Sol-gel routes to supported Friedel-Crafts alkylation catalysts

Aluminosilicate catalysts containing supported ZnCl2 and metal fluoride salts have been prepared using a sol-gel based route, tested and characterized. The activities of these ZnCl2 + metal fluoride catalysts, while greater than "Clayzic" (ZnCI2 supported on montmorillonite KIO) are not as good as supported ZnCl2 only supported on aluminosilicate. Alumina supports have also been prepared via a sol-gel route using various chemical additives to generate a mesoporous structure, loaded with ZnCl2 and tested for activity. The activities for these alumina-supported catalysts are also significantly higher than that of "Clayzic", an effective Friedel-Crafts catalyst. Characterizations of these two types of catalysts were done by magic angle spinning (MAS) NMR, diffuse reflectance infrared (DRIFT) spectroscopy and additionally for the alumina nitrogen adsorption studies were done. Supported aluminum trichloride was also investigated as an alternative to the traditional use of aluminum trichloride.

The nucleophillic substitution of various chloroanthraquinones of their possible rearrangement via aryne intermediates

The work in this thesis deals mainly with nucleophilic substitution of chloroanthraquinones as a route to various starting materials which might rearrange, via aryne intermediates to afford fused-ring heterocy1ic carboxylic acids. 1-Amino-5-chloroanthraquinone was successfully prepared by reacting 1,5-dichloroanthraquinone with sodium aZide in ref1uxing dimethylsulfoxide (DMSO). It could also be prepared from the same starting material by reaction with ammonia (gas) in DMSO in the presence of potassium fluoride. Treatment of l-amino-5-chloroanthraquinone with potassium amide in liquid ammonia or with potassium t-butoxide in t-butylbenzene returned mainly starting material, although in the latter case some 1-amino-5-hydroxyanthraquinone was also isolated. 1-Hydroxy-5-chloroanthraquinone was ultimately prepared by diazotization of the amino-analog. It was recovered almost quantitatively after treatmenu'with potassium amide in liquid ammonia. The reaction with potassium t-butoxide in t-buty1benzene was anomalous and gave 1-hydroxyanthraquinone as the only iso1able product. Acridines were successfully prepared by the action of 70% sulfuric acid on 1,5-bis(p-toluidino)-anthraquinone and 1-p-toluidino-5- ch10roanthraquinone, and in the latter case, cleavage to give an acridinecarboxylate was attempted. Substituted anthraquinones reacted with sodium azide in sulfuric acid to give azepindiones by -NH insertion. Methods for separating and identifying isomeric mixtures of these compounds were examined. Attempted decarbonylation of selected azepindiones to give acridones gave mainly what were thought to be amino-benzophenone derivatives. Chloroanthraquinones were found to react with hexamethylphosphoramide (HMPA) to give mixtures of the dimethylamino- and methylaminoderivatives. Under the same conditions halogeno-nitrobenzenes and nitrophenols were substituted to give the appropriate dimethyl aminobenzenes, except in two cases. 3-Chloronitrobenzene reacted anomalously to give a small amount of 3,3'-dichloroazobenzene and a trace of 4-dimethylamino-nitrobenzene. Pentachlorophenol reacted to give a pentachlorophenylphosphorodiamidate in good yield.

Src family kinases are required for limb trajectory selection by spinal motor axons

Signal relay by guidance receptors at the axonal growth cone is a process essential for the assembly of a functional nervous system. We investigated the in vivo function of Src family kinases (SFKs) as growth cone guidance signaling intermediates in the context of spinal lateral motor column (LMC) motor axon projection toward the ventral or dorsal limb mesenchyme. Using in situ mRNA detection we determined that Src and Fyn are expressed in LMC motor neurons of chick and mouse embryos at the time of limb trajectory selection. Inhibition of SFK activity by C-terminal Src kinase (Csk) overexpression in chickLMCaxons using in ovo electroporation resulted inLMC axons selecting the inappropriate dorsoventral trajectory within the limb mesenchyme, with medial LMC axon projecting into the dorsal and ventral limb nerve with apparently random incidence. We also detected LMC axon trajectory choice errors in Src mutant mice demonstrating a nonredundant role for Src in motor axon guidance in agreement with gain and loss of Src function in chickLMCneurons which led to the redirection ofLMCaxons. Finally, Csk-mediated SFK inhibition attenuated the retargeting ofLMCaxons caused by EphA or EphB over-expression, implying the participation of SFKs in Eph-mediated LMC motor axon guidance. In summary, our findings demonstrate that SFKs are essential for motor axon guidance and suggest that they play an important role in relaying ephrin:Eph signals that mediate the selection of motor axon trajectory in the limb.

Sels de tétraarylphosphonium : synthèse et application à la synthèse de la (–)-coniine ; capacité trans-directrice du groupement amide en cyclopropanation d’oléfines

Le développement ainsi que l’amélioration des différentes techniques de purification sont des défis importants pour la chimie d’aujourd’hui. Certaines des méthodes actuelles, tel que le greffage d’un réactif sur un support solide permettant d’accéder à un produit pur par simple filtration du milieu, comportent toutefois certains inconvénients. En effet, les propriétés de solubilité de ces polymères rendent la mise en œuvre des réactions plus difficiles. C’est dans ce contexte que le groupe du Pr. Charette a rapporté l’utilisation de réactifs liés à un sel de tétraarylphosphonium (TAP). Ces sels peuvent être solubilisés dans un solvant tel que le dichlorométhane et aisément retirés du milieu réactionnel par précipitation à l’aide d’éther diéthylique (Chapitre 1). L’un des objectifs de cette thèse a donc été lié à la découverte de deux méthodes complémentaires qui, jusqu’à présent, sont considérées comme des méthodes de choix pour la synthèse des sels de TAP fonctionnalisés (Chapitre 2). L’une d’entre elles est utilisée par Soluphase inc., une entreprise qui commercialise ces sels de TAP. L’efficacité des sels en tant que support dans la synthèse de petites molécules a été démontrée lors de la synthèse d’un produit naturel, la (–)-coniine (Chapitre 3). L’isolement des intermédiaires synthétiques instables par simple précipitation à l’aide d’un support de TAP a permis de rendre cette synthèse plus efficace que celle déjà connue. Dans le deuxième volet de cette thèse, plusieurs problèmes reliés à la synthèse de dérivés cyclopropaniques 1,1-disubstitués ont été étudiés. Ces derniers font partie intégrale de plusieurs produits naturels et de médicaments. Cependant, leur formation par une réaction de cyclopropanation d’alcènes utilisant des réactifs diazoïques possédant deux groupements de type accepteur n’est pas tâche facile (Chapitre 4). En effet, cette réaction souffre d’un faible contrôle diastéréosélectif. Par le fait même, très peu de méthodologies de synthèse ont rapporté l’utilisation de ce type de réactifs diazoïques dans des réactions de cyclopropanation stéréosélectives. L’étude du mécanisme de la réaction de cyclopropanation catalysée au Rh(II) a proposé des indices favorisant un modèle ayant des précédents dans la littérature (Chapitre 5). Ces études nous ont mené à la découverte de la «capacité trans-directrice» du groupement amide lors des réactions de cyclopropanation d’oléfines. Nous avons donc utilisé cette propriété afin de résoudre plusieurs problèmes rencontrés dans la littérature. Nous avons montré qu’elle permet l’accès à des dérivés cyclopropaniques possédant deux groupements carboxyliques géminaux avec des sélectivités élevées (Chapitre 6). Ces produits étaient accessibles que par des séquences synthétiques nécessitant plusieurs étapes. De plus, nous avons démontrés que ces nouveaux dérivés cyclopropaniques sont des outils synthétiques fort utiles dans la synthèse de produits naturels d’intérêt biologique. Cette formidable «capacité trans-directrice» du groupement amide nous a permi de résoudre le problème de la synthèse asymétrique de dérivés carboxyliques α-cyano cyclopropaniques (Chapitre 7). De plus, ce projet nous a menées à la découverte de l’effet de divers additif achiraux permettant d’augmenter la sélectivité dans certaines réactions. Cette réaction possède une vaste étendue et l’utilité de ces nouveaux dérivés cyclopropaniques a été démontrée par plusieurs transformations de groupements fonctionnels.

Narrative development and supported employment of persons with severe mental illness

Essai présenté à la Faculté des arts et des sciences en vue de l’obtention du grade de Doctorat en psychologie option psychologie clinique

Studies On Supported Cobalt (Ii), Nickel (Ii) and Copper (Ii) Complexes Of O-Phenylenediamine and Schiff Bases Derived from 3-Hydroxyquinoxaline-2-Carboxaldehyde

The thesis deals with the synthesis, characterization and catalytic activity studies of supported cobalt(ii), nickel(II) and copper(II) complexes of O-phenylenediamine and Schiff bases derived from 3-hydroxyquinoxaline -2-carboxaldehyde. Zeolite encapsulation and polymer anchoring was employed for supporting the complexes. The characterization techniques proved that the encapsulation as well as polymer supporting has been successfully achieved. The catalytic activity studies revealed that the activities of the simple complexes are improved upon encapsulation. Various characterization techniques are used such as, chemical analysis, EPR, magnetic measurements, FTIR studies, thermal analysis, electronic spectra, XRD, SEM, surface area, and GC.The present study indicated that the that the mechanism of oxidation of catechol and DTBC by hydrogen peroxide is not altered by the change in the coordination sphere around the metal ion due to encapsulation. This fact suggests outer sphere mechanism for the reactions. The catalytic activity by zeolite encapsulated complex was found to be slower than that by the neat complex. The slowing down of the reaction in the zeolite case is probably due to the constraint imposed by the zeolite framework. The rate of DTBC ( 3,5-di-tert-butylchatechol)oxidation was found to be greater than the rate of catechol oxidation. This is obviously due to the presence of electron donating tertiary butyl groups.

Studies on Catalysis by Vanadia Supported On Metal Oxides

Catalysis is an essential technology in manufacturing industries. The investigation based on supported vanadia catalysts and it’s sulfated analogues. Vanadia is a transition metal oxide and is used in oxidation reactions in chemical industry. It is more active and selective catalysts on suitable supports. The work deals with preparation of vanadia incorporated tin oxide and zirconia systems by wet impregnation. Physico-chemical characterization using instrumental techniques like BET etc. The surface acidic properties were determined by the ammonia TPD studies, Perylene absorption studies and Cumene conversion reaction. The catalytic activities of the prepared systems are tested by Friedel-Crafts benzylation of arenes and Bechmann rearrangement of Cyclohexanol oxime. Here the rector reactions are relatively rare. So to test the application of the catalyst systems for the selective oxidation of cyclohexanol to cyclohexanone and finally evaluate the catalytic activity of the systems for the vapour phase oxidative dehydrogenation of Ethylbenzene, which leads to the formation of Industrially important compound ‘styrene’ is another objective of this work

Investigations on Some Titania Supported Catalysts

Titania is a versatile metal oxide with multiple applications. Titania supported catalysts are reported to be much more active compared to conventional silica or alumina supported ones in some reactions. TiO2 (anatase) having high surface area, with better crystallinity and high onset temperature of rutilation can be prepared by thermal hydrolysis of titanyl sulfate solution under controlled conditions. Calcinations at 350oC for 6 hrs were necessary to crystallize anatase. Method of preparation and percentage of the loaded metal oxides have greater influence on surface area. Drastic decrease in surface area was observed upon rutilation. Rutilation started at different temperatures depending on the metal oxide and the method of preparation. TiO2 should be characterized with high surface area, phase purity and high onset temperature of rutilation.Which should be well above the optimum temperature of a designated reaction in which it is employed as a catalyst. Variation in physical properties, depending upon the method of preparation is greater in TiO2 supported catalysts. Methanation activity was found to be highly dependent on nickel concentration present on the surface of the pellets. The methanation activity is strongly influenced by support material. The rate and turn over frequency of methanation and toluene oxidation activity of these catalysts are also equally important from an industrial point of view.

Novel Strategies for Heterocyclic Constructions via 1, 4-Dipolar Intermediates

In the thesis entitled " Novel Strategies for Heterocyclic Constructions via 1 ,4-Dipolar Intermediates"Synthesis of a complex organic molecules essentially involves the formation of carbon-carbon and carbon-heteroatom bonds. Various synthetic methods are available for these processes involving ionic, pericyclic and radical reactions. Among the pericyclic reactions, dipolar cycloaddition reactions, introduced by Huisgen, have emerged as a very powerful tool for heterocyclic construction. Heterocyclic compounds remain an important class of organic molecules due to their natural abundance and remarkable biological activity, thus constituting an intergral part of pharmaceutical industry. In this respect, developing newer synthetic methodology for heterocyclic construction has been an area of immense interest. In recent years, 1,3-dipolar cycloaddition reactions proved to be efficient routes to a wide variety of five membered heterocycles, as attested by their application in the total synthesis of various complex organic molecules. However, the potential application of similar 1,4- dipolar cycloaddition reactions for the construction of six memebered heterocycles remained underexploited. In this context, a systematic investigation of the reactivity of 1,4-dipoles generated from nitrogen heterocycles (pyridine and its analogues) and dimethyl acetylenedicarboxy!ate (DMAD) towards various dipolarophiles has been carried out and the results are embodied.

First Example of Organocatalysis by Polystyrene-Supported PAMAM Dendrimers: Highly Efficient and Reusable Catalyst for Knoevenagel Condensations

This paper describes the first use of polystyrene-supported poly(amidoamine) (PAMAM) dendrimers as heterogeneous basic organocatalysts for carbon–carbon bond formation. Polystyrene-supported PAMAM dendrimers of first, second and third generations have been used as reusable base catalysts in Knoevenagel condensations of carbonyl compounds with active methylene compounds. The reactions proceed in short periods of time and with 100% selectivity. This novel catalyst eliminates the use of aromatic and halogenated solvents, as well as complex purification processes. The catalysts can be recycled ten times.

Characterization and Catalytic Activity of Polymer Supported Ruthenium Schiff Base Complexes Towards Catechol Oxidation

Ruthenium(III) complexes of the Schiff bases formed by the condensation of polymer bound aldehyde and the amines, such as 1,2-phenylenediamine (PS-opd), 2-aminophenol (PS-ap), and 2-aminobenzimidazole (PS-ab) have been prepared. The magnetic moment, EPR and electronic spectra suggest an octahedral structure for the complexes. The complexes of PS-opd, PS-ap, and PS-ab have been assigned the formula [PS-opdRuCl3(H2O)], [PS-apRuCl2(H2O)2], [PS-ab- RuCl3(H2O)2], respectively. These complexes catalyze oxidation of catechol using H2O2 selectively to o-benzoquinone. The catalytic activity of the complexes is in the order [PS-ab- RuCl3(H2O)2] . [PS-opdRuCl3(H2O)] [PS-apRuCl2(H2O)2]. Mechanism of the catalytic oxidation of catechol by ruthenium( III) complex is suggested to take place through the formation of a ruthenium(II) complex and its subsequent oxidation by H2O2 to the ruthenium(III) complex.

Cobalt (II), Nickel (II), and Copper (II) Complexes of Polystyrene-Supported Schiff Bases

Two novel polystyrene-supported Schiff bases, PSOPD and PSHQAD, were synthesized. A polymerbound aldehyde was condensed with o-phenylenediamine to prepare the Schiff base PSOPD, and a polymer-bound amine was condensed with 3-hydroxyquinoxaline-2-carboxaldehyde to prepare the Schiff base PSHQAD. This article addresses the study of cobalt (II), nickel (II), and copper (II) complexes of these polymer-bound Schiff bases. All the complexes were characterized, and the probable geometry was suggested using elemental analysis, diffuse reflectance ultraviolet, Fourier transform infrared spectroscopy, thermal studies, surface area studies, and magnetic measurements.

PVC Supported Liquid Membrane and Carbon Paste Potentiometric Sensors Incorporating a Mn(III)-Porphyrin for the Direct Determination of Undissociated Paracetamol

PVC supported liquid membrane and carbon paste potentiometric sensors incorporating an Mn(III)-porphyrin complex as a neutral host molecule were developed for the determination of paracetamol. The measurements were carried out in solution at pH 5.5. Under such conditions paracetamol exists as a neutral molecule. The mechanism of molecular recognition between the Mn(III)-porphyrin and paracetamol, leading to potentiometric signal generation, is discussed.The sensitivity and selectivity toward paracetamol of carbon paste and polymeric liquid membrane electrodes incorporating an Mn(III)-porphyrin host were compared. The applicability of these sensors to the direct determination of paracetamol was checked by performing a recovery test in human plasma.

Studies on the preparation of Supported nickel catalysts using bis(ethylenediamine)nickel(II) complexes as precursors

Dept.of Applied Chemistry,Cochin University of Science and Technology