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1
Barclay, Christopher H. "Friedel-Crafts chemistry at halogenated surfaces." Thesis, University of Glasgow, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.301625.
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Davies, Timothy James. "New catalysts for friedel-crafts reactions." Thesis, Heriot-Watt University, 2001. http://hdl.handle.net/10399/505.
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Skeffington, Ian. "Friedel-crafts reactions over various catalysts." Thesis, University of Manchester, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.682191.
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The work contained in this thesis covers the sulfonylation reaction between toluene and one of methanesulfonic anhydride and methanesulfonyl chloride. The desired products of these reactions are the three isomers (onho. meta and para) of methyl tolyl sulfone and the by-products are methanesulfonic acid, when methanesulfonic anhydride was used as the sulfonylating agent, and hydrogen chloride when methanesulfonyI chloride was the sulfonylating agent. When this reaction was carried out using the traditional Friedel-Crafts catalyst, AlCl) the thermodynamic isomer ratio of 60 % ortlw, 30 % para and 10 % meta was obtained. The aim of this work was to increase the selectivity of the sulfonylation reactions to the para isomer as this was required by the industrial partner (Zeneca) for use in further reactions. The two sulfonylation reactions were carried out over a range of catalysts including Alell , a silica-alumina, a montmorillonite clay and several zeolite catalysts. The main catalyst studied was zeolite Beta as in an empirical test of a range of catalsyts it had given the greatest percentage of para isomer, with a selectivity of 60 per cent obtained under certain conditions. Reaction times, temperatures and stoichiometry were amongst the variables investigated for their role in the reaction. It was found that the reaction had an initial induction period whichever solid-acid catalyst was used, and also that the reaction stopped by twenty four hours, presumably due to catalyst coking. Yields of methyl tolyl sulfone of up to fifty per cent with a selectivity of sixty per cent for the para isomer were obtained using zeolite Beta with some catalysts giving higher yields but correspondingly lower para selectivities. The catalysts were studied using a variety of analytical techniques. The analysis of the catalysts, particularly for a series of well-characterised zeolite Y’s, was compared to the catalysis results and several interesting trends were observed. The Sil Al ratio of catalysts did not have a consistent effect on the yield or selectivity, however the amount of extra› framework aluminium was shown to have a near-linear relationship to the yield. The disproportionate yield in the sulfonylation reaction for zeolite Beta was linked to the ability of zeolite Beta, much investigated recently, to have very mobile aluminiums either in the framework or dislodging from the framework. These act as Lewis acid sites.
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Velarde, Laos Edmundo, and Milka Cajahuanca. "Mecanismos de reacciones de Friedel-Crafts." Revista de Química, 2013. http://repositorio.pucp.edu.pe/index/handle/123456789/100595.
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Jayne, A. J. "Friedel-Crafts acylation reactions catalysed by solids." Thesis, Swansea University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.637410.
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The various inorganic solids that may be employed as heterogeneous catalysts in organic reactions are discussed in Chapter 1. In the present climate, heterogeneous catalysts are seen as more environmentally acceptable alternatives to homogeneous Lewis acid type catalysts. Chapter 2 describes the Friedel-Crafts acylation of aromatics. Discussion focuses on both the classical and solid catalysed reactions. The study of a pharmaceutical intermediate is described in Chapter 3. The aims of the work described were to develop an efficient and commercially viable process for the production of 1-(4-methoxyphenyl)-2-phenyl-1-butanone by the acylation of anisole over a suitable heterogeneous catalyst. In Part A of Chapter 4, the acetylation of a range of 1,2-disubstituted aromatics over solids is discussed. Part B describes the use of different anhydrides in the acylation of 2,3-dihydrobenzofuran over a number of solids to elucidate the generality of the reaction. Investigations show the influence of the solid catalyst and the effective recovery and regeneration of a zeolite catalyst. Finally, the acylation of 2,3-dihydrobenzofuran with ethyl oxalyl chloride over heterogeneous catalysts is described in Chapter 5. The reaction proved difficult with close consideration given to the reasoning behind the poor performance of the reaction; a good case in point being the amount of material unaccounted for in certain experiments. Investigations led to the isolation and characterisation of what were considered to be likely by-products of the reaction. Efforts were made to reduce the likelihood of such by-products being formed and with further attention, a yield of 73% of the corresponding para acylated product was formed in the presence of zeolite Hβ after 7 days. Having speculated that the difficulties encountered during the study of this reaction may lie with the nature of the acylating agent, the use of mixed anhydrides based on ethyl oxalyl chloride as potential acylating agents was investigated.
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Gomez, Rodrigo Amandi. "Continuous Friedel-Crafts reactions in carbon dioxide." Thesis, University of Nottingham, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.429082.
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Kaur, Jaspalne. "Friedel-Crafts acylation catalysed by heteropoly acids." Thesis, University of Liverpool, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.272747.
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Blincow, Philip John. "The synthesis of unsaturated Friedel - Crafts polymers." Thesis, Kingston University, 1986. http://eprints.kingston.ac.uk/20504/.
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A study has been undertaken to establish whether it is possible to introduce unsaturation into Friedel - Crafts ( F/C) polymers, so that they can be cured free - radically via the unsaturation. It was hoped that the hydrocarbon - only nature of the polymer backbone, and the absence of hydrophilic cure catalysts would produce a material of low water absorption. The introduction of unsaturation has been approached in two ways. The first was to synthesize Friedel - Crafts prepolymers with ethyl side - chains. The side - chains were then tb be chlorinated, and then dehydrochlorinated to produce vinyl unsaturation. The introduction of vinyl unsaturation by this method was concluded to be unsatisfactory, due to the ease of premature crosslinking of the vinyl polymer during dehydrochlorination. The second method of introducing unsaturation was to include an allyl aromatic monomer in a F/C polymerisation. Such allyl F/C prepolymers were successfully prepared, characterised, and crosslinked. The need for a high cure temperature, and the consequent ease of oxidation make the radical cure of the allyl polymers inconvenient. They may be cured at lower temperatures, without oxidation, by cross linking them via a cationic mechanism. A study of the 13 C NMR spectrum of an F/C polymer has yielded new information on the branched structure and on the routes by which the polymer is built from monomer units.
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Laouadi, Ornella Laura Nathalie. "Enantioselective Friedel-Crafts reaction catalysed by alginate aerogels." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2019. http://amslaurea.unibo.it/18622/.
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Alginates are polysaccharides derived from brown algae, available in nearly unlimited amounts at very low prices. In the presence of some divalent metals, these renewable biopolymers can readily form hydrogels, solvogels and aerogels, characterized by high surface areas, good mechanical properties, tolerance to different media, and easy manageability. For these reasons, alginates are nowadays being thoroughly studied in heterogeneous catalysis; several applications in supported metal catalysis and as heterogeneous Brønsted acids have emerged. However, none of these studies has given an answer to the following intriguing question: can we use the intrinsic chirality of alginates to induce enantioselectivity in a chemical reaction? In order to answer this question a representative reaction, the Friedel-Crafts alkylation of nitroalkenes with indoles, was tested in this master thesis. This study, which involved a large screening of a variety of alginate gels under different reaction conditions, showed that Cu2+ and Ba2+ are the best cross-linking metals to promote the Friedel-Crafts reaction. Indeed, good activity with moderate enantiomeric excesses were obtained under the optimized reaction conditions. Furthermore, these two metals allowed the access to both enantiomers of the products, an important aspect given that only one enantiomeric form of alginates is available. Finally, the heterogeneous nature of the catalysis by one of the two gels was proved, and a good recyclability was demonstrated, by showing that the same catalyst can be used at least five times with similar results.
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Kybett, Adrian Peter. "Friedel-Crafts and oxidation catalysis using supported reagents." Thesis, University of York, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328029.
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Rastogi, A. K. "The study of Friedel-Crafts type reaction mechanisms." Thesis, Open University, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377344.
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Sawazaki, David Tatsuo Atique. "Funcionalização de grafite em condições de Friedel-Crafts." Universidade de São Paulo, 2013. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-28112013-151124/.
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Neste trabalho foi realizada a funcionalização de grafite sem prévio tratamento em condições de Fridel-Crafts. Considerando que a grafite não possui hidrogênio em sua estrutura, não se observa uma reação de substituição eletrofílica. Por outro lado, o trabalho mostra o papel da umidade presente no grafite na reação de funcionalização. Dessa forma, foi proposto um mecanismo para a reação com a participação da água adsorvida na grafite estabilizando o carbocátion formado. O grafite funcionalizado obtido na reação foi utilizado como material eletródico. Para a reação de funcionalização, quatro moléculas foram utilizadas: ácido ferrocenomonocarboxílico, cloreto de 4-nitrobenzoíla, cloreto de 3,5-dinitrobenzoíla e ácido 3,4-dinitrobenzóico. Para o estudo das condições ótimas da reação, utilizou-se diferentes potências de radiação no reator de micro-ondas, sendo que a extensão da funcionalização mostrou-se sensível à variação deste parâmetro. Para a caracterização dos materiais, utilizou-se voltametria cíclica e análise térmica (TG e DTA). Resultados de infravermelho e Ramam são apresentados no Apêndice A. Os resultados eletroquímicos mostraram que os materiais funcionalizados em maiores potências apresentaram maior corrente Faradaica, mas ao mesmo tempo, o material obtido foi mais resistivo. A diferença de potencial relacionada ao processo redox do ferroceno aumentou conforme a extensão da funcionalização, uma vez que um sobrepotencial é necessário devido ao fluxo iônico (para a manutenção da eletroneutralidade) relativo ao número de espécies envolvidas. Os resultados eletroquímicos também indicaram que a funcionalização do grafite com os nitro compostos foi baixa. A análise térmica evidenciou que a reação de funcionalização do grafite com o ferroceno resultou em materiais com 15% a 20% (m/m) de material ligado ao grafite. Os materiais funcionalizados a maiores potências apresentaram maior massa ligada ao grafite. A funcionalização com os nitro compostos resultou em materiais com menos de 3% (m/m) de composto ligado ao grafite. Os resultados das duas técnicas mostraram coerência na análise da extensão da funcionalização. O material funcionalizado com o ácido ferrocenomonocarboxilico foi o que apresentou os melhores resultados e propõe-se uma explicação para tal baseado no mecanismo de reação sugerido. Com o objetivo de melhor elucidar o mecanismo da reação, foram realizadas algumas reações na ausência de alguns reagentes. Por exemplo, quando tenta-se funcionalizar o material sem a presença de cloreto de alumínio ou sem a umidade natural do grafite, a reação não ocorre.In this work natural graphite functionalization in Fridel-Crafts conditions is performed using a one-step microwave assisted reaction. Since there is no hydrogen in graphite structure, it is not possible to observe electrophilic substitution. On the other hand this work shows the role of the moisture present on graphite in the functionalization reaction under this condition. Therefore, a reaction mechanism with the participation of the water naturally adsorbed on graphite stabilizing the formed carbocation has been suggested. After the reaction, the functionalized graphite was used as electrode material. Four molecules were used to functionalize graphite: Ferrocene monocarboxylic acid, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride and 3,4-dinitrobenzoic acid. To study the optimal conditions of the reaction, the microwave radiation power was varied and the extent of the functionalization on graphite was sensitive to this parameter. Two techniques were used to characterize the materials, cyclic voltammetry and thermal analysis (TG and DTA). IR and Raman data are shown in appendix A. Electrochemical results have shown that the materials functionalized at higher microwave radiation power have higher Faradaic current, but are more resistive. The potential difference between the peaks of the redox process of ferrocene increased with the extent of functionalization. This occurs because an overpotencial is needed to compensate the ionic flux (in order to maintain the electroneutrality) related to the number of species involved. The electrochemical results also indicated that the extent of functionalization of graphite with the nitro compounds was low. The thermal analysis have shown that the functionalization of graphite with ferrocene lead to values between 15% to 20% (m/m) of compound in the material. The materials functionalized at higher microwave radiation power presented higher relative mass in the material. The reaction with the nitro compounds lead to less than 3% (m/m) of compound in the final material. The results of both techniques were coherent about the extent of functionalization. The material functionalized with ferrocene monocarboxylic acid showed the best results, and an explanation for that based on the reaction mechanism is suggested. In order to elucidate the reaction mechanism, some experiments were realized in absent of some reagents. When the reaction were carried out without aluminum chloride or with dried graphite, the reaction has not occurred.
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Fisher, Jennifer Ann. "Bismuth Triflate Catalyzed Friedel-Crafts Acylations of Sydnones." Wright State University / OhioLINK, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=wright1133799578.
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Hofmann, Matthias. "Säurefreie Friedel-Crafts Chemie in wässrigen und alkoholischen Lösungsmitteln." Diss., lmu, 2006. http://nbn-resolving.de/urn:nbn:de:bvb:19-49817.
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Crehan, Gabriel. "Friedel-crafts catalysis with zeolites and solid solvent effects." Thesis, University of Liverpool, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367807.
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Burguin, Emilie. "Zirconia based solid acids for Friedel-Crafts alkylation reactions." Thesis, University of York, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.420266.
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Landon, Philip. "Novel heterogeneous catalysts for oxidations and Friedel-Crafts reactions." Thesis, University of York, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358154.
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Aribert, Nicolas. "Acylation hétérogène de Friedel-Crafts en milieu CO2 supercritique." Phd thesis, Toulouse, INPT, 2009. http://oatao.univ-toulouse.fr/16222/1/aribert.pdf.
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L’acylation de Friedel-Crafts est parmi les réactions les plus fondamentales et les plus utiles pour former des cétones aromatiques. Bien que la mise en oeuvre de ces réactions soit habituellement pénalisante en termes de sous produits formés, de rendement atomique et de quantité de catalyseur utilisée, cette voie est encore largement utilisée dans l’industrie de la chimie fine. Ces dernières années, la prise de conscience de l’impact des activités industrielles sur l’environnement a mené les chimistes à travailler sur de nouvelles voies, moins dangereuses et plus respectueuses de l’environnement.Nous avons considéré ici l’acylation d’un dérivé du benzofurane par un chlorure d’acyle, correspondant à une étape intermédiaire pour la fabrication d’un principe actif pharmaceutique. Dans cette étude, la première proposition a consisté à remplacer les catalyseurs classiques (FeCl3 ou AlCl3) par des catalyseurs solides réutilisables. Dans ce travail, plusieurs catalyseurs (zéolites, résines échangeuses d’ions...) ont d’abord été testés dans des conditions « conventionnelles » , c’est-à-dire en utilisant un solvant organique, afin de déterminer le plus performant, en termes de réactivité, de durée de vie et de réutilisabilité. Une zéolite Y s’est avéré la plus adaptée. Cependant, l’utilisation d’un solvant organique (ici le 1,2-dichlorobenzène) reste discutable et l’utilisation du CO2 supercritique comme solvant a donc été envisagée. Pour cela, nous avons imaginé et dimensionné un réacteur tubulaire à lit fixe de catalyseur fonctionnant sous pression et en continu. Les résultats présentés montrent la faisabilité d’un tel procédé et pose les jalons pour arriver à une ou des solutions pour une meilleure mise en oeuvre industrielle des réactions de Friedel-Crafts.
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Sommer, Knut. "Neue Lewis-Säuren für die Homogene Katalyse." [S.l.] : [s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=969333773.
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Bacchelli, Caterina. "An approach to an intramolecular organocatalysed asymmetric Friedel-Crafts reaction." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amslaurea.unibo.it/9293/.
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Dillon, Christopher J. "Zeolites as catalysts for fine chemicals synthesis : Friedel-Crafts acetylation." Thesis, University of Liverpool, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.343865.
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Paras, Nick Anthony Dervan Peter B. "Enantioselective organocatalytic Friedel-Crafts alkylations of heterocycles and electron-rich benzenes /." Diss., Pasadena, Calif. : California Institute of Technology, 2004. http://resolver.caltech.edu/CaltechETD:etd-06012004-190154.
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Gardner, June Ann. "Friedel-Crafts acylation reactions using heterogeneous catalysts stimulated by microwave radiation." Thesis, University of Central Lancashire, 2004. http://clok.uclan.ac.uk/20208/.
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Ion exchanged zeolites, ion exchanged clays, sulphated zirconia and silica supported phosphotungstic acid were prepared. Characterisation of the catalysts using pyridine adsorption revealed the catalysts contained both Brønsted and Lewis acid sites. When the catalytic activities for the acylation of toluene and anisole were studied there was found to be a correlation between the Brønsted acidity and the catalytic activity. The reactivity of the catalysts is dependant upon both the concentration and the chain length of the carboxylic acid. An optimum chain length being in the range Cm-C12. An aromatic:carboxylic molar ratio of 30: I was demonstrated to be preferable to either 300:1 or 3:1. The activation energies for the acylation of toluene were determined to be in the range 165-359 ki mol' and those for anisole 67-196 kJ mor 1 . Microwave experiments were performed in both batch and flow reactors. Under both reactor configurations microwave stimulation gave consistent increases in catalyst activity. Attempts were made to correlate this with the material dielectric properties, unfortunately, no correlation was found. Under the high E-field conditions Of the single mode (flow reactor) only the zeolites proved to be sufficiently robust as to provide any meaningful data. These catalysts displayed an increased selectivity to the ortho-isomer which was maximised when hexanoic acid was used as the acylating agent. The selectivity to the ortho-isomer increased with increasing microwave power.
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Zayed, Firas [Verfasser]. "Friedel-Crafts-Acylierung im Mehrphasensystem ionische Flüssigkeit und überkritisches Kohlendioxid / Firas Zayed." Aachen : Hochschulbibliothek der Rheinisch-Westfälischen Technischen Hochschule Aachen, 2011. http://d-nb.info/101624391X/34.
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Henche, Sabrina [Verfasser], and Bernhard [Akademischer Betreuer] Hauer. "Squalen-Hopen Zyklasen vermittelte Friedel-Crafts Alkylierung / Sabrina Henche ; Betreuer: Bernhard Hauer." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2019. http://d-nb.info/1196095248/34.
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Nancarrow, P. D. "Reaction engineering and separation studies on Friedel-Crafts catalysis in ionic liquids." Thesis, Queen's University Belfast, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.426655.
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Laidlaw, Paul. "Catalysis of organic reactions by cation-exchanged zeolites." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366734.
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Stadler, Daniel Eberhard. "Diastereoselektive SN1-artige C-C-Verknüpfungen." München Verl. Dr. Hut, 2009. http://d-nb.info/993731287/04.
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Freitas, Mauricio Azevedo de. "Poli(indeno) fosfonado : síntese, propriedades e uso como eletrólito em membranas a base de PBI." reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2018. http://hdl.handle.net/10183/181807.
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Neste trabalho, um polímero eletrólito derivado do poli(indeno) (PInd) foi desenvolvido como componente de membranas poliméricas a base de polibenzimidazol (PBI) para célula a combustível de média temperatura. Foi investigado o método de síntese, envolvendo a reação de fosfonação pelo método de Friedel-Crafts assistido por catalisador ácido de Lewis AlCl3. O polímero poli(indeno) fosfonado (PPInd) foi comparado com seu análogo sulfonado, o poli(indeno) sulfonado (SPInd), e usados nas blendas com 5, 7,5 e 10% em peso com o PBI. Os polímeros precursores foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, espectroscopia de energia dispersiva, espectrometria de espalhamento Rutherford, análise termogravimétrica acoplada com espectrometria de massas e calorimetria exploratória diferencial. As blendas PPInd/PBI e SPInd/PBI foram caracterizadas por análise termogravimétrica, grau de dopagem e espectroscopia de impedância eletroquímica. A modificação realizada pelo método de Friedel-Crafts permitiu a obtenção do poli(indeno) fosfonado parcialmente solúvel em solventes orgânicos e água, com grau de modificação de 81%. Houve convergência dos teores de modificação encontrados pelas análises termogravimétrica, espectrometria de espalhamento Rutherford e espectroscopia de energia dispersiva. O polímero PPInd apresentou estabilidade química na temperatura de operação da célula a combustível de média temperatura, passando por processos de degradação típicos de sua estrutura aromática fosfonada. A degradação dos polímeros PInd, PPInd e SPInd ocorreu majoritariamente com cisão de unidades monoméricas de indeno não funcionalizado. A inserção dos polímeros modificados PPInd e SPInd no PBI resultou no aumento da condutividade iônica, tendo a blenda com 10% de PPInd apresentado o maior valor de condutividade protônica (0,015 S.cm-1), a 25 oC. O uso do poli(indeno) modificado com grupos ácido fosfônico visa aumentar a gama de eletrólitos para células a combustível de média temperatura.In this work a polymer electrolyte derivated from the poly(indene) (PInd) was developed to be used as polymer electrolyte membrane in medium-temperature fuel cells. The modification method, based on the AlCl3 assisted Friedel-Crafts reaction, was investigated as fosfonation strategy. The phosphonated poly(indene) was compared to its similar sulphonated poly(indene) and they were used in blends of 5, 7.5 and 10wt% in polybenzimidazole (PBI). Pristine polymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, energy dispersive spectroscopy, Rutherford backscattering spectrometry, thermogravimetric analysis coupled with mass spectrometry and differential scanning calometry. The PPInd/PBI and SPInd/PBI blends were characterized by thermogravimetric analysis, doping level and electrochemical impedance spectroscopy. The modification by Friedel-Crafts reaction produced phophonated poly(indene) with degree of phosphonation of 81%, partially soluble in organic solvent and water. It was found convergence on the results for degree of phosphonation calculated by thermogravimetric analysis, Rutherford backscattering spectrometry and energy dispersive spectroscopy. PPInd presented chemical and thermal stabilities within the fuel cell operating temperature, passing by typical degradation processes of macromolecules made of phosphonated aromatic structures. The degradation of PPInd and SPInd occurred mainly by cleavage of monomeric units of non-funcionalized indene. Addition of modified polymers PPInd and SPInd resulted in increase of PBI’s ionic conductivity. 10PPInd/PBI blend presented the highest ionic conductivity (0.015 S.cm-1) at 25 oC. The use of phosphonated poly(indene) on PBI membranes enlarges the variety of available polymer electrolyte membranes for medium-temperature fuel cells.
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Meßner, Julia [Verfasser], and Peter [Akademischer Betreuer] Wasserscheid. "Friedel-Crafts Alkylierung und Isomerisierung mit aciden Salzschmelzen / Julia Meßner. Gutachter: Peter Wasserscheid." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2015. http://d-nb.info/1075562325/34.
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POIRIER, JEAN-LUC. "Alkylation de l'isobutane par l'ethylene en presence de catalyseurs solides de friedel-crafts." Caen, 1994. http://www.theses.fr/1994CAEN2037.
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La reaction d'un melange d'isobutane et d'ethylene maintenu liquide a ete etudiee en presence de diverses alumines chlorees. L'influence des parametres de reaction, temperature, dilution, temps de passage a ete examinee. L'alkylat contient uniquement des alcanes. Le catalyseur initialement tres actif se desactive ensuite progressivement. A une temperature proche de 0c et a dilution elevee en ethylene, les hexanes sont les produits majoritaires, le complement etant constitue essentiellement des octanes. La selectivite pour les paraffines branchees est elevee. La reaction de monoalkylation est preponderante et conduit au 2,3-dimethylbutane. Des trimethylpentanes et dimethylhexanes sont obtenus en quantites equivalentes par alkylations successives. Cette selectivite particuliere amene a proposer un nouveau mecanisme par ion carbonium cyclopropanique. Favorisee par l'elevation de la temperature de reaction et une forte concentration en ethylene, l'oligomerisation qui est a l'origine des alcanes superieurs peut etre preponderante sur catalyseur vieilli et sur certains catalyseurs. Les sites acides forts necessaires a la reaction d'alkylation isomerisent les produits primaires d'alkylation et craquent les alcanes superieurs. L'oligomerisation necessite une force des sites moindre que l'alkylation. Une caracteristique essentielle du catalyseur alumine chloree est sa capacite a induire le transfert d'hydrogene
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Olivon, Kevin. "Procédés catalytiques et outils millifluidiques : applications aux réactions de Friedel-Crafts et d'oxydation." Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0143.
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La recherche de nouvelles méthodes pour l’acquisition de données physiques et chimiques de réactions en limitant les effet néfastes sur l’Homme est d’une grande importance pour la chimie moderne. L’utilisation de nouveaux outils miniaturisés permet de limiter les quantités de produits chimiques utilisées tout en augmentant la productivité de la recherche. En effet, l’étude de différents paramètres contrôlés simultanément permet d’augmenter le nombre d’expériences pour un temps donné. Malgré tout, cette étape doit être réalisée après détermination au préalable des paramètres clés de la réaction par l’utilisation d’outils haut débit tels que la robotique. Cesdifférents outils sont utilisés pour l’optimisation et la recherche d’une nouvelle voie de synthèse d’une réaction d’intérêt industriel.De plus, pour répondre à l’intérêt de la catalyse hétérogène dans l’industrie pour la séparation facilitée et le recyclage de ces catalyseurs, nous avons développé deux outils miniaturisés. Cesderniers permettent l’étude et l’acquisition de données de réactions chimiques catalysées par des solides. Le développement s’est inscrit en deux étapes : une caractérisation physique des outils puis l’étude d’une réaction modèle industrielle, l’acylation de l’anisole par des catalyseurs de type zéoliteThe search for new methods for the acquisition of physical and chemical reactions by limiting the effect on humans is of great importance for modern chemistry. The use of new miniaturized tools can limit the quantities of chemicals used while increasing research productivity. Indeed, the study of the various parameters monitored simultaneously increases the number of experimentsfor a given time. Nevertheless, this step must be performed after prior determination ofthe key parameters of the reaction by the use of high flow tools such as robotics. These tools are used for optimization and the search for new synthetic pathway of a reaction of industrial interest. In addition, to meet the interests of heterogeneous catalysis in industry for easier separation and recycling of these catalysts, we have developed two miniaturized tools. These allow the study and data acquisition of chemical reactions catalyzed by solid. Development was registeredin two stages : a physical characterization tools and the study of an industrial model reaction, the acylation of anisole with zeolite catalysts
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Dennison, Shelagh T. "A synthetic approach towards the pseudopterosins." Thesis, University of Southampton, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243929.
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Smutek, Bernhard. "Réactions Organiques des Alcools en Conditions Hydrothermales." Thesis, Montpellier 2, 2011. http://www.theses.fr/2011MON20180.
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Cette thèse a pour objectif d'étudier les réactions des alcools en conditions hydrothermales. Dans une phase préliminaire, le phényl-éthanediol a été étudiés. Après aldolisation, cyclisation intramoléculaire et aromatisation sont suivi en formant 1-phénylnaphthalène. L'aldolisation et la cyclisation du type de Friedel et Crafts ont été mise en œuvre.Les transformations de l'éthylène glycol et du 1,2-propanediol sont fortement dépendantes des conditions de réaction (température, durée de réaction et nature du solvant). La réaction de transformation du 1,2-propanediol permet de synthètiser les composés suivants : mésitylène, 2-méthyl-pentènal et 2-éthyl-3,5-diméthyl-cyclopent-2-ènone. Ces produits peuvent être utilisés comme biocarburant ou solvant ou peuvent constituer des matières premières pour des synthèses organiques.Les alkylations du naphthalène et du phénol ont été étudiées en détails en fonction de la nature du solvant. L'emploi d'acide chlorhydrique en concentration de 0.05mol/L à 180°C permet l'alkylation des aromats par l'alcool benzylique. D'autres solvants (acide acétique, acide formique à 1mol/L) permettent d'obtenir ces composés avec des rendements d'alkylation inférieurs. Par ailleurs, le recyclage de ces solvants est réalisable. Notons enfin que l'alcool benzylique peut polymériser et cette polymérisation est fortement influencée par la température utilisée. La polymérisation de l'alcool benzylique a été appliquée avec succès à la séparation des platinoïdes d'une solution modèle d'effluents issue du traitement du combustible nucléaireThis thesis aims to study and to apply reactions of alcohols under hydrothermal conditions.Studies on 1-phenyl-ethanediol show an aldolisation, followed by an intramolecular Friedel-Crafts type reaction and an aromatisation. Finally, it ends up by as 1-phenyl-naphthalene.Ethylene glycol reacts on itself with a strong dependence on the temperature and the solvent. The conversion of 1,2-propanediol showed similar dependences and obtained even the aromatic compound mesitylene and especially the amount of products proves dependence on the temperature and the duration of the reaction. The main compounds can be used as solvents, as biofuel and for syntheses, whereas the byproducts might be biocarburants after hydrogenation.The Friedel-Crafts type reaction is transferred to an intermolecular one. Naphthalene and phenol are studied in more detail. 0.05mol/L HCl are enough in order to benzylate an aromatic compound at 180°C. HCl can be replaced by acetic acid or formic acid, but even concentrations of 1.0mol/L do not achieve results as good as 0.05mol/L HCl. The recycling of the aqueous phase of these reactions is advantageous. Additionally, benzyl alcohol alkylates benzyl alcohol and thus it can polymerize. Higher temperatures lead to longer polymers. This polymerization can be used in the domain of nuclear fuel recycling in order to separate platinum group metals out of a model solution
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Vukovic, Vuk. "Synergistic effect of acids and HFIP on Friedel-Crafts reactions of alcohols and cyclopropanes." Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAF068.
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L'activation catalytique d'alcools vers la formation déshydrative de liaisons chimiques sans pré-activation est devenue un intérêt de recherche majeur au cours des deux dernières décennies. Dans cette thèse, l’effet synergique particulier des acides forts en tant que catalyseurs dans l’hexafluoroisopropanol (HFIP) comme solvant de diverses classes de carbocations instables dans la chimie de Friedel-Crafts a été étudié. Il a été constaté que pour la première fois, les réactions de Friedel-Crafts d'alcools benzyliques primaires fortement désactivés, catalysées par un acide, se déroulaient facilement, en raison des phénomènes d'agrégation induits par l'acide dans HFIP. Une stratégie similaire a été utilisée pour l'activation d'alcools propargyliques, comme nouvelle voie d'accès sélectif aux allènes et indènes portant la fonction CF3, à partir des mêmes composés de départ. De plus, ce système catalytique a été appliqué avec succès pour les réactions de Friedel-Crafts de cyclopropanes de type non activés et donneur-accepteur. Enfin, il a été découvert que le HFIP pouvait atténuer le réarrangement de carbocation classique dans les alkylations de Friedel-Crafts, permettant l’accès aux produits avec chaînes alkyle linéaires en une seule étape à partir d’alcools aliphatiques linéairesThe catalytic activation of alcohols towards dehydrative bond formation in the absence of pre-activation has become a major research interest over the past two decades. In this thesis, the peculiar synergistic effect of strong acids as catalysts in hexafluoroisopropanol (HFIP) as solvent on various classes of unstable carbocations in Friedel-Crafts chemistry was investigated. It was found that for the first time, Brønsted acid catalyzed Friedel-Crafts reactions of highly electronically deactivated primary benzylic alcohols proceeded smoothly due to the acid-induced aggregation phenomena in HFIP. A similar strategy was used for the activation of propargylic alcohols as a new route to selectively access CF3-substituted allenes and indenes from the same starting compounds. Furthermore, this catalytic system was succesfully applied for Friedel-Crafts reactions of unactivated and donor-acceptor cyclopropanes. Finally, it was discovered that HFIP can mitigate against classical carbocation rearrangement in Friedel-Crafts alkylations, allowing access to linear alkyl chain products in a single step from linear alkyl alcohols
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Pinho, Roseli Oliveira de. "Crisotila como suporte para acidos de Lewis na catalise de reações de Friedel-Crafts." [s.n.], 1994. http://repositorio.unicamp.br/jspui/handle/REPOSIP/250606.
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Orientador: Jose Augusto Rosario RodriguesDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Hashimoto, Sigma. "Syntheses of Polycyclic Aromatic Compounds with Heteroatom Junctions via Tandem Hetero-Friedel－Crafts Reactions." 京都大学 (Kyoto University), 2013. http://hdl.handle.net/2433/174950.
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Hofmann, Matthias. "Säurefreie Friedel-Crafts-Chemie in wässrigen und alkoholischen Lösungsmitteln von Reaktivitätsskalen zu einem neuen Synthesekonzept /." [S.l.] : [s.n.], 2006. http://edoc.ub.uni-muenchen.de/archive/00004981.
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Cullen, Stephen Ronald. "An investigation of the activity and activation of clayzic and clayfec as Friedel-Crafts catalysts." Thesis, University of York, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.261090.
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Iraqi, Ahmed. "Activation des hydrocarbures alkylations sélectives de Friedel et Crafts en catalyse acide par transfert d'hydrure /." Grenoble 2 : ANRT, 1987. http://catalogue.bnf.fr/ark:/12148/cb37606057s.
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Gomes, Junior Walter Alves. "Aplicações dos heteropoliácidos do tipo Keggin à acilação Friedel-Crafts e à síntese de chalconas." Programa de Pós-Graduação em Química da UFBA, 2008. http://www.repositorio.ufba.br/ri/handle/ri/10020.
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Os heteropoliácidos são polioxometalatos, compostos de um cluster óxido, com prótons associados, apresentando alta acidez de Brönsted, que tem atraído interesse acadêmico e industrial, devido a capacidade de promover catálise “verde”, atuando como catalisador homogênea e heterogênea. Diversas reações orgânicas já foram conduzidas neste sistema catalítico, sendo que a acilação Friedel-Crafts do metoxinaftaleno (2-MN) com anidrido acético (Ac2O) e as condensações de Claisen-Schmidt da acetofenona com benzaldeídos foram testados neste trabalho utilizando heteropoliácidos do tipo Keggin mássico (HPW), suportado em sílica (HPW-SiO2) e na forma de sal de césio (Cs2,2H0,8PW) e de potássio (K2,5H0,5PW). A acilação Friedel-Crafts do 2-MN com anidrido acético foi realizada em fase líquida, utilizando diversos solventes. Os melhores resultados de conversão e seletividade foram obtidos com nitrobenzeno. A máxima conversão foi obtida para concentrações iniciais de reagentes equivalentes ([2-MN]0 = [Ac2O]0). Dos catalisadores utilizados, as melhores conversões foram obtidas com o HPW mássico, que também se mostrou mais seletivo ao 2-acetil-6-metoxinaftaleno , chegando a 90,1%, a 130ºC em 1h de reação. O isômero cineticamente favorável, 1-acetil-2-metoxinaftaleno é formado e logo convertido a 2-acetil-6-metoxinaftaleno a 130ºC em nitrobenzeno. A temperatura de reação afeta a seletividade, mas tem pouco efeito na conversão do 2-MN. As reações de condensação de Claisen-Schmidt da acetofenona com benzaldeídos substituídos (benzaldeido, 4-clorobenzaldeído, 4-nitrobenzaldeído, 4- metoxibenzaldeído e 4-hidroxibenzaldeído) para a síntese de chalconas conduzidas sem o uso de solventes, se mostraram muito efetivas, com conversões e seletividade superiores a 60% e 90%, respectivamente, sobre HPW mássico, em fase homogênea, com uso de pequenas quantidades de catalisador (razão molar substrato/catalisador = 200 ou superior). Os sais de césio e de potássio apresentaram resultados modestos, sendo que estes materiais conduziram reações em fase heterogênea. As reações com benzaldeídos substituídos mostraram grande influência dos grupos substituintes. Além do ótimo desempenho catalítico, esses materiais mostraram possibilidade de regeneração e re-utilização.
Salvador
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Drouillard, Joe͏̈lle. "Utilisation de zéolithes dans les réactions de type Friedel-Crafts : acylation et alkylation du thiophène." Poitiers, 1995. http://www.theses.fr/1995POIT2266.
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Les derives du thiophene ont trouve ces dernieres annees de nombreux debouches dans les domaines alimentaires, agrochimique et surtout pharmaceutique. En particulier, la decouverte des proprietes anti-inflammatoires et antalgiques de certains derives aroyles des acides thienylacetiques a initie de nombreuses recherches concernant les derives du thiophene, permettant de mettre a jour l'activite therapeutique d'autres molecules. L'acylation et l'alkylation des composes aromatiques heterocycliques sont traditionnellement realisees par des reactions de type friedel et crafts, par catalyse homogene au moyen d'acides de lewis ou d'acides protoniques forts. L'utilisation de ce type de catalyseur pose des problemes a la fois d'ordre economique et environnemental. L'objectif de ce travail etait d'essayer de les remplacer par des catalyseurs non polluants et regenerables, comme les catalyseurs acides solides, en particulier les zeolithes. Les resultats obtenus en acylation et en alkylation du thiophene montrent que les performances en terme d'activite et de selectivite des zeolithes sont semblables voire superieures a celles acides de lewis. De plus ces catalyseurs sont parfaitement regenerables, et la recuperation des produits est tres facile. Une etude cinetique complete des deux reactions realisee sur une zeolithe y d'acidite moyenne nous a permis de determiner les mecanismes reactionnels. Nous avons ensuite examine l'influence de la nature du catalyseur sur son activite et sa selectivite, en faisant varier l'acidite et/ou la porosite. L'ensemble des resultats obtenus montre que de nombreux parametres, tels que la temperature, la nature de l'agent acylant ou alkylant, la nature du solvant, l'acidite et la porosite du catalyseur influent sur les vitesses des reactions d'alkylation et d'acylation du thiophene. L'effet de la porosite semble tout particulierement important, car il modifie profondement la selectivite des reactions. Il est cependant difficile d'etendre ces conclusions a d'autres reactions similaires, chaque cas necessitant une etude systematique de l'influence des divers parametres
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Hlatywayo, Tapiwa. "Coal fly ash and acid mine drainage based heterogeneous Fe catalysts Friedel-Crafts alkylation reaction." University of Western Cape, 2020. https://hdl.handle.net/11394/7295.
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Philosophiae Doctor - PhDThe catalytic support materials used in the present study are zeolite HBEA and MCM-41. These high silica zeolites were synthesised from coal fly ash (CFA) waste via a novel approach that involved a fusion step, acid assisted silica extraction and removal of Al, Ca and Na from the silica by treatment with oxalic acid. The generated silica was converted to HBEA and MCM-41 via conventional hydrothermal treatment. The metal incorporation onto HBEA was done via two approaches namely; liquid phase ion exchange (LIE) and wet impregnation (WI) while the loading on MCM-41 was only done via WI since the material does not possess exchange sites. The metal solution precursors were AMD and Fe extracted from CFA (FeAsh) via acid leaching followed by pH regulation by concentrated NaOH. This is the first time these solutions were tested as possible metal precursors in catalyst synthesis.
2021-08-30
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Gonçalves, de Almeida José Luis. "Alkylation du benzène par le 1-dodécène sur catalyseurs zéolithiques." Lyon 1, 1994. http://www.theses.fr/1994LYO10292.
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L'alkylation du benzene par le 1-dodecene pour la production des alkylbenzenes lineaires-lab, matiere premiere pour la fabrication de detergent biodegradable, a ete etudiee sur des catalyseurs zeolithiques (h-zsm-5, h-zsm-12, h-y et h-modernites), en vue de leur possible utilisation industrielle, en remplacement des catalyseurs homogenes hf, alcl#3, h#2so#4. Dans ce travail, il a ete analysee l'effet de la force et de la concentration des sites acides sur l'activite et la selectivite dans la formation de lab et de l'isomere 2-phenyl dodecane. Il a egalement ete analysee, comment la variation des proprietes structurales peuvent affecter la diffusion et la distribution des produits du lab. Il a ete mis en evidence que les caracteristiques structurales des zeolithes h-zsm-5, h-zsm-12 et h-y desaluminee jouent un role predominant par rapport aux seules caracteristiques acides et determinant sur l'activite et la selectivite. En ce qui concerne la zeolithe y, malgre la constatation que la force des sites acides augmente avec le taux de desalumination, l'activite de la reaction d'alkylation du benzene par le 1-dodecene croit proportionnellement au nombre de sites acides. La zeolithe y n'exhibe pas des effets de selectivite de forme. Pour les mordenites, l'effet decisive pour la formation des phenyl dodecanes provient de la creation d'une mesoporosite par le processus de desalumination. La presence presque exclusive des 2- et 3-phenyl dodecane, les isomeres les moins encombres, est attribuee a la selectivite de forme envers l'etat de transition ou envers les produits
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Vece, Vito. "Formation de liaisons C-C et C-O par activation électrophile de doubles liaisons catalysée par des superacides de Brönsted et de Lewis." Nice, 2011. http://www.theses.fr/2011NICE4028.
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En synthèse organique, l’utilisation des superacides de Brönsted (TfOH et Tf2NH) ou superacides de Lewis (M(n)(OTf)n et M(n)(NTf2)n) présente un intérêt considérable dans de nombreuses réactions, plus particulièrement en tant que catalyseurs pour la formation de liaisons C-O, C-N et C-C au cours desquels une activation électrophile de double liaison est nécessaire. Ces superacides peuvent ainsi être utilisés en quantité sous-stoechiométrique et demeurer souvent plus actifs et plus sélectifs que des acides de Lewis plus classiques, ce qui inscrit ces travaux de méthodologie dans la chimie verte. Nous avons mis à profit l’activité de ces catalyseurs pour réaliser des réactions de type Friedel-Crafts, des réactions tandem Friedel-Crafts-hydroalcoxylation et des réactions de cycloisomerisation. Les composés polyfonctionnalisés auxquels nous proposons un nouvel accès constituent sont porteurs d’applications potentielles nombreuses, non seulement dans le cadre de la synthèse de produits pharmaceutiques mais aussi en agrochimie ou dans l’industrie des parfums. Dans un premier chapitre, nous présentons une étude bibliographique des thèmes abordés au cours de ce travail de thèse. Dans un second chapitre, la réaction d’allylation de type Friedel-Crafts à partir de cycles aromatiques, phénoliques ou non, est étudiée et orientée vers des applications dans des synthèses d’intérêt industriel. Dans un troisième chapitre, une discussion mécanistique de cette réaction de Friedel-Crafts est ensuite présentée, appuyée par des expériences de cinétiques et par des calculs théoriques ab initio. Dans un quatrième chapitre, nous présentons ensuite une discussion sur les réactions de cyclisation de composés polyinsaturés de type diènes-1,6 ou aza-diènes. La cycloisomérisation de diènes-1,6 substitués permet l’accès à des composés nouveaux dont les squelettes présentent un intérêt dans le domaine de la parfumerie, et s’insère ainsi dans une des thématiques principales développées au laboratoire. L’application des systèmes catalytiques développés au cours de cette thèse dans la synthèse de composés possédant des propriétés odorantes a été un des objectifs de ce travailThe use of Brönsted superacids (TfOH and Tf2NH) or Lewis superacids (M(n)(OTf)n and M(n)(NTf2)n) in organic synthesis presents a high interest in a wide number of reactions, particularly for the C-O, C-N and C-C bond formation involving the electrophilic activation of a double bond. These superacids could be used in sub-stoichiometric amounts whiole remaining more active and selective than more conventional Lewis acids, therefore improving the Green Chemistry aspects of our studies. We have used these catalysts to carry out Friedel-Crafts type reactions, tandem Friedel-Crafts-hydroalkoxylation processes and cycloisomerisations. The polyfunctionalised compounds for which a novel and efficient access is proposed present potential applications in medicinal, agricultural and perfume chemistry. A first chapter is devoted to the bibliographical studies of the various topics presented in this manuscript. In a second chapter, the Friedel-Crafts type allylation reaction from aromatic cycles, phenolic or not, have been studied and oriented towards the synthesis of valuable chemicals of industrial relevance. In a third chapter, mechanistic studies based on kinetic measurements and theoretical calculations on this reaction are presented. In a fourth chapter, cyclisation reactions of polyinsaturated compounds such as 1,6-dienes and aza-dines are presented. The cycloisomerisation of substituted 1,6-dienes allowed the access to several new compounds of interest in fragrance chemistry, a central interest of our laboratory. The application of the catalytic systems studied in the synthesis of compounds with odorant properties has
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Elmamouni, Elhachemia. "Nouvelles applications de la réaction de Passerini dans des réactions de type Friedel-Crafts et Tsuji-Trost." Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLX011/document.
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L’élaboration de synthèses rapides et efficaces de molécules complexes à partir de substrats de départ simples en utilisant un minimum d’étapes constitue un véritable enjeu de la chimie organique contemporaine. Dans ce contexte, les réactions multicomposant, grâce à leur capacité à créer plusieurs liaisons en une étape, offrent une grande efficacité pour synthétiser des structures d’une grande complexité moléculaire. Par ailleurs, la catalyse organométallique s’est considérablement développée ces dernières années, pour devenir un outil de choix pour la formation de liaisons carbone-carbone. La réaction de Tsuji-Trost est notamment un des plus connues dans ce domaineDans le cadre de cette thèse, la découverte de post-condensations originales à partir d’adduits obtenus par les réactions multicomposant impliquant un isonitrile est l’axe majeur de nos recherches. Ces réactions permettent un accès efficace à un large éventail de composés hétérocycliques.Tout d’abord, nous avons développé une nouvelle voie efficace de synthèse des indolylacétamides via une cascade Passerini/Friedel-Crafts à partir d’adduits de Passerini et d’indoles en présence d’un acide de Lewis. Une version monotope de cette cascade a été ainsi développée.Par ailleurs, nous avons exploité la réactivité des hydrazones N-monosubstitués en tant que bis-nucléophile 1,3 en vue de préparer divers dérivés de 2-pyrazolines via une cascade Tsuji-Trost/Cyclisation pallado-catalysée à partir des adduits de Passerini ou de phosphonates. Dans le but de préparer des 2-pyrazolines énantiosélectivement enrichis, une version énantiosélective de cette cascade a été également réalisée à partir d’adduits de Passerini.Enfin, la mise au point d’une nouvelle cascade Tsuji-Trost/Cyclisation exploitant l’allyle méthyle carbonate a permis l’accès rapide à des motifs hétérocycliques de type oxazolidine-2,4-diones en exploitant le dioxyde de carbone généré in situThe development of rapid and efficient syntheses of complex molecules from simple starting substrates using a minimum of steps is a real challenge of contemporary organic chemistry. In this context, multicomponent reactions, thanks to their ability to create several one-step bonds, offer a high efficiency in synthesizing structures of great molecular complexity. Moreover, organometallic catalysis has developed considerably in recent years, becoming a tool of choice for the formation of carbon-carbon bonds. The Tsuji-Trost reaction is specially well known in this field.In this thesis, the discovery of the original post-condensations from the adducts obtained by multicomponent reactions involving isonitrile is the major axis of our research. These reactions allow efficient access to a wide range of heterocyclic compounds.First, we have developed a new efficient pathway for the synthesis of indolylacetamides via the Passerini/Friedel-Crafts cascade from the Passerini adducts and indole in the presence of a Lewis acid. A one-pot version of this cascade has been also developed.Furthermore, we have exploited the reactivity of N-monosubstituted hydrazones as 1,3-bis-nucleophile in order to prepare various 2-pyrazoline derivatives via a pallado-catalyzed Tsuji-Trost/Cyclisation cascade from the Passerini adducts or Phosphonates. In order to prepare enantioselectively enriched 2-pyrazolines, the enantioselective version of this cascade was also realized from the Passerini adduct.Finally, the development of a new Tsuji-Trost/Cyclization cascade from the Passerini adducts and the allyl methyl carbonate provide straight fast and efficient access to oxazolidine-2,4-diones heterocyclic units by exploiting the carbon dioxide generated in situ
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Kirk, Andrew. "Mesoporous supports for the catalysis of Friedel-Crafts alkylation and cyclialkylation reactions with sulfur-containing aromatics." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq31041.pdf.
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Montagne, Fabienne. "Les sels de terres rares en catalyse hétérogène des réactions de Friedel-Crafts : applications en polycondensation." Dijon, 1997. http://www.theses.fr/1997DIJOS033.
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En chimie fine, le réactif universel des réactions d'alkylation et d'acylation de composés aromatiques selon Friedel-Crafts est le trichlorure d'aluminium mais l'emploi de cet acide de Lewis présente plusieurs inconvénients : la réaction est au mieux stoechiométrique, le réactif est d'un usage unique et les effluents sont nuisibles à l'environnement. Les sels de terres rares déposés sur un support minéral sont d'excellents catalyseurs des réactions de Friedel-Crafts ; leur activité catalytique est nettement plus élevée que celle des chlorures de terres rares et leurs analogues coordonnés non supportés. Les conditions opératoires sont douces, l'isolement des produits ne nécessite pas d'hydrolyse et les catalyseurs, facilement éliminés du milieu réactionnel par simple filtration, sont recyclables. Différentes techniques d'analyse ont été utilisées pour caractériser les catalyseurs supportés et étudier l'influence des divers traitements sur la nature de l'espèce déposée. Après avoir évalué leurs performances catalytiques dans deux réactions tests, la gamme de réactivité des catalyseurs supportés a été étudiée. Les catalyseurs supportés ont également été étudiés dans des réactions conduites sous irradiation micro-ondes. Les différents tests ont confirmé qu'un accroissement de la température, module par la puissance du rayonnement micro-ondes, s'accompagne d'une augmentation du rendement ; la sélectivité est semblable à celle obtenue pour les réactions effectuées en chauffage traditionnel. L'application des réactions d'alkylation de type Friedel-Crafts à des réactions de polycondensation a conduit à la synthèse de nouveaux polybenzyles solubles, dont les caractéristiques physico-chimiques ont été déterminées.
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Ricci, Jérémy. "La catalyse par les triflates et triflimidures métalliques : réaction d'allylation de Friedel-Crafts et alkenylation intramoléculaire." Nice, 2009. http://www.theses.fr/2009NICE4038.
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Les composes aromatiques polyfonctionnalisés constituent une importante classe d’intermédiaires et peuvent présenter un intérêt non seulement dans le domaine pharmaceutique, mais aussi dans la chimie des arômes et parfums. L’objectif de ce travail concerne la mise au point d’une méthode catalytique permettant les réactions d’allylation de composés aromatiques par réaction de Friedel-Crafts et des réactions de cyclisation intramoléculaire. Les triflates métalliques [M+n(OSO2CF3)n], des acides de Lewis forts, sont considérés comme des “superacides” de Lewis. L’allylation de nombreux composés aromatiques a été développée en utilisant des acétates d’allyle comme réactifs. La méthode nécessite un petite quantité d’In(OTf)3 (1 % molaire), s’effectue à température ambiante et les molécules cibles sont obtenues avec des rendements compris entre 50 et 90 %. La réaction catalytique d’allylation sur des dérives phénoliques a aussi été étudiée. Les produits de cyclisation intramoléculaire ont été obtenus avec de bons rendements. Cette même méthode est appliquée dans le cas de réaction de Friedel-Crafts type alkénylation intramoléculaire. Les produits ont été obtenus quantitativement. Une étude complémentaire avec un composé allylique chiral ainsi que d’autres réactions ont permis de proposer des mécanismes réactionnelsAromatic polyfunctionalised compounds constitute an important class of intermediates and may present a wide scope of applications not only in the pharmaceutical field, but also in flavour and fragrance chemistry. The scope of this work was focused on the elaboration of a catalytic system promoting allylation of aromatics compounds by Friedel-Crafts method and intramolecular cyclisation reaction. Trifluoromethanesulfonate catalysts [M+n(OSO2CF3)n] are strong Lewis acids, considered as Lewis « superacids ». The allylation of various aromatic compounds, using acetates as the allylating agents has been developed. The method requires only a low amount of In(OTf)3 (1 mol%), operate at room temperature and the target molecules are obtained in yields of 50-90%. Allylation reactions with phenol derivatives have also been examined in catalytic reactions. Products involving intramolecular cyclisation are obtained with good yields. The same method is also extended for intramolecular Friedel-Crafts alkenylation reactions. Products are obtained quantitatively. A complementary study with chiral allylic acetate and other experiences led to a proposed reaction mechanism
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Dinut, Aurélia Viorica. "Etude des sélectivités de la réaction d'alkylation de friedel-crafts catalysée par des complexes de lanthanides." Paris 11, 2010. http://www.theses.fr/2010PA112166.
Full textAbstract:
La réaction d’alkylation de Friedel-Crafts est une des plus anciennes réactions de formation de liaison C-C et constitue toujours une méthode attrayante pour introduire des substituants sur des composés aromatiques. Ce travail porte sur l’étude de la réaction d’Alkylation de Friedel-Crafts impliquant des électrophiles tels que les imines et les trifluoropyruvates. La réaction d’aza-Friedel-Crafts impliquant des imines a été effectuée en présence de di iodure de samarium. Celui-ci a montré une bonne activité catalytique et a permis l’accès à de nouveaux produits tels que des triarylméthanes, des esters a-animés et des diarylméthylamines. Pour ces deux derniers composés une deuxième réaction de Friedel-Crafts, toujours catalysée par le d iodure de samarium, a été réalisée utilisant un composé aromatique différent de la première étape. Cette méthodologie nous a permis l’accès à de nouveaux produits de double alkylation non symétriques tels que des diarylacétates et des triarylméthanes. Une étude énantiosélective de la réaction d’aza-Friedel-Crafts a été également entreprise, notamment en employant l’iodobinaphtolate de samarium comme catalyseur chiral ; une énantiosélectivité maximale de 78 % est alors obtenue. L’addition énantiosélective de différents composés indoliques sur des dérivés de trifluoropyruvates a été étudiée en présence d’un nouveau système catalytique à base de triflate d’ytterbium et de pyridylalkylamines chirales conduisant à des excès énantiomériques allant jusqu’à 83%. D’autre part, l’alkylation de l’anisole, du phénol et des naphtols par le trifluoropyruvates de méthyle a été efficacement réalisée en présence de FeCI₃ et InCI₃Friedel-Crafts alkylation reaction is one of the most fundamental C-C bond forming reactions in organic synthesis. This work concerns the study of Friedel-Crafts alkylation reaction involving various arenes and electrophiles such as imines and trifluoropyruvates. The addition of electron-rich aromatic compounds to imines, known as the aza-Friedel-Crafts reaction has been realized in the presence of a catalytic amount of samarium diiodide. This one showed good activity and provided access to new products such as triarylmethanes, a-amino esters and diarylamines. For the latter two compounds, a second Friedel-Crafts reaction, catalyzed by samarium diiodide, was performed using an aromatic compound different from the first step. This methodology has provided new unsymmetrical diarylesters and triarylmethanes. The study of the asymmetric aza-Friedel-Crafts reaction was also undertaken using samarium iodobinaphtholate as a chiral catalyst; maximum selectivity of 78% is then obtained. The enantioselective addition of various indole derivatives to alkyl trifluopyruvates is described in the presence of a new catalytic system based on ytterbium triflate and chiral pyridylalkylamines. Good yields and high enantioselectivities (up to 83% ee) in the Friedel-Crafts alkylation were obtained. This is the first report concerning the use of a chiral ytterbium complex in asymmetric Friedel-Crafts alkylation reactions. Moreover, the alkylation of anisole, phenol and naphthols by methyl trifluopyruvate was affectively performed in the presence of iron chloride (II) and indium chloride (III)