial process (simulation at thermodynamic equilibrium). Wood prehydrolysis and softwood lead to a lower conversion of black liquor.Hydrothermal liquefaction produces a biocrude which can be burnt and phenolic platform compounds. Indeed, lignin is depolymerized into reactive fragments which can be degraded into platform phenolic molecules. Moreover, the recombination of these fragments, leading to biocrude formation, is favored by the carbohydrates derivatives in black liquor. Wood prehydrolysis and hardwood lead to better energetic and phenolic molecules yields.Sodium recovery is satisfactory for both processes. Substitution of Tomlinson recovery by a hydrothermal process is then possible.

Made available in DSpace on 2016-06-02T19:39:32Z (GMT). No. of bitstreams: 1 5020.pdf: 1446710 bytes, checksum: 36799f21e9a4eac620a708772b82d4f9 (MD5) Previous issue date: 2013-02-25 / The Learning Management System (LMS) has become extremely attractive because of the development of tools that enable synchronous and asynchronous interaction between users connected to the internet. The system has being adopted by many educational institutions, especially in the higher education ones. In this paper we describe the development, use and evaluation of a course built on the LMS Moodle with the main objective of checking its potential to complement the lessons of subject "Experimentação para o ensino de Química 1 e 2", offered to undergraduate students in Chemistry of Universidade Federal de São Carlos (UFSCar). Moodle course area was built to provide students some materials and activities that allow communication about issues related to experiment on teaching with a focus on environmental sustainability and Green Chemistry. Undergraduate chemistry students voluntarily participated in the research during the first and second semesters of 2012. The data was collected through the textual productions in forums with the participation of all undergraduates and where there was a questionnaire and a final evaluation of the course "Experimentação para o ensino de Química 2". Throughout the course the students used the environment as a privileged place to express themselves and to build the collective knowledge, since this tool has provided to licensees recognition and appropriation of another training space that supports debate which is not possible in the classroom very often. We conclude that virtual learning environments focused on teacher education can enhance the work done in the classroom. / Com o desenvolvimento das ferramentas que permitem a interação sincrônica e assincrônica entre usuários conectados à internet, os ambiente virtuais de aprendizagem (AVA) tornaram-se extremamente atrativos, sendo adotados por diversas instituições de ensino, principalmente as de ensino superior. No presente trabalho descrevemos a elaboração, utilização e a avaliação de um curso construído no AVA Moodle com o objetivo principal de averiguarmos seu potencial para complementar as aulas da disciplina Experimentação para o ensino de Química 1 e 2 , ofertadas aos licenciandos em Química da Universidade Federal de São Carlos (UFSCar), do campus de São Carlos. A área do curso no Moodle foi construída para disponibilizar materiais de estudo e atividades que permitissem o diálogo a respeito de questões relativas à experimentação voltada ao ensino com enfoque na sustentabilidade socioambiental e Química Verde. Participaram voluntariamente da pesquisa licenciandos em Química no primeiro e segundo semestres de 2012. Os dados foram coletados por intermédio das produções textuais em fóruns que contaram com a participação de todos os licenciandos, de um questionário e da avaliação final da disciplina Experimentação para o ensino de Química 2 . Ao longo da disciplina os alunos utilizaram o ambiente como um locus privilegiado para expressarem-se e para a construção do saber coletivo, visto que essa ferramenta propiciou aos licenciandos o reconhecimento e apropriação de um espaço formativo que favorece o debate, muitas vezes, não possível de ocorrer em sala de aula. Conclui-se que os ambientes virtuais de aprendizagem voltados à formação docente podem potencializar o trabalho realizado em sala de aula.

Made available in DSpace on 2015-05-14T13:21:06Z (GMT). No. of bitstreams: 1 parte1.pdf: 1561006 bytes, checksum: 92830d9ef59f992edaa0a7616cdb4412 (MD5) Previous issue date: 2011-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study was conducted in order to develop the synthesis of new Morita-Baylis-Hillman adducts of (MBHA) water soluble (29-34) with potential parasitic activity, using glycerol (1) as raw material. Two synthetic routes were carried out producing twelve new MBHA (23 - 34), six of which have hydrophilic characteristics 29-34 (main target of the work) and six more hydrophobic 23 28 (as synthesis intermediates), and these intermediaries are also important for comparative studies of structure and biological activity (SAR). Starting from glycerol (1), we synthesize the 2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylates (21, 94%) and from this, two synthetic routes were investigated to produce the 29- 34 adducts. On Route 1, the adducts 29-34 were produced in one-step (54 - 82%) from the Michael acceptor 2,3-dihydroxypropyl acrylate 22, which was prepared in 100% yield from 21. In route 2, MBHA intermediates 23 - 28 were prepared directly from 21 (90 - 100%) and these adducts were subsequently processed in adducts 29-34 (70 - 90%). In the synthesis of adduct 32 was observed the formation of the Michael addition product 47 and Indolizines unprecedented 48 as co-products of synthesis and characterized only by CGMS during the synthetic route 2. All syntheses in this work were developed in industry standards convenient. The activation reaction by microwave irradiation (MW) was widely used in most steps of this synthetic work, leading to high chemical yields and reduced reaction times. / Este trabalho foi realizado no intuito de desenvolver a síntese de novos adutos de Morita-Baylis-Hillman (AMBH) hidrossolúveis (29-34) com potenciais atividades antiparasitárias, usando o glicerol (1) como matéria-prima. Duas rotas sintéticas foram desenvolvidas conduzindo a doze AMBH inéditos (23 - 34), dos quais seis possuem as características hidrofílicas 29-34 (alvo principal do trabalho) e as outras seis mais hidrofóbicas 23 - 28 (como intermediários de síntese), sendo que estes intermediários são também importantes para estudos comparativos entre estrutura e atividades biológicas (SAR). Partindo do glicerol (1), sintetizamos o acrilato de 2,2-dimetil-1,3-dioxalila (21, 94%) e a partir deste, duas rotas sintéticas foram investigadas para os adutos-alvo 29- 34. Na rota 1, os adutos 29-34 foram produzidos em uma única etapa sintética (54 - 82%) a partir do aceptor de Michael acrilato de 2,3- dihidroxipropila 22, que foi preparado em 100% de rendimento a partir de 21. Na rota 2, os AMBH intermediários 23 28 foram preparados em 90 - 100% diretamente de 21 e estes adutos foram subseqüentemente transformados nos adutos 29-34 (70 - 90%). Na síntese do aduto 32 foi observado a formação do produto de adição de Michael 47 e da indolizina inédita 48 como co-produtos de síntese e caracterizados apenas por CGMS, durante a rota sintética 2. Todas as sínteses neste trabalho foram desenvolvidas em padrões convenientes a indústria. A ativação reacional por irradiação de microondas (MO) foi amplamente utilizada na maioria das etapas sintéticas deste trabalho, conduzindo aos altos rendimentos químicos e aos tempos reacionais reduzidos.

De nos jours, l’industrie chimique est de plus en plus confrontée à la question de son impact environnemental. Dans le même temps, elle doit faire face à la diminution des ressources de matières premières importantes tels que les métaux de transition, tout en respectant des contraintes économiques. Ces travaux de thèse avaient pour but de tenter de répondre à ces exigences, par le développement de méthodologies de synthèse basées sur l’utilisation de catalyseurs hétérogènes recyclables. En combinant les propriétés catalytiques de certains ions métalliques avec les propriétés de catalyseurs solides tels que les polyoxométallates ou les zéolithes, nous avons pu mettre au point de nouveaux outils pour la synthèse organique. Les polyoxométallates dopés à l’argent ont démontré leur efficacité dans le réarrangement d’alcynyloxiranes en furanes. La synthèse de spiroacétals et d’acétals par dihydroalkoxylation d’alcyne diols a été effectuée pour la première fois en catalyse à l’argent, via l’utilisation de zéolithes. En perspective, nous avons mis en évidence les applications potentielles de ces procédés verts dans la synthèse totale de molécules plus complexes. Les premiers résultats suggèrent que de telles synthèses plus respectueuses de l’environnement ont tout intérêt à être davantage utilisées à l’avenir. / Nowadays, the modern chemical industry has to deal with increasing environmental concerns, including the disposal of waste and its economic impact, or the diminution of important worldwide resources such as transition metals. In this Ph.D. thesis, we aimed to bring improvement in this area by the development of green processes, based on the use of recyclable heterogeneous catalysts. By combining the catalytic properties of several metal cations with the properties of solid catalysts such as polyoxometalates or zeolites, we were able to set up new tools for organic synthesis. Silver-doped polyoxometalates proved to be very efficient catalysts in the rearrangement of alkynyloxiranes to furans. Acetals and spiroketals were synthetized by dihydroalkoxylation of alkynediols under catalysis with silver-zeolites. As a perspective, we highlighted the potential applications of such green procedures in the total synthesis of more complex molecules. The first results suggested that these environmental friendly processes should gain increasing interest in the future.

Ces dernières années, les coûts et la demande en énergie n’ont cessé d’augmenter. Par conséquent, l’humanité fait face à de graves menaces environnementales telles que l'augmentation des rejets de CO2. À cet égard, la communauté internationale doit parvenir à réduire de son empreinte carbone et à veiller à ce que les besoins en énergie thermique soient couverts de manière durable. D’importantes quantités de chaleur résiduaire à basse température (60 - 100°C) sont libérées quotidiennement dans l'atmosphère par de nombreuses installations industrielles. Les thermo-transformateurs de chaleur à absorption constituent un outil intéressant car ils peuvent revaloriser des chaleurs résiduaires pour produire de la chaleur utile pour le chauffage et la production d’eau chaude. Actuellement, les mélanges de travail utilisés dans les pompes à absorption sont les systèmes {ammoniac + eau} et {eau + bromure de lithium}. Cependant, ces deux fluides de travail présentent certains inconvénients tels que la toxicité, la cristallisation et la corrosivité. Par conséquent, il est important de rechercher de nouveaux mélanges de travail. Cette étude a pour objectif d’évaluer l’intérêt d’utiliser des mélanges constitués de liquides ioniques et d'eau au sein de thermo-transformateurs à absorption. Tout d'abord, les propriétés thermodynamiques de ces systèmes binaires (pression de vapeur, densité, capacité thermique et enthalpie d’excès) ont été mesurées dans un large domaine de température et de composition. Ces données expérimentales ont été corrélées à l’aide de modèles thermodynamiques adéquats. Ensuite, les performances de ces fluides de travail ont été évaluées. Les résultats montrent que les systèmes binaires {H2O + Ils} sont une alternative prometteuse aux fluides de travail traditionnels tels que {H2O + LiBr} / Recently, the cost and use of energy continually rise. Hence, humans are close to face serious environmental problems such as increasing CO2 discharges. In this regard, global community is to achieve the ambitious objective of reducing carbon footprint and to ensure that the heating demand is covered in a sustainable manner. Since, enormous amounts of low-temperature waste heat are released on daily bases from many industrial plants to the atmosphere at temperatures between 60 - 100°C. Absorption heat transformers (AHT) are interesting because they can recover low temperature waste heat from different industrial activities and renewable energy sources such as solar and geothermal. AHT can be used to upgrade waste heat to produce useful heat for heating and hot water supplies. Nowadays, the standard working pairs used for AHTs are {ammonia + water} and {water + lithium bromide}. However, both of the working pairs show questionable behavior such as toxicity, crystallization and corrosiveness. Therefore, exploring new working pairs which do not exhibit limitations become of great importance. This work includes an investigation to analyze the AHT systems using {water + ionic liquids} binary systems as working fluids. First, basic thermodynamic properties including vapor pressure, density, heat capacity as well as excess enthalpy of these binary systems were measured at various temperatures with different ionic liquid concentrations. The thermodynamic properties data were correlated by different equations, respectively. The correlated values were significantly consistent with the experimental data. Next, simulation of the AHT performance based on the thermodynamic properties of the new working pairs and on the mass and energy balance for each component of the system were performed. Results show that the {H2O + ILs} binary systems are promising alternatives to replace the already used {H2O + LiBr} working pairs