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Organic Chemistry, Volume 4: Fundamentals of Carbanion Chemistry provides information pertinent to carbanion chemistry. This book explores several topics, including carbonium ions, carbanions, carbenes, and carbon radicals. Comprised of six chapters, this volume starts with an overview of the variation of the kinetic and thermodynamic acidities of carbon acids with substituents and environments. This text then explores the methods of carbanion stabilization by substituents and discusses the various types of stabilization. Other chapters explain the stereochemistry of hydrogen–deuterium exchange and examine the stereochemistry of substitution reactions of organometallic compounds. This book discusses as well the structure and immediate environment of reaction intermediates through the use of stereochemical techniques. The final chapter considers the unsaturated anionic rearrangements of carbanions, carbonium ions, as well as carbon radicals and other rearrangements. Chemists, organic chemists, researchers, and graduate students interested in the field of carbanion chemistry will find this book extremely useful.
This book was prepared with the idea of collecting some of the multitudinous new literature on carbanions and pre- senting it along with the fundamentals of carbanion chemi- stry. Some 400 papers from the period 1976 to 1982 have been assimilated into the book along with about an equal number of references (many to reviews) from the earlier literature. The material is organized under the headings Structures (with emphasis on the results of X-ray studies since they unambiguously show the molecular geometry), Preparations, and Reactions. Reactions, the largest topic, is divided into reactions with electrophiles, eliminations, oxidations, and rearrangements. Under these headings, carbanions without resonance stabilization (0' carbanions) are generally discus- sed first, and are further subdivided into Sp3 (alkyl) followed by Sp2 (vinyl and aryl) followed by sp (acetylenic); resonance- stabilized (n) hydrocarbon anions such as allyl and benzyl follow; lastly, heteroatom-containing n carbanions such as enolates are considered. Some references to carbanion equivalents are included at the end. Tucson, Arizona U.S.A. Robert B. Bates May 1983 Craig A. Ogle Table of Contents I. Introduction 1 II. Structures . 3 1. Non-delocalized (0") 3 a. Sp3 ..... . 3 b. Sp2 and sp . . . 7 2. Delocalized (n) . . 8 a. Hydrocarbon Anions 8 b. Heteroatom-containing Carbanions 10 III. Preparations. . . . . 13 13 1. From Alkyl Halides 13 a. With Metals . . 15 b. With Organometallics . 17 2. From Alkanes by Proton Abstraction 17 a. Acidities of CH Protons. . 21 b. Base-solvent Systems . . . 25 3. From Unsaturated Compounds 25 a. By Reduction . . . . . .
First/second year text in chemistry.
An up-to-date, comprehensive guide to LITHIUM CHEMISTRY Although lithium has been the subject of numerous individualstudies, this intriguing element has rarely been examined from thebroad perspective many researchers require. Lithium Chemistry: ATheoretical and Experimental Overview fills this void by providingthe most thorough and up-to-date overview available of currenttheories and experimental data. Supported by nearly two hundred illustrations, this book draws uponthe expertise of prominent researchers in the field, and treats thefull range of modern applications and techniques. The result is aunique and invaluable guide to lithium studies for researchers andgraduate students working in the fields of organic, inorganic, andorgano-metallic chemistry. Lithium Chemistry: A Theoretical and Experimental Overview assumesa background in quantum chemistry and experimental physicalchemistry at the graduate level and includes coverage of thesemajor topics: * Bonding, structures, and energies in organolithium compounds * Theoretical studies of aggregates of lithium compounds * Comparison of lithium and hydrogen bonds * Lithium atom matrix reactions with small molecules * NMR of organolithium compounds * Aspects of the thermochemistry of lithium compounds * The structure of lithiated amines and lithiated ethers--fromcarbanions to carbenoids * Complexes of inorganic lithium salts * Structures of lithium salts of heteroatom compounds * Synthetic ionophores for lithium ions
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Survey of Progress in Chemistry, Volume 4 considers the principles common to all chemistry that undergo major developments and modifications, including aqueous solutions, carbanions, stable isotopes, nitrogen fixation, ionizing radiation, and organic compound luminescence. This volume is organized into six chapters. The first chapter surveys first the theories of water and aqueous solutions structure, followed by the evaluation of temperature, pressure, and electrolytes on water. This chapter emphasizes the role of water structure in biological systems. The second chapter covers the generation, capture, mechanism of stabilization, and isomerization of carbanions, while the separation and practical applications of isotopes are examined in the third chapter. The following chapter describes the mechanism of nitrogen fixation by those cells capable of fixing nitrogen. The concluding chapters explore some aspects of the energy transfer process and the formation of intermediate molecular species. These chapters also evaluate the luminescence of organic systems. This book is of value to college chemistry teachers and students.
This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds. It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as "green" chemistry, where utilization and disposal of chemical waste or by-products in an environmentally safe way is as important as achieving the desired end products by all chemists nowadays. The treatment progresses from elementary to advanced material in straightforward fashion. The more advanced topics are not developed in an overly rigorous way so that upper-level undergraduates, graduates, and newcomers to the field can grasp the concepts easily.
This volume contains fundamental knowledge regarding the structure and mechanisms of organic sulfur chemistry. Topics include sulfur bondings, effects of sulfur groups, stereochemistry around sulfur, substitution, ligand coupling within s-sulfurane, oxidation, reduction and rearrangement. References in this work total over 2,300. Anyone with an interest in organic sulfur chemistry will find this book to be fascinating reading.