The synthetic strategy of this study mainly depends upon the asymmetric desymmetrization of meso norbornene type an anhydride. Asymmetric desymmetrization was achieved by using chinchona alkaloids under kinetically controlled conditions. The resultant mono ester carboxylic acid was epimerized to trans configuration. Subsequent esterification followed by lithium aluminum hydride reduction afforded the first chiral diol ligand with 98 % ee. Transformation of diol to corresponding trans diamine was achieved via Mitsunobu-Gabriel combination. The resultant diamine was first transformed into salen type ligand with 3,5-di-tert-butyl-2-hydroxybenzaldehyde. Throughout this process, no racemization was observed and all the ligands tested in asymmetric reactions have 98 % ee value. The second part of the thesis involves the asymmetric test reactions of the chiral ligands to check the effectiveness of them. The first testing method was diethylzinc addition to benzaldehyde. The ligands showed moderate effectiveness. The salen type ligand was tested in asymmetric epoxidation and aziridination reactions and it showed good effectiveness. Another applied method was desymmetrization of meso 2-cyclohexene-3,4-diol in which 2-(diphenylphosphino)benzoic acid attached trans-diol and trans-diamine type ligands were tested. Since norbornene type strained bicyclic systems are available in ring opening methathesis polymerization (ROMP) reactions, trans-diamine was subjected to ROMP to get an enlarged macromolecular system

This thesis deals mainly with two oxidation reactions: water oxidation and aerobic oxidation, both of which have been applied in a biomimetic fashion. In the former reaction molecular oxygen is generated whereas in the latter it was used as terminal oxidant in oxidation reactions. The first part of this thesis describes the synthesis of different ruthenium and manganese complexes that could potentially act as catalysts for water oxidation. This part includes a discussion of the stability and reactivity of a new manganese(III) amide-type complex, that has been used as a catalyst for both epoxidation of stilbene and alcohol oxidation. The second part of this thesis discusses the synthesis of two new hybrid catalysts consisting of hydroquinone linked cobalt(II) salophen and cobalt(II) salmdpt, which have been used as oxygen-activating catalysts in aerobic oxidation reactions. The former catalyst was applied to the Pd-catalyzed reactions such as 1,4-diacetoxylation of cyclohexadiene whereas the latter was applied to the Ru-catalyzed oxidation of secondary alcohols to ketones. Moreover, these two hybrid catalysts could be used in the Pd-catalyzed carbocyclization of enallenes. In all cases molecular oxygen was used as the stoichiometric oxidant.

Zugl.: Köln, Univ., Diss., 2008

Techn. Hochsch., Diss., 2001--Aachen.

Techn. Hochsch., Diss., 2002--Aachen.

Neste trabalho foi realizado o estudo de transformações de óleo de soja com o catalisador VO(acac)2 em meio homogêneo e heterogêneo. Estes processos catalíticos estão de acordo com os conceitos de química limpa, no sentido de economia de reagentes e diminuição de subprodutos, enquanto que a matéria-prima, óleo vegetal, foi escolhida por ser de fonte renovável, sustentável e abundante no Rio Grande do Sul e no Brasil. A reação de transesterificação do óleo de soja foi realizada através do sistema VO(acac)2 e VO(acac)2 suportado em uma argila celadonita, cujo depósito localiza-se na região de Ametista do Sul – RS. O sistema heterogêneo foi caracterizado pelas técnicas de DRX, BET, BJH, ATG, FTIR, CHN, MEV/EDS e ICP/OES. O teor de vanádio impregnado na argila foi de 1,06 %. O melhor rendimento das reações de transesterificação foi de 36 % e 30 % para os sistemas homogêneo e heterogêneo, respectivamente, para as condições de 2 % em mol e 5 % em mol de vanádio, a 65 ºC de temperatura e 48 horas de reação. Alguns testes foram realizados em reações de epoxidação. Do sistema celadonita/VO(acac)2 foi obtido conversão de 44 %, 15 % de monoepóxido e 34 % de seletividade, em 3 horas de reação. A avaliação quantitativa das reações foi realizada por RMN de 1H. / This work presents the study of soybean oil reactions with VO(acac)2 in homogeneous and heterogeneous catalytic systems. The catalytic systems follow the green chemistry principles of economy of reagents and reduction in sub-products of the reaction while the starting material, soybean oil, was chosen as a renewable source, sustainability of its crop and abundancy. Soybean oil transesterification reactions were done with the catalytic system VO(acac)2 and VO(acac)2 supported in celadonita, which is a mineral found in Ametista do Sul / RS. The heterogeneous system was characterized by the XRD, BET, BJH, TGA, FTIR, CHN, SEM/EDX and ICP/OES techniques. The amount of vanadium impregnated in the clay it was 1,06%. The best conditions for transesterification reaction gave 36 % yield for homogeneous system and 30 % yield for heterogeneous system, using 2 % molar and 5 % molar of vanadium, respectively, at 65 ºC of temperature and 48 hours of reaction. Some tests on epoxidation reactions were performed. With celadonita/VO(acac)2 system it was obtained a conversion of 44%, 15% of monoepoxide and 34 % of selectivity after 3 hours of reaction. The quantitative evaluation of the reactions was made by 1H NMR.

Submitted by Marcos Wanderley (marcos.wanderley@ufcg.edu.br) on 2018-07-31T20:22:18Z No. of bitstreams: 1 FILIPE SAMPAIO BATISTA - DISSERTAÇÃO(PPGEPM) 2017.pdf: 4329942 bytes, checksum: 55ad9fec74dbaf8ba526dbb0b3c5b8ff (MD5) / Made available in DSpace on 2018-07-31T20:22:18Z (GMT). No. of bitstreams: 1 FILIPE SAMPAIO BATISTA - DISSERTAÇÃO(PPGEPM) 2017.pdf: 4329942 bytes, checksum: 55ad9fec74dbaf8ba526dbb0b3c5b8ff (MD5) Previous issue date: 2017-03-08 / CNPq / Neste trabalho são avaliados dois polímeros à base de óleo de soja como redutores de filtrado em fluidos de perfuração sintéticos à base N-parafina, visando sua utilização na perfuração de poço de petróleo e gás. Realizou-se o estudo em duas etapas: primeiramente, a caracterização dos polímeros ( POS1A e POS2A) por meio das análises de espectroscopia no infravermelho por transformada de Fourier (FTIR), microscopia óptica (MO), termogravimétrica (TGA), térmica diferencial (DTA) e ensaio de toxicidade; na segunda etapa, a avaliação dos polímeros como redutores de filtrado por meio das propriedades reológicas (viscosidade aparente (VA), viscosidade plástica (VP), limite de escoamento (LE)), da estabilidade elétrica (EE) e do volume de filtrado HPHT (VF) de acordo com as normas da API. Ainda nesta etapa, como critério de balizamento, foram avaliados fluidos sem redutores e com redutor de filtrado padrão, utilizado pela indústria. Os resultados indicam que o polímero POS2A possui maior diâmetro médio de partículas e melhor distribuição dos grãos que POS1A. Os espectros de FTIR dos polímeros indicam a existência de funções carboniladas, ácido carboxílico e éster. A termogravimetria indicou que os polímeros possuem boa estabilidade térmica. O polímero POS2A apresentou baixíssima toxicidade e o POS1A nenhuma toxicidade. Os fluidos apresentaram curvas de fluxos de plásticos de Bingham. Os polímeros não apresentaram influências significativas sobre as propriedades de VA, VP, LE e EE. A presença de polímeros no sistema reduziu os volumes de filtrado HPHT dos fluidos e foram competitivos com o redutor utilizado pela indústria, entretanto, superaram os resultados apenas para os fluidos com concentração de 2g de POS2A, na razão óleo/água 60/40. / In this work we evaluated two soybean oil-based polymers as filtrate reducers in synthetic N-paraffin-based drilling fluids, aiming their use in oil and gas well drilling. This study was conducted in two stages: First, the characterization of the polymers (POS1A and POS2A) by analysing through the Fourier spectroscopy analysis in transformed infrared (FTIR), optical microscopy (OM), thermogravimetric (TGA), differential thermal ((DTA) and toxicity test; In the second stage, the evaluation of the polymers as filtration reducers by means of the rheological properties (apparent viscosity (AV), plastic viscosity (PV), flow limit (FL)), electrical stability (ES) and HPHT filtrate volume (FV) in accordance with API standards. Still in this stage, as a beacon criterion, we evaluate fluids with no reducers and with standard filter reducer, used by the industry. The results indicate that the POS2A polymer has a higher mean particle diameter and better grain distribution than POS1A. The FTIR spectra of the polymers indicate the existence of carbonylated functions, carboxylic acid and ester. Thermogravimetry indicated that the polymers have good thermal stability. The POS2A polymer presented a very low toxicity and POS1A had no toxicity at all. The fluids showed Bingham plastic flow curves. The polymers had no significant influence on the properties of AV, PV, FL and ES. The presence of polymers in the system reduced the volumes of HPHT filtrates from the fluids and were competitive with the reducer used by the industry, however, they exceeded the results only for fluids with a concentration of 2g of POS2A in the 60/40 oil / water ratio.

Neste trabalho foi realizado o estudo de transformações de óleo de soja com o catalisador VO(acac)2 em meio homogêneo e heterogêneo. Estes processos catalíticos estão de acordo com os conceitos de química limpa, no sentido de economia de reagentes e diminuição de subprodutos, enquanto que a matéria-prima, óleo vegetal, foi escolhida por ser de fonte renovável, sustentável e abundante no Rio Grande do Sul e no Brasil. A reação de transesterificação do óleo de soja foi realizada através do sistema VO(acac)2 e VO(acac)2 suportado em uma argila celadonita, cujo depósito localiza-se na região de Ametista do Sul – RS. O sistema heterogêneo foi caracterizado pelas técnicas de DRX, BET, BJH, ATG, FTIR, CHN, MEV/EDS e ICP/OES. O teor de vanádio impregnado na argila foi de 1,06 %. O melhor rendimento das reações de transesterificação foi de 36 % e 30 % para os sistemas homogêneo e heterogêneo, respectivamente, para as condições de 2 % em mol e 5 % em mol de vanádio, a 65 ºC de temperatura e 48 horas de reação. Alguns testes foram realizados em reações de epoxidação. Do sistema celadonita/VO(acac)2 foi obtido conversão de 44 %, 15 % de monoepóxido e 34 % de seletividade, em 3 horas de reação. A avaliação quantitativa das reações foi realizada por RMN de 1H. / This work presents the study of soybean oil reactions with VO(acac)2 in homogeneous and heterogeneous catalytic systems. The catalytic systems follow the green chemistry principles of economy of reagents and reduction in sub-products of the reaction while the starting material, soybean oil, was chosen as a renewable source, sustainability of its crop and abundancy. Soybean oil transesterification reactions were done with the catalytic system VO(acac)2 and VO(acac)2 supported in celadonita, which is a mineral found in Ametista do Sul / RS. The heterogeneous system was characterized by the XRD, BET, BJH, TGA, FTIR, CHN, SEM/EDX and ICP/OES techniques. The amount of vanadium impregnated in the clay it was 1,06%. The best conditions for transesterification reaction gave 36 % yield for homogeneous system and 30 % yield for heterogeneous system, using 2 % molar and 5 % molar of vanadium, respectively, at 65 ºC of temperature and 48 hours of reaction. Some tests on epoxidation reactions were performed. With celadonita/VO(acac)2 system it was obtained a conversion of 44%, 15% of monoepoxide and 34 % of selectivity after 3 hours of reaction. The quantitative evaluation of the reactions was made by 1H NMR.

Orientador: Prof. Dr. Dalmo Mandelli / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Nas últimas décadas, a oxidação de compostos orgânicos tem atraído muitos estudos. Este tipo de reação leva à obtenção de produtos de grande aplicação na indústria farmacêutica, de plásticos e fragrâncias. Com o objetivo de promover processos que reduzam a quantidade de subprodutos, resíduos de reação e elevem os rendimentos reacionais é necessário desenvolver novos catalisadores ativos e seletivos, que também possuam custo e toxicidade relativamente baixos, Assim, os oxidantes preferenciais para esses processos são oxigênio molecular e peróxido de hidrogênio. Uma área que tem ganhado mais importância na literatura moderna é a utilização de catalisadores que não possuem metais de transição na oxidação de compostos orgânicos. Neste trabalho foi estudada a oxidação de alquenos (incluindo terpenos) com H2O2, utilizando-se como catalisadores Al(NO3)3 e Ga(NO3)3, e os efeitos da adição de co-catalisadores. Os melhores resultados foram obtidos usando o Ga(NO3)3 como catalisador, obtendo um rendimento de 80% na epoxidação do cicloocteno e de 26% na epoxidação do dec-1-eno após 8 h de reação utilizando acetato de etila como solvente. Na epoxidação da carvona o produto majoritário foi o epóxido interno, próximo a carbonila, utilizando o catalisador de Ga e o THF como solvente com rendimento superior a 40%. Foram testados diferentes co-catalisadores, ácidos ou bases, para as reações de epoxidação do cicloocteno. O ácido acético levou a ligeiros incrementos no rendimento, enquanto que ácido 2-pirazinocarboxílico (PCA) e o ácido trifluoracético (TFA) aceleraram a reação e foram os mais eficientes. Na epoxidação do dec-1-eno, a adição de PCA aumentou em cerca de 15 vezes a velocidade de reação, enquanto que na epoxidação da carvona alterou drasticamente a seletividade, favorecendo a formação de epóxido externo em detrimento do interno. / In recent decades, the oxidation of organic compounds has attracted many studies. Such reaction leads to products with wide application in pharmaceutical, plastic and fragrances industry. In order to promote processes that reduce the amount of byproducts, reaction residues and to increase reaction¿s yields it is necessary to develop new active and selective catalysts, which also have relatively low cost and toxicity. Thus, preferred oxidants for these processes are molecular oxygen and hydrogen peroxide. One area that has gained more importance in modern literature is to use transition metal-free catalysts in the oxidation of organic compounds. In this work, we studied the oxidation of alkenes (including terpenes) with H2O2, using catalysts such as Al(NO3)3 and Ga(NO3)3, evaluating the effects of the addition of co-catalysts. The best result was obtained using Ga(NO3)3 as catalyst, giving a yield of 80% in the epoxidation of cyclooctene and 26% in the epoxidation of 1-decene after 8 h of reaction using ethyl acetate as solvent. In the epoxidation of carvone the major product was the internal epoxide, near to the carbonyl group, using gallium salt and THF as solvent with yields higher than 40%. Different co-catalysts were tested, either acid or basic, for the reactions of epoxidation of cyclooctene. Acetic acid led to a slight increase in the yield, while PCA and TFA accelerated the reaction and were the most efficient. In the epoxidation of dec-1-ene the addition of the PCA increased almost 15 the initial rate of the reaction, while in the epoxidation of carvone it changed the selectivity improving the yield to the external epoxide.

Dans le contexte actuel du développement durable, l'industrie chimique, souvent montrée du doigt par les institutions et le grand public pour son impact négatif sur l'Homme et l'environnement, doit développer des voies de synthèse compétitives et plus éco-compatibles. La préparation d'époxydes à partir d'oléfines représente aujourd'hui un enjeu essentiel du point de vue de la production d'intermédiaires clés pour l'industrie chimique. Basé sur les nombreuses études publiées dans la littérature, ce travail de thèse a eu pour objectif d'étudier le potentiel des liquides ioniques, solvants novateurs aux propriétés uniques, et des ultrasons de puissance, méthode non conventionnelle d'activation, pour l'époxydation d'oléfines catalysée par des porphyrines métallées. Les protocoles expérimentaux de synthèse des liquides ioniques sélectionnés ont été améliorés au regard des principes de la chimie verte et évalués par des indicateurs spécifiques. Ensuite, les mécanismes des réactions d'époxydation ont été mis en évidence grâce à l'utilisation de porphyrines chirales et à l'étude des paramètres sonochimiques en milieu liquide ionique. Finalement, la stabilité des liquides ioniques sous irradiation ultrasonore a été étudiée ; ainsi, leurs produits de dégradation et leurs mécanismes de formation ont été identifiés. / In the current context of sustainable development, the chemical industry, often pointed at by the institutions and the general public for its negative impact on humans and the environment, needs to develop more competitive and more eco-friendly synthetic routes. The preparation of epoxides from olefins is today a critical issue in terms of production of key intermediates for the chemical industry. Based on numerous studies published in the literature, this PhD thesis has aimed at investigating the potential of ionic liquids, innovative solvents with unique properties, and power ultrasound, unconventional method of activation, for the epoxidation of olefins catalyzed by metalloporphyrins. The experimental protocols used for the synthesis of the selected ionic liquids have been improved according to the principles of green chemistry and evaluated by specific indicators. Then, the mechanisms of epoxidation reactions have been evidenced thanks to the use of chiral porphyrins and the study of sonochemical parameters in ionic liquids medium. Finally, the stability of ionic liquids under ultrasonic irradiation has been studied. Their degradation products and their formation mechanisms have been identified.