A survey of substitution reactions conducted in a phosphonium bistriflimide ionic liquid is presented. The results demonstrate high selectivity favoring substitution over typically competitive elimination and solvolytic processes even when challenging secondary and tertiary electrophiles are employed. The first reports of Kornblum substitution reactions in an ionic liquid are described that proceed with very high chemoselectivity in favor of nitro over nitroso products and elimination side products. The structure-reactivity study indicates that these reactions proceed through a narrow spectrum of pathways ranging from straight SN2 to a preassociation pathway along a saddle point that approaches the SN1 limit. The lack of any basic entity in the phosphonium bistriflimide ionic liquid appears to prevent any potential base-mediated elimination reactions, which makes this a highly selective medium for use in general substitution reactions. A general, high yielding procedure is described for the esterification of carboxylic acids through carboxylate alkylation in phosphonium salt ionic liquid. The product ester can be readily isolated using a standard extraction protocol or by direct solvent freedistillation allowing ionic liquid re-use. The reaction takes place at relatively low temperature in comparison to other processes reported in ionic liquids. Biologically important BZE (benzoate) esters were synthesized and a proposed solvolysis mechanism investigated in ionic liquids. The Pd-mediated Buchwald-Hartwig amination reaction of aryl halides in phosphonium salt ionic liquid consisting of a trihexyl(tetradecyl)phosphonium cation with a range of anions has been investigated. A pronounced anionic effect was uncovered with the reaction proceeding readily with weakly nucleophilic diarylamines only in the presence of non-coordinating anions. A mechanism is postulated to explain these results involving a rate limiting ligand exchange step that proceeds through a dissociative pathway. A novel non solvated crystal structure of tris(dibenzylideneacetone) palladium(0) in phosphonium salt ionic liquids is reported. This research provided insights concerning the use of ionic liquids in palladium catalyzed Buchwald-Hartwig amination reaction. New synthetic methods were developed for the preparation of trialkyl (methyl) phosphonium ionic liquids, with this novel "green" protocol, the use of iodomethane is eliminated and oxidation of trialkyl phosphines can be reduced. / Thesis / Doctor of Philosophy (PhD)

Yes / A series of novel nopyl-derived chiral phosphonium ionic liquids have been successfully synthesised and characterised. Analysis of each novel ionic liquid was conducted in order to confirm structure, purity and thermal stability.

Ce travail de thèse réalisé à l’Institut de Chimie Moléculaire de l’Université de Bourgogne et en collaboration avec le PET Research Centre, porte sur la synthèse d’une nouvelle classe de pinces à fluorures dérivés d’aminoacides dans le but de piéger les ions [18F]-fluorures par formation d’une liaison B-F et d’évaluer leur potentiel en tant qu’agent d’imagerie TEP. Les travaux ont tout d’abord concerné la conception, la synthèse et la caractérisation des nouveaux sels de phosphoniums boronatés et trifluoroborates dérivés d’aminoacides. Ainsi, par quaternisation de l’o-boronate phényl phosphine avec des β-iodo amino esters ou des γ-iodo amino esters, les sels correspondants sont obtenus sans racémisation et avec des rendements atteignant 88%. La saponification des phosphoniums boronatés aminoesters donne les dérivés avec la fonction acide libre, tandis que l’acidolyse par HCl mène à l’amine correspondante offrant ainsi, l’opportunité d’un couplage ultérieur à une biomolécule. Ensuite, les dérivés trifluoroboratés sont facilement préparés par réaction de KHF2 en solution dans un mélange hydroalcoolique. Les études de stabilités en milieux aqueux des phosphoniums o-trifluoroborates aminoacides ont permis d’établir que ces dérivés sont extrêmement stables à l’hydrolyse. Enfin, la [18F]-radiosynthèse des sels de phosphonium boronatés a été étudiée selon deux méthodes: par échange isotopique 18F-19F direct à partir d’un trifluoroborate et par marquage direct d’un sel de phosphonium boronaté en présence d’un mélange de fluorures [18F] et KHF2. Intéressement, après une synthèse totale de 50 minutes comprenant le séchage azéotropique, la synthèse et la purification, [18F]-203c a été obtenu avec un rendement radiochimique de 10% corrigé de la décroissance, une pureté radiochimique ≥97% et une activité spécifique de 0.13 GBq/µmol. / This thesis project, which is part of a collaboration between the Institut de Chimie Moléculaire de l’Université de Bourgogne and the Positron Emission Tomography Research Centre, is about the synthesis of fluoride pincers derived from amino acids based on 18F-B bond construction to get a new class of PET imaging agents. First, this project concerned the design, synthesis and characterisation of new boronato and trifluoroborato phosphonium amino acid salts. Quaternisation of o-boronate phenyl phosphine with β-iodo amino esters or γ-iodo amino ester leads to the corresponding salts without racemisation and in yields up to 88%. Saponification of boronato phosphonium amino esters afford the free carboxylic acid derivatives, whereas HCl acidolysis leads to the corresponding amino compounds which offers the opportunity of further biomolecule coupling. Then, o-trifluoroborate phosphonium salts are efficiently prepared by reaction with KHF2 in solution on hydroalcoholic mixture. The kinetic stabilities of these o-trifluoroborate phosphoniums have shown extremely stable compounds to hydrolysis. Finally, [18F]-radiosyntheses of phosphonium salts was studied according to two methods : by 18F-19F isotopic exchange from trifluoroborate or by carrier added preparation of [18F]-fluoride ions from boronate phosphonium salts. Satisfactingly, after a total synthesis of 50 minutes (including azeotropic drying, synthesis and purification), [18F]-203c was obtained with a RCY on 10% decay corrected, a RCP ≥ 97% and a specific activity of 0.13 GBq/µmol.

Os líquidos iônicos (LIs) são eletrólitos promissores para uso em baterias de lítio e outros dispositivos eletroquímicos, devido às suas propriedades físico-químicas únicas como, por exemplo, ampla faixa de temperatura como liquido, boa condutividade, baixa pressão de vapor e estabilidade térmica, química e eletroquímica. Um LI é composto normalmente por um cátion orgânico e um ânion orgânico ou inorgânico. Neste trabalho, foram sintetizados novos líquidos tanto modificando o ânion como o cátion. Em ambos os casos procurou-se LIs com ótimas propriedades de transporte e que melhorassem a condutividade do lítio em relação condutividade total da mistura LI - sal de lítio. Em primeira instância, foram sintetizados e caracterizados os seguintes líquidos iônicos derivados do ânion [B(CN)4]-: [BMPYR][B(CN)4] (N-butil-N-metilpirrolidínio tetracianoborato), [BMP][B(CN)4] (N-nbutil- N-metilpiperidínio tetracianoborato) e [BMMI][B(CN)4] (1-n-butil-2,3-dimetilimidazólio tetracianoborato), sendo os dois primeiros são líquidos na temperatura ambiente. Quando comparados com os derivados de bis(trifluorometanosulfonil)imideto, [Tf2N]-, os líquidos iônicos derivados de tetracianoborato apresentam melhores valores de condutividade e viscosidade, sendo isto refletidos em um maior valor do parâmetro condutividade do lítio (σLi). Além disso, estes LI possuem maior estabilidade química e eletroquímica. Utilizou-se a técnica de espectroscopia Raman para estudar os líquidos [BMPYR][B(CN)4] e [BMP][B(CN)4] e suas misturas com sal de lítio (0,1 molL-1 de LiB(CN)4), demostrando-se que a interação entre o íon lítio e o ânion tetracianoborato é muito baixa, o que explica o altos valores do número de transporte e condutividade do lítio nestes sistemas. já através da Modificação do cátion, foram sintetizados cinco líquidos iônicos derivados de fosfônio, usando sempre o ânion [Tf2N]-. Entre eles são líquidos na temperatura unicamente os LIs [P2225][Tf2N] (Bis(trifluormetilsulfonil)imideto de trieltilpentilfosfônio) e [P222(201)][Tf2N] (Bis(trifluormetilsulfonil)imideto de trietil(2-metoxietil)fosfônio). Estes líquidos apresentaram excelentes propriedades de transporte e estabilidade eletroquímica quando comparados com seus equivalentes derivados de nitrogênio. Quando se adicionou o sal de lítio, LiTf2N, em concentrações de 1 e 2 molL-1 , os líquidos apresentaram um decréscimo das propriedades de transporte, embora demostrarem efeito menor em comparação com os líquidos iônicos derivados de nitrogênio, apresentando inclusive maiores valores nos números de transporte e de condutividade do lítio nas misturas estudadas. / Ionic liquids (ILs), are of great interest nowadays as electrolytes for lithium ion batteries due their unique characteristics, which include: liquid state over a wide temperature range; nonvolatility, which assures thermal stability and nonflammability; high ion content, which results in high ionic conductivity; and excellent chemical and electrochemical stability. ILs consists of an organic cation and an inorganic or organic anion. In order to improve the transport properties, the cation and anion of the ionic liquid were changed. Three ionic liquids derived from the anion [B(CN)4]- were synthetized and chararacterized: [BMPYR][B(CN)4] (N-n-butyl-N-methylpyrrolidinium tetracyanoborate) [BMP][B(CN)4] (N-n-butyl-Nmethylpiperidinium tetracyanoborate) and [BMMI][B(CN)4] (1-n-butyl-2,3-dimethylimidazolium tetracyanoborate). The first two are liquid at room temperature. When comparing these ionic liquid with the analogous ones containing the anion Tf2N, it was found that ILs derivates from tetracyanoborate have better transport properties which is reflected in a larger value of parameter conductivity of lithium (σLi). Moreover these ILs have higher chemical and electrochemical stability. The Raman spectroscopy was employed to study the BMPYRB(CN)4 and BMPB(CN)4 liquids and their mixtures with lithium salt (0.1 mol L-1 of LiB(CN)4); it was demonstrated that the interaction between the lithium ion and anion tetracyanoborate is very low, which explains the high values of conductivity and transport numbers of lithium in these systems. Furthermore five ionic liquids from the phosphonium cation was synthesized always using the anion [Tf2N]-; being liquid at room temperature only the ILs [P2225][Tf2N] (triethyln-pentylphosphonium bis(trifluoromethylsulfonyl)imide) and [P222(201)][Tf2N] (triethyl (2- methoxyethyl) phosphonium bis(trifluoromethylsulfonyl imide) imide). It was found that these liquids have excellent transport properties and electrochemical stability when compared with their counterparts derived from nitrogen; furthermore, when lithium salt LiTf2N, was added at concentrations of 1 and 2 mol L-1, the ILs containing the phosphonium cations have also shown a decrease in the transport properties, however, the effect is less pronounced when compared to ionic liquids derived from nitrogen, presenting higher transport number and lithium ion conductivity.

The focus of this work is to synthesize and immobilize novel rigid tetraphosphine linkers via the formation of phosphonium groups and by direct adsorption of tetraphosphine salts on oxide surfaces. These methods offer the possibility to study the mechanism of the phosphonium formation in more detail by utilizing solid-state NMR spectroscopy. It has also been a point of interest to study the linkers and catalysts under realistic conditions, in the presence of solvents. Therefore, HRMAS (high-resolution magic angle spinning) NMR spectra of several phosphonium salts, adsorbed on SiO2, have been studied. This technique allows one to probe the leaching and mobility of the linkers on the surface. The mobilities of the linkers and the catalysts are crucial factors for the performance and design of the immobilized catalysts. Finally, since the exact mode of binding to the surface is unknown and is being discussed in the literature, for example, as hydrogen bonding between the F atoms in BF4- and surface silanol protons, the influence of the counteranion on the binding of phosphonium salts on silica surfaces is of utmost interest. For surface mobility studies a monolayer of phosphonium salts on the silica surface, both without solvent and in the presence of solvent, has been studied via 31P and 2H CP/MAS and HRMAS. Our findings show that the integrity of the tetraphosphine scaffold linkers is based upon how it is immobilized. The best system is formed when the phosphine is immobilized on the SiO2 support by adding Cl(CH2)3Si(OEt)3 to the reaction mixture. In this way, phosphonium salts are obtained, which are bound to the surface irreversibly by electrostatic interactions, as proven by solid-state NMR. In addition, leaching and mobility studies prove that the solvents play a crucial role, and the more polar solvents, such as DMSO, lead to the most extensive leaching due to the solvents' strong adsorption on the SiO2 surface. Leaching studies also show that the counteranion has an influence on the binding of the phosphoniumn salts on the SiO2 surface. The leaching proceeds in the following manner: BF4- > I- > Br- > Cl-. This is an indication that there is an additional interaction between the anion and, most probably, the surface silanol protons.

A series of hydrophobic ionic liquids (ILs) have been employed to extract acetic acid (AcOH) or formaldehyde (HCHO) from aqueous solutions at atmosphere pressure. The ILs, mainly trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) carboxylate based ILs, were tested as a function of the anion chain length, which ranges from isobutyrate ([IB]-) to dodecanoate ([D]-). Most of these ILs show a large two-phase region and high extraction efficiency. Furthermore, tetraoctylphosphonium ([P8,8,8,8]+) and trihexyl(tetradecyl)ammonium ([N6,6,6,14]+) based ILs were also investigated to study the effect of the cation on extraction performance. Besides pure IL extraction, the mixture of IL and other chemicals, such as matched carboxylic acid, alkane and ester, were also investigated on extraction. The matched carboxylic acid could enhance the extraction performance and thus could be called ‘enhancer’. A balance point could be found for the ratio IL/enhancer to obtain a better extraction in each {H2O + AcOH + IL/enhancer} system, compared with the corresponding pure IL liquid-liquid equilibrium (LLE). Several ILs, including [P6,6,6,14]+ based ILs and imidazolium based ILs, were investigated on extraction of HCHO. Among these ILs, the imidazolium based ILs performed better than the [P6,6,6,14]+ based ILs in terms of two-phase region, hydrophobicity of IL-rich phase and partition coefficient/relative selectivity. The UNIQUAC method was employed to correlate the LLE data for pure IL systems. Some physical property data, such as density and viscosity, of ILs were correlated. The Joback group contribution method was used to predict the heat capacities of some ILs in this work. These correlations with low deviations made it possible for ILs to be further studied in Aspen process modelling.

Os líquidos iônicos (LIs) são eletrólitos promissores para uso em baterias de lítio e outros dispositivos eletroquímicos, devido às suas propriedades físico-químicas únicas como, por exemplo, ampla faixa de temperatura como liquido, boa condutividade, baixa pressão de vapor e estabilidade térmica, química e eletroquímica. Um LI é composto normalmente por um cátion orgânico e um ânion orgânico ou inorgânico. Neste trabalho, foram sintetizados novos líquidos tanto modificando o ânion como o cátion. Em ambos os casos procurou-se LIs com ótimas propriedades de transporte e que melhorassem a condutividade do lítio em relação condutividade total da mistura LI - sal de lítio. Em primeira instância, foram sintetizados e caracterizados os seguintes líquidos iônicos derivados do ânion [B(CN)4]-: [BMPYR][B(CN)4] (N-butil-N-metilpirrolidínio tetracianoborato), [BMP][B(CN)4] (N-nbutil- N-metilpiperidínio tetracianoborato) e [BMMI][B(CN)4] (1-n-butil-2,3-dimetilimidazólio tetracianoborato), sendo os dois primeiros são líquidos na temperatura ambiente. Quando comparados com os derivados de bis(trifluorometanosulfonil)imideto, [Tf2N]-, os líquidos iônicos derivados de tetracianoborato apresentam melhores valores de condutividade e viscosidade, sendo isto refletidos em um maior valor do parâmetro condutividade do lítio (σLi). Além disso, estes LI possuem maior estabilidade química e eletroquímica. Utilizou-se a técnica de espectroscopia Raman para estudar os líquidos [BMPYR][B(CN)4] e [BMP][B(CN)4] e suas misturas com sal de lítio (0,1 molL-1 de LiB(CN)4), demostrando-se que a interação entre o íon lítio e o ânion tetracianoborato é muito baixa, o que explica o altos valores do número de transporte e condutividade do lítio nestes sistemas. já através da Modificação do cátion, foram sintetizados cinco líquidos iônicos derivados de fosfônio, usando sempre o ânion [Tf2N]-. Entre eles são líquidos na temperatura unicamente os LIs [P2225][Tf2N] (Bis(trifluormetilsulfonil)imideto de trieltilpentilfosfônio) e [P222(201)][Tf2N] (Bis(trifluormetilsulfonil)imideto de trietil(2-metoxietil)fosfônio). Estes líquidos apresentaram excelentes propriedades de transporte e estabilidade eletroquímica quando comparados com seus equivalentes derivados de nitrogênio. Quando se adicionou o sal de lítio, LiTf2N, em concentrações de 1 e 2 molL-1 , os líquidos apresentaram um decréscimo das propriedades de transporte, embora demostrarem efeito menor em comparação com os líquidos iônicos derivados de nitrogênio, apresentando inclusive maiores valores nos números de transporte e de condutividade do lítio nas misturas estudadas. / Ionic liquids (ILs), are of great interest nowadays as electrolytes for lithium ion batteries due their unique characteristics, which include: liquid state over a wide temperature range; nonvolatility, which assures thermal stability and nonflammability; high ion content, which results in high ionic conductivity; and excellent chemical and electrochemical stability. ILs consists of an organic cation and an inorganic or organic anion. In order to improve the transport properties, the cation and anion of the ionic liquid were changed. Three ionic liquids derived from the anion [B(CN)4]- were synthetized and chararacterized: [BMPYR][B(CN)4] (N-n-butyl-N-methylpyrrolidinium tetracyanoborate) [BMP][B(CN)4] (N-n-butyl-Nmethylpiperidinium tetracyanoborate) and [BMMI][B(CN)4] (1-n-butyl-2,3-dimethylimidazolium tetracyanoborate). The first two are liquid at room temperature. When comparing these ionic liquid with the analogous ones containing the anion Tf2N, it was found that ILs derivates from tetracyanoborate have better transport properties which is reflected in a larger value of parameter conductivity of lithium (σLi). Moreover these ILs have higher chemical and electrochemical stability. The Raman spectroscopy was employed to study the BMPYRB(CN)4 and BMPB(CN)4 liquids and their mixtures with lithium salt (0.1 mol L-1 of LiB(CN)4); it was demonstrated that the interaction between the lithium ion and anion tetracyanoborate is very low, which explains the high values of conductivity and transport numbers of lithium in these systems. Furthermore five ionic liquids from the phosphonium cation was synthesized always using the anion [Tf2N]-; being liquid at room temperature only the ILs [P2225][Tf2N] (triethyln-pentylphosphonium bis(trifluoromethylsulfonyl)imide) and [P222(201)][Tf2N] (triethyl (2- methoxyethyl) phosphonium bis(trifluoromethylsulfonyl imide) imide). It was found that these liquids have excellent transport properties and electrochemical stability when compared with their counterparts derived from nitrogen; furthermore, when lithium salt LiTf2N, was added at concentrations of 1 and 2 mol L-1, the ILs containing the phosphonium cations have also shown a decrease in the transport properties, however, the effect is less pronounced when compared to ionic liquids derived from nitrogen, presenting higher transport number and lithium ion conductivity.

No description available.

<p> This thesis describes the development of the Wittig olefination reaction of stabilized, semistabilized allylic trialkylphosphorus ylides with various aldehydes to afford E olefins mainly (E>89%). Since the steric demand of trialkylphosphorus ylides was decreased, aldehydes achieved high E selectivity. On the other hand, predominant or exclusive formation of Z olefms was achieved by using allylic triphenylphosphorus ylides and aromatic aldehydes like benzylaldehyde, while the combination of allylic triphenylphosphorus ylides and such sterically hindered aldehydes as cyclohexanecarboxaldehyde led to E olefm formation upon ylide formation with LiHMDS. In the case of olefination reactions of aldehydes with dimethyl thiazole ylide, it was shown that among the aromatic aldehydes only 4-nitrobenzaldehyde reacted with this ylide and provided a pure E olefin product (41% yield). Dimethylmalonyltributylphosphorane (DMTP) reacted with aromatic aldehydes in toluene at 125 °C to give the corresponding alkenes. 4-Nitrobenzaldehyde· gave the alkene in a much higher yield (81%), followed by 4-chlorobenzaldehyde (31%). With benzaldehyde, the corresponding olefin was isolated in only 14% yield under these conditions. Clearly, this highly stabilized ylide only enters into reaction with electron deficient aldehydes. A possible approach to Z-a, P-unsaturated aldehydes was investigated through the olefination of an acetal-ylide followed by hydrolysis. However, E acetal olefins were in fact isolated from this 2'-(1,3-dioxolanyl)-triethylphosphorus ylide with aromatic aldehydes in good yields (62%-76%). This result is still mechanistically interesting in view of the chemoselective formation of such an ylide in the presence ofthree ethyl substituents on phosphorus. </p> <p> Class of flavonoids: Sakuranetin, Naringenin and (28)-7-methoxy-6hydroxyflavanone, have been isolated from the diseased bark of Prunus sp. The structures were elucidated based on the spectroscopic data. Locations of 4-keto, 5-0H and 7-methoxy were deduced from COSY and HMBC spectra. Such compounds are of interest for their potential antibiotic activity against vancomycin-resistant strains of microbes. </p> / Thesis / Master of Science (MSc)

Ion-containing macromolecules continue to stimulate new opportunities for emerging electro-active applications ranging from high performance energy devices to water purification membranes. Progress in polymer synthesis and engineering now permit well-defined, ion-containing macromolecules with tunable morphologies, mechanical performance, ion conductivity, and 3D structure in order to address these globally challenged technologies. Achieving tailored chemical compositions with high degrees of phase separation for optimizing conductivity and water adsorption remains a constant synthetic challenge and presents an exciting opportunity for engineering sophisticated macromolecular architectures. This dissertation will introduce unprecedented charged polymers using conventional free radical and anionic polymerization to incorporate ionic functionalities based on phosphonium cations. This new class of copolymers offers unique properties with ionic functionality for tailorable electro-active performance. / Ph. D.