Metal-Catalyzed Oxidations of Organic Compounds: Mechanistic Principles and Synthetic focuses on the oxidative transformations of functional groups. This book explores oxidation as being extensively used in the laboratory synthesis of fine organic chemicals and in the manufacture of large-volume petrochemicals. Organized into two parts encompassing 13 chapters, this book starts with an overview of the mechanistic principles of oxidation–reduction in biochemical, organic, and inorganic systems. This text then proceeds with a discussion of the use of molecular oxygen, hydrogen peroxide, and alkyl hydroperoxides as primary oxidants. Other chapters explore stoichiometric oxidations with metal oxidants, which include permanganate and chromic acid. This book discusses as well the synthetic applications of catalytic oxidations as well as the technology of petrochemical oxidation. The final chapter deals with the autoxidations of sulfur, phosphorus, and nitrogen compounds. This book is intended for chemists involved in organic synthesis, catalysis, and organometallic chemistry, both in academic institutions and in industrial laboratories.

Chromium oxidation, well known and widely explored in organic chemistry since the very beginning of this science, is a topic of current interest for the organic chemist as evidenced by the continuous development of new techni ques and procedures reported in the literature. Chromium oxidation is a simple process which can be easily performed in the laboratory and scaled up in industry as well. Although almost every oxidizable organic functional group may undergo chromium oxidation, the most important fields of appli cation are the oxidation of alcohols, allylic and benzylic oxidation, oxidative degradation and oxidation of some organometallic compounds. A high degree of selectivity is often possible by choosing the most suitable reagent among those several ones now available. This book takes account of the various functional groups that undergo oxidation and the entire literature up to 1982. It has been written in the hope to help the synthetic organic chemist in his experimental work. For this purpose a number of tables comprising yields and references have been included; detailed descriptions of typical procedures are meant to show the experimental conditions and the scope of the reactions. We wish to thank Dr. Mario Orena for his valuable scientific and technical assistence and Prof. Bruno Camerino, who read the entire manuscript and corrected many of the errors. Bologna, February 1984 Gianfranco Cainelli Giuliana Cardillo Table of Contents I. Introduction . . . . . . . . . . .

This volume results from the Eighth Basic Symposium held by the Institute of Food Technologists in Anaheim, California on June 8-9, 1984. The theme of the symposium was "Chemical Changes in Food during Processing." The speakers included a mix of individuals from academic institu tions, governmental agencies, and the food industry. Twenty speakers discussed topics ranging from the basic chemistry relating to food constituents to the more applied aspects of chemical changes in food components during food processing. It was the intent of the organizers to bring together a group of speakers who could address the chemistry of changes in food compo nents during processing from a mechanistic point of view. As a con sequence, the proceedings of this symposium emphasize the basic chemistry of changes in food constituents from a generic perspective which is intended to provide the reader with a background to address more specific problems that may arise.

Oxidative catalysis by metalloporphyrin systems occupies a prominent role in the current research in the fields of chemical and biological catalysis. Our particular interest and approach has been to collect in the same volume papers dealing with both the chemical and biological aspects of the reactivity of heme systems because of the realization that a better understanding of the complementary discipline can be extremely useful for the researchers from either field. The current progress of the research on synthetic metalloporphyrin catalysts has led to the development of several systems that are able to reproduce the heme-enzyme mediated oxygenation and oxidation reactions, at least in terms of reaction types, mechanisms and often rates. These achievements have stimulated the of creating metalloporphyrin catalysts which are both ambitious project efficient and stable enough to become competitive for large-scale industrial processes. Although this project is still far from being realized, the efforts in this direction parallel those aimed at the application of heme enzymes to chemical technologies, e. g. for the mild, selective oxidation of organics or the detoxification of pollutants. Both the two approaches will be advantageous because while the enzyme systems can achieve selectivities which are probably unattainable by synthetic catalysts, the latter can be active under experimental conditions that would readily inactivate the enzymes.

C-H, C-O, C-C, and C-Heteroatom bond forming processes by using metal-ligand approaches for the synthesis of organic compounds of biological, pharmacological and organic nanotechnological utility are the key areas addressed in this book. Authored by a European team of leaders in the field, it brings together innovative approaches for a variety of catalysis reactions and processes frequently applied in organic synthesis into a handy reference work. It covers all major types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is paid to the improvements in efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation, and cross-coupling reactions, and to their utilization in industry. The result is a valuable resource for advanced researchers in both academia and industry, as well as graduate students in organic chemistry aiming for chemo-, regio- or stereoselective synthesis of organic compounds by using novel catalytic systems.

Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an international team of leading chemists representing both industry and academia. The book begins with a chapter on environmentally benign oxidants and then covers: Selective oxidations catalyzed by TS-1 and other metal-substituted zeolites Selective catalytic oxidation over ordered nanoporous metallo-aluminophosphates Selective oxidations catalyzed by mesoporous metal-silicates Liquid phase oxidation of organic compounds by supported metal-based catalysts Selective liquid phase oxidations in the presence of supported polyoxometalates Selective oxidations catalyzed by supported metal complexes Liquid phase oxidation of organic compounds by metal-organic frameworks Heterogeneous photocatalysis for selective oxidations with molecular oxygen All the chapters dedicated to specific types of catalysts follow a similar organization and structure, making it easy to compare the advantages and disadvantages of different catalysts. The final chapter examines the latest industrial applications, such as the production of catechol and hydroquinone, cyclohexanone oxime, and propylene oxide. With its unique focus on liquid phase heterogeneous oxidation catalysis, this book enables researchers in organic synthesis and oxidation catalysis to explore and develop promising new catalytic materials and synthetic routes for a broad range of industrial applications.

Oxidation reactions are an important chemical transformation in both academia and industry. Among the major advances in the field has been the development of catalytic processes, which are not only selective and efficient, but also allow the replacement of common stoichiometric oxidants with molecular oxygen, ideally from air at atmospheric pressure. This results in processes with higher atom efficiency, where water is the only side product in line with the principles of green chemistry. Focusing on the use of molecular oxygen as the terminal oxidant, this book covers recent advances in both heterogeneous and homogeneous systems, with and without metals and on the “taming” of the highly reactive oxygen gas by use of micro-flow reactors and membranes. A useful reference for industrial and academic chemists working on oxidation processes, as well as green chemists.