Crown Ethers and Cryptands introduces the broad and basic principles of crown ether and cryptand chemistry at the advanced undergraduate, graduate and working professional level. The book provides a brief introduction, outlining the history of the field and goes on to cover syntheses, complexation of cations and molecules, complex structures, applications and recent developments. It aims to acquaint readers with the scope and principles of the field, providing a bibliography of reviews and books as reference to further reading and citations of the original literature.
This book introduces the broad and basic principles of crown ether and cryptand chemistry at the advanced undergraduate, graduate and working professional level.
Crown Ethers and Cryptands introduces the broad and basic principles of crown ether and cryptand chemistry at the advanced undergraduate, graduate and working professional level. The book provides a brief introduction, outlining the history of the field and goes on to cover syntheses, complexation of cations and molecules, complex structures, applications and recent developments. It aims to acquaint readers with the scope and principles of the field, providing a bibliography of reviews and books as reference to further reading and citations of the original literature.
The synthesis of macrocycles is an art in itself. Template-controlled synthesis provides elegant access to fascinating macrocyclic structures. Polyazamacrocycles, crown ethers, cryptands, rotaxanes, knots -- the range of macrocyclic compounds is as broad as their potential application as molecular switches, in ion exchange, electron transfer or catalysis. This book provides authoritative information on all aspects of template-controlled macrocyclizations. It covers in depth the current state of research on template processes - novel synthetic techniques and mechanistic approaches. The critical discussion of the diverse synthetic routes includes the detailed characterization of the broad variety of macrocyclic products. References to applications of macrocyclic compounds and over 1,500 citations make this handbook an indispensable tool for chemists in academia and industry. Researchers in organic and supramolecular chemistry, biotechnology, and inorganic chemistry will find inspiration for the design, synthesis, and myriad uses of new synthetic macrocycles.
The scientific and practical interest in coronands (crown ethers), cryptands, podands as complexing agents for cations as well as for anions and neutral low molecular species is undeniable 1,2). The chemistry of crown compounds is steadily increasing. About 250 original papers dealing with crown chemistry appeared only in 1980. New molecules· with crown ether properties are constantly synthesized and new applications discov,?red. Owing to lack of space, only a small number of the original publications is men tioned here. Thus, in the literature compilation only some, but relevant works are selected for each chapter. Whenever possible, reference is made to reviews or review-like articles alone by means of which origin,al works can be consulted. The reviews given under ref. 1) are considered to be the most relevant. The formulae presented in the figures should be understood as representative structures outlining a specific field. 2 Classification of Oligo-/Multidentate Neutral Ligands and of their Complexes Today, a distinction is made between the classical ring oligoethers (crown ethers) and monocyclic coronands, oligocyclic spherical cryptands and the acyclic podands with respect to topological aspects 3). This classification and the topology are illustrated in Fig. 1, each figure representing the minimum number of donor atoms and chain segments characteristic of each class of compounds. Multidentate mono cyclic ligands with any type of donor atoms are called coronands ("crown compounds"), while the term crown ether should be reserved for cyclic oligoethers exclusively containing oxygen as donor atom.
Cryptands were introduced by Jean-Marie Lehn in 1969 as cage-shaped selective ligands for alkali and alkaline-earth metal ions, which lie at the heart of supramolecular chemistry. This book reports on much of the research in the field since the '70s, and looks at, amongst other topics, metal coordination chemistry, anion coordination chemistry, the encapsulation and taming of reactive anions, the formation of cascade complexes and the design of fluorescent sensors for ionic analytes.Cryptands and Cryptates has been written as a coursebook, structured as a series of lectures for graduate students or advanced researchers in chemistry, materials science, chemical biology and nanotechnology. It is fully illustrated to show experiments and results, and is intended to stimulate further interest in this fertile field of supramolecular chemistry.Chapters are preceded by a Foreword by Jean-Marie Lehn.
Provides deep insight into the concepts and recent developments in the area of supramolecular chemistry in water Written by experts in their respective field, this comprehensive reference covers various aspects of supramolecular chemistry in water?from fundamental aspects to applications. It provides readers with a basic introduction to the current understanding of the properties of water and how they influence molecular recognition, and examines the different receptor types available in water and the types of substrates that can be bound. It also looks at areas to where they can be applied, such as materials, optical sensing, medicinal imaging, and catalysis. Supramolecular Chemistry in Water offers five major sections that address important topics like water properties, molecular recognition, association and aggregation phenomena, optical detection and imaging, and supramolecular catalysis. It covers chemistry and physical chemistry of water; water-mediated molecular recognition; peptide and protein receptors; nucleotide receptors; carbohydrate receptors; and ion receptors. The book also teaches readers all about coordination compounds; self-assembled polymers and gels; foldamers; vesicles and micelles; and surface-modified nanoparticles. In addition, it provides in-depth information on indicators and optical probes, as well as probes for medical imaging. -Covers, in a timely manner, an emerging area in chemistry that is growing more important every day -Addresses topics such as molecular recognition, aggregation, catalysis, and more -Offers comprehensive coverage of everything from fundamental aspects of supramolecular chemistry in water to its applications -Edited by one of the leading international scientists in the field Supramolecular Chemistry in Water is a one-stop-resource for all polymer chemists, catalytic chemists, biochemists, water chemists, and physical chemists involved in this growing area of research.
An advanced-level textbook of organic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of the four-volume series, entitled “A Textbook of Organic Chemistry – Volume I, II, III, IV”. CONTENTS: CHAPTER 1. Nature of Bonding in Organic molecules: Delocalized Chemical Bonding; Conjugation; Cross Conjugation; Resonance; Hyperconjugation; Tautomerism; Aromaticity in Benzenoid and Nonbenzenoid Compounds; Alternant and Non-Alternant Hydrocarbons; Huckel’s Rule: Energy Level of p-Molecular Orbitals; Annulenes; Antiaromaticity; Homo-Aromaticity; PMO Approach; Bonds Weaker than Covalent; Addition Compounds: Crown Ether Complexes and Cryptands, Inclusion Compounds, Cyclodextrins; Catenanes and Rotaxanes CHAPTER 2. Stereochemistry: Chirality; Elements of symmetry; Molecules with more than one chiral centre: diastereomerism; Determination of relative and absolute configuration (octant rule excluded) with special reference to lactic acid, alanine & mandelic acid; Methods of resolution; Optical purity; Prochirality; Enantiotopic and diastereotopic atoms, groups and faces; Asymmetric synthesis: cram’s rule and its modifications, prelog’s rule; Conformational analysis of cycloalkanes (upto six membered rings); Decalins; Conformations of sugars; Optical activity in absence of chiral carbon (biphenyls, allenes and spiranes); Chirality due to helical shape; Geometrical isomerism in alkenes and oximes; Methods of determining the configuration CHAPTER 3. Reaction Mechanism: Structure and Reactivity: Types of mechanisms; Types of reactions; Thermodynamic and kinetic requirements; Kinetic and thermodynamic control; Hammond’s postulate; Curtin-Hammett principle; Potential energy diagrams: Transition states and intermediates; Methods of determining mechanisms; Isotope effects; Hard and soft acids and bases; Generation, structure, stability and reactivity of carbocations, carbanions, free radicals, carbenes and nitrenes; Effect of structure on reactivity; The Hammett equation and linear free energy relationship; Substituent and reaction constants; Taft equation CHAPTER 4. Carbohydrates: Types of naturally occurring sugars; Deoxy sugars; Amino sugars; Branch chain sugars; General methods of determination of structure and ring size of sugars with particular reference to maltose, lactose, sucrose, starch and cellulose. CHAPTER 5. Natural and Synthetic Dyes: Various classes of synthetic dyes including heterocyclic dyes; Interaction between dyes and fibers; Structure elucidation of indigo and Alizarin CHAPTER 6. Aliphatic Nucleophilic Substtitution: The SN2, SN1, mixed SN1 and SN2, SNi , SN1’, SN2’, SNi’ and SET mechanisms; The neighbouring group mechanisms; neighbouring group participation by p and s bonds; anchimeric assistance; Classical and nonclassical carbocations; Phenonium ions; Common carbocation rearrangements; Applications of NMR spectroscopy in the detection of carbocations; Reactivity- effects of substrate structure, attacking nucleophile, leaving group and reaction medium; Ambident nucleophiles and regioselectivity; Phase transfer catalysis. CHAPTER 7. Aliphatic Electrophilic Substitution: Bimolecular mechanisms – SE2 and SEi; The SE1 mechanism; Electrophilic substitution accompained by double bond shifts; Effect of substrates, leaving group and the solvent polarity on the reactivity CHAPTER 8. Aromatic Electrophilic Substitution: The arenium ion: mechanism, orientation and reactivity, energy profile diagrams; The ortho/para ratio, ipso attack, orientation in other ring systems; Quantitative treatment of reactivity in substrates and electrophiles; Diazonium coupling; Vilsmeir reaction; Gattermann-Koch reaction CHAPTER 9. Aromatic Nucleophilic Substitution: The ArSN1, ArSN2, Benzyne and SRN1 mechanisms; Reactivity – effect of substrate structure, leaving group and attacking nucleophile; The von Richter, Sommelet-Hauser, and Smiles rearrangements CHAPTER 10. Elimination Reactions: The E2, E1 and E1cB mechanisms; Orientation of the double bond; Reactivity –effects of substrate structures, attacking base, the leaving group and the medium; Mechanism and orientation in pyrolytic elimination CHAPTER 11. Addition to Carbon-Carbon Multiple Bonds: Mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals; Regio–and chemoselectivity: orientation and reactivity; Addition to cyclopropane ring; Hydrogenation of double and triple bonds; Hydrogenation of aromatic rings; Hydroboration; Michael reaction; Sharpless asymmetric epoxidation. CHAPTER 12. Addition to Carbon-Hetero Multiple Bonds: Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles; Addition of Grignard reagents, organozinc and organolithium; Reagents to carbonyl and unsaturated carbonyl compounds; Wittig reaction; Mechanism of condensation reactions involving enolates – Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions; Hydrolysis of esters and amides; Ammonolysis of esters.
In many fields, most notably medicine and molecular biology, the understanding of the structure and function of carbohydrates and glycoconjugates remains vital. This new volume contains critical reviews covering the latest findings in both chemical and biological sciences, and demonstrates the interdisciplinary nature of modern carbohydrate research. This book addresses diverse applications that continue to be major challenges for carbohydrate chemists. The book starts with a review of Gérard Descotes contribution to the field as a pioneer of French modern carbohydrate chemistry. Green nanocatalytic oxidation of free sugars, photosensitive glycomacrocycles, the application of disaccharides in supramolecular chemistry, recent advances in the radiation chemistry of polysaccharides, and the cell wall pectic rhamnogalacturonan II, an enigma in plant glycobiology are just some of the diverse topics presented in Volume 45. This set of reports will certainly benefit any researcher who wishes to learn about the latest developments in the carbohydrate field.
Supramolecular chemistry is ‘chemistry beyond the molecule’ - the chemistry of molecular assemblies and intermolecular bonds. It is one of today’s fastest growing disciplines, crossing a range of subjects from biological chemistry to materials science; and from synthesis to spectroscopy. Supramolecular Chemistry is an up-to-date, integrated textbook that tells the newcomer to the field everything they need to know to get started. Assuming little in the way of prior knowledge, the book covers the concepts behind the subject, its breadth, applications and the latest contemporary thinking in the area. It also includes coverage of the more important experimental and instrumental techniques needed by supramolecular chemists. The book has been thoroughly updated for this second edition. In addition to the strengths of the very popular first edition, this comprehensive new version expands coverage into a broad range of emerging areas. Clear explanations of both fundamental and nascent concepts are supplemented by up-to-date coverage of exciting emerging trends in the literature. Numerous examples and problems are included throughout the book. A system of “key references” allows rapid access to the secondary literature, and of course comprehensive primary literature citations are provided. A selection of the topics covered is listed below. Cation, anion, ion-pair and molecular host-guest chemistry Crystal engineering Topological entanglement Clathrates Self-assembly Molecular devices Dendrimers Supramolecular polymers Microfabrication Nanoparticles Chemical emergence Metal-organic frameworks Gels Ionic liquids Supramolecular catalysis Molecular electronics Polymorphism Gas sorption Anion-pinteractions Nanochemistry Supramolecular Chemistry is a must for both students new to the field and for experienced researchers wanting to explore the origins and wider context of their work. Review: "At just under 1000 pages, the second edition of Steed and Atwood's Supramolecular Chemistry is the most comprehensive overview of the area available in textbook form...highly recommended." —Chemistry World, August 2009
