Studies on the Synthesis and Transformations of A Few Dibenzoylalkene – Type Systems

The aim of the study is to synthesise several dibenzoylakene-type systems such as acenaphthenone-2-ylidene ketones 47 and phenanthrenone-9-ylidene ketones 48 by the condensation reaction of acenaphthenequinone and phenanthrenequinone with methyl ketones. Here studies the thermal and photochemical transformations of acenaphthaenone-2-ylidene ketones 3a-c.These acenaphthenone –2-ylidene ketones underwent extensive decomposition on heating. The objectives of present study is to synthesise acenaphthenone-2-ylidene ketones by the Claisen-Schmidt condensation of acenaphthenequinone and methyl ketones, it is to synthesise phenanthrenone –9-ylidene ketones by the Claisen-Schmidt condensation of phenanthrequinone and methyl ketones, thermal studies on acenaphthenone-2-ylidene ketones and phenanthrenone-9-ylidene ketones, photochemical studies on acenaphthenone-2-ylidene ketones and phenanthrenone –9-ylidene ketones to establish the generality of dibenzoyalkene rearrangement. Cyclic voltammetric studies on these dibezoyalkenes to compare their redox behaviour with that of the cis and trans isomers of dibenzoyl-ethylene, dibenzoylstilbene. These results should provide some information about their reactivity, and to assess and exploit the potential of these systems as quinonemethides. This study conclude that a number of new dibenzolalkene-type systems have been synthesized by the Claisen-Schmidt condensation of 1,2-diketones such as phenanthequinone and acenaphthenequinone with methyl ketones. Some of these compounds have been shown to undergo interesting photochemical transformations. Based on the results it is conclude that phenanthjrenone-9-ylidene ketones are excellent Michael acceptors. Methanol adds to these to yield the corresponding furanols. These furanols are unstable and are slowly converted to phenanthro-2 (3H)-furanones.

Studies on the Synthesis and Transformations of a Few Dibenzoylalkene-type Systems

The aim of the study is to synthesise several dibenzoylakene-type systems such as acenaphthenone-2-ylidene ketones 47 and phenanthrenone-9-ylidene ketones 48 by the condensation reaction of acenaphthenequinone and phenanthrenequinone with methyl ketones. Here studies the thermal and photochemical transformations of acenaphthaenone-2-ylidene ketones 3a-c.These acenaphthenone –2-ylidene ketones underwent extensive decomposition on heating. The objectives of present study is to synthesise acenaphthenone-2-ylidene ketones by the Claisen-Schmidt condensation of acenaphthenequinone and methyl ketones, it is to synthesise phenanthrenone –9-ylidene ketones by the Claisen-Schmidt condensation of phenanthrequinone and methyl ketones, thermal studies on acenaphthenone-2-ylidene ketones and phenanthrenone-9-ylidene ketones, photochemical studies on acenaphthenone-2-ylidene ketones and phenanthrenone –9-ylidene ketones to establish the generality of dibenzoyalkene rearrangement. Cyclic voltammetric studies on these dibezoyalkenes to compare their redox behaviour with that of the cis and trans isomers of dibenzoyl-ethylene, dibenzoylstilbene. These results should provide some information about their reactivity, and to assess and exploit the potential of these systems as quinonemethides. This study conclude that a number of new dibenzolalkene-type systems have been synthesized by the Claisen-Schmidt condensation of 1,2-diketones such as phenanthequinone and acenaphthenequinone with methyl ketones. Some of these compounds have been shown to undergo interesting photochemical transformations. Based on the results it is conclude that phenanthjrenone-9-ylidene ketones are excellent Michael acceptors. Methanol adds to these to yield the corresponding furanols. These furanols are unstable and are slowly converted to phenanthro-2 (3H)-furanones

Studies on the Synthesis and Transformations of a Few 2(3H)- and 3(2H)-Furanones

The thesis entitled studies on the synthesis and transformations of a few 2(3H)- and 3(2H)- furanones. Furanones represent an interesting class of heterocyclic compounds, which constitute the central ring system of many natural products. The derivatives of furan is divided, depending on their structure 2(3H)-furanones(I), 2(5H)-furanones(II), and 3(2H)-furanones(III). Systems I&II are unsatured gama lactones known as ‘butenolides’. Compounds of this type also known as ‘crotonolactones’ based on the parent crotonic acid. In conclusion a number of 2(3H)-and 3(2H)- furanones were synthesized from dibenzoylalkene precursors and were characterized on the basis of spectral analytical and X-ray data. On direct irradiation 3,3-bis(4-chloropheneyl)-5-aryl-3H-furan -2-ones underwent decarbonylation to yield the corresponding alpha, beta- unsaturated carbonyl compounds and upon sensitized irradiation they underwent dimersation arising through a 2+2 cycloaddition reaction. Our studies on 3(2H)-furanones revealed that these compounds are thermally stable, while they undergo extensive decomposition to intractable mixtures under the influence of light. Similarly, the novel dibenzoylalkenes- type systems containing hetroatomatic rings synthesized by us also underwent extensive decomposition under the influence of heat. Some of the 3(2H)-furanones synthesized by us exhibit remarkable anti-proliferative activity.

Synthesis and Characterization of Chlorinated Paraffin Wax-Bound Paraphenylenediamine Antioxidant and ItsApplication in Natural Rubber

ABSTRACT: p-Phenylenediamine was chemically attached to low molecular weight chlorinated paraffin wax. The polymer-bound p-phenylenediamine was characterized by vapor-phase osmometry (VPO), proton magnetic resonance spectroscopy ('H-NMR), infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The efficiency and permanence of the polymer-bound p-phenylenediamine as an antioxidant was compared with a conventional amine-type antioxidant in natural rubber vulcanizates. The vulcanizates showed improved aging resistance in comparison to vulcanizates containing a conventional antioxidant. The presence of liquid polymer-bound p-phenylenediamine also reduces the amount of the plasticizer required for compounding.

Studies on the Synthesis and Transformations of a few Bicyclic and Dispiro Compounds

In this thesis, we report our endeavours in the synthesis of a few polycyclic compounds. We were interested in the synthesis of a few bicyclic compounds designed to undergo interesting photochemical transformations including tripletmediated di-π-methane rearrangement and/or competing singlet-mediated electrocyclic reactions. Our target molecules have "inbuilt" structural features which will potentially alter the photochemistry of the substrate under consideration.The present investigation was undertaken to test our hypothesis on selective intramolecular quenching of singlet or triplet excited states of molecules.We adopted Dies-Alder reaction for the synthesis of several of the bicyclic compounds we were interested in. Some of the precursor dienes synthesised by us are capable of undergoing intramolecular cycloaddition reactions as well. So, it was important to delineate the conditions and structural features that will enable a particular molecule to undergo intermolecular and intramolecular Dies-Alder reaction when treated with a suitable dienophile.Though, the main focus of this thesis is on the synthesis of bicyclic and tricyclic systems capable of undergoing di-π-methane rearrangement, in the last chapter of this thesis, we describe our findings on the synthesis of a few dispirocompounds. These systems were encountered as unexpected products in the attempted synthesis of novel dibenzoylalkene-type systems. Consequently, a brief survey on the synthesis and transformations of dibenzoylalkenes is also included as an integral part of this thesis.

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.

Growth and characterisation of p-type delafossite transparent conducting thin films for heterojunction applications

In the present studies, various copper delafossite materials viz; CuAlO2, CuGaO2, CuFeO2 , CuGa1-xFexO2, CuYO2 and CuCaxY1-xO2 were synthesised by solid state reaction technique. These copper delafossite materials were grown in thin film form by rf magnetron sputtering technique. In general copper delafossites exhibit good optical transparency. The conductivity of the CuYO2 could be improved by Ca doping or by oxygen intercalation by annealing the film in oxygen atmosphere. It has so far been impossible to improve the p-type conductivity of CuGaO2 significantly by doping Mg or Ca on the Ga site. The ptype conductivity is presumed to be due to oxygen doping or Cu Vacancies [6]. Reports in literature show, oxygen intercalation or divalent ion doping on Ga site is not possible for CuGaO2 thin films to improve the p-type conductivity. Sintered powder and crystals of CuFeO2 have been reported as the materials having the highest p-type conductivity [14, 15] among the copper and silver delafossites. However the CuFeO2 films are found to be less transparent in the visible region compared to CuGaO2. Hence in the present work, the solid solution between the CuGaO2 and CuFeO2 was effected by solid state reaction, varying the Fe content. The CuGa1-xFexO2 with Fe content, x=0.5 shows an increase in conductivity by two orders, compared to CuGaO2 but the transparency is only about 50% in the visible region which is less than that of CuGaO2 The synthesis of α−AgGaO2 was carried out by two step process which involves the synthesis of β-AgGaO2 by ion exchange reaction followed by the hydrothermal conversion of the β-AgGaO2 into α-AgGaO2. The trace amount of Ag has been reduced substantially in the two step synthesis compared to the direct hydrothermal synthesis. Thin films of α-AgGaO2 were prepared on silicon and Al2O3 substrates by pulsed laser deposition. These studies indicate the possibility of using this material as p-type material in thin film form for transparent electronics. The room temperature conductivity of α-AgGaO2 was measured as 3.17 x 10-4 Scm-1and the optical band gap was estimated as 4.12 eV. A transparent p-n junction thin film diode on glass substrate was fabricated using p-type α-AgGaO2 and n-ZnO.AgCoO2 thin films with 50% transparency in the visible region were deposited on single crystalline Al2O3 and amorphous silica substrates by RF magnetron sputtering and p type conductivity of AgCoO2 was demonstrated by fabricating transparent p-n junction diode with AgCoO2 as p-side and ZnO: Al as n-side using sputtering. The junction thus obtained was found to be rectifying with a forward to reverse current of about 10 at an applied voltage of 3 V.The present study shows that silver delafossite thin films with p-type conductivity can be used for the fabrication of active devices for transparent electronics applications.

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Novel Synthesis of Carbocycles and Heterocycles Employing Zwitterions Derived from Allenic Esters

Carbon-carbon and carbon-heteroatom bond formations constitute the central events in organic synthesis. In view of this, much of the research in organic synthesis has been focused on devising novel and efficient methods for such bond constructions. In general, polar, pericyclic and radical methodologies are employed for this purpose. The polar and radical reactions proceed via reactive intermediates such as carbanions, enols/enolates, enamines, carbocations, radical cations, radical anions, carbenes, zwitterions etc. In recent years, there has been enormous interest in the chemistry of zwitterionic species largely from the standpoint of their applications in multicomponent reactions (MCRs) and organocatalytic reactions. Zwitterions formed by the addition of nucleophiles to electrophilic π-systems such as acetylenic esters and azoesters have been the subject of extensive investigations; their synthetic utility, however, remained largely unexplored. Investigations in a number of laboratories, including our own, have shown that zwitterions of the type mentioned above on reaction with electrophiles give rise to carbo- and heterocyclic products by 1,3- or 1,4-dipolar cycloadditions. Recently, allenoates, another class of active π-systems were introduced to this field. Against this background, a systematic investigation of the reactions of various zwitterions derived from allenoates with different electrophiles especially 1,2-diones, were carried out. The results of these studies are embodied in the thesis entitled “Novel Synthesis of Carbocycles and Heterocycles Employing Zwitterions Derived from Allenic Esters”.