Nitrenes and Nitrenium Ions


Book Description

Featuring contributions respected leaders in the field, Nitrene and Nitrenium Ions is the first comprehensive book to explore the role of reactive intermediate nitrene and nitrenium ions in chemistry and biochemistry. Covering a broad range of topics, including ultrafast studies, computational studies, behavior in aqueous solution, electronic structures, and reactions with aromatic compounds, this valuable resource will empower graduate students and researchers to better understand and expand their synthetic utility.




Reactive Intermediate Chemistry


Book Description

Reactive Intermediate Chemistry presents a detailed and timely examination of key intermediates central to the mechanisms of numerous organic chemical transformations. Spectroscopy, kinetics, and computational studies are integrated in chapters dealing with the chemistry of carbocations, carbanions, radicals, radical ions, carbenes, nitrenes, arynes, nitrenium ions, diradicals, etc. Nanosecond, picosecond, and femtosecond kinetic realms are explored, and applications of current dynamics and electronic structure calculations are examined. Reactive Intermediate Chemistry provides a deeper understanding of contemporary physical organic chemistry, and will assist chemists in the design of new reactions for the efficient synthesis of pharmaceuticals, fine chemicals, and agricultural products. Among its features, this authoritative volume is: Edited and authored by world-renowned leaders in physical organic chemistry. Ideal for use as a primary or supplemental graduate textbook for courses in mechanistic organic chemistry or physical chemistry. Enhanced by supplemental reading lists and summary overviews in each chapter.




Reviews of Reactive Intermediate Chemistry


Book Description

The chemistry of reactive intermediates is central to a modern mechanistic and quantitative understanding of organic chemistry. Moreover, it underlies a significant portion of modern synthetic chemistry and is integral to a molecular view of biological chemistry. Reviews in Reactive Intermediate Chemistry presents an up-to-date, authoritative guide to this fundamental topic. Although it follows Reactive Intermediate Chemistry by the same authors, it serves as a free-standing resource for the entire chemical and biochemical community. The book includes: Relevant, practical applications Coverage of such topics as mass spectrometry methods, reactive intermediates in interstellar medium, quantum mechanical tunnelling, solvent effects, reactive intermediates in biochemical processes, and excited state surfaces Discussions of emerging areas, particularly those involving dynamics and theories Concluding sections identifying key directions for future research are provided at the end of each chapter




Azides and Nitrenes


Book Description

Azides and Nitrenes: Reactivity and Utility provides information pertinent to the fundamentals aspects of the chemistry of azides and nitrenes. This book discusses the mechanism and synthetic applications of alkyl azides. Organized into 10 chapters, this book begins with an overview of the properties and chemistry of alkyl azides and alkylnitrenes. This text then examines the various pathways to the preparation of vinyl azides. Other chapters consider the magnetic resonance spectrum of phenyl azide, which may be taken as a representative to which more complex examples can be related. This book discusses as well the acyl azides and acylnitrenes that have their nitrogen function attached to electron-withdrawing groups not possessing a heteroatom bearing an unshared electron pair next to the nitrogen function. The final chapter deals with the main uses for organic azides involved in photochemical cross-linking of polymeric systems. This book is a valuable resource for chemists, spectroscopists, and theoreticians.




Organic reactive intermediates


Book Description

Organic Chemistry: A Series of Monographs, Volume 26: Organic Reactive Intermediates focuses on the study of reactive intermediates. This book discusses the methods of formation and investigation, factors affecting the stability, and reactions of the intermediate. Other topics include the formation and reaction of free radicals; kinetic aspects of free-radical chain reactions; electronic states and structures of carbenes; and formation of transient carbenes and carbenoids in solution. The intermediacy of nitrenes in reactions; electronic structure and spectra; methods of investigating carbonium ions; and reactions of carbonium ions are also elaborated. This publication likewise covers the preparation of carbanions; factors affecting the stability of carbanions; reactions involving radical ions; and methods of investigating arynes. This volume serves as a textbook for the first graduate-level course, as well as a reference for industrial chemists interested in organic reaction mechanisms.




Orbital Interaction Theory of Organic Chemistry


Book Description

A practical introduction to orbital interaction theory and its applications in modern organic chemistry Orbital interaction theory is a conceptual construct that lies at the very heart of modern organic chemistry. Comprising a comprehensive set of principles for explaining chemical reactivity, orbital interaction theory originates in a rigorous theory of electronic structure that also provides the basis for the powerful computational models and techniques with which chemists seek to describe and exploit the structures and thermodynamic and kinetic stabilities of molecules. Orbital Interaction Theory of Organic Chemistry, Second Edition introduces students to the fascinating world of organic chemistry at the mechanistic level with a thoroughly self-contained, well-integrated exposition of orbital interaction theory and its applications in modern organic chemistry. Professor Rauk reviews the concepts of symmetry and orbital theory, and explains reactivity in common functional groups and reactive intermediates in terms of orbital interaction theory. Aided by numerous examples and worked problems, he guides readers through basic chemistry concepts, such as acid and base strength, nucleophilicity, electrophilicity, and thermal stability (in terms of orbital interactions), and describes various computational models for describing those interactions. Updated and expanded, this latest edition of Orbital Interaction Theory of Organic Chemistry includes a completely new chapter on organometallics, increased coverage of density functional theory, many new application examples, and worked problems. The text is complemented by an interactive computer program that displays orbitals graphically and is available through a link to a Web site. Orbital Interaction Theory of Organic Chemistry, Second Edition is an excellent text for advanced-level undergraduate and graduate students in organic chemistry. It is also a valuable working resource for professional chemists seeking guidance on interpreting the quantitative data produced by modern computational chemists.




Radical and Radical Ion Reactivity in Nucleic Acid Chemistry


Book Description

Comprehensive coverage of radical reactive intermediates in nucleic acid chemistry and biochemistry The Wiley Series on Reactive Intermediates in Chemistry and Biology investigates reactive intermediates from the broadest possible range of disciplines. The contributions in each volume offer readers fresh insights into the latest findings, emerging applications, and ongoing research in the field from a diverse perspective. The chemistry and biochemistry of reactive intermediates is central to organic chemistry and biochemistry, and underlies a significant portion of modern synthetic chemistry. Radical and Radical Ion Reactivity in Nucleic Acid Chemistry provides the only comprehensive review of the chemistry and biochemistry of nucleic acid radical intermediates. With contributions by world leaders in the field, the text covers a broad range of topics, including: A discussion of the relevant theory Ionization of DNA Nucleic acid sugar radicals Halopyrimidines Oxidative, reductive, and low energy electron transfer Electron affinity sensitizers Photochemical generative of reactive oxygen species Reactive nitrogen species Enediyne rearrangements Phenoxyl radicals A unique compilation on the cutting edge of our understanding, Radical and Radical Ion Reactivity in Nucleic Acid Chemistry provides an unparalleled resource to student and professional researchers in such fields as organic chemistry, biochemistry, molecular biology, and physical chemistry, as well as the industries associated with these disciplines.




Carbon-Centered Free Radicals and Radical Cations


Book Description

Covers the most advanced computational and experimental methods for studying carbon-centered radical intermediates With its focus on the chemistry of carbon-centered radicals and radical cations, this book helps readers fully exploit the synthetic utility of these intermediates in order to prepare fine chemicals and pharmaceutical products. Moreover, it helps readers better understand their role in complex atmospheric reactions and biological systems. Thoroughly up to date, the book highlights the most advanced computational and experimental methods available for studying and using these critically important intermediates. Carbon-Centered Free Radicals and Radical Cations begins with a short history of the field of free radical chemistry, and then covers: A discussion of the relevant theory Mechanistic chemistry, with an emphasis on synthetic utility Molecular structure and mechanism, focusing on computational methods Spectroscopic investigations of radical structure and kinetics, including demonstrations of spin chemistry techniques such as CIDNP and magnetic field effects Free radical chemistry in macromolecules Each chapter, written by one or more leading experts, explains difficult concepts clearly and concisely, with references to facilitate further investigation of individual topics. The authors were selected in order to provide insight into a broad range of topics, including small molecule synthesis, polymer degradation, computational chemistry as well as highly detailed experimental work in the solid, liquid, and gaseous states. This volume is essential for students or researchers interested in building their understanding of the role of carbon-centered radical intermediates in complex systems and how they may be used to develop a broad range of useful products.




Handbook of Free Radical Initiators


Book Description

Free radical initiators–chemical molecules which easily decompose into free radicals–serve as reactive intermediates in synthetic methodologies such as organic and polymer synthesis as well as in technological processes, oligomerization, network formation, and kinetic research. The Handbook of Free Radical Initiators presents an up-to-date account of the physicochemical data on radical initiators and reactions of radical generation. Individual chapters include: Dialkyl Peroxides and Hydroperoxides Diacyl Peroxides, Peresters, and Organic Polyoxides Azo-Compounds Bimolecular Reactions of Free Radical Generation by Ozone, Dioxygen, Hydroperoxides, and Haloid Molecules Free Radical Abstraction Reactions Free Radical Addition Reactions Free Radical Recombination and Disproportoination Reactions Professionals and academic researchers in chemical engineering, pharmaceuticals, biotechnology, plastics, and rubbers will find the Handbook of Free Radical Initiators to be a distinguished, vital resource.




Writing Reaction Mechanisms in Organic Chemistry


Book Description

Presentation is clear and instructive: students will learn to recognize that many of the reactions in organic chemistry are closely related and not independent facts needing unrelated memorization. The book emphasizes that derivation of a mechanism is not a theoretical procedure, but a means of applying knowledge of other similar reactions and reaction conditions to the new reaction. - Brief summaries of required basic knowledge of organic structure, bonding, stereochemistry, resonance, tautomerism, and molecular orbital theory - Definitions of essential terms - Typing and classification of reactions - Hints (rules) for deriving the most likely mechanism for any reaction