Aromatic C-nitroso Compounds

This book is designed to collect and review the research covering main directions in investigations of aromatic nitroso compounds in last decades, and to present both, the academic aspects of this chemistry, as well as the open field of its applicability. The book is divided in five chapters. The basic structural properties of the nitroso aromatic molecules are described in the first chapter. The second chapter is an overview of the methods of preparations of aromatic nitroso and polynitroso compounds, including classical synthetic methods and some new preparative approaches. The third part deals with the physico-chemical properties of nitroso aromates and azodioxides, its structure, crystallography, quantum chemical calculations, spectroscopy, typical reactions, and especially it is focused on the dimerizations in the solid-state. In the fourth chapter is represented organometallic chemistry of nitroso aromatic molecules and its applications in catalysis. The last part of the book deals with the behavior of this class of compounds in the biological systems, reactions with biomolecules and the use in toxicology. Aromatic C-nitroso Compounds Preface Contents Introduction Chapter 1: Molecular Structures 1.1 Calculated Molecular Structures 1.2 Experimental Geometries References Chapter 2: An Overview of Synthetic Methods for Preparation of Nitrosoaromatic Compounds 2.1 Reductive Methods 2.2 Oxidative Methods 2.3 Solid-State Syntheses 2.4 Enzyme Catalyzed Oxidations 2.5 Direct Nitrosation 2.6 Heteroaromatic Compounds 2.7 Nitrosoaromatic Compounds with More Nitroso Groups 2.8 Synthesis of Azoxides and Azodioxides References Chapter 3: Molecular Properties and Spectroscopy 3.1 Physical Organic Chemistry 3.1.1 Nature of the -NO Group 3.1.2 Nucleophilic Properties 3.1.3 Reactions with Nucleophiles 3.1.3.1 Oxygen as Nucleophile 3.1.3.2 Sulfur as Nucleophile 3.1.3.3 Carbon as Nucleophile 3.1.3.4 Nitrogen as Nucleophile 3.1.4 Superacid Medium 3.1.5 Nitroso Cycloadditions 3.1.5.1 Stepwise Cycloadditions 3.2 Dimerizations and Spectroscopy 3.2.1 NMR Spectroscopy 3.2.1.1 1H NMR 3.2.1.2 Multinuclear NMR 3.2.1.3 13C NMR 3.2.1.4 14N NQR 3.2.1.5 15N NMR Spectra 3.2.1.6 17O NMR 3.2.2 UV-VIS Spectroscopy 3.2.3 Photoelectron Spectroscopy 3.3 Monomer-Dimer Equilibrium 3.3.1 Dimerizations and Polymerizationsof Dinitroso Compounds 3.3.2 Vibrational Spectroscopy 3.3.3 Kinetics of Dimerization in Solid-State 3.3.4 Cross Dimerizations 3.3.5 Dimerizations of Heteroaromatic Derivatives 3.3.6 Calculations of the Reaction Path 3.4 Electrochemistry 3.4.1 Aromatic Nitroso Compounds as Spin Traps 3.5 Photochemistry 3.5.1 Photoreactions Including Nitrosoaromatic Intermediates References Chapter 4: Organometallic Compounds 4.1 Structures and Properties of Nitrosoaromatic-Metal Complexes 4.2 Nitrosoaromatic-Heme Complexes References Chapter 5: Biological Systems 5.1 Reactions with Fatty Acids and Steroids 5.2 Reactions with Thiol Consisting Biomolecules 5.3 Redox Reactions and Nitrosoaryl Compounds in Biological Systems References Index This volume will present the reader with an update on the scientific research on organic chemistry of nitroso compounds that was performed in the last two decades. The overview will include the original synthetic applications of nitroso compounds, but will also cover the discovery of novel physico-chemical phenomena and their potential future uses. The properties that form the basis for this technological potential originate from the intriguing property of C-nitroso molecules to form dimers through the formation of a relatively weak nitrogen-nitrogen double bond. The equilibrium between the different monomeric and dimeric forms, which appears under controlled environmental parameters, opened new areas of research in organic chemistry. The novel paradigm presented in this volume includes insight into the original problem of organic reactivity and synthesis, but also sheds light on the solid-state reaction mechanisms. A number of fascinating photochemical, electrochemical, supramolecular, and biological properties, as well as advanced techniques in spectroscopy, now enables us to use these compounds as molecular models for studying a number of general chemical concepts. ℗