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Polymer-supported organic catalysts are largely insoluble in most reaction solvents, which allows for easy recovery and recycling of the catalysts. They are generally stable, readily available, and environmental friendly, so they have attracted the interest of many synthetic chemists in the industrial and academic fields. In this book, different types of polymer-supported catalysts based on peptides, polystyrene, polyethers, poly(acrylic acid), poly(ethylene imine), poly(2-oxazoline), poly(isobutylene), poly(norbornene), etc., as well as metals are included with their synthetic organic synthesis applications. It is believed that this work will be of interest to organic chemists, material scientists, chemical engineers, polymer scientists and technologists.
A comprehensive resource on techniques and applications for immobilizing catalysts Catalyst Immobilization: Methods and Applications covers catalyst immobilization topics including technologies, materials, characterization, chemical activity, and recyclability. The book also presents innovative applications for supported catalysts, such as flow chemistry and machine-assisted organic synthesis. Written by an international panel of expert contributors, this book outlines the general principles of catalyst immobilization and explores different types of supports employed in catalyst heterogenization. The book?s chapters examine the immobilization of chiral organocatalysts, reactions in flow reactors, 3D printed devices for catalytic systems, and more. Catalyst Immobilization offers a modern vision and a broad and critical view of this exciting field. This important book: -Offers a guide to supported and therefore recyclable catalysts, which is one of the most important tools for developing a highly sustainable chemistry -Presents various immobilization techniques and applications -Explores new trends, such as 3D printed devices for catalytic systems -Contains information from a leading international team of authors Written for catalytic chemists, organic chemists, process engineers, biochemists, surface chemists, materials scientists, analytical chemists, Catalyst Immobilization: Methods and Applications presents the latest developments and includes a review of the innovative trends such as flow chemistry, reactions in microreactors, and beyond.
In today's world, the need to limit the use of nonrenewable resources and the importance of recycling has been recognized. One important contribution of chemists toward the general goal of limiting their use is to find catalysts that can be reused and recycled thereby limiting the need for expensive metal precursors and metal waste. Strategies to recycle catalysts are multifold and range from the employment of soluble polymers as catalyst supports to the use of membrane-encapsulated catalyst. The use of soluble polymers as a support not only offers the advantage of being soluble under the catalytic reaction conditions but also, to be removable by changing the conditions of the surrounding media. Despite the great potential of these soluble supported catalysts, their use is very limited in today's synthesis. In addition, no set of rules have been established to guide the synthesis of efficient supported catalysts. In order to establish a "tool box" for the synthesis of supported catalysts, the study of several parameters such as the choice of the support and the choice and the stability of the catalyst are necessary. To establish this set of rules, a limited number of catalytic transformations, were studied. These catalytic reactions are the Heck-Mizoroki, Suzuki-Miyaura and Sonogashira coupling reactions. These transformations became fundamental for the synthesis of drugs and materials. The first and second chapters provide background information by describing and evaluating the main supports that were previously used for catalysts and the two main catalysts that are used in this thesis, the palladium pincer complex and the palladium N-heterocyclic complex. In chapter 3, the synthesis of a soluble polymer supported catalyst is described. The polymer chosen for the study is poly(norbornene), and the catalyst is a 1,3-disubstituted benzene ligand with sulfurs in the side-chains able to chelate to the metal center, better known as pincer ligand. These ligands are abbreviated by the three atoms that coordinate to the metal center, in this study, SCS. The metal used for the investigation of the activity of this supported pincer is palladium. The importance of the nature of the linkage on the stability of the Pd-SCS pincer complex has been reported in the literature, leading to the synthesis of Pd-SCS pincer complex tethered to the polymer via an ether and an amide linkage. The synthesized poly(norbornene) supported Pd-SCS pincer complexes were evaluated using the Heck transformation of iodobenzene with n-butyl acrylate. Kinetic studies and leaching tests using poly(vinyl pyridine) and mercury were carried out resulting in the conclusion that the active species during the catalysis is not the palladium pincer complex but a leached palladium (0) species. In chapter 4, Pd-PCP pincer complexes with the ether and amide tether were synthesized. Kinetic and poisoning studies were carried out resulting in a similar conclusion. Furthermore, 31P NMR experiments were conducted to investigate the unstability of the complex. Following this study, in-situ XAS as well as computational calculations were carried out. The conclusion from this investigation argues that triethylamine is a key ingredient for the decomposition of the Pd-PCP complex. The overall conclusion from these two different studies is thta Pd(II) pincer complexes decomposes during the Heck reaction when triethylamine is used for the coupling of iodobenzene to n-butyl acrylate in DMF at 120°C. Stemming from this investigation, a reported more stable complex, Pd-NHC, was tethered onto poly(norbornene). The system was evaluated using Suzuki-Miyaura, Heck and Sonogashira reactions. Similar poisoning and kinetic studies were utilized to investigate the stability of the supported NHC Pd complexes. The result of this investigation suggests that supported Pd-NHC complexes are stable under Suzuki-Miyaura and Sonogashira but decompose under Heck conditions. However, when the system was recycled, a decrease in activity for the Suzuki-Miyaura transformation and solubility was observed. In chapter 6, gold monolayer protected clusters (MPC) were investigated as potential candidates as supports. To examine the potential of MPC as a support, a NHC-Pd complex was graphted onto the particles. To functionalize the gold nanoparticles, a new method was developed. Using azide moieties added to the gold nanoparticles, the catalyst was added via microwave assisted 1,3 dipolar cycloaddition. The system was evaluated using Suzuki-Miyaura transformations under microwave conditions. The system exhibited quantitative conversions for a variety of substrates. However, when the system was recycled, aggregation of the particles and decrease in catalytic activity was observed. In summary, this thesis describes the synthesis and evaluation of poly(norbornene) supported Pd-pincer and Pd-NHC complexes and of gold nanoparticles supported Pd-NHC complex. It also detail the combination of kinetic and poisoning studies developed to evaluate a potential supported catalyst.
This book comprehensively covers researches on enzymatic polymerization and related enzymatic approaches to produce well-defined polymers, which is valuable and promising for conducting green polymer chemistry. It consists of twelve chapters, including the following topics: The three classes of enzymes, oxidoreductases, transferases and hydrolases, have been employed as catalysts for enzymatic polymerization and modification; Well-defined polysaccharides are produced by enzymatic polymerization catalyzed by hydrolases and transferases; Hydrolase-catalyzed polycondensation and ring-opening polymerization are disclosed to produce a variety of polyesters; Polyesters are synthesized by in-vivo acyltransferase catalysis produced by microorganisms; Enzymatic polymerization catalyzed by appropriate enzymes also produces polypeptides and other polymers; Poly(aromatic)s are obtained by enzymatic polymerization catalyzed by oxidoreductases and their model complexes; Such enzymes also induce oxidative polymerization of vinyl monomers; Enzymatic modification of polymers is achieved to produce functionalized polymeric materials; The enzymatic polymerization is a green process with non-toxic catalysts, high catalyst efficiency, green solvents and renewable starting materials, and minimal by-products; Moreover, renewable resources like biomass are potentially employed as a starting substrate, producing useful polymeric materials. This book is not only educative to young polymer chemists like graduate students but also suggestive to industrial researchers, showing the importance of the future direction of polymer synthesis for maintaining a sustainable society.
Organic chemistry has played a vital role in the development of diverse molecules which are used in medicines, agrochemicals and polymers. Most ofthe chemicals are produced on an industrial scale. The industrial houses adopt a synthesis for a particular molecule which should be cost-effective. No attention is paid to avoid the release of harmful chemicals in the atmosphere, land and sea. During the past decade special emphasis has been made towards green synthesis which circumvents the above problems. Prof. V. K. Ahluwalia and Dr. M. Kidwai have made a sincere effort in this direction. This book discusses the basic principles of green chemistry incorporating the use of green reagents, green catalysts, phase transfer catalysis, green synthesis using microwaves, ultrasound and biocatalysis in detail. Special emphasis is given to liquid phase reactions and organic synthesis in the solid phase. I must congratulate both the authors for their pioneering efforts to write this book. Careful selection of various topics in the book will serve the rightful purpose for the chemistry community and the industrial houses at all levels. PROF. JAVED IQBAL, PhD, FNA Distinguished Research Scientist & Head Discovery Research Dr. Reddy's Laboratories Ltd.
The need to improve both the efficiency and environmental acceptability of industrial processes is driving the development of heterogeneous catalysts across the chemical industry, including commodity, specialty and fine chemicals and in pharmaceuticals and agrochemicals. Drawing on international research, Supported Catalysts and their Applications discusses aspects of the design, synthesis and application of solid supported reagents and catalysts, including supported reagents for multi-step organic synthesis; selectivity in oxidation catalysis; mesoporous molecular sieve catalysts; and the use of Zeolite Beta in organic reactions. In addition, the two discrete areas of heterogeneous catalysis (inorganic oxide materials and polymer-based catalysts) that were developing in parallel are now shown to be converging, which will be of great benefit to the whole field. Providing a snapshot of the state-of-the-art in this fast-moving field, this book will be welcomed by industrialists and researchers, particularly in the agrochemicals and pharmaceuticals industries.
A timely overview of fundamental and advanced topics of conjugated polymer nanostructures Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications is a comprehensive reference on conjugated polymers for energy applications. Distinguished academic and editor Srabanti Ghosh offers readers a broad overview of the synthesis, characterization, and energy-related applications of nanostructures based on conjugated polymers. The book includes novel approaches and presents an interdisciplinary perspective rooted in the interfacing of polymer and synthetic chemistry, materials science, organic chemistry, and analytical chemistry. This book provides complete descriptions of conjugated polymer nanostructures and polymer-based hybrid materials for energy conversion, water splitting, and the degradation of organic pollutants. Photovoltaics, solar cells, and energy storage devices such as supercapacitors, lithium ion battery electrodes, and their associated technologies are discussed, as well. Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications covers both the fundamental topics and the most recent advances in this rapidly developing area, including: The design and characterization of conjugated polymer nanostructures, including the template-free and chemical synthesis of polymer nanostructures Conjugated polymer nanostructures for solar energy conversion and environmental protection, including the use of conjugated polymer-based nanocomposites as photocatalysts Conjugated polymer nanostructures for energy storage, including the use of nanocomposites as electrode materials The presentation of different and novel methods of utilizing conjugated polymer nanostructures for energy applications Perfect for materials scientists, polymer chemists, and physical chemists, Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications also belongs on the bookshelves of organic chemists and any other practicing researchers, academics, or professionals whose work touches on these highly versatile and useful structures.