Isotopic Exchange and The Replacement of Hydrogen in Organic CompoundsPDF电子书下载

SECTION Ⅰ．Types of Reagents and Reactions 1

1．Oxidizing and Reducing Agents 2

2．Acids and Bases 2

3．Acidlike Substances 4

4．Nucleophilic and Electrophilic Reagents 7

5．Wide Definitions of Acids and Bases 9

6．Relative and Approximate Nature of the Classification of Reagents 10

7．Donor-acceptor Interaction 12

8．Heterolytic and Homolytic Reactions 16

9．Place of Hydrogen Exchange Among Other Reactions 19

10．Summary 19

Literature Cited 19

SECTION Ⅱ．Acid-Base Catalysis of Hydrogen Exchange 21

1．Introduction 21

2．Comparison of the Rates of Hydrogen Exchange with Amphoteric and Protophilic Solvents 22

3．Comparison of the Rates of Hydrogen Exchange with Amphoteric and Protogenic Solvents 25

4．Effect of the Dielectric Constant of the Solvent and the Polarity of Its Molecules on the Hydrogen Exchange Rate 27

5．Effect of the Substrate and Catalyst Charge on the Hydrogen Exchange Rate 29

6．Effect of Dual Reactivity of a Substance on Hydrogen Exchange 33

A．Acceleration of Acid Exchange by a Base 33

B．Acceleration of Basic Exchange by an Acid 33

C．Inversion of Relative Rates of Hydrogen Exchange with Amphoteric and Protophilic Solvents 35

D．Inhibition of Acid Hydrogen Exchange by an Acid 36

7．Effect of Steric Hindrance on Hydrogen Exchange 38

8．Decrease in the Activity of a Catalyst on Its Reaction with the Substrate 40

9．Activation of a Catalyst by a Change of Solvent 41

10．Catalytic Activity of Complexes of Hydrogen Acids with Acidlike Substances in Hydrogen Exchange 42

11．Br？nsted＇s Relation in Hydrogen Exchange 43

A．Rate and Equilibrium of Protolyte Ionization 43

B．Br？nsted＇s Relation in Hydrogen Exchange 46

12．Hammett＇s Relation in Hydrogen Exchange 48

A．Hammett＇s Acidity Function 48

B．Reaction Rate and Acidity Function 54

C．Hammett＇s Relation in Hydrogen Exchange 59

13．Salt Effect in Hydrogen Exchange 64

14．Acid-Base Catalysis of Hydrogen Exchange in H-H，B-H，N-N，As-h，P-H，O-H，and S-H Bonds 66

A．Exchange in H-H Bond 66

B．Exchange in B-H Bond 67

C．Exchange in N-H Bond 67

D．Exchange in P-H Bond 70

E．Exchange in As-H Bond 70

F．Exchange in O-H Bond 71

G．Exchange in S-H Bond 72

15．Heterogeneous Acid-Base Hydrogen Exchange 72

16．Summary 73

Literature Cited 74

SECTION Ⅲ．Hydrocarbons as Acids and Bases 80

Introduction 80

Literature Cited 82

Chapter 1．Hydrocarbons as Acids 82

1．Metallation of Hydrocarbons 83

A．Reactions of Hydrocarbons with Alkali Metals 83

B．Reactions of Hydrocarbons with Bases 84

2．Saltlike Nature of Organoalkali Compounds 86

A．Electrical Conductivity of Solutions 87

B．Ionic Reactions 88

3．Carbanions 88

A．Formation of Carbanions 88

B．Spectra of Carbanions 89

4．Comparison of the Strengths of Carbo Acids by Metallation Reactions 92

A．General Comparison 92

B．Classes of Hydrocarbons 93

5．Isotopic Exchange of Hydrogen 96

A．Amphoteric Solvents 96

B．Liquid Ammonia 98

C．Liquid Exchange Between Hydrocarbons 114

6．Isomerization of Unsaturated Hydrocarbons 116

A．Nature of Reaction 116

B．Isomerization of Hydrocarbons by Bases 117

C．Rules of Isomerization 117

7．Alkylation by Olefins 119

A．Michael and Analogous Reactions 119

B．Alkylation of Amines and Ammonia by Olenfins 120

C．Alkylation of Aromatic Hydrocarbons 120

D．Dimerization of Olefins 123

8．Summary 124

Literature Cited 124

Chapter 2．Hydrocarbons as Bases 130

1．Introduction 130

2．Carbonium Ions 130

A．Rupture of a Bond Between Carbon and an Electronegative Atom or Group 131

B．Exchange Between a Carbonium Ion and a Hydrocarbon 133

C．Elimination of a Hydride Ion 133

D．Addition of a Proton to an Unsaturated Hydrocarbon 134

E．Addition of a Carbonium Ion to an Aromatic Hydrocarbon 135

F．Detection of a Carbonium Ion by Deuterium Exchange 135

3．Equilibrium Reactions of Hydrocarbons with Acids 136

A．Introduction 136

B．Liquid Hydrogen Fluoride 137

C．Sulfuric Acid 149

D．Hydrogen Chloride and Bromide 152

E．Carbonium Salts of Haloaluminic Acids 157

F．Carboxylic Acids 159

4．Equilibrium Reactions of Basic Hydrocarbons with Acidlike Substances 161

A．Introduction 161

B．Sulfur Dioxide 161

C．Halogens 162

5．Irreversible Reactions of Basic Hydrocarbons with Acidlike Substances 165

6．Isotopic Exchange of Hydrogen Between Hydrocarbons and Acids 167

A．Introduction 167

B．Aromatic Hydrocarbons 168

C．Unsaturated Aliphatic Hydrocarbons 180

D．Saturated Hydrocarbons 181

7．Summary 187

Literature Cited 188

Conclusion 195

Section Ⅳ．Mechanism of Acid-Base Interaction 197

1．Br？nsted＇s Theory of Acids and Bases 197

2．Deviations from Br？nsted＇s Theory and the Need for Development of the Latter 199

3．Noncoulombic Interaction in Solutions of Acids and Salts 200

4．Acid-Base Reactions in Aprotic Solvents 202

A．Application of Br？nsted＇s Theory 202

B．Inadequacy of Br？nsted＇s Theory 202

5．N．A．Izmailov＇s Theory of the Dissociation of Acids and Bases 202

A．Comparison of the Strengths of Acids in Different Solvents 203

B．Reasons for Deviations from Br？nsted＇s Theory 204

C．N．A．Izmailov＇s Theory 206

6．The Role of the Hydrogen Bond in Acid-Base Interaction 212

A．Donor-Acceptor Interaction in the Formation of a Hydrogen Bond 213

B．Polarity of Molecular Compounds of Acids with Bases 214

C．Displacement of Bond Vibration Frequency in the Infrared Absorption Spectrum on the Formation of a Hydrogen Bond 220

D．Other Manifestations of a Hydrogen Bond 229

7．Range of Protolytic Reactions 233

8．Definitions of Acids and Bases 236

9．Summary 237

Literature Cited 238

SECTION Ⅴ．Mechanisms of Hydrogen Replacement Reactions 242

Introduction 242

Chapter 1．Replacement of Hydrogen by Reaction with a Nucleophilic Reagent 244

1．Attack of the Reagent on the Hydrogen Atom of a CH Bond 244

A．Electrophilic Substitution Hypothesis and Criticism of It 245

B．Metallation-A Protophilic Substitution Reaction 245

2．Attack of the Reagent on the Carbon Atom of a CH bond 248

A．General Principles 248

B．Chichibabin＇s Reaction 249

C．Replacement of Hydrogen in Nitro Compounds 251

D．Replacement of Hydrogen in Hydrocarbons 253

3．Summary 253

Literature Cited 253

Chapter 2．Replacement of Hydrogen by Reaction with an Electrophilic Reagent 255

1．Orientation Rules 255

2．Relation of the Reactivity of a Substance to the＂Activity＂of the Reagent 257

3．Partial Rate Factors of the Repalcement of Hydrogen Atoms in an Aromatic Ring 258

A．Definition 258

B．Relation Between the＂Activity＂of the Reagent and the＂Selectivity＂of the Replacement 259

C．Change in the Reactivity of a Substance in Catalysis 262

D．Calculation of the Relative Reactivity of Substances from Partial Rate Factors 263

4．Reason for Selectivity of Replacement 264

5．Role of the Steric Factor in the Replacement of Hydrogen 266

6．Participation of Associative and Ionization Processes in Hydrogen Replacement Reactions 269

7．Summary 273

Literature Cited 273

Chapter 3．Mechanisms of Hydrogen Exchange 275

1．Comparison of Rules of Hydrogen Exchange and Other Replacements of Hydrogen in Aromatic Compounds 275

A．Basic Hydrogen Exchange 275

B．Acid Hydrogen Exchange 279

2．Mechanisms of Hydrogen Exchange 283

A．A．I．Brodskii＇s Classification 283

B．Associative and Ionization Mechanisms of Hydrogen Exchange 286

3．Summary 290

Literature Cited 291

Conclusion 293

Appendix：Preparation of Deuterated Organic Compounds 295

1．Introduction 295

2．Methods of Preparing Deuterated Organic Compounds 296

3．Synthesis of Deuterated Organic Compounds 297

A．Reduction 297

B．Hydration and Hydrolysis 298

C．Ammonolysis 299

D．Condensation 300

E．Decarboxylation 300

4．Isotopic Exchange of Hydrogen 300

A．Hydrogen Exchange with Heavy Water and Deuteroalcohol 300

B．Hydrogen Exchange with Deuterosulfuric Acid 301

C．Hydrogen Exchange with DC1+A1C13 301

D．Hydrogen Exchange With Liquefied Gases 302

5．Comparison of Methods of Preparing Deuterium Compounds 304

Literature Cited 306