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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Réactions de Meerwein.

Allard, Michel, January 1900 (has links)
Thèse--Sc. phys.--Paris 6, 1971. / Bibliogr.
2

Réactions photorédox appliquées à la valorisation du monoxyde de carbone et du 1,3-butadiène / Photoredox reactions applied to the valorisation of carbon monoxide and 1,3-butadiene

Gosset, Cyrille 25 October 2019 (has links)
Le domaine de la photocatalyse connait un intérêt important car il permet le développement de procédés éco-compatibles et l’emploi de conditions douces. De nombreux photocatalyseurs organiques ou organométalliques tels que les xanthènes, les complexes de ruthénium ou d’iridium ont été développés. A ce jour, très peu d’exemples décrivent la valorisation de gaz tels que le monoxyde de carbone et le 1,3-butadiène dans des réactions de catalyse photorédox. Dans ce contexte, les travaux présentés dans la thèse ont reporté la synthèse d’acides arylcarboxyliques et la fonctionnalisation en α d’aldéhydes photocatalysées respectivement par le ruthénium tris(bipyridine) et l’éosine Y, sous pression de monoxyde de carbone. La valorisation du 1,3-butadiène est également décrite par arylation de Meerwein à partir de sels d’aryldiazonium, associée à la réaction de Ritter photocatalysée par le ruthénium tris(bipyridine). L’arylation de Meerwein a également été associée à d’autres nucléophiles tels que les isonitriles, de même qu’à des étapes de cyclisation pour les synthèses de dihydroisoquinoléines et d’isochromanones. Enfin, la synthèse de phtalides par cyclisation intramoléculaire et photocatalysée par le 4CzIPN a été effectuée. / Photocatalysis field is of great interest because it allows development of eco-friendly processes and use of mild conditions. Many organic and organometallic photocatalysts, such as xanthenes, as well as ruthenium and iridium complexes were then developed. To date, very few examples describe recovery of gases such as carbon monoxide and butadiene by photoredox catalysis. Therefore, the work presented in this thesis has reported synthesis of arylcarboxylic acids and fonctionalisation in position α of aldehydes, photocatalysed respectively by ruthenium tris(bipyridine) and eosin Y, under pressure of carbon monoxide. Valorisation of butadiene has also been described using Meerwein arylation from aryl diazonium salts, associated with Ritter reaction, photocatalysed by ruthenium tris(bipyridine). Meerwein arylation has also been conjugated to nucleophiles other than nitriles, as well as cyclisation steps for dihydroisoquinoleines and isochromanones synthesis. Finally, phtalides synthesis was carried out by intramolecular cyclisation, photocatalysed by 4CzIPN.
3

Wagner- Meerwein rearrangement in the Cubylcarbinyl and Homocubylcarbinyl systems

Odom, Rosaline Yvonne 01 August 1978 (has links)
No description available.
4

Functionalized Metal-Organic Frameworks for Catalytic Applications

Xie, Feng 10 1900 (has links)
The development and design of efficient catalysts are essential for catalytic energy technologies, accompanied with the fundamental understanding of structure-property relationships of these catalysts. Metal-organic frameworks (MOFs), as the new class of promising catalysts, have been intensively investigated primarily in their fundamental electrochemistry and the broad spectrum of catalytic applications due to their structural flexibility, tailorable crystalline, and multi-functionality. In this work, we combine experiments and mechanism investigation to gain a fundamental understanding of how the surface property and the structure of MOFs affect their catalytic performance. With the aim of material design for MOFs catalysts, we developed two novel superhydrophilic and aerophobic metal-organic frameworks (AlFFIVE-1-Ni MOFs and FeFFIVE-1-Ni MOFs) used as electrocatalysts for the first time during oxygen evolution reactions (OER). Under the facilitation of hydrophilicity and aerophobicity, developed FeFFIVE-1-Ni MOFs electrocatalysts deliver optimal OER performance, better than that of the state-of-art RuO2 and referred NiFe-BDC MOFs electrocatalysts. Most importantly, the practical strategy demonstrated that the hydrophilic and aerophobic structure of MOFs does indeed deliver the optimal electrocatalytic performance. With the aim of investigating the structural transformation process of metal-organic framework, we used a series of advanced characterization techniques to monitor the structure evolution and defects presence for post-heating treated UiO-66 MOFs. The structural and electronic features of UiO-66 MOFs were intensely studied in their hydroxylated, dehydroxylated, defected, and pyrolytic forms. Meanwhile, one concept about the framework situation, quasi-MOF (like a transition state, defined high activation along the structure evolution corresponding to the presence of many defects), was presented and demonstrated. Compared with pristine UiO-66 MOF, the Quasi-MOF with the presence of active defects showed enhanced catalytic activity on the Meerwein-Ponndorf-Verley reduction reaction, which offers an opportunity to understand the structure-property relationship along with the structure evolution process of UiO-66 MOFs.
5

Zirconium Metal Organic Frameworks as Heterogeneous Catalysts for Meerwein-Ponndorf-Verley Reactions

Mautschke, Hans-Hilmar 04 November 2019 (has links)
[ES] Se han preparado varios materiales metal orgánicos de circonio MOF-808 para evaluar sus propiedades catalíticas en reacciones tipo Meerwein-Ponndorf-Verley (MPV) para la reducción de compuestos carbonílicos. En particular, se han sintetizado compuestos tipo MOF-808 modificados en los que una pequeña fracción de los ligandos trimesato presentes en el MOF original se ha reemplazado por ligandos dicarboxilato, como una estrategia para inducir la creación controlada de defectos estructurales. Los ligandos utilizados han sido: isoftalato (MOF-808-IPA), 3,5-piridindicarboxilato (MOF-808-Pydc), 5- aminoisoftalato (MOF-808-NH2) y 5-hidroxiisoftalato (MOF-808-OH). Todos los materiales obtenidos presentan una elevada cristalinidad y son isoreticulares respecto al MOF-808 original. Se ha evaluado la actividad catalítica del MOF-808 original y de los materiales modificados en reacciones tipo MPV, utilizando ciclohexanona como compuesto modelo. Todos los materiales presentan una elevada actividad catalítica, superior a la del tereftalato de circonio UiO-66 utilizado como referencia. Esta mayor actividad catalítica se corresponde a un mayor número de iones Zr4+ con insaturación coordinativa presentes en el MOF-808 con respecto al UiO-66. Además, los materiales MOF-808-IPA y MOF-808-Pydc presentan una mayor actividad que el MOF-808 original, lo que se debe a la presencia de centros activos menos congestionados estéricamente debido a la introducción de los ligandos dicarboxilato. Una ventaja adicional de compuestos MOF-808 con respecto al UiO-66 es su sistema de poros más grande, lo que permite la conversión de moléculas de mayor tamaño. Para evaluar esta característica, se ha utilizado un compuesto de gran tamaño, la estrona, capaz de penetrar en los poros del MOF-808 pero no en el UiO-66. En consecuencia, el MOF-808 es capaz de convertir por completo la estrona de forma selectiva a estradiol, mientras que el UiO-66 apenas presenta actividad. Además, cuando se usa el MOF-808 como catalizador, se produce una cantidad considerable del isómero 17alfa-estradiol, difícil de obtener por otros medios, por lo que las propiedades de diastereoselectividad del MOF-808 en reacciones MPV resultan de gran interés preparativo. Con el fin de estudiar en mayor detalle la diastereoselectividad de reacciones MPV catalizadas por MOF-808, se ha estudiado la reducción de ciclohexanonas substituidas: 3-metilciclohexanona (3MeCH), 2-metilciclohexanona (2MeCH) y 2-fenil-ciclohexanona (2PhCH). En función del alcohol utilizado como reductor y de la posición del grupo substituyente en la ciclohexanona, el MOF-808 favorece selectivamente la formación de uno u otro isómero, con una diastereoselectividad variable: 82%, 61% y 94%, respectivamente para 3MeCH, 2MeCH y 2PhCH. Es posible racionalizar estos resultados considerando la formación preferencial de uno u otro estado de transición en el espacio confinado disponible dentro de los poros del MOF. Las características energéticas del proceso se han analizado mediante el uso combinado de estudios cinéticos y cálculos teóricos. Finalmente, en vista las interesantes propiedades del MOF-808 como catalizador para reacciones MPV, se ha extendido con éxito el uso de este material a la preparación de compuestos hidroxiesteroides de difícil obtención y de interés farmacológico mediante la reducción quimio-, regioy diastereoselectiva del correspondiente oxoesteroide. De esta forma, se han conseguido obtener en un solo paso de reacción y con una elevada selectividad los siguientes compuestos: 17alfa-estradiol, 5alfa- androstan-3beta,17alfa-diol y epitestosterona, lo que demuestra el potencial del MOF-808 como catalizador para la síntesis de compuestos de alto valor añadido. / [CA] S'han preparat varis materials metall orgànics de zirconi MOF-808 per avaluar les seves propietats catalítiques en reaccions tipus Meerwein-Ponndorf-Verley (MPV) per a la reducció de composts carbonílics. En particular, s'han sintetitzat composts tipus MOF-808 modificats en els que una petita fracció dels lligands trimesat presents en el MOF original s'han reemplaçat per lligands dicarboxilats, com una estratègia per induir la creació controlada de defectes estructurals. Els lligands utilitzats han sigut: isoftalat (MOF-808-IPA), 3,5-piridindicarboxilat (MOF-808-Pydc), 5-aminoisoftlatat (MOF-808- NH2) i 5-hidroxiisoftalat (MOF-808-OH). Tots els materials preparats presenten una elevada cristal·linitat i són isoreticular respecte al MOF-808 original. S'ha avaluat l'activitat catalític del MOF-808 original i dels materials modificats en reaccions tipus MPV, utilitzant ciclohexanona com a compost model. Tots els materials presenten una elevada activitat catalítica, superior a la del tereftalat de zirconi UiO-66 utilitzat com a referència. Aquesta major activitat catalítica es correspon a un major nombre d'ions Zr4+ amb insaturació coordinativa presents en el MOF-808 respecte a l'UiO-66. A més, els materials MOF-808-IPA i MOF-808-Pydc presenten una major activitat que el MOF-808 original, el que és debut a la presència de centres actius menys congestionats estèricament debut a la introducció dels lligands dicarboxilat. Un avantatge addicional dels MOF-808 respecte a l'UiO-66 és el seu sistema de porus més gran, que permet la conversió de molècules de major tamany. Per avaluar aquesta característica, s'ha utilitzat un compost de gran taman, l'estrona, capaç de penetrar en els porus del MOF-808 però no en els de l'UiO-66. En conseqüència, el MOF-808 és capaç de convertir completament l'estrona de forma sel·lectiva a l'estradiol, mentre que l'UiO-66 gairebé no presenta activitat catalítica. A més, quan s'usa el MOF- 808 com a catalitzador, es produeix una quantitat considerable de l'isòmer 17alfa-estradiol, difícil d'obtenir per altre medis, de manera que les propietats de diastereoselectivitat del MOF-808 en reaccions MPV resulten de gran interès preparatiu. Per tal d'estudiar en major detall la diastereoselectivitat de reaccions MPV catalitzades per MOF-808, s'ha estudiat la reducció de ciclohexanones substituïdes: 3-metilciclohexanona (3MeCH), 2- metilciclohexanona (2MeCH) i 2-fenil-ciclohexanona (2PhCH). En funció de l'alcohol usat com a reductor i de la posició del grup substituent en la ciclohexanona, el MOF-808 afavoreix selectivament la formació d'un o de l'altre isòmer, amb una diastereoselectivitat variable: 82%, 61% y 94%, respectivament per a 3MeCH, 2MeCH y 2PhCH. És possible racionalitzar aquest resultats considerant la formació preferent d'un o l'altre estat de transició en l'espai confinat disponible dins dels porus del MOF. Les característiques energètiques del procés s'han analitzat mitjançant l'ús combinat d'estudis cinètics i càlculs teòrics. Finalment, en vista de les interessants propietats del MOF-808 com a catalitzador per a reaccions MPV, s'ha estès amb èxit l'ús d'aquest material a la preparació de composts hidroxiesteroids de difícil obtenció i d'interès farmacològic mitjançant la reducció quimio-, regio- i diastereoselectiva del corresponent oxoesteroid. D'aquesta manera, s'ha aconseguit obtenir en un únic pas de reacció i amb una elevada selectivitat els següents composts: 17alfa-estradiol, 5alfa-androstan-3beta,17alfa-diol i epitestosterona, el que demostra el potencial del MOF-808 com a catalitzador per a la síntesi de composts d'alt valor afegit. / [EN] Various zirconium-containing MOF-808 compounds have been prepared as potential catalysts for the Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl compounds. Modified MOF-808 have been synthethized in which a small fraction of the trimesate ligands present in pristine MOF-808 has been replaced by dicarboxylate ligands, as a strategy to induce a controlled creation of defects. The linkers used are: isophthalate (MOF-808-IPA), 3,5-pyridinedicarboxylate (MOF-808-Pydc), 5-aminoisophthalate (MOF-808-NH2) and 5-hydroxyisophthalate (MOF-808-OH). All these compounds are highly crystalline and isoreticular with pristine MOF-808. The catalytic activity of pristine and defect engineered MOF-808 has been evaluated for MPV reactions, using cyclohexanone as model substrate. All the materials show a higher catalytic activity than that of zirconium terephthalate UiO-66 used as reference. This higher activity is attributed to the higher amount of coordinatively unsaturated Zr4+ ions in MOF-808 than in UiO-66. Moreover, MOF- 808-IPA and MOF-808-Pydc are more active than pristine MOF-808, which is due to the creation of less sterically crowded sites due to the introduction of defective dicarboyxlate linkers. A further advantage of MOF-808 over UiO-66 is the presence of a wider pore system, which allows converting bulkier substrates. To evaluate this characteristic, a bulky ketone has been used; estrone, which can enter the pores of MOF-808 but not those of UiO-66. Accordingly, MOF-808 can fully convert estrone selectively to estradiol, while UiO-66 shows barely any catalytic activity. Interestingly, when MOF- 808 is used as catalysts, a noticeable amount of the isomer 17alpha-estradiol is produced, which is difficult to obtain by other means. Therefore, the diastereoselective properties of MOF-808 for MPV reactions are interesting from the preparative point of view. In order to investigate in more detail the diastereoselective properties of MOF-808 for MPV reactions, various substituted cyclohexanones have been considered: 3-methylcyclohexanone (3MeCH), 2- methylcyclohexanone (2MeCH) and 2-phenylcyclohexanone (2PhCH). Depending on the alcohol used as reducing agent and the position of the substituent in the cyclohexanone molecule, MOF-808 selectively favors the formation of one isomer or the other with a different diastereoselectivity: 82%, 61% and 94%, respectively for 3MeCH, 2MeCH y 2PhCH. These results can be rationalized by considering the preferential formation of a given transition state in the confined space available inside the MOF pores. The energetic characteristics of the process have been analyzed by a combined use of kinetic studies and theoretical calculations. Finally, in view of the interesting properties of MOF-808 as catalyst for MPV reactions, this material has been successfully applied to the preparation of a number of challenging hydroxysteroid compounds with pharmacologic interest through a chemo-, regio- and diastereoselective reduction of the corresponding oxosteroid. In this way, it has been possible to prepare in one single reaction step the following compounds: 17alpha-estradiol, 5alpha-androstan-3beta,17alpha-diol and epitestosterone. This demonstrates the high potential of MOF-808 as a catalysts for the synthesis of high added value compounds. / I want to thank the European Union’s Horizon 2020 research and innovation program for a contract under the Marie Sklodowska-Curie grant agreement No. 641887 (Project acronym: DEFNET). / Mautschke, H. (2019). Zirconium Metal Organic Frameworks as Heterogeneous Catalysts for Meerwein-Ponndorf-Verley Reactions [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/130203 / TESIS
6

Transferring pharmaceutical batch technology to continuous flow

Peterson, Olga Yuris 28 February 2011 (has links)
The current trend in the pharmaceutical industry is towards continuous flow processes. Continuous flow reactor technology can produce a cheaper, better quality product at reduced energy and environmental cost through more efficient mass and heat transfer. It also enables a simplified and faster approach to bulk production by scaling out as opposed to scaling up. The research presented here focuses on the configuration and installation of a continuous flow system into the laboratory, and the transfer of a Meerwein-Ponndorf-Verley (MPV) reduction from batch to continuous mode. The Corning® glass continuous flow reactor in our laboratory utilizes specially-designed mixing structures for enhanced mass transfer. Additionally, the glass reactor offers nonreactivity and corrosion resistance over a wide range of temperature and pressure, which conventional steel reactors do not allow. The MPV reduction is a well-known method to prepare primary and secondary alcohols from aldehydes and ketones, respectively. The traditional MPV reduction protocol (Al(OiPr)₃ in isopropanol) was modified to enable the technological transfer from batch to continuous mode. This is the first time MPV reduction reactions were carried out in continuous mode. As a result, the MPV reduction of the model compound, benzaldehyde, was successfully conducted with 60% less catalyst and product yield was improved up to 20% (average of 10%) in continuous flow reactions as compared to current batch technology. These results are being used to develop a technology roadmap for the pharmaceutical industry to implement continuous flow processes in their manufacturing operations.
7

Heterogeneous catalytic conversion of biomass-derived carbohydrates to furanic biofuel additives and chemicals

Elsayed, Islam 13 December 2019 (has links)
Increasing energy demand and various problems associated with fossil fuels such as environmental pollution, global warming and diminishing petroleum reserves have greatly stimulated production of fuels and chemicals from renewable sources. Lignocellulosic biomass has been considered as one of the potential sources for a variety of fuels and industrial chemicals. 5-Hydroxymethylfurfural (HMF) has been identified as an excellent platform molecule because it is a flexible intermediate for the synthesis of bio-renewable fuels and materials. HMF can be easily obtained from acid-catalyzed hydration of biomass-derived carbohydrates (hexoses) in various media. HMF can be converted to energy products such as 2,5-bis(alkoxymethyl)furans (BAMFs), monomers for high-value polymers such as 2,5-bis(hydroxymethyl)furan (BHMF), and valuable intermediates for fine chemicals. Recently, magnetic nanoparticle based catalysts attracted more attention due to their good stability and easy separation from the reaction mixture by a permanent magnet. This unique magnetic separation property makes MNPs more effective than conventional filtration or centrifugation as it prevents loss of the catalyst. This dissertation work focuses on, firstly, studying the effectiveness of silica coated magnetite (Fe3O4) nanoparticles MNPs supported with sulfonic acid groups (Fe3O4@SiO2-SO3H) on the dehydration of glucose to HMF. Secondly, preparing a cost-effective catalytic transfer hydrogenation system for the selective transformation of HMF into BHMF via Meerwein-Ponndorf-Verley (MPV) reaction over the copper iron magnetic catalyst supported on activated carbon in ethanol solvent with the absence of molecular hydrogen. Thirdly, producing alkoxymethylfurans (AMFs) which are considered a potential biofuels by using two-step sequential reactions with cheap heterogeneous zinc-iron oxides magnetic nanocatalyst for the hydrogenation of HMF to furfuryl alcohols in various alcohols solvents in the absence of molecular hydrogen followed by solid Brønsted acid catalyst for the etherification reaction of furfuryl alcohol derivatives. All prepared heterogeneous catalysts were characterized by FTIR, XRD, H2-TPR, XPS, ICP-OES, HRTEM-EDX, and N2 adsorption-desorption isothermal analyses (BET and BJH) and were tested for recyclability. The chemical products were identified by high performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), and products quantities were calculated by using calibration curves of chemical standards. Various reaction conditions such as reaction temperature, reaction time, catalyst amount, and alcohol type were optimized.

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