Isotopic Exchange and the Replacement of Hydrogen in Organic Compounds

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.- A. Acceleration of Acid Exchange by a Base.- B. Acceleration of Basic Exchange by an Acid.- C. Inversion of Relative Rates of Hydrogen Exchange with Amphoteric and Protophilic Solvents.- D. Inhibition of Acid Hydrogen Exchange by an Acid.- 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.- A. Rate and Equilibrium of Protolyte Ionization.- B. Brønsted’s Relation in Hydrogen Exchange.- 12. Hammett’s Relation in Hydrogen Exchange.- A. Hammett’s Acidity Function.- B. Reaction Rate and Acidity Function.- C. 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.- A. Exchange in H-H Bond.- B. Exchange in B-H Bond.- C. Exchange in N-H Bond.- D. Exchange in P-H Bond.- E. Exchange in As-H Bond.- F. Exchange in O-H Bond.- G. Exchange in S-H Bond.- 15. Heterogeneous Acid-Base Hydrogen Exchange.- 16. Summary.- Literature Cited.- Section III. Hydrocarbons as Acids and Bases.- Literature Cited.- 1, Hydrocarbons as Acids.- 1. Metallation of Hydrocarbons.- A. Reactions of Hydrocarbons with Alkali Metals.- B. Reactions of Hydrocarbons with Bases.- 2. Saltlike Nature of Organoalkali Compounds.- A. Electrical Conductivity of Solutions.- B. Ionic Reactions.- 3. Carbanions.- A. Formation of Carbanions.- B. Spectra of Carbanions.- 4. Comparison of the Strengths of Carbo Acids by Metallation Reactions.- A. General Comparison.- B. Classes of Hydrocarbons.- 5. Isotopic Exchange of Hydrogen.- A. Amphoteric Solvents.- B. Liquid Ammonia.- C. Liquid Exchange Between Hydrocarbons.- 6. Isomerization of Unsaturated Hydrocarbons.- A. Nature of Reaction.- B. Isomerization of Hydrocarbons by Bases.- C. Rules of Isomerization.- 7. Alkylation by Olefins.- A. Michael and Analogous Reactions.- B. Alkylation of Amines and Ammonia by Olefins.- C. Alkylation of Aromatic Hydrocarbons.- D. Dimerization of Olefins.- 8. Summary.- Literature Cited.- 2. Hydrocarbons as Bases.- 1. Introduction.- 2. Carbonium Ions.- A. Rupture of a Bond Between Carbon and an Electronegative Atom or Group.- B. Exchange Between a Carbonium Ion and a Hydrocarbon.- C. Elimination of a Hydride Ion.- D. Addition of a Proton to an Unsaturated Hydrocarbon.- E. Addition of a Carbonium Ion to an Aromatic Hydrocarbon.- F. Detection of a Carbonium Ion by Deuterium Exchange.- 3. Equilibrium Reactions of Hydrocarbons with Acids.- A. Introduction.- B. Liquid Hydrogen Fluoride.- C. Sulfuric Acid.- D. Hydrogen Chloride and Bromide.- E. Carbonium Salts of Haloaluminic Acids.- F. Carboxylic Acids.- 4. Equilibrium Reactions of Basic Hydrocarbons with Acidlike Substances.- A. Introduction.- B. Sulfur Dioxide.- C. Halogens.- 5. Irreversible Reactions of Basic Hydrocarbons with Acidlike Substances.- 6. Isotopic Exchange of Hydrogen Between Hydrocarbons and Acids.- A. Introduction.- B. Aromatic Hydrocarbons.- C. Unsaturated Aliphatic Hydrocarbons.- D. Saturated Hydrocarbons.- 7. Summary.- Literature Cited.- Conclusion.- Section IV. Mechanism of Acid-Base Interaction.- 1. Brønsted’s Theory 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.- A. Application of Brønsted’s Theory.- B. Inadequacy of Brønsted’s Theory.- 5. N. A. Izmailov’s Theory of the Dissociation of Acids and Bases.- A. Comparison of the Strengths of Acids in Different Solvents.- B. Reasons for Deviations from Brønsted’s Theory.- C. N. A. Izmailov’s Theory.- 6. The Role of the Hydrogen Bond in Acid-Base Interaction.- A. Donor-Acceptor Interaction in the Formation of a Hydrogen Bond.- B. Polarity of Molecular Compounds of Acids with Bases.- C. Displacement of Bond Vibration Frequency in the Infrared Absorption Spectrum on the Formation of a Hydrogen Bond.- D. Other Manifestations of a Hydrogen Bond.- 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.- 1. Attack of the Reagent on the Hydrogen Atom of a CH Bond.- A. Electrophilic Substitution Hypothesis and Criticism of It.- B. Metallation - A Protophilic Substitution Reaction.- 2. Attack of the Reagent on the Carbon Atom of a CH Bond.- A. General Principles.- B. Chichibabin’s Reaction.- C. Replacement of Hydrogen in Nitro Compounds.- D. Replacement of Hydrogen in Hydrocarbons.- 3. Summary.- Literature Cited.- 2. Replacement of Hydrogen by Reaction with an Electrophilic Reagent.- 1. Orientation Rules.- 2. Relation of the Reactivity of a Substance to the “Activity” of the Reagent.- 3. Partial Rate Factors of the Replacement of Hydrogen Atoms in an Aromatic Ring.- A. Definition.- B. Relation Between the “Activity” of the Reagent and the “Selectivity” of the Replacement.- C. Change in the Reactivity of a Substance in Catalysis.- D. Calculation of the Relative Reactivity of Substances from Partial Rate Factors.- 4. Reason for Selectivity of Replacement.- 5. Role of the Steric Factor in the Replacement of Hydrogen.- 6. Participation of Associative and Ionization Processes in Hydrogen Replacement Reactions.- 7. Summary.- Literature Cited.- 3. Mechanisms of Hydrogen Exchange.- 1. Comparison of Rules of Hydrogen Exchange and Other. Replacements of Hydrogen in Aromatic Compounds.- A. Basic Hydrogen Exchange.- B. Acid Hydrogen Exchange.- 2. Mechanisms of Hydrogen Exchange.- A. A. I. Brodskii’s Classification.- B. Associative and Ionization Mechanisms of Hydrogen Exchange.- 3. Summary.- 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.