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The inhibitive action of alcohols on the oxidation of sodium sulfite ...Alyea, Hubert N. January 1928 (has links)
Thesis (Ph. D.)--Princeton University, 1928.
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The inhibitive action of alcohols on the oxidation of sodium sulfite ...Alyea, Hubert N. January 1928 (has links)
Thesis (PH. D.)--Princeton University, 1928.
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Hifenização da eletroforese capilar com sistema eletroquímico em fluxo: desenvolvimento de instrumentação para a determinação de íons metálicos com pré-concentração eletroquímica e para o estudo da oxidação de alcoóis / Hyphenation of capillary electrophoresis with an electrochemical flow system: development of instrumentation aiming metallic ions determination by electrochemical preconcentration and study of alcohols oxidationLopes, Fernando Silva 15 August 2014 (has links)
Um sistema completo foi desenvolvido para o novo acoplamento de uma célula eletroquímica em fluxo com um eletroforese capilar equipado com detector condutométrico sem contato (EC-CE-C4D). Este acoplamento compreendeu o design da interface EC-CE, um potenciostato protegido contra fuga de alta tensão, subsistema de controle de fluxo por bombas solenóide e um equipamento CE-C4D adaptado para a aplicação. Um software dedicado para aquisição de dados, controle e operação do sistema foi desenvolvido na ferramenta gráfica de programação LabView. O sistema foi inicialmente aplicado na eletrodeposição de traços dos metais Cd2+, Pb2+, Cu2+, Zn2+ e Tl+, seguida pela redissolução e separação destes por CE, o que resultou em fator de pré-concentração de até 55 vezes para todos os metais, exceto Zn2+. Os metais acumulados foram redissolvidos na matriz original da amostra para permitir a separação e determinação conjunta com cátions majoritários (p. ex. alcalinos e alcalinos terrosos e amônio, se acima do LD). Para amostras cuja matriz possa causar interferência, pouco antes da injeção no CE, foi realizado processo de cleanup pela redissolução dos metais no eletrólito de separação. Experimentos pra separação bidimensional com o potencial de deposição ou redissolução voltamétrica como primeira dimensão e o tempo de eletromigração como segunda dimensão foram propostos e demonstrados. A oxidação eletroquímica de espécies orgânicas na interface EC-CE surgiu como um segundo campo de aplicação para: a) derivatização de analitos neutros tornando-os carregados ou ionizaveis, p. ex., conversão de álcoois alifáticos de cadeia curta em carboxilatos que possam ser separados e quantificados por CE-C4D; b) investigação/monitoramento de processos de eletrodo pela detecção de produtos carregados ou ionizáveis de reação de eletrodo, p. ex., investigação de condições experimentais para eletrooxidação de glicerol objetivando-se a síntese de produtos com maior valor comercial. / A complete instrumental system was developed for the new coupling of an electrochemical flow cell to capillary electrophoresis with contactless conductivity detection (EC-CE-C4D) and comprising an innovative design of the EC-CE interface, a potentiostat circuit protected from high voltage leakages, a solenoid pump based flow management subsystem, and a CE-C4D equipment tailored for this application. Dedicated software for data acquisition, devices control and operation automation was developed in LabVIEW graphical programming tool. The system was first applied to the electrodeposition of traces of Cd2+, Pb2+, Cu2+, Zn2+ and Tl+ , followed by stripping and separation by CE, allowing a 55-fold preconcentration factor in 6 min for all metals but Zn2+. The accumulated metals were stripped into the original sample matrix to allow their separation together with the sample\'s major cations (e.g. alkaline and alkaline earth metals and ammonium, if above LOQ). For samples with a matrix that originates interferences, cleanup was achieved by stripping the metals into background electrolyte shortly before injection in the capillary. Two-dimensional separations with voltammetric deposition or stripping potential as one dimension and electromigration time as the second one were proposed and demonstrated. Electrochemical oxidation of organic species in the EC-CE interface emerged as a second field of application for: a) derivatization of neutral analytes into charged or ionizable species, e.g., conversion of short chain aliphatic alcohols into carboxylates that can been determined by CE-C4D; b) investigation/monitoring of electrode processes by detection of charged or ionizable reaction products of electrode reactions, e.g., investigation of experimental conditions for glycerol electro-oxidation aiming the synthesis of commercially valuable products.
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Hifenização da eletroforese capilar com sistema eletroquímico em fluxo: desenvolvimento de instrumentação para a determinação de íons metálicos com pré-concentração eletroquímica e para o estudo da oxidação de alcoóis / Hyphenation of capillary electrophoresis with an electrochemical flow system: development of instrumentation aiming metallic ions determination by electrochemical preconcentration and study of alcohols oxidationFernando Silva Lopes 15 August 2014 (has links)
Um sistema completo foi desenvolvido para o novo acoplamento de uma célula eletroquímica em fluxo com um eletroforese capilar equipado com detector condutométrico sem contato (EC-CE-C4D). Este acoplamento compreendeu o design da interface EC-CE, um potenciostato protegido contra fuga de alta tensão, subsistema de controle de fluxo por bombas solenóide e um equipamento CE-C4D adaptado para a aplicação. Um software dedicado para aquisição de dados, controle e operação do sistema foi desenvolvido na ferramenta gráfica de programação LabView. O sistema foi inicialmente aplicado na eletrodeposição de traços dos metais Cd2+, Pb2+, Cu2+, Zn2+ e Tl+, seguida pela redissolução e separação destes por CE, o que resultou em fator de pré-concentração de até 55 vezes para todos os metais, exceto Zn2+. Os metais acumulados foram redissolvidos na matriz original da amostra para permitir a separação e determinação conjunta com cátions majoritários (p. ex. alcalinos e alcalinos terrosos e amônio, se acima do LD). Para amostras cuja matriz possa causar interferência, pouco antes da injeção no CE, foi realizado processo de cleanup pela redissolução dos metais no eletrólito de separação. Experimentos pra separação bidimensional com o potencial de deposição ou redissolução voltamétrica como primeira dimensão e o tempo de eletromigração como segunda dimensão foram propostos e demonstrados. A oxidação eletroquímica de espécies orgânicas na interface EC-CE surgiu como um segundo campo de aplicação para: a) derivatização de analitos neutros tornando-os carregados ou ionizaveis, p. ex., conversão de álcoois alifáticos de cadeia curta em carboxilatos que possam ser separados e quantificados por CE-C4D; b) investigação/monitoramento de processos de eletrodo pela detecção de produtos carregados ou ionizáveis de reação de eletrodo, p. ex., investigação de condições experimentais para eletrooxidação de glicerol objetivando-se a síntese de produtos com maior valor comercial. / A complete instrumental system was developed for the new coupling of an electrochemical flow cell to capillary electrophoresis with contactless conductivity detection (EC-CE-C4D) and comprising an innovative design of the EC-CE interface, a potentiostat circuit protected from high voltage leakages, a solenoid pump based flow management subsystem, and a CE-C4D equipment tailored for this application. Dedicated software for data acquisition, devices control and operation automation was developed in LabVIEW graphical programming tool. The system was first applied to the electrodeposition of traces of Cd2+, Pb2+, Cu2+, Zn2+ and Tl+ , followed by stripping and separation by CE, allowing a 55-fold preconcentration factor in 6 min for all metals but Zn2+. The accumulated metals were stripped into the original sample matrix to allow their separation together with the sample\'s major cations (e.g. alkaline and alkaline earth metals and ammonium, if above LOQ). For samples with a matrix that originates interferences, cleanup was achieved by stripping the metals into background electrolyte shortly before injection in the capillary. Two-dimensional separations with voltammetric deposition or stripping potential as one dimension and electromigration time as the second one were proposed and demonstrated. Electrochemical oxidation of organic species in the EC-CE interface emerged as a second field of application for: a) derivatization of neutral analytes into charged or ionizable species, e.g., conversion of short chain aliphatic alcohols into carboxylates that can been determined by CE-C4D; b) investigation/monitoring of electrode processes by detection of charged or ionizable reaction products of electrode reactions, e.g., investigation of experimental conditions for glycerol electro-oxidation aiming the synthesis of commercially valuable products.
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Oxydation par l’oxygène moléculaire d’alcools en phase liquide en synthons carbonyles / Liquid phase oxidation of alcohols to carbonyl synthons with molecular oxygenFrassoldati, Antonio 22 November 2011 (has links)
L’oxydation sélective des alcools en aldéhydes, acides ou cétones est une transformation très importante en chimie. L’emploi d’oxygène moléculaire comme oxydant permet de se placer dans une perspective de chimie verte, avec la production d’eau comme seul sous-produit principal. L’oxydation d’alcools primaires (1-octanol et géraniol) et d’alcools secondaires (2-octanol, 1-phénylethanol et alcools hétéroaromatiques dérivés de la pyridine) a été étudié en présence de catalyseurs au platine supportés sur charbon sous pression d’air, en solvant organique ou mélange à de l’eau. Les résultats ont montré une forte influence du solvant sur l’activité catalytique, avec un effet promoteur très important de l’eau sur la réaction. Cet effet a été discuté sur la base de différentes hypothèses. La promotion des catalyseurs au platine par le bismuth a permis d’observer des modifications de l’activité avec un effet positif en particulier dans l’oxydation des alcools hétéroaromatiques secondaires. La désactivation observée lors de l’oxydation de certains substrats a été analysée et des solutions ont été proposées pour la surmonter. / The selective alcohols oxidation to aldehydes, acids and ketones is an important transformation in chemistry. The use of molecular oxygen as oxidant is in adequation with a green chemistry perspective, since water is the only by-product. The oxidation of primary alcohols (1-octanol and geraniol) and secondary alcohols (2-octanol, 1-phenylethanol and pyridine substituted alcohols) has been studied in the presence of platinum supported carbon catalysts under air pressure in organic or mixed organic/aqueous media. The results have shown a strong influence of the solvent on the catalytic activity, with an important promoting effect of water on the reaction. This effect has been discussed based on several hypotheses. The promotion of platinum supported catalysts by bismuth has shown some modifications of the activity, with a positive effect in particular in the oxidation of secondary heteroaromatic alcohols. The deactivation observed during the oxidation reaction of some substrates has been analyzed and some solutions have been proposed to overcome the problem.
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Chemistry Of Molybdenum Xanthate [Mo02(Et2NCS2)] : Applications In Organic SynthesisMaddani, Mahagundappa R 11 1900 (has links)
The thesis entitled ‘Chemistry of molybdenum xanthate (MoO2[Et2NCS2]2): Applications in organic synthesis’ is presented in 4 chapters. Molybdenum (IV and VI) oxo-complexes are the subject of significant interest due to their functional and structural similarities with several molybdo-enzymes.1 Literature survey suggests that, molybdenum (VI as well as IV) xanthate2 1 resembles the active sites of various molybdo-enzymes. Therefore, in the present thesis, we are presenting our attempts directed towards exploiting molybdenum xanthate 1 in developing various useful methodologies.
Figure 1: Molybdenum xanthate
Chapter 1 discloses the utility of molybdenum xanthate (1) in catalytic, aerobic oxidation of organic azides and alcohols as presented in part A and B.
Part A: A mild molybdenum xanthate catalyzed, chemoselective oxidation of benzylic azides to the corresponding aldehydes3 under aerobic condition is described. This oxidation turned out to be a general method and a variety of benzylic azides were oxidized to the corresponding aldehydes. This oxidation protocol tolerates a variety of functional groups including alcohols, esters, ketones, halides and olefins. More importantly, the oxidation of azides stops at corresponding aldehyde stage without further oxidation to the corresponding carboxylic acids. A few examples are presented in scheme 1.
Part B: As our attempts to oxidize alcohols with molybdenum xanthate 1 were unsuccessful (Chapter 1, Part A), we have attempted supporting the reagent 1 and investigated its utility in the oxidation of alcohols. As a consequence, polyaniline supported molybdenum xanthate (MoO2[Et2NCS2]2) is designed and used in an aerobic and mild chemoselective oxidation of alcohols4 to the corresponding aldehydes and ketones. The scheme to use polyaniline as the support for molybdenum xanthate was derived from the fact that polyaniline is known to increase the redox activity of various metal complexes by coordinating to the metal centre.5 The present oxidation strategy tolerates a variety of functional groups such as olefin, ketones, sulfides, tertiary amines, propargyl group etc. This oxidation strategy also works very well for the oxidation of secondary benzylic alcohols. Interestingly, the supported catalyst can be filtered after the reaction and reused for further oxidation without loss of its activity. Some representative examples are presented in Scheme 2.
Chapter 2 describes the chemoselective and efficient reduction of azides to the corresponding amines. In this chapter, we have shown that a catalytic amount of molybdenum xanthate (1, MoO2[S2CNEt2]2) with PhSiH3 is an effective catalyst for the reduction of azides to the corresponding amines.6 This reduction of azides by 1, was inspired by the reductive silylation of aldehydes through the activation of silanes.7 This reduction tolerates a variety of reducible functional groups such as olefin, aldehydes, ketones, esters, amides and ethers, acetals etc. This strategy was also extended to various aliphatic azides to synthesize amine and their N-Boc derivatives in good yields. Scheme 3 illustrates few examples.
Chapter 3 discloses convenient methods for the synthesis of substituted thiourea derivatives as presented in part A and B.
Part A: A convenient method for the synthesis of tri-substituted thiourea derivatives by the reaction of primary amines with molybdenum dialkyl dithiocarbamates is presented in Part A.8 Primary amines on reaction with molybdenum xanthate produce corresponding thioureas in moderate to good yields. Similar reactions with propargylamine and 2-aminoethanol produce cyclic thiaoxazolidine and oxazolidine derivatives respectively. This methodology has been successfully adopted for the synthesis of amino acids derived chiral thioureas. Some examples are presented in Scheme 4.
Scheme 4: Molybdenum xanthate mediated synthesis of thioureas
Part B: An efficient method for the synthesis of symmetrical and unsymmetrical substituted thiourea9 derivatives by simple condensation of amine and carbon disulfide in aqueous medium is extensively studied. Present method describes the involvement of amino dithiol moiety as an intermediate. Though this method is not successful with secondary amines and aryl amines, it works smoothly with aliphatic primary amines to afford various di- and tri-substituted thiourea derivatives. The present method is also useful in synthesizing various substituted 2-mercapto imidazole heterocycles in moderate yields. A few examples are seen in Scheme 5.
Scheme 5: Synthesis of thiourea derivatives in aqueous medium
Chapter 4 describes a chemoselective deprotection10 of terminal acetonides (isopropylidines) by using aqueous TBHP (70%). A variety of acetonide derivatives on reaction with aq. TBHP in water:t-BuOH (1:1) as solvent mixtures furnish the corresponding acetonide deprotected diol products in good yields. This unprecedented deprotection strategy, tolerates a variety of acid sensitive functional groups such as silyl ether, trityl, olefin, propargyl, methoxymethyl ether, N-Boc, lactones, esters etc. A few examples are documented in Scheme 6.
Scheme 6: Chemoselective deprotection of acetonides
(For structural formula pl see the pdf file)
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Catalyseurs hétérogènes à base de polysaccharides pour des réactions pallado-catalysées / Heterogeneous catalysts based on polysaccharides for palladium-catalyzed reactionsOuchaou, Kahina 09 November 2012 (has links)
Les travaux de thèse présentés dans ce manuscrit portent essentiellement sur la préparation, le criblage et l’utilisation des catalyseurs hétérogènes à base de polysaccharides. L’objectif principal du projet de thèse a plus particulièrement consisté à évaluer deux polysaccharides : les alginates et le chitosane en tant que supports renouvelables pour la catalyse hétérogène. Ces deux types de polysaccharides ont des structures et des propriétés physico-chimiques très différentes : les alginates sont connus pour être de bons complexants de métaux di ou trivalents de par la présence des fonctions carboxylates dans leur matrice, le chitosane résulte quant à lui de l’assemblage d’unités N-glucosamine pouvant être facilement modifiées chimiquement.Dans un premier temps, nos travaux ont essentiellement portés sur des catalyseurs bimétalliques Mn+ Pd supportés sur alginate dont nous avons évalué l’activité catalytique dans les réactions de couplage C—C de Mizoroki-Heck, Sonogashira et Suzuki-Miyaura. D’une manière générale, seuls les catalyseurs à base de nanoparticules de palladium ont montré une réactivité intéressante pour la catalyse de la réaction de Suzuki-Miyaura. Par la suite, nous avons également étudié les réactions d’oxydations d’alcools catalysées par du palladium (II) complexé à l’alginate. Cette étude nous a permis d’identifier deux catalyseurs actifs vis-à-vis de l’oxydation d’alcools allyliques et benzyliques.Dans un deuxième temps, nous avons développé de nouveaux ligands de type NHC en vue de les greffer sur la matrice chitosane : un ligand NHC pour les réactions de métathèse d’oléfines, et plusieurs ligands NHC de type pincer CNC pour les réactions de couplage C—C dans l’eau. Bien que les performances catalytiques des systèmes hétérogènes correspondant soient limitées, ces travaux ont conduit à l’élaboration de nouveaux ligands amphiphiles construits autour d’un noyau pyrazine porteurs de quatre ligands carbéniques. Après complexation de métaux tels que le palladium ou l’or, ces systèmes conduisent à des nanocatalyseurs ayant des performances catalytiques intéressantes. Enfin, dans un troisième temps, nous avons développé une nouvelle réaction de cyanation décarboxylante pallado-catalysée permettant de transformer en une étape des acides carboxyliques aromatiques en benzonitriles correspondants. Outre son intérêt synthétique, cette réaction présente un grand intérêt pour le marquage isotopique. / This work describes the preparation, screening and use of heterogeneous catalysts based on polysaccharides. The main goal of our project was to evaluate two polysaccharides: alginates and chitosan as renewable supports for heterogeneous catalysis.Alginates are known to form gels with most di- and multivalent cations due to the presence of the carboxylate functions of their matrix. And chitosan is an attractive polysaccharide for application in catalysis owing to the presence of readily functionalizable amino group and its insolubility in organic solvents.First, our work focused on evaluating the catalytic activity of bimetallic Mn+-Pd catalysts supported on alginate in C—C coupling reactions. Among them, one system demonstrated remarkable catalytic properties for the Suzuki-Miyaura coupling. Then, the oxidation of alcohols catalyzed by Alginate-Mn+-Pd2+ catalyst was investigated. Two catalysts demonstrated good activity for oxidation of benzylic and allylic alcohol.In a second time, we developed new NHC ligands in order to anchor them on chitosan: two new NHC ligands for olefin metathesis and several NHC pincer CNC ligands for C—C coupling reactions in water. A palladium complex obtained with one our new ligand bearing long alkyl chains showed good activity in the Suzuki-Miyaura coupling in pure water.Finally, a new palladium (II) catalyzed decarboxylative cyanation reaction was investigated. This methodology is the first example of direct conversion of aryl carboxylic acid into the corresponding aryl nitrile. This reaction is well adapted to labeled compound synthesis.
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