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Activité leishmanicide de plantes issues de la pharmacopée traditionnelle Péruvienne et de molécules de synthèse; étude relation structure activité.Estevez, Yannick 28 September 2009 (has links) (PDF)
Les Leishmanioses du nouveau monde sont des parasitoses aux conséquences socio-économiques lourdes. En effet les traitements disponibles requièrent pour la plus part des administrations parentérales et sont coûteux pour les populations concernées. La recherche de nouvelles molécules actives est donc une nécessité. Pour contribuer à l'effort de recherche d'alternative thérapeutiques, nous nous sommes intéressés d'une part aux pharmacopées traditionnelles de populations vivant en zone d'endémie (deux ethnies de l'Amazonie péruvienne : Chayahuita et Yanesha) et d'autre part, nous avons également étudiés l'activité de drogues synthétisées sur la base de molécules ayant un certain degré d'activité antiparasitaire. Nous avons également contribué à l'amélioration éthique de nos modèles biologiques afin d'optimiser le criblage de composés leishmanicides potentiels en développant un modèle remplaçant l'utilisation de souris pour l'extraction de macrophages par des cellules Thp1.
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Synthèse et caractérisation de copolymères dérivés de quinoxaline et de carbazoleBreton, Anne-Catherine 18 April 2018 (has links)
En raison de la demande croissante pour de nouvelles formes d'énergie renouvelable au cours des dernières années, la recherche sur les matériaux organiques pour d'éventuelles applications en photovoltaïque a rapidement progressé. Ainsi, tout récemment, des performances intéressantes ont été obtenues à partir de dispositifs dont la couche active était constituée d'un mélange de [6,6]-phényl-C₆₁-butyrate de méthyle (PCBM) et d’un polymère semi-conducteur. Puis, dans le dessein d’améliorer les performances des matériaux organiques, les chercheurs ont ensuite tenté de moduler les niveaux d'énergie et la largeur de bande interdite des polymères conjugués. Une façon de parvenir à moduler les propriétés électroniques de ces molécules est d'utiliser une séquence de donneurs-accepteurs dans la chaîne du polymère. Le groupe de recherche du Dr Leclerc participe aussi activement à cette quête de nouvelles sources d'énergie. Entre autre, nous synthétisons et caractérisons des copolymères contenant des unités hautement déficientes en électrons, les quinoxalines, et des unités riches en électrons, les carbazoles. La polymérisation de plusieurs unités de quinoxaline portant des groupements substituants de nature différente nous a ainsi permis d’élaborer une famille complète de co-polymères semi-conducteurs. Nous évaluons ensuite l'impact de l'ajout de ces substituants par les propriétés électroniques et optiques afin d'identifier parmi les polymères synthétisés, ceux qui possèdent des propriétés adéquates pour des applications en cellules photovoltaïques. Pour terminer, les polymères sont testés en les incorporant dans la couche active des cellules photovoltaïques pour évaluer leurs performances. Des taux de conversion énergétique variant entre 1,24% et 3,37% ont ainsi été obtenus. Pour ces polymères, nous avons aussi réalisé plusieurs essais sur le type de solvant, le ratio polymère :PCBM, la nature de l’électrode ou, encore, sur l’ajout d’additifs pouvant permettre d’optimiser leur utilisation dans la fabrication des cellules photovoltaïques.
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Funcionalização dirigida de quinoxalinas visando à preparação de substâncias bioativas / Directed functionalization of quinoxalines aiming the synthesis of bioactive compoundsFerreira, Samuel Remotto Alves 11 November 2016 (has links)
Desde sua descoberta em meados do século XIX, os reagentes organometálicos têm sido amplamente utilizados na síntese orgânica, sendo bastante eficientes na formação de novas ligações carbono-carbono. A escolha do reagente organometálico ideal para determinada reação envolve conhecimentos relacionados à sua natureza química e à própria reatividade do substrato. O núcleo quinoxalínico apresenta um grande potencial para a química medicinal, estando presente em diversos produtos naturais e sintéticos que apresentam atividade biológica. Apesar disso, existem poucos estudos na literatura sobre a aplicação de reagentes organometálicos na funcionalização de quinoxalinas. A reação de metalação dirigida usando bases organometálicas é uma poderosa ferramenta para funcionalização de substratos aromáticos. Contudo, exemplos da aplicação desta estratégia na funcionalização de quinoxalinas são bastante raros. Assim, este trabalho teve como principal objetivo investigar a reatividade dos reagentes organometálicos derivados de zinco, magnésio e lítio em reações de metalação de quinoxalinas substituídas com grupos funcionais nas posições C-2 e C-6. Embora as quinoxalinas substituídas com grupos éster, amida e fenil na posição C-2 não tenham apresentado a reatividade esperada frente aos amidetos mistos de zinco e magnésio (TMPZnCl?MgCl2?LiCl, TMP2Zn?2MgCl2?2LiCl, TMPMgCl?LiCl e TMP2Mg?2LiCl), uma nova metodologia foi desenvolvida utilizando TMPLi como base, na presença de ZnCl2, que permitiu a preparação de vários derivados difuncionalizados em bons rendimentos, muitos dos quais de estrutura inédita. Quinoxalinas não substituídas nas posições C-2 e C-3 possuem reconhecida intolerância à presença de reagentes organometálicos, rendendo preferencialmente produtos de dimerização. Desta forma, uma contribuição importante deste trabalho foi o desenvolvimento de uma metodologia de funcionalização da quinoxalina de estrutura mais simples em micro-ondas, mediada pelo sistema TMPMgCl?LiCl/ZnCl2, que permitiu a preparação de diversos derivados arilados em rendimentos que variaram de razoáveis a bons (25 a 94%). Além disso, a metodologia mostrou-se bastante eficiente para síntese de ligantes bidentados de interesse para a área de catálise / Since its discovery in the mid-nineteenth century, organometallic reagents have been widely used in organic synthesis, being very effective in the formation of new carbon-carbon bonds. The choice of the ideal organometallic reagent for certain reaction involves knowledge related to their chemical nature and reactivity of the substrate itself. The quinoxaline core has great potential for medicinal chemistry and is present in many natural and synthetic products presenting biological activity. Nevertheless, there are few studies on the application of organometallic reagents in the functionalization of quinoxalines. The directed metalation reaction using metal bases is powerful synthetic tool for functionalization of aromatic substrates. However, examples on the application of such strategy to the functionalization of of quinoxalines are very rare. This work mainly aimed to investigate the reactivity of organometallic reagents of zinc, magnesium and lithium in the metalation of quinoxalines substituted with functional groups at the C-2 and C-6 positions. Although C-2 substituted quinoxalines with ester and amide groups have not shown the expected reactivity with mixed amides of zinc, magnesium and lithium (TMPZnCl?MgCl2?LiCl, TMP2Zn?2MgCl2?2LiCl, TMPMgCl?LiCl and TMP2Mg?2LiCl), a new methodology was developed using TMPLi as a base in the presence of ZnCl2, allowing the preparation of various difuncionalized derivatives in good yields, many of them new compounds. Quinoxalines unsubstituted at the C-2 and C-3 positions have recognized intolerance to the presence of organometallic reagents, preferably yielding dimerization products. Thus, an important contribution of this work was the development of a functionalization methodology of the simplest quinoxaline in microwave mediated by the TMPMgCl?LiCl/ZnCl2, allowing the preparation of various arylated derivatives in yields ranging from reasonable to good (25 to 94%). Furthermore, the methodology could be applied to the synthesis of bidentate ligands of interest for catalysis
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Studies of novel immunosuppressive agents in experimental arthritis /Dang, Thi Ngoc Dzung, January 2006 (has links)
Diss. (sammanfattning) Stockholm : Karolinska institutet, 2006. / Härtill 4 uppsatser.
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Synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers and reaction chemistry of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at triosmium carbonyl clusters.Poola, Bhaskar 12 1900 (has links)
Quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been synthesized as possible specific metal host systems. The synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been described. The characterization of these host systems have been fully achieved in solution by using various techniques such as IR, 1H NMR, and 13C NMR spectroscopic methods, high-resolution mass spectrometry (HRMS), elemental microanalysis, and X-ray crystallographic analysis in case of one quinoxaline-functionalized, cage-annulated oxacrown ether compound. The synthesis of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) is described. The substitution of the MeCN ligands in the activated cluster 1,2-Os3(CO)10(MeCN)2 by the diphosphine ligand bmi proceeds rapidly at room temperature to furnish a mixture of bridging and chelating Os3(CO)10(bmi) isomers and the ortho-metalated product HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)N(tolyl-p)C(O)]. Thermolysis of the bridging isomer 1,2-Os3(CO)10(bmi) under mild conditions gives the chelating isomer 1,1-Os3(CO)10(bmi), whose molecular structure has been determined by X-ray crystallography. The kinetics for the ligand isomerization have been investigated by UV-vis and 1H NMR spectroscopy in toluene solution over the temperature range of 318-348 K. On the basis of kinetic data conducted in the presence of added CO and the Eyring activation parameters, a non-dissociative phosphine migration across one of the Os-Os bonds is proposed. Orthometalation of one of the phenyl groups associated with the bmi ligand is triggered by near-UV photolysis of the chelating cluster 1,1- Os3(CO)10(bmi).
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A Study of Some 1-alkyl-1,2-dihydro-3-hydroxybenzo[g]quinoxaline-5,10-dionesBrown, Jerry 08 1900 (has links)
The experiment in this thesis involves a study of some 1-alkyl-1,2-dihydro-3-hydroxybenzo[g]quinoxaline-5,10-diones.
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Исследование электрохимического восстановления 2-замещеных хиноксалинов в апротонной среде. Количественное определение вольтамперометрическим методом : магистерская диссертация / Study of electrochemical reduction of 2-substituted quinoxalines in an aprotic medium. Quantification by voltammetric methodЛыкова, Ю. А., Lykova, Yu. A. January 2020 (has links)
Объектами исследования являются 2-замещеные хиноксалины. Целью данной работы является изучение химических свойств хиноксалина и его производных. В работе рассматривалось восстановление производных хиноксалина (окислительно-восстановительные свойства, потенциал восстановления, ЭПР спектр, квантово-химический расчеты). Сравнение восстановительных свойств синтезированного ряда производных хиноксалина. Определено количество электронов, участвующих в процессе восстановления производных хиноксалина. Смоделирован процесс восстановления. Доказан одноэлектронный переход хиноксалина. Далее приводится количественное определение производных хиноксалина вольтамперометрическим способом. Изучение свойств хиноксалина является важной задачей, так как вновь синтезированные производные хиноксалинов проявляют химическую и биологическую активность. Из-за значительного увеличения вирусов и необходимости поиска новых лекарственных препаратов, исследование производных хиноксалинов и их химической активности, а также количественное определение новых синтезированных хиноксалинов является нужной и важной задачей. В работе доказан одноэлектронный переход хиноксалина экспериментальными и расчетными методами (ЭПР спектр, квантово-химический расчеты, хроноамперометрия). Также был построен ряд восстановительной активности хиноксалина и его производных. После чего были выбраны производные для количественного определения вольтамперометрическим методом. Результаты показали, что одноэлектронный переход хиноксалина свойственен и для его производныхРазработаны методики количественного определения формальдегида в объектах фармации на примере ЛП «Эндофальк» и товарного уротропина от ПАО «Метафракс». Правильность полученных результатов подтверждена сравнением с результатами независимых методов анализа, прописанных в ФС РФ XIV издания на субстанции уротропина и «Макрогола 3350». / The object of research is 2-substituted quinoxalines. The goal of this work is to study the chemical properties of quinoxaline and its derivatives. This goal is divided into the following tasks: 1) Study of literature sources on the use of quinoxaline derivatives, chemical and electrochemical properties of these compounds, possible published methods for quantitative determination of quinoxaline derivatives by voltammetric method. 2) Study of reducing properties of compounds of quinoxalin derivatives (redox properties, reduction potential, EPR spectrum, quantum chemical calculations). Comparison of reducing properties of a synthesized series of quinoxaline derivatives. 3) Determination of the number of electrons involved in the reduction of quinoxaline derivatives. Modeling the reduction process. Proof of a single-electron quinoxalin transition. 4) Quantitative determination of quinoxalin derivatives by voltammetric methods.
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