A. I. Shatenshtein

Isotopic Exchange and the Replacement of Hydrogen in Organic Compounds

• Broschiertes Buch

Produktbeschreibung

Hydrogen replacement reactions play an outstanding part in organic chemistry. They include such industrially important processes as halogenation, nitration, sulfona tion, alkylation, and direct amination and metallation of organic substances. It is no accident that the data obtained in the investigation of these reactions have been used extensivel y in the solution of a series of fundamental problems in theoretical organ ic chemistry and this tendency still exists. Isotopic exchanges of hydrogen also belong to this group of chemical conversions. They have attracted considerable attention as they are the simplest and, to some ex tent, models of hydrogen replacement reactions, which are convenient for elucidating the mechanism of hydrogen replacement and the effects of interaction between atoms in organic molecules. The mechanisms of hydrogen replacement reactions are examined in this mono graph and the most space is allocated to hydrogen isotope exchanges. The mechan isms of all the given reactions are interpreted from the point of view of the acid base properties of the reagents. In this connection, a large section of the book is de voted to a thorough substantiation of the thesis that hydrocarbons participating in the given reactions act as acids or bases. Problems of acid-base catalysis and the mech anism of acid -base interaction are also discussed. Thus, a considerable part of the book is concerned with problems of the theory of acids and bases.

Produktdetails

• Verlag: Springer / Springer US / Springer, Berlin
• Artikelnr. des Verlages: 978-1-4684-1538-4
• Softcover reprint of the original 1st ed. 1962
• Seitenzahl: 328
• Erscheinungstermin: 30. März 2012
• Englisch
• Abmessung: 254mm x 178mm x 18mm
• Gewicht: 619g
• ISBN-13: 9781468415384
• ISBN-10: 1468415387
• Artikelnr.: 39500199

Inhaltsangabe

Section I. Types of Reagents and Reactions.- 1. Oxidizing and Reducing Agents.- 2. Acids and Bases.- 3. Acidlike Substances.- 4. Nucleophilic and Electrophilic Reagents.- 5. Wider Definitions of Acids and Bases.- 6. Relative and Approximate Nature of the Classification of Reagents.- 7. Donor-acceptor Interaction.- 8. Heterolytic and Homolytic Reactions.- 9. Place of Hydrogen Exchange Among Other Reactions.- 10. Summary.- Literature Cited.- Section II. Acid-Base Catalysis of Hydrogen Exchange.- 1. Introduction.- 2. Comparison of the Rates of Hydrogen Exchange with Amphoteric and Protophilic Solvents.- 3. Comparison of the Rates of Hydrogen Exchange with Amphoteric and Protogenic Solvents.- 4. Effect of the Dielectric Constant of the Solvent and the Polarity of Its Molecules on the Hydrogen Exchange Rate.- 5. Effect of the Substrate and Catalyst Charge on the Hydrogen Exchange Rate.- 6. Effect of Dual Reactivity of a Substance on Hydrogen Exchange.- 7. Effect of Steric Hindrance on Hydrogen Exchange.- 8. Decrease in the Activity of a Catalyst on Its Reaction with the Substrate.- 9. Activation of a Catalyst by a Change of Solvent.- 10. Catalytic Activity of Complexes of Hydrogen Acids with Acidlike Substances in Hydrogen Exchange.- 11. Brønsted's Relation in Hydrogen Exchange.- 12. Hammett's Relation in Hydrogen Exchange.- 13. Salt Effect in Hydrogen Exchange.- 14. Acid-Base Catalysis of Hydrogen Exchange in H-H, B-H, N-H, As-H, P-H, O-H, and S- H Bonds.- 15. Heterogeneous Acid-Base Hydrogen Exchange.- 16. Summary.- Literature Cited.- Section III. Hydrocarbons as Acids and Bases.- Literature Cited.- 1, Hydrocarbons as Acids.- Literature Cited.- 2. Hydrocarbons as Bases.- Literature Cited.- Conclusion.- Section IV. Mechanism of Acid-Base Interaction.- 1. Brønsted'sTheory of Acids and Bases.- 2. Deviations from Brønsted's Theory and the Need for Development of the Latter.- 3. Noncoulombic Interaction in Solutions of Acids and Salts.- 4. Acid-Base Reactions in Aprotic Solvents.- 5. N. A. Izmailov's Theory of the Dissociation of Acids and Bases.- 6. The Role of the Hydrogen Bond in Acid-Base Interaction.- 7. Range of Protolytic Reactions.- 8. Definitions of Acids and Bases.- 9. Summary.- Literature Cited.- Section V. Mechanisms of Hydrogen Replacement Reactions.- 1. Replacement of Hydrogen by Reaction with a Nucleophilic Reagent.- Literature Cited.- 2. Replacement of Hydrogen by Reaction with an Electrophilic Reagent.- Literature Cited.- 3. Mechanisms of Hydrogen Exchange.- Literature Cited.- Conclusion.- Appendix: Preparation of Deuterated Organic Compounds.- 1. Introduction.- 2. Methods of Preparing Deuterated Organic Compounds.- 3. Synthesis of Deuterated Organic Compounds.- A. Reduction.- B. Hydration and Hydrolysis.- C. Ammonolysis.- D. Condensation.- E. Decarboxylation.- 4. Isotopic Exchange of Hydrogen.- A. Hydrogen Exchange with Heavy Water and Deuteroalcohol.- B. Hydrogen Exchange with Deuterosulfuric Acid.- D. Hydrogen Exchange with Liquefied Gases.- 5. Comparison of Methods of Preparing Deuterium Compounds.- Literature Cited.