1. The Problem of Tautomerism.- 1. Tautomerism as Dynamic Isomerism.- 2. Degenerate Tautomerism.- 3. Methods for Investigating Tautomeric Systems.- 4. Butlerov's and Laar's Tautomeric Systems.- 5. Tautomerism and the Mechanisms of Organic Reactions.- 6. Classification of Tautomeric Reactions.- 7. Conclusion.- References.- 2. Carbonotropy.- 1. The Problem of Carbonotropy.- 2. Sigmatropic Acyl and Aryl Rearrangements.- 3. Acylotropic Tautomerism.- 4. Tautomeric Rearrangements of Aryl Groups.- 5. Carbonotropic Tautomerism in Ions, Radicals and Cyclopolyenes.- References.- 3. General Principles of the Design of Tautomeric Systems.- 1. Possibilities of Quantum Mechanical Prediction of Tautomeric Reactions.- 2. Stereochemical Approach to the Design of Tautomeric Compounds.- References.- 4. The Mechanisms of Nucleophilic Substitution at the Main Group Element and Design of Intramolecular Tautomeric Systems.- 1. Tautomeric Rearrangements of Carbon-containing Groups.- 2. Silylotropic Tautomerism.- 3. Tautomeric Migrations of Phosphorus-containing Groups.- 4. Tautomeric Rearrangements of As-containing Groups.- 5. Tautomeric Rearrangements of Sulfur-containing Groups.- References.- 5. Dyotropic and Polytropic Tautomeric Systems.- 1. Scope and Definition.- 2. The Mechanism and Energetics of the Dyotropic Reactions.- References.- 6. Dissociative and Photochemical Mechanisms of Intramolecular Tautomerism.- 1. Heterolytic Dissociative Mechanism.- 2. Homolytic Dissociative Mechanism.- 3. Ion-Radical Mechanism.- 4. Photo-Initiated Carbonotropic Rearrangements.- References.
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Zustand: New. 1. The Problem of Tautomerism.- 1. Tautomerism as Dynamic Isomerism.- 1.1. Molecular Structure and Isomerism.- 1.2. Bond Rupture Formation Criterion.- 1.3. Tautomerism and Rearrangements.- 1.4. Thermodynamic and Activational Scale of Tautomeric Processes.- . Artikel-Nr. 5833744
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Taschenbuch. Zustand: Neu. Molecular Design of Tautomeric Compounds | V. I. Minkin (u. a.) | Taschenbuch | Understanding Chemical Reactivity | 312 S. | Englisch | 2011 | Springer | EAN 9789401071406 | Verantwortliche Person für die EU: Springer Verlag GmbH, Tiergartenstr. 17, 69121 Heidelberg, juergen[dot]hartmann[at]springer[dot]com | Anbieter: preigu. Artikel-Nr. 105624965
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Taschenbuch. Zustand: Neu. Neuware - Until the early seventies, tautomeric i. e. fast and reversible rearrangement reactions accompanied by migrations of carbon-centered groups - were practi cally unknown. For a long time it was assumed that the family of tautomeric reactions was confined to proto tropic transformations only. However, the discovery in the fifties of the reversible metallotropic rearrangements showed the domain of migratory tautomerism to be substantially broader. The synthesis of the metallotropic compounds was based on the substitution of a proton in prototropic compounds by an organometallic group. This approach rarely proved fruitful when attempting to effect tautomeric rearrangements of organic and organometallic groups formed by the elements to the right of carbon in the Periodic Table. By contrast, a novel approach involving an analysis of the steric requirements inherent in the structure of the transition state of a reactive center and an examination of the stereodynamic possibilities has given rise to a target-oriented molecular design of compounds capable of rapid and reversible intramolecular migration of the type indicated. The implementation of this ap proach, which is the subject of the present book, has already led to the preparation of new tautomeric compounds in which such heavy organic migrants as acyl, aryl, sulfinyl, phosphoryl, arsinyl, and other groups migrate in molecules at a frequency 6 9 of 10 -10 S-I at ambient temperature, i. e. , at the rates comparable with protonic migrations. Artikel-Nr. 9789401071406
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Taschenbuch. Zustand: Neu. Neuware -1. The Problem of Tautomerism.- 1. Tautomerism as Dynamic Isomerism.- 2. Degenerate Tautomerism.- 3. Methods for Investigating Tautomeric Systems.- 4. Butlerov's and Laar's Tautomeric Systems.- 5. Tautomerism and the Mechanisms of Organic Reactions.- 6. Classification of Tautomeric Reactions.- 7. Conclusion.- References.- 2. Carbonotropy.- 1. The Problem of Carbonotropy.- 2. Sigmatropic Acyl and Aryl Rearrangements.- 3. Acylotropic Tautomerism.- 4. Tautomeric Rearrangements of Aryl Groups.- 5. Carbonotropic Tautomerism in Ions, Radicals and Cyclopolyenes.- References.- 3. General Principles of the Design of Tautomeric Systems.- 1. Possibilities of Quantum Mechanical Prediction of Tautomeric Reactions.- 2. Stereochemical Approach to the Design of Tautomeric Compounds.- References.- 4. The Mechanisms of Nucleophilic Substitution at the Main Group Element and Design of Intramolecular Tautomeric Systems.- 1. Tautomeric Rearrangements of Carbon-containing Groups.- 2. Silylotropic Tautomerism.- 3. Tautomeric Migrations of Phosphorus-containing Groups.- 4. Tautomeric Rearrangements of As-containing Groups.- 5. Tautomeric Rearrangements of Sulfur-containing Groups.- References.- 5. Dyotropic and Polytropic Tautomeric Systems.- 1. Scope and Definition.- 2. The Mechanism and Energetics of the Dyotropic Reactions.- References.- 6. Dissociative and Photochemical Mechanisms of Intramolecular Tautomerism.- 1. Heterolytic Dissociative Mechanism.- 2. Homolytic Dissociative Mechanism.- 3. Ion-Radical Mechanism.- 4. Photo-Initiated Carbonotropic Rearrangements.- References. 296 pp. Englisch. Artikel-Nr. 9789401071406
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