Selective N-monomethylation of aniline using Zn1-x CoxFe2O4( x=0, 0.2, 0.5, 0.8 and 1.0)type systems

A series of ferrites having the general formula Zn1-xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)were prepared by soft chemical route. The materials were characterized by adopting various physico-chemical methods. The reaction of aniline with methanol was studied in a fixed-bed reactor system as a potential source for the production of various methyl anilines. It was observed that systems possessing low ‘ x’ values are highly selective and active for N-monoalkylation of aniline leading to N-methylaniline. Reaction parameters were properly varied to optimize the reaction conditions for obtaining N-methylaniline selectively and in better yield. Among the systems Zn0.8Co0.2Fe2O4 is remarkable due to its very high activity and excellent stability. Under the optimized conditions N-methylaniline selectivity exceeded 98%. Even at a methanol to aniline molar ratio of 2, the yield of N-methylaniline was nearly 50%, whereas its yield exceeded 71% at the molar ratio of 5. ZnFe2O4, though executed better conversion than Zn0.8Co0.2Fe2O4 in the initial period of the run, deactivates quickly as the reaction proceeds. The Lewis acidity of the catalysts is mainly responsible for the good performance. Cation distribution in the spinel lattice influences their acido-basic properties and, hence, these factors have been considered as helpful parameters to evaluate the activity of the systems.

A comparative study of medium and large pore zeolites in alkylation reactions

In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of 0xylene.The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/AI ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation / acylation reactions.The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta offers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Structural and catalytic investigation of vanadia supported on ceria promoted with high surface area rice husk silica

Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.

Fixed bed reactor performance of invertase immobilized on montmorillonite

Invertase was immobilized on acid activated montmorillonite via two independent procedures, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and their activity was tested in a fixed bed reactor. XRD revealed that the enzyme was situated on the periphery of the clay and the side chains of different amino acid residues were involved in intercalation with the clay matrix. NMR demonstrated that tetrahedral Al was linked to the enzyme during adsorption and the octahedral Al was involved during covalent binding. Secondary interaction of the enzyme with Al was also observed. N2 adsorption studies showed that covalent binding of enzymes caused pore blockage since the highly polymeric species were located at the pore entrance. The fixed bed reactor proved to be efficient for the immobilized invertase. The optimum pH and pH stability improved upon immobilization. The kinetic parameters calculated also showed an enhanced efficiency of the immobilized systems. They could be used continuously for long period. Covalently bound invertase demonstrated greater operational stability.

Study of cyclohexanol decomposition reaction over the ferrospinels, A1−xCuxFe2O4 (A=Ni or Co and x=0, 0.3, 0.5, 0.7 and 1), prepared by ‘soft’ chemical methods

Preparation of simple and mixed ferrospinels of nickel, cobalt and copper and their sulphated analogues by the room temperature coprecipitation method yielded fine particles with high surface areas. Study of the vapour phase decomposition of cyclohexanol at 300 °C over all the ferrospinel systems showed very good conversions yielding cyclohexene by dehydration and/or cyclohexanone by dehydrogenation, as the major products. Sulphation very much enhanced the dehydration activity over all the samples. A good correlation was obtained between the dehydration activities of the simple ferrites and their weak plus medium strength acidities (usually of the Brφnsted type) determined independently by the n-butylamine adsorption and ammonia-TPD methods. Mixed ferrites containing copper showed a general decrease in acidities and a drastic decrease in dehydration activities. There was no general correlation between the basicity parameters obtained by electron donor studies and the ratio of dehydrogenation to dehydration activities. There was a leap in the dehydrogenation activities in the case of all the ferrospinel samples containing copper. Along with the basic properties, the redox properties of copper ion have been invoked to account for this added activity.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Transition metal complexes of quinoxaline based Schiff base ligands: Synthesis,characterization and catalytic activity study

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.The convenient route of synthesis and thermal stability of Schiff base complexes have contributed significantly for their possible applications in catalysis,biology,medicine and photonics.Significant variations in cataltytic activity with structure and type are observed for these complexes.The thesis deals with synthsis and characterization of transition metal complexes of quinoxaline based Schiff base ligands and their catalytic activity study.The Schiff bases synthesized in the present study are quinoxaline-2-carboxalidine-2-amino-5-methylphenol,3-hydroxyquinoxaline-2-carboxalidine-2-amino-5-methylphenol,quinoxaline-2-aminothiophenol.They provide great structural diversity during complexation.To the best of our knowledge, the transition metal complexes of quinoxaline based Schiff bases are poorly utilised in academic and industrial research.

Studies on the Surface Properties and Catalytic Activity of Metal Chromites on Thermal Decomposition of Ammonium Perchlorate

Department of Applied Chemistry, Cochin University of Science and Technology

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

Effect of silver nano particles on the fluorescence quantum yield of Rhodamine 6G determined using dual beam thermal lens method

Nano structured noble metals have very important applications in diverse fields as photovoltaics, catalysis, electronic and magnetic devices, etc. Here, we report the application of dual beam thermal lens technique for the determination of the effect of silver sol on the absolute fluorescence quantum yield (FQY) of the laser dye rhodamine 6G. A 532 nm radiation from a diode pumped solid state laser was used as the excitation source. It has been observed that the presence of silver sol decreases the fluorescence quantum efficiency. This is expected to have a very important consequence in enhancing Raman scattering which is an important spectrochemical tool that provides information on molecular structures. We have also observed that the presence of silver sol can enhance the thermal lens signal which makes the detection of the signal easier at any concentration.

Studies on Surface Properties and Catalytic Activity of Some Chromites and Related Spinels

The prime intension of the present work was a synthetic investigation of the preparation, surface properties and catalytic activity of some transition metal substituted copper chromite catalysts. Homogeneous co-precipitation method is employed for the preparation of catalysts. Since the knowledge about the structure and composition of the surface is critical in explaining the reactivity and selectivity of a solid catalyst. a systematic investigation of the physico-chemical properties of the prepared systems was carried out. The catalytic activity of these systems has also been measured in several oxidation reactions of industrial as well as environmental relevance. The thesis is dedicated to several aspects of chromite spinels giving emphasis to its preparation, characterization and catalytic performance towards oxidation reactions.

Studies on metal complexes of some tridentate acylhydrazones

Studies on transition metal complexes have achieved a great interest due to their versatile applications.The convenient route for synthesis,the nature of ligands and stability of metal complexes has significant contributions in their applications in medicine,biology,catalysis and photonics.The present work deals wth the synthesis and characterization of metal complexes of some tridentate acylhydrazones .Hydrazones are promising ligands in coordination chemistry with interesting binding modes and applications.The acylhydrazones chosen for the current study are capable of forming complexes in different forms through tautomerism.

Ordered mesoporous silica as supports for immobilization of biocatalyst

Mesoporous materials are of great interest to the materials community because of their potential applications for catalysis,separation of large molecules,medical implants,semiconductors,magnetoelectric devices.The thesis entitled 'Ordered Mesoporous Silica as supports for immobilization of Biocatalyst' presents how the pore size can be tuned without the loss in ordered structure for the entrapment of an industially important biocatalyst-amylase.Immobilization of enzymes on ordered mesoporous material has triggered new ooportunities for stabilizing enzymes with improved intrinsic and operational stabilities.

Organic Synthesis Mediated by Heterogeneous Catalysts

Catalysis is a technologically important field which determines the quality of life in future. Catalyst research in pharmaceutical industry,fine chemical synthesis and emission control demands supported catalysts in bulk quantities.In the present work it was observed that clay supported catalysts mentioned in various chapters could also be used for the synthesis of similar molecules. The K10Ti catalyst can be used for the synthesis similar substituted imidazole derivatives under solvent free conditions and synthetically important Mannich bases of substrates containing various substitutes.Al-pillared saponite can be used for acetalation of other polyhydroxy compounds like glycerol,mannitol etc.Cu-Pd KSF catalyst has found application in C-C bond forming reactions which can be applied to other reactions and similar methods can be adopted for the synthesis of other catalyst by changing the transition metals. Montmorillonite K10 catalysed synthesis of triarylpyridines can be extended to the synthesis tetrasubstuted pyroles.K10Ti can also be utilized for the synthesis of similar heterocycles.

Palladium Catalyzed Carbon-Carbon/Carbonheteroatom Bond Formation Reactions Utilizing Pentafulvene Derived Bicyclic Hydrazines

The reactions involving fulvenes and its derivatives have received a great deal of attention over the years in synthetic organic chemistry. Functionalizations of fulvenes provide versatile and powerful approaches to various polycyclic systems and natural products. They serve as versatile intermediates in the construction of various ring systems through inter- as well as intramolecular cycloadditions. Compared to the rich literature on the cycloaddition reactions of pentafulvenes, much less attention has been paid to the synthetic utilization of their cycloadducts. Tactical manipulations on the chosen adduct offer the prospects for designing a variety of useful molecular skeletons. Addition of heterodienophiles to fulvenes offers an efficient strategy towards the synthesis of azabicyclic olefins. However, there have been no serious attempts to study the synthetic utility of these substrates. In this context and with the intention of utilizing pentafulvenes towards synthetically important molecules, author decided to explore the reactivity of pentafulvene derived azabicyclic olefins. Our attention was focused on the synthetic potential associated with the ring opening of fulvene derived bicyclic hydrazines under palladium catalysis. It was envisioned that the desymmetrization of these adducts using various soft nucleophiles will provide a novel access to synthetically and biologically important alkylidene cyclopentenes. The investigations along this line form the focal theme of this thesis entitled “PALLADIUM CATALYZED CARBONCARBON/ CARBON-HETEROATOM BOND FORMATION REACTIONS UTILIZING PENTAFULVENE DERIVED BICYCLIC HYDRAZINES