Synthesis, spectral and structural studies of transition metal complexes of N(4)-substituted semicarbazones

The thesis is an introduction to our attempts to evaluate the coordination behaviour of a few compounds of our interest. Semicarbazones and their metal complexes have been an active area of research during the past years because of the beneficial biological activities of these substances. Tridentate NNO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are well-authenticated compounds in this field and their synthesis and characterization are well desirable. Hence, we decided to develop a research program aimed at the synthesis and characterization of novel semicarbazones derived from 2-benzoylpyridine and 2-acetylpyridine and their transition metal complexes. In addition to various physicochemical methods of analysis, single crystal X—Ray diffraction studies were also used for the characterization of the complexes.

The ligating versatility of halides and pseudohalides in copper(II) complexes- monomers, dimers and chains”

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2008-2013. The thesis brings to light, our attempts to evaluate the coordination behavior of some compounds of interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are well-authenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of copper complexes with halides and pseudohalides. In addition to single crystal X-ray diffraction studies, various physico-chemical methods of analysis were also used for the characterization of the complexes

Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2009-2012. The thesis is an introduction to our attempts to evaluate the coordination behavior of some compounds of our interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are wellauthenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of new N4- phenylsemicarbazones derived from 2-formylpyridine and 3-ethoxysalicylaldehyde and their transition metal complexes and new transition metal complexes of 2- benzoylpyridine-N4-phenylsemicarbazone. In addition to various physicochemical methods of analysis, single crystal X-ray diffraction studies were also used for the characterization of the complexes.

Model Compound Studies on the Devulcanization of Natural Rubber Using 2, 3-Dimethyl-2-Butene

The mechanism of devulcanization of sulfur-vulcanized natural rubber with aromatic disulfides and aliphatic amines has been studied using 23-dimethyl-2-butene (C5H1,) as a low-molecular weight model compound. First C6H12 was vulcanized with a mixture of sulfur, zinc stearate and N-cyclohexyl-2-benzothiazylsulfenamide (CBS) as accelerator at 140 °C, resulting in a mixture of addition products (C(,H 1 i-S,-C5H 1 i ). The compounds were isolated and identified by High Performance Liquid Chromatography (HPLC) with respect to their various sulfur ranks. In it second stage, the vulcanized products were devulcanized using the agents mentioned above at 200 °C. The kinetics and chemistry of the breakdown of the sulfur-hridges were monitored. Both devulcanization agents decompose sulfidic vulcanization products with sulfur ranks equal or higher than 3 quite effectively and with comparable speed. Di phenyldisulfide as devulcanization agent gives rise to a high amount of mono- and disulfidic compounds formed during the devulcanization, hexadecylamine, as devulcanization agent, prevents these lower sulfur ranks from being formed.

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

Polycyclic aromatic hydrocarbons and toxic trace metals in seawater and sediments from the west coast of India and their bioaccumulation in some selected species of fishes

Polycyclic Aromatic Hydrocarbons and other toxic compounds from industrial effluents are noted for their high potency for skin, lung, bladder and gastrointestinal cancers. Increased industrialization, and population growth led to greater production of wastes, Pesticides and PAHs have received attention due to their carcinogenic effects. The main objectives of the study were; to collect base line data on the concentration of PAHs in seawater and sediment from the west coast of India, the concentration of PAHs in certain species of fishes, the comparative levels of PAHs in fish, the influence of sediment characteristics on the concentration of PAH in sediment, changes in PAH concentration in water, sediment and fish, to provide a base line concentration of trace metals in water, sediment and fish, the seasonal changes in content of selected trace metals in water, sediment and fish from the west coast of India. The present study revealed that a predominance of silt and clay at all stations in the off Cochin area. The study has provided comprehensive information available to date for PAHs in seawater, sediment and fishes from the west cost of India especially from the Quilon to Mangalore region.

Recycling of NR Based Cured Latex Material Reclaimed with 2,2'-Dibenzamidodiphenyldisulphide in a TruckTire Tread Compound

It is observed that reclamation of natural rubber latex based rubber using 2,2'-dibenzamidodiphenvldisulphide as reclaiming agent is an optional methodology for recycling of waste latex rubber (WLR). For progressive replacement of virgin natural rubber by the reclaim, two alternatives curing system were investigated: adjustment or reduction of the curing system with increasing reclaim content, to compensate for the extra amount of curatives brought along by the reclaim. For fixed curing system, as if the reclaim were equivalent to virgin NR. The cure behavior, final crosslink density and distribution, mechanical properties, and dynamic viscoelastic properties of the blends with reclaimed WLR are measured and compared with the virgin compound. The morphology of the blends, sulfur migration, and final distribution are analyzed.The mechanical and dynamic viscoelastic properties deteriorate for both curing systems, but to a lesser extent for fixed curing system compared to adjusted curing system. With the fixed cure system, many properties like tensile strength and compression set do still deteriorate, but tan 6 and Mrrr„/Murxr, representative for the rolling resistance of tires are improved. On the other hand, with the adjusted cure system both mechanical and dynamic properties still deteriorate.

Novel1, 3-Dipolar Cycloaddition Reactions of Acyclic Carbonyl Ylides and Related Chemistry

The thesis entitled novel 1,3-dipolar cycloaddition reactions of acyclic carbonyl ylides and related chemistry embodies the results of the investigations carried out to explore the reactivity of acyclic carbonyl ylides,generated by the reaction of dicarbomethoxy carbine and aldehydes towards dipolarophiles such as activated styrenes,1,2-and 1,4-quinones. In conclusion ,we have explored the reactivity pattern of acyclic carbonyl ylides derived from dicarbomethoxycarbene and aldehyde towards activated styrenes with a view to develop a stereoselective synthesis of highly substituted tetrahydrofuran derivatives. It was also found that the ylide could be trapped by various 1,2-and 1,4-diones to form dioxolane derivatives. It is noteworthy that the cycloaddition is highly region- and stereoselective. With isatins the ylide preferentially adds to the more electrone deficient carbonyl group making it regiospecific. Hetrocyclic compounds are of pivotal importance in organic chemistry, and enormous efforts have been devoted to develop new methodologies for their synthesis. It is noteworthy in this context that, 1,3-dipolar cycloaddition reaction,otherwise called Huisgen reaction, constitutes one of the most efficient methods for the synthesis of five membered heterocycles. Among the various dipoles, carbonyl ylides have received substiancial attention in recent years largely due to their utility in the synthesis of a wide range of oxygen hetrocycles, which are often found as structural subunits of many bioactive natural products.

A Simple Free-Space Method for Measuring the Complex Permittivity of Single and Compound Dielectric Materials

A simple and efficient method for determining the complex permittivity of dielectric materials from both reflected and transmitted signals is presented. It is also novel because the technique is implemented using two pyramidal horns without any focusing mechanisms. The dielectric constant of a noninteractive and distributive (NID) mixture of dielectrics is also determined

Two novel bis-azomethines derived from quinoxaline-2-carbaldehyde

The Schiff base compounds N,N0-bis[(E)-quinoxalin-2-ylmethylidene] propane-1,3-diamine, C21H18N6, (I), and N,N0-bis[(E)- quinoxalin-2-ylmethylidene]butane-1,4-diamine, C22H20N6, (II), crystallize in the monoclinic crystal system. These molecules have crystallographically imposed symmetry. Compound (I) is located on a crystallographic twofold axis and (II) is located on an inversion centre. The molecular conformations of these crystal structures are stabilized by aromatic pye stacking interactions.

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.

Studies on metal complexes with acylhydrazones based on heterocyclic carbonyl compounds

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

Distribution of Polycyclic Aromatic Hydrocarbons in the Cochin Estuary and Backwaters

Department of Chemical Oceanography,Cochin University of Science and Technology