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The Chemistry of Permanganate Complexes Having Reducing Ligands – Beliefs and Facts

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The Chemistry of Permanganate Complexes Having Reducing Ligands – Beliefs and Facts Exploring New Horizons in Chemical Sciences-2019 IT-1 The chemistry of permanganate complexes having reducing ligands – beliefs and facts László Kótaia*, R. P. Pawarb, Fernanda Paiva Franguellia, Péter Németha and Imre Miklós Szilágyia aResearch Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary. bDepartment of Chemistry, Deogiri college, Aurangabad (MS) - 431 005 India. Correspoding author: [email protected] Abstract: Compounds containing redox active permanganate anions and complex cations with reducing ligands (M=Ag, Cu, Zn, Cd, Fe, Ni, Cr, Co, L=NH3, pyridine, 2,2’-bipyridine and urea) are used not only as selective and mild oxidants in organic chemistry but as precursors for nanocatalyst synthesis in low- temperature solid phase redox reactions. Their synthesis in pure form is challenging due to the high reactivity of the reactants toward each other. Here we show some new synthesis methods and application fields as well. Structural studies of these complexes show that the main reason for the appearance of unusual quasi-intramolecular solid phase redox reactions observed at these complexes is the existence of hydrogen bonds (N-H…O-Mn in ammine complexes and -C-H…O-Mn in pyridine complexes) between the reducing ligands and oxidizing anions. The [M(NH3)4](MnO4)2 type complexes (M=Cu, Zn and Cd) can be transformed into transition metal manganites (MMn2O4) used as sensors in NOx or CH3SH detection (M=Cd), as catalysts in hydrocarbon processing (M=Zn) or in oxidation of methane or exhaust gases (M=Cu). The known traditional routes to obtain crystalline MMn2O4-type spinels resulted in crystalline (micrometer size) forms due to high synthesis temperature (>500 °C). Our new method is performed around 100 °C and results in amorphous and highly defective nanosized spinel catalysts with superior activity. The pyridinesilver complexes result in Ag/Mn3O4 composites can be used as a catalyst in an anticancer drug (Gefitinib) manufacture. International Symposium Organized by Department of Chemistry Deogiri College, Aurangabad (MS) India Page 1 Exploring New Horizons in Chemical Sciences-2019 IT-2 Exploring methodology and molecular hybridization strategies against communicable and noncommunicable diseases Prof. Rajshekhar Karpoormath Departemnt of Chemistry, University of KwaZulu-Natal, Durban, South Africa. Email: [email protected] Abstract: Quinazolinones are important heterocyclic scaffolds that are core moieties of many biologically active molecules and are privileged structures in drug development. These are widespread in both natural products and pharmaceuticals and are core structures in several marketed drugs such as Methaqualone, Etaqualone, Afloqualone, Chloroqualone, Quinethazone, Fluproquazone, Tiacrilast, Raltitrexed etc.We herein report a simple and highly efficient microwave-assisted, copper-catalyzed and ligand-free synthetic method for 2-substituted 4(3H)-quinazolinones as domino reaction. This reaction proceeds via self-condensation of substrate (2-bromo/iodobenzamide) in the presence of a strong base and copper catalyst. The substituted quinazolinones were obtained in one-pot reaction by intramolecular cyclization (condensation) via Ullmann–type intermediate. Both the intermediates and quinazolinones were obtained in good yield and can be further used as building blocks for developing the potential novel drug-like compounds. Tuberculosis is a chronic necrotizing bacterial infection caused by Mycobacterium tuberculosis (Mtb), which has been a bane to humanity for centuries and remains as one of the rampant health problems in the world. We here in report design and synthesis of styryl hydrazine thiazole hybrids from dehydrozingerone (bearing styryl portion) by hybridization approach as potential antimycobacterials against Multi Drug Resistance strains of Mtb. International Symposium Organized by Department of Chemistry Deogiri College, Aurangabad (MS) India Page 2 Exploring New Horizons in Chemical Sciences-2019 IT-3 A Step towards Sustainable Polymers: Utilization of Cashew Nut Shell Liquid (CNSL) and Lignin-Derived Aromatic Chemicals for Synthesis of Difunctional Monomers Suitable for Preparation of High Performance Polymers. Prakash P. Wadgaonkar Polymers and Advanced Materials Laboratory, Polymer Science and Engineering Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune-411 008 E-mail: [email protected]; [email protected] Abstract: Polymer is one of the most versatile materials having myriad of applications - from packaging to biomedical devices. Of late, the glittering concept of ‘sustainability’ has been able to infiltrate within the domain of polymer science and technology to significant extent - in both academia and industries. This field continues to grow rapidly. Along with polymer, other ingredients that are used to make polymer compounds and products would also be sustainable in future. Sustainable materials are defined as materials that can be produced without depletion of non-renewable resources and without disturbing the equilibrium between the environment and key natural resource systems. The range of these materials is huge - from natural rubber, bio-derived monomers and polymers to recyclable materials, etc. How the future polymeric materials could be developed using scientific principles would be discussed in this presentation. It is also interesting to demonstrate how science is helping to restore environment and society. The objectives of our research program since the last ten years have been to design and synthesize monomers and polymers from agricultural waste products, utilize bio-based monomers for synthesis of high performance polymers and understand structure-property relationship. In this context, cashew nut shell liquid (CNSL) and lignin-derived aromatic chemicals were explored as renewable starting materials to generate a library of difunctional monomers suitable for preparation of high performance polymers. These results will be covered in the presentation. International Symposium Organized by Department of Chemistry Deogiri College, Aurangabad (MS) India Page 3 Exploring New Horizons in Chemical Sciences-2019 IT-4 Chemistry of 1, 2, 3-selenadiazoles and their utility in nanotechnology Pawan K Khanna Quantum Dots R & D Lab, Department of Applied Chemistry, Defence Institute of Advanced Technology (DIAT), Ministry of Defence, Govt. of India, Girinagar, Pune-411021, India. * Email: [email protected] Abstract: The present lecture deals with various aspects of 1, 2, 3-selenadiazole and their role in materials chemistry and nanotechnology. The significance of selenadiazole will be highlighted throughout the session by adopting various experimental strategies. Chemistry of organoselenium compounds will be discussed by taking specific examples of a variety of selenadiazoles in order discuss their materials applications. Many reported and new semicarbazones and selenadiazoles will be covered in detail by rapid solventless practices. For example, the syntheses of bis(cycloalkeno)-1,4-diselenins from the corresponding cycloalkeno-1, 2, 3-selenadiazoles by a solvent-free microwave irradiation method will bring new ideas and information to the participants. The reactions of selenadiazoles with metal salts for useful semiconductor nanoparticles. Cd (II) and Zn (II) complexes as precursors for the preparation of the corresponding metal selenide quantum dots will be explained. Like wise the synthesis of magic-sized and regular sized quantum dots using different series of 1, 2, 3-selenadiazoles will be discussed along with polymorphs of selenium from cycloocteno- 1, 2, 3-selenadiazole by microwave irradiation. Understanding of organoselenium compounds, organometallic chemistry, inorganic chemistry, and materials chemistry will thus be effectively created in the minds the participants and other audience. International Symposium Organized by Department of Chemistry Deogiri College, Aurangabad (MS) India Page 4 Exploring New Horizons in Chemical Sciences-2019 IT-5 Transition State Models for Understanding Asymmetric Catalysis Raghavan B. Sunoj Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076 India. Email: [email protected] Abstract: Computational quantum chemistry has been increasingly employed toward rationalizing the stereochemical outcome in catalytic reactions. The approach typically involves the identification of kinetically significant transition states and intermediates. In our laboratory, ab initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-heteroatom bond-forming reactions of immediate practical significance. The key objective of our research is to gain molecular insights on the factors responsible for stereoselectivity and to exploit such insights toward in silico design of novel asymmetric catalysts. A number of examples wherein the conventional transition state models required systematic refinements toward accounting the observed product distribution and stereochemical outcome will be presented. Through this talk, we intend to propose the need for a timely rethink on a number of working hypotheses on asymmetric induction that places an over-emphasis on steric interaction. In general, the presentation would encompass a few contemporary themes in the domain of asymmetric multi-catalytic reactions. Interesting interpretations/rationalizations of experimental observations besides meaningful guidelines for rational improvements
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