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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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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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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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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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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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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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Karrepu, Venkateswara Reddy. "FRIEDEL-CRAFTS ACYLATION STUDIES ON 3-ALKYL-1-(PHENYLSULFONYL)INDOLES USING ALUMINUM CHLORIDE AND BISMUTH TRIFLATE." Wright State University / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=wright1333733182.
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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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Fishlock, Daniel. "The Catalytic Intramolecular Friedel-Crafts Acylation of Meldrum's Acid Derivatives and The Total Synthesis of Taiwaniaquinol B." Thesis, University of Waterloo, 2005. http://hdl.handle.net/10012/1226.
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The intramolecular Friedel-Crafts acylation of aromatics with Meldrum?s acid derivatives catalyzed by metal trifluoromethanesulfonates and other Lewis acids is reported. Meldrum?s acids are easily prepared, functionalized, handled, and purified. The synthesis of polysubstituted 1-indanones from benzyl Meldrum's acids was investigated thoroughly, and it was shown that a variety of catalysts were effective, whilst accommodating a diversity of functional groups under mild conditions. The scope, limitations, and functional group tolerance (terminal alkene and alkyne, ketal, dialkyl ether, dialkyl thioether, aryl methyl ether, aryl TIPS and TBDPS ethers, nitrile- and nitro-substituted aryls, alkyl and aryl halides) for a variety of 5-benzyl (enolizable Meldrum?s acids) and 5-benzyl-5-substituted Meldrum?s acids (quaternarized Meldrum?s acids), forming 1-indanones and 2-substituted-1-indanones respectively, are delineated. This method was further applied to the synthesis of 1-tetralones, 1-benzosuberones, and the potent acetylcholinesterase inhibitor donepezil.
Mechanistic investigations were undertaken to determine the rate-determining step in the acylation sequence using Meldrum?s acid, as well as to examine the role of the Lewis acid catalyst. Enolizable Meldrum?s acid derivatives can react via an acyl ketene intermediate under thermal conditions, while quaternarized Meldrum?s acid derivatives are thermally stable and only act as effective Friedel-Crafts acylating agents in the presence of a Lewis acid catalyst.
The total synthesis of (±)-Taiwaniaquinol B was completed. This natural product was the first ever isolated containing an unusual 6-5-6 fused ring system, and it also contains a hexasubstituted aromatic ring, and two all-carbon quaternary centers. This synthesis was accomplished via an intramolecular Friedel-Crafts acylation/carbonyl a-tert-alkylation reaction that exploits the unique chemistry of Meldrum?s acid. This novel methodology can be used to access a variety of highly substituted fused ring systems of various sizes.
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NASS, OLIVIER. "Syntheses et reactions de complexes spiraniques de dienes fer-tricarbonyle : acylation intramoleculaire de friedel-crafts et cyclocarbonylation." Université Louis Pasteur (Strasbourg) (1971-2008), 1997. http://www.theses.fr/1997STR13230.
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La decomplexation avec carbonylation de dienes fer tricarbonyle 1,1,3-trisubstitues a ete reexaminee en vue d'un acces stereocontrole a des sesquiterpenes spiro4. 5decaniques. Les complexes precurseurs ont ete prepares par homologation de cyclohexanones par transposition de meyer-schuster, conversion en dienes exocycliques et complexation diastereoselective. L'etude de cette cycloaddition 4+1 formelle a permis de verifier sa stereospecificite, l'accessibilite de cyclopenten-2-ones spirobicycliques et tricycliques, et de preciser les possibilites et limites d'ordre sterique du procede. L'acylation intramoleculaire de friedel-crafts, inedite pour ces complexes de fer, a d'autre part ete examinee au depart de derives dieniques substitues en position 1 par un residu carboxyalkyle. Apres optimisation, les cycles a 5 et 6 carbonnes ont ete formes avec des rendements respectifs de 75 et 55%. Un acces simple et rapide a des complexes de 2h-pyrannes bicycliques inedits, analogues heterocycliques des cyclohexadienes fer tricarbonyle, a par ailleurs ete mis en evidence. Un important potentiel synthetique est envisageable pour ces composes. Une reflexion a ete engagee sur l'interet general de la sous-structure diene fer tricarbonyle en tant que groupement stereodirecteur. La synthese de complexes optiquement purs par complexation diastereoselective, et la modification stereoselective de cetones et d'alcools au voisinage immediat du site de coordination ont ete analyses, documentes et illustres par des exemples concrets. Ce memoire revele les caracteristiques reactionnelles et structurales inhabituelles des complexes de dienes exocycliques prepares. Il est d'autre part illustratif de divers concepts stereochimiques, de l'incidence des ruptures de symetrie sur le deroulement d'une reaction, et de l'interet particulier des composes meso et de la notion de pseudoasymetrie.
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Bernardon, Claire. "Les zéolithes comme catalyseurs "verts" pour la synthèse organique : de leur synthèse à façon à leurs applications en chimie organique." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF017/document.
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Les zéolithes, aluminosilicates cristallins poreux, sont des catalyseurs acides hétérogènes très largement utilisés dans l’industrie chimique. Ces catalyseurs permettent de répondre très précisément à de nombreuses exigences économiques et environnementales contemporaines. Pour cela, les zéolithes s’appuient sur des propriétés uniques, comme la sélectivité de forme, ou encore la présence d’une double acidité de Lewis et de Brønsted, pour offrir de nouveaux outils à la synthèse organique. Ce sont plus de 230 structures qui ont été décrites à ce jour mais ce sont bien des centaines de milliers d’assemblages possibles, ce qui laisse un vaste choix quant à l’expansion de cette recherche. Dans ce travail, nous avons cherché à (i) mieux comprendre la cristallisation des zéolithes en présence d’un déchet issu de l’industrie sucrière, la bagasse de canne à sucre ; (ii) pour cela, différentes techniques ont été employées et développées afin de permettre une caractérisation précise de chaque zéolithe, notamment leur acidité, paramètre clé de leur réactivité ; (iii) une fois bien identifiés, ces catalyseurs ont été engagés dans des réactions modèles, une réaction de Diels-Alder ainsi qu’une acylation de Friedel-Crafts. Ainsi, un catalyseur le plus « idéal » possible regroupant toutes les propriétés requises aura pu être conçu sur mesure. Cette thèse s’essaie à une meilleure compréhension de la croissance cristalline des aluminosilicates poreux, et cela, via la synthèse de différentes zéolithes dont les propriétés intrinsèques sont optimisées puis utilisées de façon à obtenir les meilleurs résultats dans des réactions de catalyse acide ; en accord avec la chimie verte et ses préceptesZeolites are crystalline porous aluminosilicates and useful heterogeneous catalysts in chemical industries. They represent one of the significant solutions to main environmental concerns. Thanks to their particular properties like shape selectivity and intrinsic acidities of Lewis and Brønsted, zeolites offer unbeatable abilities in organic synthesis. More than 230 structures have already been discovered, which afford thousands discovery and offer a lot of possibilities.This work was focused on (i) a better understanding of zeolite crystallisation in the presence of an additional component from sugar industry, sugarcane bagasse; (ii) several characterization techniques have been used for a precise structure – properties understanding, mainly for their acidity; (iii) tailored-made catalysts have been tested in model reactions like Diels-Alder and Friedel-Crafts acylation. Hence, optimal catalysts exhibiting required properties could be prepared. This Thesis also aimed to explain zeolite crystallization thanks to sacrificial additional template.BEA, MFI, FAU and LTA zeolites have been prepared then optimized for catalytic testing in different reactions, while keeping in mind the Green Chemistry concept
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Pokharel, Uttam Raj. "ORGANOMETALLIC HETEROCYCLES AND ACENE-QUINONE COMPLEXES OF RUTHENIUM, IRON AND MANGANESE." UKnowledge, 2012. http://uknowledge.uky.edu/chemistry_etds/6.
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A variety of organometallic-fused heterocycles and acene quinones were prepared and characterized. This work was divided into three parts: first, the synthesis of 5,5-fused heterocyclic complexes of tricarbonylmanganese and (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium; second, the synthesis of 1,2-diacylcyclopentadienyl p-cymene complexes of ruthenium(II); and third, synthesis of cyclopentadienyl-fused polyacenequinone complexes of ruthenium, iron and manganese.
The first examples of the convenient, versatile and symmetric cyclopentadienyl-fused heterocycle complexes of (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium(II) and tricarbonylmanganese(I) were synthesized starting from (1,2-dicarbophenoxycyclopentadienyl)sodium. The sodium salt was transmetalated using [MnBr(CO)5] and 1/4 [Ru(μ3-Cl)(Cp*)]4 to give [Mn(CO)3{η5-C5H3(CO2Ph)2-1,2}] and [Ru{η5-C5H3(CO2Ph)2-1,2}(Cp*)]. The diester complexes were saponified under basic conditions to obtain the corresponding dicarboxylic acids. The dicarboxylic acids were used to synthesize unique cyclopentadienylmetal complexes including diacyl chlorides, anhydrides, thioanhydrides and p-tolyl imides of ruthenium and manganese.
Similarly, a series of 1,2-diacylcyclopentadienyl-p-cymene cationic complexes of ruthenium were synthesized using thallium salt of 2-acyl-6-hydroxyfulvene and [Ru(η6-p-cymene)(μ-Cl)Cl]2 in a 2:1 ratio with an intension of converting them into heterocycle-fused cationic sandwich complexes. However, our attempts of ring closing on 1,4-diketons with sulfur or selenium were unsuccessful. A methodology involving the synthesis of metallocene-fused quinone complexes was employed starting from pentamethylruthenocene-1,2-dicarboxylic acids. The diacyl chloride was prepared in situ from the dicarboxylic acids and used for Friedel-Crafts acylation. We observed single-step room-temperature diacylation of aromatics, including benzene, o-xylene, toluene, 1,4-dimethoxybenzene and ferrocene with pentamethylruthenocene-1,2-diacyl chloride to obtain the corresponding quinone complexes. Similarly, we synthesized mononuclear and binuclear γ-quinones by aldol condensation of 1,2-diformylcyclopentadienylmetal complexes with cyclohexane-1,4-dione or 1,4-dihydroxyarenes.
The third methodology involves the Friedel-Crafts acylation of ferrocene with 2-carbomethoxyaroyl chlorides followed by saponification, carbonyl reduction, and ring closing by second Friedel-Crafts acylation to give Ferrocene-capped anthrone-like tricyclic and tetracyclic ketones. The oxidation of the ketones gave [3,4-c]-fused α-quinone complexes of iron. The oxidative and reductive coupling, enolization and C-alkylation of the anthrone complex were studied. Solvolysis of α-carbinol gave α-ferrocenylcarbenium salt, which underwent dimerization on treatment with non-nucleophilic base. We were successful to trap the in situ generated trimethylsilylenol ether of ferrocene-anthrone using dienophiles like N-phenylmaleimide or dimethylacetylenedicarboxylate under Diels-Alder conditions.
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Nascimento, Leandro Fontanetti do. "Grafite funcionalizada em condições de Friedel-Crafts mediada por radiação de microondas: novo material para construção de eletrodos de pasta de carbono." Universidade de São Paulo, 2007. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-04072007-151512/.
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A modificação e/ou a funcionalização de eletrodos têm por objetivos o desenvolvimento de métodos eficazes para a preparação de eletrodos quimicamente modificados (EQMs) que possam aliar melhorias em sua sensibilidade, seletividade e reatividade em relação aos eletrodos base. Entretanto, a estabilidade e a reprodutibilidade dos EQMs quanto ao processo de lixiviação dos modificadores precisam ser melhorados para que se possam obter eletrodos mais robustos com longo tempo de análise. Uma das possibilidades para se obter eletrodos mais estáveis é por meio de uma ligação estável do tipo covalente entre o eletrodo base e o modificador. Desta forma este trabalho tem por objetivo a funcionalização da grafite por meio de uma reação covalente entre os modificadores cloreto de 4-nitrobenzoíla (4-NB), cloreto de 3,4-dihidroxibenzoíla (3,4-DHB) e do cloreto de 2,2?-bipiridina 4,4?-dicarbonílico (2,2-BP) por meio de uma reação de acilação de Friedel-Crafts assistida por radiação de microondas. O material de síntese foi caracterizado por voltametria cíclica, espectroscopia de infravermelho, curvas termogravimétricas e térmicas diferenciais e espectroscopia de impedância eletroquímica em comparação com a mistura física entre a grafite e os modificadores. Além disso, realizou-se uma generalização da síntese de Friedel-Crafts para outros substratos carboníferos eletródicos como os nanotubos e as fibras de carbono, além de algumas aplicações dos materiais funcionalizados, como exemplos, a grafite funcionalizada e as fibras de carbono funcionalizadas com o derivado bipiridínico (GFT-2,2BP e CNF-2,2BP), por meio de uma ligação entre as bipiridinas funcionalizadas covalentemente nos materiais carboníferos e alguns complexos de rutênio tais como [Ru(bpy)2(OH2)2](PF6)2, [RuCl2(PPh3)3] e do precursor RuCl3.3H2O em eletrooxidações de compostos orgânicos. Para a grafite funcionalizada com nitro derivado (GFT-4NB), realizou-se a eletrooxidação de NADH sobre o potencial redox da hidroxilamina/nitroso. Os resultados dos experimentos de EIS demonstram que a grafite funcionalizada possui uma maior resistência que o material obtido por mistura física. Isto seria esperado já que a formação da ligação covalente afeta a deslocalização de elétrons pi. Finalmente esta metodologia seria uma plataforma geral para a preparação de grafite covalentemente modificada com derivados cujas moléculas possui aplicações de interesse. Assim, o material obtido por este método pode ser usado em aplicações como em eletrodos de pasta de carbono, eletrodos impressos, filmes finos e nanocompósitos e mesmo como um catalisador em reações químicas. Desde que a resposta eletroquímica é muito sensível ao eletrólito, este trabalho abriu uma larga variedade de estudos para entender a interação desses materiais no meio aquoso e orgânico.Modification and/or functionalization of eletrodic materials have been investigated in order to improve the application of chemically modified electrode (CME) regards on their sensitivity, selectivity and reactivity comparing with unmodified substrate. However, the stability and reproducibility of these CME are one of the most important goals to achieve mainly regarding on the lixiviation of the modifier molecule. Quimisorption is one way to obtain very stable modified materials, since the redox mediator is attached to the substrate by covalent bound. Still it is very important to study the stability and chemical reactivity of these materials. The aim of this work is to synthesize graphite, carbon nanotube and carbon fiber with 4-nitrobenzoíl chloride (4-NB), 3,4-dihidroxibenzoíl chloride (3,4-DHB) and 2,2-bipyridine- 4,4-dicarbonil chloride (2,2-BP) in Friedel-Crafts condition mediated by microwave radiation. The materials were characterized by cyclic voltammetry (CV), using carbon paste electrode (CPE), infrared spectroscopy (IR), thermo gravimetric (TG) and differential thermal analysis (DTA) and electrochemical impedance spectroscopy (EIS). All of the synthesized graphite derivatives were compared with the respective physical mixtures. Moreover, graphite derivatives with bipyridine were used as a ligand in the synthesis with [Ru(bpy)2(OH2)2](PF6)2, [RuCl2(PPh3)3] and RuCl3.3H2O. These products were used as electrocatalysts to oxidize alcohols in comparison with the complex incorporated in graphite. Graphite obtained from 4-NB reaction was employed to oxidize NADH in the redox potential of hydroxylamine/nitroso derived. Results from EIS measurements have show that graphite functionalized has higher resistance than the material obtained by physical mixture. This would be expected since the covalent bound would affect a pi electron dislocation. In conclusion, this methodology would be a general platform to prepare graphite and derivatives covalently bounded to molecules that have interesting application. In addition, it\'s been shown that the catalytic property of the respective function organic hasn\'s changed after reaction with carbon substrate. Thus the material obtained by this method could be used in applications such as carbon paste electrodes, finger print electrodes, thin films and nanocomposites and even as a catalyst in chemical reaction. Since the electrochemical response is very sensitive regards on the electrolyte, this work opened a wide range of studies to understand the interaction of these materials in aqueous and organic medium.
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Ratinaud, Céline. "Pyrroloazépinediones, pyrrolopyridinediones, pyrrolopyrrolones : synthèse et recherche d'inhibiteurs de topoisomérases et de kinases." Paris 11, 2006. http://www.theses.fr/2006PA112362.
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Le travail décrit dans ce mémoire porte sur la synthèse d'analogues de composés isolés d'éponges marines ayant un potentiel thérapeutique intéressant. Le premier objectif de ce travail était de développer une nouvelle voie de synthèse de dérivés de pyrroloazépinediones et pyrrolopyridinediones. Les étapes clefs du schéma réactionnel proposé sont une acylation régiosélective de Friedel-Crafts de dérivés pyrroliques par des α ou β-aminoacides N-protégés, suivie d'une cyclisation par lactamisation. La synthèse des systèmes pyrrolopyridinediones s'est avérée difficile. C'est néanmoins la première fois qu'est décrite l'acylation de Friedel-Crafts de dérivés pyrroliques désactivés par une fonction ester, par la glycine. La réactivité particulière vis-à-vis des α-aminoacides, autres que la glycine, a été à l'origine de trois molécules originales de type pyrrolopyrrolones. L'étude d'acylation par la β-alanine ainsi que les essais de cyclisation correspondants ont permis de synthétiser les dérivés d'azépinediones souhaités. Les réactions ont été mises au point à l'échelle de quelques dizaines de grammes avec de très bons rendements. Le deuxième objectif de ce travail était d'exploiter la réactivité de la fonction carbonyle des dérivés d'azépinediones préparés pour introduire des pharmacophores et moduler l'activité pharmacologique. Deux analogues de l'hyménialdisine, alcaloïde marin, ont été préparés et les synthèses de plusieurs oximes ont été réalisées avec des rendements convenables. Les résultats pharmacologiques obtenus à ce jour sont encore modestes. Trois dérivés synthétisés ont montré des activités à des concentrations de l'ordre du micromolaireThe work described in this manuscript deals with the synthesis of analogues of marine metabolites isolated from sponges. Our objective was directed to a research of a new scaffold inspired from nature and from previously known biological results on kinases ans topoisomerases inhibitors. The first aim of this work was to develop new syntheses of pyrroloazepinediones and pyrrolopyridinediones derivatives. The key steps of our synthesis are a regioselective Friedel-Crafts acylation of pyrrolic derivatives with N-protected α or β-aminoacids, followed by a cylization-lactamisation. The synthesis of pyrrolopyridinediones systems was quite difficult. Lt's nevertheless the first lime that a Friedel-Crafts acylation of pyrrolic derivatives desactivated by an ester function with glycine is described. The particular reactivity with regard to α-aminoacids, besides glycine, was the origin of three pyrrolopyrrolone type original molecules. The acylation study with β-alanine and the further cylization attempts permitted to synthesize the desired azepinediones derivatives. These reactions are realized on multigrams of material. The second aim of this work was to use the carbonyl function reactivity of the prepared pyrroloazepinediones derivatives to introduce pharmocophores for pharmacological activity discovery and modulation. The developed chemistry allowed us the synthesis of marin hymenialdisin analogues. Several oximes have also been prepared with good yields. The pharmacological results in cell proliferation as well as in kinases inhibitions are as yet modest
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Peyronneau, Magali. "Nouveaux catalyseurs pour les réactions d'alkylsulfonylation et de chlorosulfinylation : nouveau procédé de synthèse des triflates métalliques." Toulouse 3, 2003. http://www.theses.fr/2003TOU30076.
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Les réactions d'acylation et de sulfonylation selon Friedel-Crafts impliquent à l'échelle industrielle l'emploi de quantités au moins stœchiométriques de catalyseurs (en particulier AlCl3) en raison de leur complexation avec les cétones ou les sulfones formées. Ces procédés engendrent ainsi la formation de déchets en grande quantité suite à l'hydrolyse nécessaire pour décomplexer les produits. Ce travail concerne la recherche et l'étude de nouveaux catalyseurs des réactions de Friedel-Crafts, et plus particulièrement de la réaction d'alkylsulfonylation, pouvant être utilisés en quantités réellement catalytiques. Ainsi, des systèmes catalytiques basés sur une synergie entre des chlorures métalliques (BiCl3 et SbCl3) et l'acide triflique (TfOH, Tf = SO2CF3) ont été étudiés et ont permis de synthétiser de nombreuses méthylsulfones aromatiques par réaction du chlorure de méthanesulfonyle (MeSO2Cl). Cette étude a également permis de découvrir que le chlorure de gallium est le premier chlorure métallique possédant une activité catalytique vis-à-vis de cette réaction. .Acylation and sulfonylation Friedel-Crafts reactions needs the use of a stœchiometric amount of catalyst (in particular AlCl3) because of the complexation of this latter with ketones and sulfones formed. So, this process generates significant amounts of wastes due to the required hydrolytic step to isolate the product. This work concerns the discovery and the study of new Friedel-Crafts reaction catalysts, and particularly for alkylsulfonylation reaction that be used in truly catalytic amount. These catalytic systems based on a synergy between metallic chlorides (BiCl3 and SbCl3) and triflic acid (TfOH, Tf = SO2CF3) have been studied and they allowed to synthesize some aromatics methylsulfones by reaction between methanesulfonyl chloride (MeSO2Cl) and aromatics. .
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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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Duquenne, Christophe. "Vers une réaction de Friedel-Crafts "verte". Mise en évidence de nouveaux catalyseurs recyclables dérivés de l'indium (III) : application à l'acylation des composés aromatiques." Rennes 1, 2003. http://www.theses.fr/2003REN10012.
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Ce travail aborde l'acylation de Friedel-Crafts. La première partie étudie les catalyseurs à base d'indium. Des conditions opératoires spécifiques permettent d'atteindre des températures élevées réduisant alors la charge catalytique à 1% en chlorure d'indium dont la capacité de recyclage est démontrée. Mais celui-ci est trop hygroscopique. L'activité d'autres dérivés est examinée et l'oxyde d'indium donne les meilleurs résultats. La conversion du toluène s'effectue avec 0. 5% de catalyseur. Aucune perte d'activité n'est observée après dix recyclages et la désactivation des substrats n'est pas rédhibitoire. Une transformation de l'oxyde est démontrée. La seconde partie concerne les liquides ioniques, synthèse (pyridinium, imidazolium et phosphonium) et utilisation : pour les chlorométallates, les meilleurs résultats sont obtenus avec InCl3, pour les autres liquides ioniques la combinaison avec les dérivés du fer ou de l'indium est inhibante avec les substrats désactivés.
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Silva, Bruno Henrique Sacoman Torquato da. "Estudos sobre a utilização do pentacloreto de Nióbio, como ácido de Lewis, em reações de acilação de Friedel-Crafts, visando à síntese de compostos com potencial aplicação como corantes sensibilizadores /." Bauru, 2018. http://hdl.handle.net/11449/153383.
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Orientador: Luiz Carlos da Silva FilhoResumo: A reação de acilação de Friedel-Crafts é uma das mais importantes reações de formação de ligações carbono-carbono em compostos aromáticos. As reações de acilação de Friedel-Crafts ocorrem basicamente por meio da reação entre compostos aromáticos com haletos de acila ou anidridos na presença de um ácido de Lewis. Assim, neste trabalho foi estudado o uso do pentacloreto de nióbio como ácido de Lewis nas reações de acilação de Friedel-Crafts visando à síntese de corantes sensibilizadores. Os derivados de fluoresceína foram sintetizados a partir de derivados fenólicos e derivados de anidrido, na presença de NbCl5 e sob aquecimento. Os produtos de interesse foram obtidos com rendimentos de 54 a 90% e em curtos tempos reacionais que variaram de 50 a 200 minutos. As fluoresceínas apresentaram absorção e emissão de luz dentro do comprimento de onda do visível, com alta intensidade e altos valores de rendimento quântico de fluorescência (0,60 a 0,93) quando dissolvidos em soluções alcalinas. Os derivados de fluoresceínas foram aplicados na confecção de células solares de Gratzel apresentando eficiências de conversão que variaram de 0,11 a 0,23%. Também foi estudado a aplicação dos derivados de fluoresceínas como corantes iniciadores em reações de fotopolimerização de resinas de dimetacrilato. Estas resinas tem sido largamente utilizadas na odontologia, devido as suas propriedades como baixa toxicidade, baixa solubilidade em água e alta resistência mecânica. As fluoresceínas promoveram... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The Friedel-Crafts acylation reaction is one of the most important reactions for the formation of carbon-carbon bonds. The Fridel-Crafts acylation reaction occurs basically by a reaction between aromatic compounds with acyl halides or anhydrides in the presence of a Lewis acid. Thus, in this work it was studied the use of niobium pentachloride as Lewis acid in Friedel-Crafts acylation reaction, aiming the synthesis of sensitizing dyes. The fluorescein derivatives were synthesized from phenolic derivatives and anhydride derivatives, in the presence of NbCl5 and under heating. The products of interest where obtained in yields of 54 to 90% and in short reaction times ranging from 50 to 200 minutes. The fluorescein derivatives presented absorption and emission within the range of visible and with high intensity and high fluorescence quantum yield (0,60 to 0,93) when dissolved in alkaline pH. Due to these good results obtained in the photophysical study, the fluorescein derivatives were applied in Gratzel solar cells, presenting convertion efficiencies that ranging from 0.11 to 0.23%. It has also been studied the application of fluorescein derivatives as initiator dyes in photopolymerization reactions of dimethacrylated resins. This resins have been widely used in dentistry, due this properties as, low toxicity, low solubility in water and high mechanical resistance. The fluoresceins promoted the photopolymerization of dimethacrylated resins with conversion values ranging from 1.2... (Complete abstract click electronic access below)
Doutor
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Zeytinci, Serhat. "Synthesis Of Ferrocenyl Substituted Aziridines." Master's thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12607285/index.pdf.
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A new method for the efficient synthesis of ferrocenylenones was developed. Acryloyl, methacryloyl, crotonyl, cinnamoyl, and β
-methylcrotonyl chlorides reacted with ferrocene in the presence of a Lewis acid (EtAlCl2 or EtAlCl2-Me3Al) to give the corrosponding ferrocenylenones (acryloyl, methacryloyl, crotonyl, cinnamoyl, and &
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-methylcrotonylferrocenes) in good isolated yields. Using the Gabriel-Cromwell reaction, acryloyl and crotonoylferrocenes were converted to the novel ferrocenyl substituted aziridines with benzylamine, isopropylamine and furfurylamine. The aziridines were isolated in good to excellent yields.
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Lussari, Natália. "Estudos visando a síntese total da (+)-cis-triquentrina A." Universidade de São Paulo, 2017. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-22112017-140847/.
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Triquentrinas A são produtos naturais marinhos com atividade biológica e alta complexidade estrutural. Estes fatores tornam estes alcaloides e compostos análogos, como os herbindóis, alvos para a síntese total e plataforma para o desenvolvimento de novas metodologias sintéticas. Nesta Dissertação de Mestrado, procurou-se completar a síntese estereosseletiva da (+)-cis-triquentrina A empregando-se intermediários sintéticos protegidos com o grupo benzila que poderão ser usados para a futura prospecção de novos compostos com atividade biológica. A rota proposta baseia-se na obtenção do ácido (S)-3-(1-benzil-4-etil-1H-indol-7-il)butanóico, um intermediário-chave já descrito por Silva e colaboradores no percurso da síntese total da (+)-trans-triquentrina A, e da finalização da síntese de acordo com a abordagem proposta pelo grupo de RajanBabu para conversão do análogo protegido com grupo tosila à (+)-cis-triquentrina A. A resolução enzimática do intermediário-chave com lipase de Pseudomonas cepacia imobilizada em terra diatomácea foi otimizada, resultando em rendimentos de 32% e 99% ee na metade do tempo descrito anteriormente. Na etapa-chave da síntese, o (S)-ácido foi submetido a uma acilação de Friedel-Crafts intramolecular na presença de anidrido trifluoroacético que produziu o produto de ciclização desejado com 40% de rendimento. Na etapa final da síntese, o intermediário sintético protegido com grupo benzila não pode ser convertido à (+)-cis-triquentrina A, empregando-se a metodologia desenvolvida para a redução do composto análogo tosilado, dada a diferença de reatividade imposta pela troca do grupo protetor. As etapas realizadas até o penúltimo intermediário sintético (S)-8, consta com 10 etapas e rendimento global de 1,3%. viii As diferenças eletrônicas e estruturais relacionadas a diferentes grupos protetores poderão ser refletidas em variações na atividade antiproliferativa de indóis relacionados a triquentrinas. Ainda no interesse de preparar moléculas para envio à análises de atividade antiproliferativa preparou-se um composto relacionado à síntese da trans-triquentrina A tendo como etapa-chave uma contração de anel mediada por I(III) em 21% de rendimento, cujo trabalho foi incluído nos anexos.Trikentrins A are marine natural products with biological activity and high structural complexity. These factors make these alkaloids and analogous compounds, such as herbidoles, targets for total synthesis and platform for the development of new synthetic methodologies. In this Master\'s Dissertation, we attempted to complete the stereoselective synthesis of (+)-cis-trikentrin A using synthetic intermediates protected with the benzyl group that could be used for the future prospection of new compounds with biological activity. The proposed route is based on the preparation of (S)-3-(1-benzyl-4-ethyl-1H-indol-7-yl) butanoic acid, a key intermediate already described by Silva et al., in the course of total synthesis (+)-trans-triquentrin A, and the final part of the synthesis according to the approach proposed by the RajanBabus group for conversion of the protected analogue with tosyl group to (+)-cis-trikentrin A. The enzymatic resolution of the key intermediate with Pseudomonas cepacia lipase immobilized on diatomaceous earth was optimized, resulting in 32% yield and 99% ee in half the time described above. In the key step of the synthesis, the (S)-acid was subjected to an intramolecular Friedel-Crafts acylation in the presence of trifluoroacetic anhydride which yielded the desired cyclization product in 40% yield. In the final step of the synthesis, the synthetic intermediate protected with benzyl group couldnt be converted to (+)-cis-trikentrin A, employing the methodology developed for the reduction of the tosylated analogous compound, given the difference of reactivity imposed by exchange of the protective group. The steps carried out up to the synthetic intermediate (S)-8, consists of 10 steps and overall yield of 1.3%. Electronic and structural differences related to different protective groups may be reflected in variations in the antiproliferative activity of indoles related to trikentrins. A compound related to the synthesis of trans-triquentrin A having as its key step an I(III) mediated ring contraction in 21% yield was also prepared in the interest of preparing molecules for antiproliferative activity analysis, whose work was included in the appendix.
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Sreeramoju, Mahendra K. "PREPARATION, CHARACTERIZATION AND APPLICATIONS OF FUNCTIONALIZED CARBON NANO-ONIONS." UKnowledge, 2013. http://uknowledge.uky.edu/chemistry_etds/20.
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Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects.
This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation and Billups reductive alkylation were used to functionalize N-CNOs to improve their dispersion properties in aqueous and organic solvents. Functionalized N-CNOs were characterized using various techniques such as TGA, TG-MS, Raman spectroscopy and pH-titrimetry. We designed an experimental method to isolate polycyclic aromatic adsorbates formed on the surface of oleum oxidized N-CNOs (ON-CNOs) and characterized them.
A-CNOs, on the other hand are bigger than N-CNOs with diameters ranging from 20—40 nm. In this dissertation, we discuss the preparation of graphene structures by unzipping of A-CNOs using KMnO4 as oxidizing agent. These graphene structures were characterized using powder X-ray diffraction, TGA, BET nitrogen adsorption/desorption studies and compressed powder conductivity.
This dissertation also focuses on lithiation/delithiation studies of N-CNOs, A- CNOs and A-CNO-derived graphene structures to use them as negative electrode materials in lithium-ion batteries. The cycling performances of these materials at a charge/discharge rate of C/10 were discussed. The cycling performance of N-CNOs was tested at faster charge/discharge rate of C.
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Gonnot, Vanessa. "Synthèse de molécules d'intérêts thérapeutique: Rhéine et Méquitazine : Mise au point de procédés de synthèse." Strasbourg 1, 2007. http://www.theses.fr/2007STR13241.
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De nouvelles voies de synthèse de composés à visée thérapeutique ont été développées en collaboration avec les Laboratoires Pierre Fabre. Le premier chapitre a porté sur une nouvelle voie de synthèse de la Méquitazine faisant intervenir une réaction de substitution allylique catalysée par du palladium sur substrat original. La dernière étape d’hydrogénation asymétrique pourrait conduire à l’énantiomère biologiquement actif de la Méquitazine. Deux nouvelles voies de synthèse de la Rhéine basées sur une réaction d’ortho-métallation ont été élaborées dans le deuxième chapitre. La première voie a été optimisée de manière industrialisable, et la deuxième voie permet d’obtenir la Rhéine en trois étapes grâce à un changement d’électrophile. La sélectivité de la dernière étape d’acylation de Friedel Crafts en sel fondu a été augmentée grâce à une étude du réarrangement de Hayashi. Dans un troisième chapitre, une nouvelle méthode de conversion des -fluorocyanhydrines en aldéhydes a été élaboréeThis Ph-D work in collaboration with Laboratoires Pierre Fabre has lead to the developpment of new synthetic routes to biologically active coumpounds. In chapter 1, we have synthetised Mequitazine by a new route. Key step is a palladium-catalysed allylic substitution on a new allylic substrate. Racemic Mequitazine is obtained by hydrogenation in the last step, but this route could lead to biologically active Mequitazine enantiomer by the mean of an asymmetric hydrogenation catalyst. Two new ways for the synthesis of Rhein has been developped in chapter 2. They are both based on ortho-metallation reaction. The first route has been optimised so that it can be used industrially, while the second one, by changing the electrophile, leads to Rhein in only three steps. Last step’s Friedel Crafts’acylation selectivity has been improved by detailed study of Hayashi rearrangement in molten salt. In a third chapter, a new method for converting -fluorocyanhydrines into aldehydes has been studied
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CASTANY, MARIE-HELENE. "Les triflates du germanium en synthese organometallique et organique." Toulouse 3, 1998. http://www.theses.fr/1998TOU30267.
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Cette these presente la synthese et la reactivite de triflates du germanium en tant qu'agents de germylation et catalyseur acide de lewis. Le premier chapitre decrit plusieurs voies de synthese de mono- et ditriflates du germanium par action de l'acide triflique sur differents composes organomettaliques. Le deuxieme chapitre est consacre a la germylation de nombreuses fonctions organiques a partir des triflates du germanium ou de chlorogermanes. Pour ces deux voies de synthese, une etude mecanistique est menee afin d'interpreter la regiochimie et la stereochimie de la germylation. Le troisieme chapitre met en evidence l'activite catalytique des triflates germanies en tant qu'acide de lewis dans la reaction d'aldolisation croisee entre les enols o- et c- germanies et un aldehyde, un acetal ou une imine. La diastereoselectivite observee pour ces reactions a pu etre interpretee a partir d'un mecanisme d'approche a interactions steriques et electrostatiques minimales faisant intervenir des etats de transitions ouverts ou cycliques. La reaction de friedel et crafts, sous catalyse par le triflate de trimethylgermanium, fait l'objet du dernier chapitre.
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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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Eck, Geneviève. "Synthèse partielle de la frédéricamycine A." Paris 6, 1986. http://www.theses.fr/1986PA066466.
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Le but du travail a été la synthèse d'un composé spirannique dicétonique modèle : le spiro (indane)-1,2'-(dimethoxy-4',7'indanedione-1',3')1. La première voie envisagée s'inspire de la synthèse de dialkyl-2,2 indanediones-1,3 par double réaction de Friedel-Crafts entre le dimethoxy-1,4 benzène et un chlorure d'acide dialkyl malonique. Ainsi, dans un premier temps le dimethoxy-1,4 benzène et l'acide cyclopentane dicarboxylique-1,1, en présence du réactif acide méthanesulfonique-anhydrique, fournissent le composé spirannique dicetonique résultat d'une double condensation avec un rendement de 45% : le spiro (dimethoxy)4,7 indanedione-1,3)-2, l'-(cyclopentane). La même réaction entre le dimethoxy-1,4 benzène et l'acide indane dicarboxylique-1,1 donne le composé 1 modèle avec un rendement de 8%. La deuxième voie étudiée a été la synthèse avec un rendement de 27% spiro (indane)-1,2'-(dimethoxy-4'7') 2 par alkylation du carbethoxy-1 indane par le chloromethyl-1 dimethoxy-2,5 benzène, saponification puis cyclisation par acylation intramoléculaire du produit obtenu. La transformation du compose monocétonique 2 en composé dicétonique 1 se fait par oxydation de la position benzylique avec un rendement de 8%. La derniere methode de construction de la structure spirannique de la frédéricamycine A a été la synthèse du spiro (indane)-1,1'-(cyclopentene-3'one-2') 3 par acylation desilylation du compose resultant de la saponification du produit d'alkylation du carbechoxy-1 indane par le (chloro-3 propenyl-1) trimethylsilane. Le produit 3 constituerait un accepteur de Michael pour une réaction de Hauser avec une phenylsulfonyl-3 isobenzofuranone-1 (3h) et fournirait ainsi un compose naphtoquinonique semblable à la frédéricamycine A.
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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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Hu, Gong Ming, and 胡宮銘. "Friedel-crafts acylation of ��-substituted succinic anhydride with benzene." Thesis, 1994. http://ndltd.ncl.edu.tw/handle/64537984616244806212.
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Hwu, Gong Ming, and 胡宮銘. "Friedel-Crafts Acylation of α-Substituted Succinic Anhydride with Benzene." Thesis, 1994. http://ndltd.ncl.edu.tw/handle/74930130575574526560.
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You, Wei-Jhu, and 尤偉竹. "Studies on Friedel–Crafts Acylation by Supported Heteropoly Acid Catalysts." Thesis, 2009. http://ndltd.ncl.edu.tw/handle/88776300245375457226.
Full textAbstract:
碩士龍華科技大學
工程技術研究所
97
Currently among the heterogeneous catalysts used in Friedel-Crafts acylation reactions, the heteropoly acids supported by zeolite or some highly stabe metal oxides are often used. But current methods of preparing supported heteropoly acid catalysts are rather complicated and time-consuming; that is why the supported heteropoly acid catalysts have not been widely used in the industry. In this study, we use the Dry Gel Conversion (DGC) technique combined with the Steam Assisted Conversion (SAC) technique to prepare a series of HPW/SiO2 catalysts by changing preparation parameters. By using this method, we found that the preparation procedures can be simplified significantly. The HPW/SiO2 catalysts were characterized by XRD, TEM, and FT-IR their activities were tested through the acylation of anisole and veratrole. The XRD patterns show that the catalysts are amorphous, and the amount of supported catalyst can be reduced by rising SAC temperature and increasing SAC time. The TEM pictures indicate that the catalysts are covered by supports. By means of pyridine adsorption and FT-IR, we realize that there is more Bronsted acid than Lewis acid. By comparing the conversions of the acylation of anisole and the acylation of veratrole with different catalysts, the optimal catalyst and reaction condition can be found.
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Huang, Shu-Ru, and 黃淑如. "Regioselectivity in Friedel-Crafts Acylation Reaction:3- Substituted Phthalic Anhydrides." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/58048175611625547153.
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SHEN, HENG-GUANG, and 沈恆光. "The Friedel-Crafts acylation of benzene with ▫-substituted succinic anhydrides." Thesis, 1991. http://ndltd.ncl.edu.tw/handle/56457060161344045410.
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Lee, Wen-Juing, and 李文俊. "friedel-Crafts acylation of N-carboxy-a-amino acid anhydride with toluene." Thesis, 1998. http://ndltd.ncl.edu.tw/handle/74736827950072815819.
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Chen, Jing-Feng, and 陳璟豐. "Studies LaZSM-5 on the vapour-phase Friedel-Crafts Acylation of Anisole、Thioanisole and Propionic Anhydride." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/67275505192377007380.
Full textAbstract:
碩士龍華科技大學
工程技術研究所
100
This study is the sol-gel method hydrothermal method and ion exchange method synthesized catalyst. By XRD, SEM discuss the catalyst synthesized in different silicon and aluminum ratio. The ion discuss method doped lanthanum catalyst by ICP to investigate. Catalyst activity and selectivity of the acylation reaction to test. The results showed that the catalyst for MFI structure found by XRD, The lower the Si/Al catalyst more difficult to synthesize. MFI structure is not damaged by ion-exchange experiments. The catalyst of lanthanum ion concentration determined by ICP Proved that lanthanum ions to the ion exchange method for mixed. Alkali adsorption combined with DSC detected, the catalyst Browne's acid obvious than Lewis acid. Acylation reaction to the synthesis catalyst, Anisole or Thioanisole mix Propionic Anhydride Acylation Reaction, Using GC/MS detection, the best reaction conditions. Catalyst prepared by ion exchange in the gas phase reaction temp. of 250 ℃, the catalyst weight of 0.5 g, the flow of liquid of 10 ml/hr, mole ratio Anisole/ Propionic Anhydride of 10, Conversion efficiency is best. Compared with the Reference, The LaZSM-5 conversion efficiency is better, Preferably 99%.
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Chen, Teyu, and 陳德宇. "Studies on heterogeneous solid acid nanocatalysts on liquid phase Friedel-Crafts Acylation of Anisole and Propionic Anhydride." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/79378034840987577282.
Full textAbstract:
碩士龍華科技大學
工程技術研究所
101
In this study we synthesized two kinds of solid acid nanocatalysts based on zeolites and heteropoly acids by sol-gel method and ion exchange method.Beta zeolite was synthesized by varying silicon to aluminum ratio and heteropoly acid catalyst with various loading of 12-Tungstophosphoric acid (HPW). The catalysts samples are fully characterized by SEM, XRD, TGA, DSC, ICP and BET to find out the morphology, phase purity, surface structure, surface and structure, acid type, metal content, pore size and surface area. The nanozeolite XRD results confirmed that doping of La3+and Zn2+ did not destroy structure and ICP showed doping ion is successful.The DSC studies on pyridine adsorbed catalyst samples showed that they possessed more Lewis acid than Bronsted acid. We had tested the synthesized catalysts for the acylation of anisole with propionic anhydride. We used GC/MS to identify the products. We optimized the reaction parameter for this two catalyst and the best parameter is anisole/propionic mole ratio 10, the reaction temperature is 60℃and90℃, catalyst weight is 0.5g, and in this best parameter the conversion will go up to96% and 99%.
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Wu, Yao-Peng, and 巫耀朋. "Aryl imidazolium ionic liquid−catalyzed Friedel−Crafts acylation, thioesterification, acetylation, and regioselective reductive ring opening of benzylidene acetals." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/7sw7sz.
Full textAbstract:
碩士國立中興大學
化學系所
107
Aryl imidazolium ionic liquids successfully catalyzed Friedel−Crafts acylation, thioesterification, per-O-acetylation, and regioselective reductive ring opening of benzylidene acetals in the sealed tubes. These reactions can form a C−C bond, a C−S bond, a C−O bond, and C−H bond with high atom economy. Two ionic liquids exhibited high activity and catalyzed essential reactions with good to excellent yields.
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Moon, David Thompson. "The Conjugate Addition of Novel Nucleophiles and Catalytic Intramolecular Tandem [1,5]-Hydride Shift / Cyclization and Friedel-Crafts Acylation with Alkylidene Meldrum’s Acid Derivatives." Thesis, 2008. http://hdl.handle.net/10012/4061.
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Investigations into the conjugate addition of phenols and sp3-hybridized carbons bound to tin, boron and silicon by transition metal catalysts through novel transmetallation pathways were undertaken with limited success. An intramolecular Lewis acid-catalyzed tandem [1,5]-hydride shift / cyclization and Friedel-Crafts acylation reaction with alkylidene Meldrum’s acid derivatives has been accomplished.
The use of metal phenolates as nucleophiles for transition metal catalyzed conjugate addition onto alkylidene Meldrum’s acids is explored, and the ambident nucleophilic property of metal phenolates allow for the C-alkylation and O-acylation with alkylidene Meldrum’s acids, producing substituted 3,4-dihydrocoumarins in modest yields.
The transmetallation of rhodium complexes with alkyl boron, tin and silicon derivatives and subsequent conjugate addition onto alkylidene Meldrum’s acid derivatives is investigated without success.
An intramolecular Lewis acid-catalyzed [1,5]-hydride shift / cyclization reaction promoted by electron-rich aromatic rings is employed with alkylidene Meldrum’s acid derivatives to furnish spiro Meldrum’s acids in excellent yields. These can subsequently be used as electrophiles in the Friedel-Crafts acylation reaction, and a tandem, one-pot variation of this reaction has been accomplished in moderate to good yields. Preliminary investigations into the scope and limitations of this transformation are outlined.