A presente tese trata das reações de sulfanilação de algumas 2-sulfinilciclanonas racêmicas pelo método de catálise por transferência de fase (CTF), seja usando cloreto de benziltrietilamônio (TEBAC) seja usando catalisador quirálico. As reações de sulfanilação pelo método de CTF empregando TEBAC, forneceram produtos sulfanilados em altos rendimentos (75-93%), enquanto que as reações empregando a mesma metodologia, utilizando catalisadores quirálicos, conduziram não só a altos rendimentos, mas também a um aumento no excesso diastereomérico. Foram determinadas as configurações relativas da 2metilsulfanil- 2-metilsulfinilciclopentanona e 2-p-tolilsulfanil-2metilsulfinilcicloexanona pela análise de difração de Raios-X como sendo 2S*SS*. A parte final da Tese contém reações de sulfanilação da 2-metilsulfinilciclopentanona e 2-metilsulfinilcicloexanona opticamente ativas. É digno de nota que estas, ao contrário da 2-p-tolilsulfinil ciclanonas, descritas na literatura, conduziram a produtos sulfanilados estáveis. Finalmente, a tese mostra um exemplo de condensação aldólica assimétrica partindo da 2-metilsulfanil-2-metilsulfinilcicloexanona opticamente ativa. Com base no conhecimento da configuração deste último composto, foi possível esclarecer o mecanismo da indução assimétrica. / This thesis presents the sulfanylation reactions of some racemic 2-methylsulfinil cyclanones, by phase transfer catalysis (PTC) method, employing as catalysts either benzyltriethylammonium chloride (BTAC) or some optically active catalysts. The sulfanilation reactions, employing BTAC furnished the sulfanylated products in high yields (75-93%) while the reactions performed by the same methodology, using chiral catalysts, led to higher yields and also to an increase in the diastereomeric excess. The relative configuration of 2-metilsulfanyl-2-methylsufinylcyclopentanone and of 2-p-tolylsulfanyl-2-methylsulfinylcyclohexanone, as determined by X-Ray diffraction analysis, showed to be 2S*SS*. The final part of this thesis reports the sulfanylation reactions of the optically active 2-methylsulfinylcyclopentanone and 2-methylsulfinylcyclohexanone, which, in contrast to the p-tolyl derivatives, described in the Iiterature, were stable derivatives. Finally, on the basis of the relative configuration of the optically active 2-methylsulfanyl-2-methylsulfinylcyclohexanone, it became possible to propose the stereochemical course of the asymmetric aldol reaction of this compound with an ester enolate.

A busca por membranas com propriedades adequadas a separação de gases em escala industrial tem levado a modificação e sIntese de polImeros de engenharia, com objetivo de obter membranas com propriedades adequadas. Uma das modificaçoes que tem se apresentado promissora é a inserção de grupos sulfônicos em polImeros comerciais. Espera-se que o polImero sulfonado apresente um aumento na permeação de gases polares, em relação a gases apolares, devido a sua estrutura mais polar e flexIvel. Neste contexto, o objetivo do presente trabalho é a sIntese e caracterização de membranas de poli(éter imida) sulfonada para a permeação de gases. Um planejamento experimental foi desenvolvido, em diferentes condiçoes reacionais de temperatura, tempo e excesso de um dos reagentes (ácido acético), para a sIntese de poli(éter imida) sulfonada (SPEI). Através deste planejamento, constatou-se que as variáveis que mais influenciam o grau de sulfonação são a temperatura e o tempo. O polImero com o maior grau de sulfonação, determinado por capacidade de troca iônica (IEC= 92 mEq H+/g), foi utilizado para o preparo da membrana de SPEI, obtida pela técnica de inversão de fase por evaporação do solvente, utilizando-se clorofórmio como solvente. Este filme foi caracterizado a partir das seguintes análises: espectroscopia de infravermelho (FTIR), calorimetria diferencial de varredura (DSC), análise termogravimétrica (TGA) e microscopia eletrônica de varredura (MEV), a fim de avaliar a influência da inserção do grupo sulfônico na matriz polimérica. O espectro de infravermelho de SPEI apresentou bandas relacionadas as vibraçoes assimétricas em 1240 cm-1 (ligação O=S=O), ligação simétrica em 1171 cm-1 (O=S=O) e ligação S-O entre 1010-1024 cm-1. Isto indica a presença de grupos sulfônicos. A análise de DSC foi realizada entre 150-250C. Nesta faixa, não foram observadas alteraçoes na temperatura de transição vItrea (Tg) do polImero modificado (217C). Acredita-se que a decomposição do grupo sulfona aconteça antes da temperatura atingir o Tg do polImero. Esta suposição é confirmada na análise de TGA. As imagens de MEV mostraram que foram obtidos filmes livres de poros e defeitos. A membrana da SPEI foi utilizada no ensaio de permeaçao dos gases 02, N2 e C02, a fim de determinar a permeabilidade e seletividade da membrana. As permeabilidades encontradas para o gas oxigênio foram de 0,76 barrer para a PEI e 0,46 barrer para a SPEI. A seletividade do dióxido de carbono em relaçao ao oxigênio aumentou de 3,5, na membrana de PEI, para 4,83, na membrana de SPEI. Em relaçao ao nitrogênio, as permeabilidades medidas foram 0,064 barrer e 0,043 barrer, para a PEI e para a SPEI, respectivamente, enquanto a seletividade em relaçao ao C02 aumentou de 41,1 para 55,5. Estes resultados indicam que o efeito de sorçao predominou devido ao aumento das interaçöes moleculares, reduzindo assim o volume livre, o que tornou a membrana sulfonada mais compacta, com permeabilidade menor e maior seletividade. Estes resultados corroboram com a premissa de que a sulfonaçao é um processo promissor para o desenvolvimento de membranas mais eficientes. / The search for membranes with suitable properties for gas separation in industrial scale has led to the modification and synthesis of engineering polymers with the purpose of obtaining membranes with superior properties. 0ne of the modifications that have been considered promising is the insertion of sulfonic groups in commercial polymers. Due to its structure more polar and flexible, it is expected that the sulfonated polymer present an increase in polar gas permeation in relation to nonpolar gases. In this context, the objective of this work is the synthesis and characterization of membranes of poly (ether imide) sulfonated for the permeation of gases. An experimental design was developed in different reaction conditions of temperature, time and an excess of one of the reagents (acetic acid), for the synthesis of poly (ether imide) sulfonated, SPEI. Through this planning, it was found that the variables that most influenced the degree of sulfonation are temperature and time. The polymer with the highest degree of sulfonation, by ion exchange capacity (IEC = 92 mEq H+ I g), was used to prepare SPEI membrane obtained by the technique of solvent evaporation, using chloroform. This film was characterized from the following analysis: infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) to evaluate the influence of insertion of the sulfonic group in the polymer matrix. The infrared spectrum showed bands of SPEI related to asymmetric vibrations at 1240cm- 1 (S = 0 = 0), in symmetric stretch at 1171 cm-1 (0 = S = 0) and S0 stretch between 1010-1024cm-1. This indicates the presence of sulfonic groups. The DSC analysis was carried out between 150-250C. In this range, there are no significant changes in glass transition temperature of the modified polymer (217C). It is believed that the decomposition of the sulfone group occurs before the temperature reaches the Tg of the polymer. This assumption is confirmed in the TGA analysis. The images of SEM showed that films were obtained free of pores and defects. The membrane SPEI obtained by the technique of solvent evaporation, was used for testing permeation of gases 02, N2 and C02 in order to determine the permeability and selectivity of the membrane. The permeabilities found for oxygen were 0.76 barrer for PEI and 0.46 barrer for SPEI. The selectivity of carbon dioxide relative to oxygen increased from 3.5 to 4.83. Regarding nitrogen, the permeability measurements were 0.064 barrer and 0.043 barrer for the PEI and the SPEI, respectively, while the selectivity relative to C02 increased from 41.1 to 55.5. These results indicate that the predominant effect of sorption due to increased molecular interactions, thus reducing the free volume, made the membrane sulfonated more compact with lower permeability and higher selectivity. These results agree with the premise that the sulfonation is a promising process for the development of more efficient membranes.

Les travaux présentés sont une contribution à l'étude des polyélectrolytes pour piles à combustible à mem-brane échangeuse de protons. Ils s'appuient sur deux outils d'investigation, l'étude de molécules modèles et des mesures précises de conductivité. Sur le plan des matériaux, l'optimisation du protocole de sulfonation de polysulfones a permis de réduire voire d'éliminer les coupures de chaîne tout en obtenant des taux de sulfonation reproductibles. Il est ainsi possible d'améliorer les propriétés mécaniques des membranes denses élaborées à partir de ces polyélectroly-tes avant test en pile d'EME (Électrode/Membrane/Électrode). En parallèle, la fonctionnalisation de silicium microporeux a permis de préparer des polyélectrolytes bénéficiant de la tenue mécanique du séparateur de silicium. Sur le plan des caractérisations physicochimiques et électrochimiques, les molécules modèles, porteuses des mêmes fonctions et groupes que ceux des polymères associés, permettent d'amplifier les réponses à des solli-citations électrochimiques ou thermiques. En ce sens, elles simulent un vieillissement accéléré des polyélec-trolytes. Enfin, les mesures de conductivité apportent un éclairage nouveau sur cette caractérisation. Le sys-tème de mesure mis au point permet d'obtenir des valeurs de conductivité dans une large gamme de tempéra-ture et d'humidité relative et ce avec une incertitude réduite.

No description available.

A busca por membranas com propriedades adequadas a separação de gases em escala industrial tem levado a modificação e sIntese de polImeros de engenharia, com objetivo de obter membranas com propriedades adequadas. Uma das modificaçoes que tem se apresentado promissora é a inserção de grupos sulfônicos em polImeros comerciais. Espera-se que o polImero sulfonado apresente um aumento na permeação de gases polares, em relação a gases apolares, devido a sua estrutura mais polar e flexIvel. Neste contexto, o objetivo do presente trabalho é a sIntese e caracterização de membranas de poli(éter imida) sulfonada para a permeação de gases. Um planejamento experimental foi desenvolvido, em diferentes condiçoes reacionais de temperatura, tempo e excesso de um dos reagentes (ácido acético), para a sIntese de poli(éter imida) sulfonada (SPEI). Através deste planejamento, constatou-se que as variáveis que mais influenciam o grau de sulfonação são a temperatura e o tempo. O polImero com o maior grau de sulfonação, determinado por capacidade de troca iônica (IEC= 92 mEq H+/g), foi utilizado para o preparo da membrana de SPEI, obtida pela técnica de inversão de fase por evaporação do solvente, utilizando-se clorofórmio como solvente. Este filme foi caracterizado a partir das seguintes análises: espectroscopia de infravermelho (FTIR), calorimetria diferencial de varredura (DSC), análise termogravimétrica (TGA) e microscopia eletrônica de varredura (MEV), a fim de avaliar a influência da inserção do grupo sulfônico na matriz polimérica. O espectro de infravermelho de SPEI apresentou bandas relacionadas as vibraçoes assimétricas em 1240 cm-1 (ligação O=S=O), ligação simétrica em 1171 cm-1 (O=S=O) e ligação S-O entre 1010-1024 cm-1. Isto indica a presença de grupos sulfônicos. A análise de DSC foi realizada entre 150-250C. Nesta faixa, não foram observadas alteraçoes na temperatura de transição vItrea (Tg) do polImero modificado (217C). Acredita-se que a decomposição do grupo sulfona aconteça antes da temperatura atingir o Tg do polImero. Esta suposição é confirmada na análise de TGA. As imagens de MEV mostraram que foram obtidos filmes livres de poros e defeitos. A membrana da SPEI foi utilizada no ensaio de permeaçao dos gases 02, N2 e C02, a fim de determinar a permeabilidade e seletividade da membrana. As permeabilidades encontradas para o gas oxigênio foram de 0,76 barrer para a PEI e 0,46 barrer para a SPEI. A seletividade do dióxido de carbono em relaçao ao oxigênio aumentou de 3,5, na membrana de PEI, para 4,83, na membrana de SPEI. Em relaçao ao nitrogênio, as permeabilidades medidas foram 0,064 barrer e 0,043 barrer, para a PEI e para a SPEI, respectivamente, enquanto a seletividade em relaçao ao C02 aumentou de 41,1 para 55,5. Estes resultados indicam que o efeito de sorçao predominou devido ao aumento das interaçöes moleculares, reduzindo assim o volume livre, o que tornou a membrana sulfonada mais compacta, com permeabilidade menor e maior seletividade. Estes resultados corroboram com a premissa de que a sulfonaçao é um processo promissor para o desenvolvimento de membranas mais eficientes. / The search for membranes with suitable properties for gas separation in industrial scale has led to the modification and synthesis of engineering polymers with the purpose of obtaining membranes with superior properties. 0ne of the modifications that have been considered promising is the insertion of sulfonic groups in commercial polymers. Due to its structure more polar and flexible, it is expected that the sulfonated polymer present an increase in polar gas permeation in relation to nonpolar gases. In this context, the objective of this work is the synthesis and characterization of membranes of poly (ether imide) sulfonated for the permeation of gases. An experimental design was developed in different reaction conditions of temperature, time and an excess of one of the reagents (acetic acid), for the synthesis of poly (ether imide) sulfonated, SPEI. Through this planning, it was found that the variables that most influenced the degree of sulfonation are temperature and time. The polymer with the highest degree of sulfonation, by ion exchange capacity (IEC = 92 mEq H+ I g), was used to prepare SPEI membrane obtained by the technique of solvent evaporation, using chloroform. This film was characterized from the following analysis: infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) to evaluate the influence of insertion of the sulfonic group in the polymer matrix. The infrared spectrum showed bands of SPEI related to asymmetric vibrations at 1240cm- 1 (S = 0 = 0), in symmetric stretch at 1171 cm-1 (0 = S = 0) and S0 stretch between 1010-1024cm-1. This indicates the presence of sulfonic groups. The DSC analysis was carried out between 150-250C. In this range, there are no significant changes in glass transition temperature of the modified polymer (217C). It is believed that the decomposition of the sulfone group occurs before the temperature reaches the Tg of the polymer. This assumption is confirmed in the TGA analysis. The images of SEM showed that films were obtained free of pores and defects. The membrane SPEI obtained by the technique of solvent evaporation, was used for testing permeation of gases 02, N2 and C02 in order to determine the permeability and selectivity of the membrane. The permeabilities found for oxygen were 0.76 barrer for PEI and 0.46 barrer for SPEI. The selectivity of carbon dioxide relative to oxygen increased from 3.5 to 4.83. Regarding nitrogen, the permeability measurements were 0.064 barrer and 0.043 barrer for the PEI and the SPEI, respectively, while the selectivity relative to C02 increased from 41.1 to 55.5. These results indicate that the predominant effect of sorption due to increased molecular interactions, thus reducing the free volume, made the membrane sulfonated more compact with lower permeability and higher selectivity. These results agree with the premise that the sulfonation is a promising process for the development of more efficient membranes.

A presente tese trata das reações de sulfanilação de algumas 2-sulfinilciclanonas racêmicas pelo método de catálise por transferência de fase (CTF), seja usando cloreto de benziltrietilamônio (TEBAC) seja usando catalisador quirálico. As reações de sulfanilação pelo método de CTF empregando TEBAC, forneceram produtos sulfanilados em altos rendimentos (75-93%), enquanto que as reações empregando a mesma metodologia, utilizando catalisadores quirálicos, conduziram não só a altos rendimentos, mas também a um aumento no excesso diastereomérico. Foram determinadas as configurações relativas da 2metilsulfanil- 2-metilsulfinilciclopentanona e 2-p-tolilsulfanil-2metilsulfinilcicloexanona pela análise de difração de Raios-X como sendo 2S*SS*. A parte final da Tese contém reações de sulfanilação da 2-metilsulfinilciclopentanona e 2-metilsulfinilcicloexanona opticamente ativas. É digno de nota que estas, ao contrário da 2-p-tolilsulfinil ciclanonas, descritas na literatura, conduziram a produtos sulfanilados estáveis. Finalmente, a tese mostra um exemplo de condensação aldólica assimétrica partindo da 2-metilsulfanil-2-metilsulfinilcicloexanona opticamente ativa. Com base no conhecimento da configuração deste último composto, foi possível esclarecer o mecanismo da indução assimétrica. / This thesis presents the sulfanylation reactions of some racemic 2-methylsulfinil cyclanones, by phase transfer catalysis (PTC) method, employing as catalysts either benzyltriethylammonium chloride (BTAC) or some optically active catalysts. The sulfanilation reactions, employing BTAC furnished the sulfanylated products in high yields (75-93%) while the reactions performed by the same methodology, using chiral catalysts, led to higher yields and also to an increase in the diastereomeric excess. The relative configuration of 2-metilsulfanyl-2-methylsufinylcyclopentanone and of 2-p-tolylsulfanyl-2-methylsulfinylcyclohexanone, as determined by X-Ray diffraction analysis, showed to be 2S*SS*. The final part of this thesis reports the sulfanylation reactions of the optically active 2-methylsulfinylcyclopentanone and 2-methylsulfinylcyclohexanone, which, in contrast to the p-tolyl derivatives, described in the Iiterature, were stable derivatives. Finally, on the basis of the relative configuration of the optically active 2-methylsulfanyl-2-methylsulfinylcyclohexanone, it became possible to propose the stereochemical course of the asymmetric aldol reaction of this compound with an ester enolate.

This dissertation presents a discussion of blocky and randomly functionalized sulfonated syndiotactic polystyrene copolymers. These copolymers have been prepared over a range of functionalization (from 2% to 10%) in order to assess the effect of the incorporation of these polar side groups on both the thermal behavior and morphology of these polymer systems. The two different architectures are achieved by conducting the reaction in both the heterogeneous gel-state to obtain blocky copolymers and in the homogeneous solution state to obtain randomly functionalized copolymers. In order to compare both the thermal properties and morphology of these two systems several sets of samples were prepared at comparable levels of sulfonation. Thermal analysis of these two systems proved that the blocky functionalized copolymers provided superior properties with regard to the speed and total amount of the crystalline component of sulfonated syndiotactic polystyrene. Above 3% functionalizion the randomly functionalized copolymer was no longer able to crystallize, whereas, the blocky functionalized copolymer is able to crystallize even at a functionalization level of 10.5% sulfonate groups. When considering the morphology of these systems even at low percentages of sulfonation it is clear that the distribution of these groups is different based on the amplitude of the signal measured by small angle x-ray scattering. Additionally, methods were developed to describe both the distribution of ionic multiplets, which varies between blocky and randomly functionalized systems, but also the distribution of crystals. At a larger scale ultra-small angle x-ray scattering was employed to attempt to understand the clustering of ionic multiplets in these systems. Randomly functionalized polymers should a peak that is attributed to ion clusters, whereas blocky polymers show no such peak. Additional studies have also been done to look at the analysis of crystallite sizes in these systems when there are multiplet polymorphs present, it was observed the polymorphic composition is drastically different. All of these studies support that these systems bear vastly different thermal behavior and possess significantly different morphologies. This supports the hypothesis that this gel-state heterogeneous functionalization procedure produces a much different chain architecture compared to homogeneous functionalization in the solution-state. / Doctor of Philosophy / Polymers are a class of chemicals that are defined by having a very large set of molecules that are chemically linked together where each unit (monomer) is repeated within the chemical structure. In particular, this dissertation focuses on the construction what are termed as "blocky" copolymers, which are defined by having two chemically different monomers that are incorporated in the polymer chain. The "blocky" characteristic of these polymers means that these two different monomers are physically segregated from each other on the polymer chain, where long portions of the chain that are of one type, followed by another section of the polymer that has the other type of monomer. The goal of creating this type of structure is to try to take advantage of the properties of both types of monomers, which can create materials with superior synergistic properties. In this case a hydrophobic (water hating) monomer is combined with a hydrophilic (water loving) chain. This hydrophobic component in the polymer is able to crystallize, which provides mechanical and thermal stability in the material by acting as a physical tether to hold neighboring chains together. With the other set of hydrophilic monomers, which in this case have an ionic component incorporated, we can now take advantage of this chemical components ability to aide in the transportation of ions. Transportation of ions is useful in a variety of commercially relevant applications, two of the most important applications of these ionic materials is in membranes that can be used to purify water or membrane materials in fuel cell technologies, specifically for proton exchange membranes. The focus of this research in particular was to create a simple synthesis technique that can create these blocky polymer chain architectures, which is done by performing the reaction while the polymer is made into a gel. The key to this is that the crystals within the gel act as a barrier to chemical reactions, creating conditions where we have substantial portions of the material that are able to be functionalized and the crystals within the material that are protected from being functionalized. By looking at the thermal characteristics, such as melting temperatures and amount of crystals within these systems we have seen that functionalizing these polymers in the heterogeneous gel state gives substantially better properties than functionalizing these materials randomly. Much like oil and water, incompatible polymer chains will phase separate from each other. In this case the hydrophobic and ionic components will phase separate from each other. The shape and distribution of these phase separated structure will dictate many of the material properties, which can be described by modeling the data collected from x-ray scattering experiments. All of this information will tell us based on the initial conditions that these polymers were created in, what properties should be expected based on the morphology and thermal behavior. This gives a better understanding of how to fine tune these properties based on the structure of the gel and chemical reaction conditions.

The thesis entitled “Copper-Catalyzed Novel Oxidative Transformations: Construction of Carbon-Hetero Bonds” is divided into two main sections. Section A deals with the utility of azide as a nitrogen source for C-N bond formation, which is further divided into 4 chapters, and section B presents decarboxylative radical coupling reaction for C-heteroatom bond formation which is further divided in to two chapters. Section A Chapter 1 describes an approach for the direct synthesis of nitrile from the corresponding alcohols using azide as a nitrogen source. Nitrile functionality is a versatile and ubiquitous which occurs in a variety of natural products. Nitrile functionality can be easily transformed into a variety of functional groups and products such as aldehydes, ketones, acids, amines, amides and nitrogen-containing heterocycles, such as tetrazoles and oxazoles. In this chapter a successful attempt for developing a novel methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been described. This strategy uses DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)2·6H2O. A few representative examples are highlighted in Scheme 1.1 Scheme 1. Oxidative conversion of alcohols to nitriles Second chapter represents a protocol for the synthesis of 1,5-disubstituted tetrazoles from the corresponding secondary alcohols. Among heterocyles, tetrazole and its derivatives are important class of nitrogen containing molecules. Due to their well-known biological activities as well as vast applications in pharmaceuticals and material science, they are potential targets for synthetic organic chemists. Therefore, a simple and user-friendly method for the synthesis of tetrazole is desirable. In this chapter, a mild and convenient method to synthesize 1,5-disubstituted tetrazoles using easily accessible secondary alcohols by employing TMSN3 as a nitrogen source is developed. This reaction is performed in the presence of a catalytic amount of Cu(ClO4)2·6H2O using DDQ as an oxidant under ambient conditions (Scheme 2).2 Scheme 2. Oxidative conversion of secondary alcohols to tetrazoles Third chapter presents a method for synthesizing amides from their corresponding secondary alcohols. Amide functionality is a crucial backbone in peptide chemistry, it also serve as an important precursor or intermediate for variety of organic transformations. In this contention, a mild and convenient method to synthesize amides using easily accessible secondary alcohols by employing TMSN3 as a nitrogen source is developed. This reaction is performed in the presence of a catalytic amount of Cu(ClO4)2·6H2O using DDQ as an oxidant under ambient conditions (Scheme 3).3 Scheme 3. Oxidative conversion of secondary alcohols to amides Additionally, the application of this methodology has also been revealed for the synthesis azides directly from their alcohols. Some of the representative examples are shown in the Scheme 4.3 Scheme 4. Direct conversion of alcohols to their azides. Fourth chapter describes highly chemoselective Schmidt reaction. The classical Schmidt reaction involves the formation of new carbon-nitrogen bonds in a reaction of a carbon-centred electrophile with hydrazoic acid followed by loss of nitrogen, which usually occurs via a rearrangement. It is well known that under the Schmidt reaction conditions, ketones and carboxylic acids are converted into their corresponding amides and amines respectively, whereas aldehydes furnish a mixture of formanilides and nitriles. In this chapter, Schmidt reaction of aldehydes to obtain their nitriles without formation of the corresponding formanilide is presented (Scheme 5).4 It was also observed that aromatic ketones and acids functionalities were intact under the reaction condition, unlike the conventional Schmidt reaction. Scheme 5. Highly chemoselective Schmidt reaction Section B It is divided into two chapters, describes a copper catalyzed decarboxylative radical coupling for the synthesis of vinyl sulfones and nitroolefins (Scheme 6). Scheme 6. General strategy for the second part First chapter narrates a strategy for synthesizing nitroolefins from the α,β-unsaturated carboxylic acids. Nitroolefins represent a unique class of nitro compounds, which have multifaceted utility in organic synthesis. They possess antibacterial, rodent-repelling, and antitumor activities. They serve as important intermediates in organic synthesis. Nitroolefins also react with a variety of nucleophiles, and their electron-deficient character renders them as a powerful dienophiles in Diels-Alder reactions. In our attempt to use the decarboxylative strategy, this chapter describes a method for the nitrodecarboxylation of substituted cinnamic acid derivatives to their corresponding nitroolefins. This nitrodecarboxylation reaction is performed using catalytic amount of CuCl in the presence of air using TBN as a nitrating source (Scheme 7).5 Besides, the reaction provides a useful method for the synthesis of β,β-disubstituted nitroolefin derivatives which are generally difficult to access from other conventional methods. Scheme 7. Decarboxylative nitration Second chapter presents a new protocol for the synthesis of vinyl sulfones from the α,β-unsaturated carboxylic acid. Vinyl sulfones are versatile building blocks, which find their utility as Michael acceptors and used in cycloaddition reactions. This functional group has also been shown to potently inhibit a variety of enzymatic processes, and thus provides unique properties for drug design and medicinal chemistry. Vinyl sulfones are prominent in medicinal chemistry owing to their wide presence in pharmaceutically active molecules, such as enzyme inhibitors and biological activity. In this chapter, we report a method for the construction of C-S bonds via ligand promoted decarboxylative radical sulfonylation of ,-unsaturated carboxylic acids to synthesize vinyl sulfones using Cu catalysis (Scheme 8).6 This is the first report for this particular conversion. Scheme 8. Decarboxylative sulfonation

No description available.

This thesis focuses on the synthesis and characterization of various poly(arylene ether)s to improve the efficiency of gas separation and water desalination membranes. This class of polymers includes polymers such as poly(arylene ether sulfone), poly(arylene ether ketone) and poly(phenylene oxide) which offer excellent thermal and mechanical stability and usually have high enough rigidity to support gas separation and water desalination operations. Besides the plethora of properties offered by the homopolymers, these polymers can also be post-modified to cater to specific needs. For example, the polyphenylene oxides have been brominated to increase the permeability for gas separation applications. Blending is another viable method to impart desirable properties to polymers. Bisphenol A based poly(arylene ether ketone) (BPAPAEK) has been blended with commercially available poly(2,6-dimethylphenylene oxide)s (PPO) of different molecular weights in a fixed ratio (66/34 wt/wt) and in various ratios of a 22000 g/mol PPO. All the blends were UV crosslinked to minimize plasticization by condensable gases and analyzed for gel fractions, whereas, only the 22,000 g/mol blends were tested for transport properties since they yielded the highest gel fractions and exhibited the best mechanical properties. The crosslinking reduced the free volume and improved the selectivity with some drop in permeability. The blends with 90% of the 22000 g/mol PPO by weight was plotted closest to the upperbound. A phosphine oxide based poly(arylene ether ketone) (POPAEK) was blended with the various PPOs in a similar manner. The results were compared to the BPAPAEK based blends in terms of miscibility behavior and transport properties. It was found that the POPAEK based blends had higher permeability due to the higher fractional free volumes of the POPAEK. The POPAEK was more compatible with the PPOs than BPAPAEK as seen by analyzing various blend permeability models, mechanical properties and scanning electron microscope images. Moreover, blends with both the PAEKs displayed only a small drop in mechanical properties, such as the Young's modulus and the yield strength in comparison to the parent polymers. Hydroquinone based poly(arylene ether sulfone) oligomers were synthesized, post-sulfonated and chemically crosslinked to determine the effect of water uptake, fixed charge concentration and block length of oligomers on the salt permeability and the hydrated mechanical properties of the networks. The sulfonic acid groups were placed strategically and quantitatively on the hydroquinone units. The strategic placement of the acid groups may help in maintaining high rejection of monovalent ions in the presence of divalent ions, as shown in unpublished work by our group. It was found that the water uptake and fixed charge density had the opposite effects on the salt permeability. Also, the salt permeability varied differently for 5000g/mol and 10000g/mol block based networks. Another polymer that was investigated in this thesis was poly(2-ethyl-2-oxazoline) (PEtOx). An elaborate account of synthesis of monofunctional, heterobifunctional and telechelic poly(2-ethyl-2-oxazoline)s using different initiators including methyl triflate, activated alkyl halides (e.g., benzyl halides), and non-activated alkyl halides has been presented in this thesis. Endgroup functionalities and molecular weight distributions were studied by SEC, 1H NMR and titrations. The oligomers initiated with the benzyl or xylyl chloride had a PDI of 1.3-1.4 which is broader than expected for a living cationic ring opened polymer. This was attributed to the participation of covalent species which propagated slowly in the activated halide reactions. These oligomers were quantitatively terminated as proven by NMR and titrations. Due to the molecular weight distributions and quantitative termination these oligomers were deemed to be desirable for drug delivery applications. / PHD