Aromatic C-Nitroso Compounds

ISBN-13: 9789400763364 / Angielski / Twarda / 2013 / 156 str.

Vančik, Hrvoj

Opis

This book collects and reviews research covering aromatic nitroso compounds, presenting both academic aspects and the open field of its applicability. Covers basic structural properties, methods of preparation, reactions with biomolecules and more.

Spis treści

Introduction: Aliphatic and aromatic nitroso compounds

1. Molecular structures
1.1  Calculated molecular structures
1.2 Experimental geometries

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

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 ¹HNMR
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 polymerizations of dinitroso compounds
3.3.2 Vibrational spectroscopy
3.3.3 Kinetics of dimerisation 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

4. Organometallic compounds
4.1 Structures and properties of nitrosoaromatic-metal complexes
4.2 Nitrosoaromatic-heme complexes

5. Bilological systems
5.1 Reactions with fatty acids and steroides
5.2 Reactions with thiol consisting biomolecules
5.3 Redox reactions and nitrosoaryl compounds in biological systems

References

SUBJECT INDEX

Blurb

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.