About the book

This four-volume textbook is designed for a systematic study of organic chemistry. The material presented in the book is divided into two parts and covers a considerably wider field than the normal university treatment of the subject. Part One (the first three volumes) is constructed along "classical" lines. Part Two (Volume IV) is intended for attentive reading rather than for close study. Volume IV is devoted to the following topics: organoelement compounds, nonbenzenoid aromatic systems, carbanions, free radicals, carbenes, carbonium ions, elimination reactions, isoprenoids, alkaloids of the heterocyclic series, proteins, nucleotides, and polynucleotides, enzymes.

This book has been translated from the second revised Russian edition published in two volumes in 1974. The first Russian edition (in two volumes) was published in 1969.

The book may be used for self-study and for reading the course of organic chemistry at universities and chemical higher schools. It will undoubtedly be of interest to post-graduates, teachers, scientists, and engineers working in the field of organic chemistry.

PART TWO

Chapter 12. Organoelement Compounds

12.1. Active Organometallic Compounds of Groups I, II, and III 11

12.2. Group I of the Periodic System 15

12.3. Group II of the Periodic System 21

12.4. Group III of the Periodic System 48

12.5. Group IV of the Periodic System 57

12.6. Group V of the Periodic System 64

12.7. Group VI of the Periodic System 88

12.8. Group VII of the Periodic System 90

12.9. Organometallic Compounds of Transition Metals 100

 A. Metal Carbonyls 108

 B. Olefin n-Complexes of Transition Metals 117

 C. Metalloarenes 124

 D. Metallocenes 129

Chapter 13. Non-Benzenoid Aromatic Systems

13.1. Diamagnetic Properties of Aromatic Systems 135

13.2. Aromatic Systems with Two ?-Electrons 136

13.3. Aromatic Systems with Four ?-Electrons 141

13.4. Aromatic Systems with Six ?-Electrons 142

 A. The Cyclopentadienyl Anion 142

 B. The Tropylium Ion 158

13.5. Aromatic Systems with More Than Six n-Electrons 163

 A. Azulene 163

 B. Annulenes 169

 C. Porphyrins 170

Chapter 14. Carbanions 171

Chapter 15. Free Radicals

15.1. Electron Paramagnetic Resonance 191

15.2. The Formation of Free Radicals 192

15.3. Free-Radical Reactions 193

 A. Elementary Acts 196

15.4. Free-Radical Chain Reactions 201

 A. Homolytic Substitution 201

 B. Autoxidation Reactions 209

 C. Radical Addition to Double Bonds 213

15.5. The Telomerization (Oligomerization) Reactions 217

15.6. The Kinetics of Chain Reactions 219

 A. Determination of Chain-Transfer Constants in Radical Telomerization Reactions 224

Chapter 16. Carbenes 228

Chapter 17. Carbonium Ions 233

17.1. Hydride Shifts 241

Chapter 18. Mechanisms of Chemical Reactions 248

18.1. The Structure of the Transition State 249

Chapter 19. Elimination Reactions 263

Chapter 20. Rearrangements 272

20.1. Skeletal Rearrangements 272

20.2. Rearrangements Involving Carbenes and Carbenoids as Intermediates 290

20.3. Rearrangements Involving the Migration of n-Bonds 294

20.4. Hydride Shifts 300

20.5. Homolytic Rearrangements 302

Chapter 21. Isoprenoids 305

21.1. Terpenes and Terpenoids 306

 A. Monoterpenes and Terpenoids 320

 B. Sesquiterpenes and Sesquiterpenoids 321

 C. Diterpenes, Tetraisoprenoids, and Carotenoids 325

21.2. Resin Acids 326

21.3. Steroids 329

 A. Sterols (Steroid Alcohols) 337

 B. The Configuration of Steroids 342

 C. The Bile Acids 344

 D. The Steroid Hormones 355

 E. Genins and Saponins 356

Chapter 22. Alkaloids of the Heterocyclic Series 356

22.1. Alkaloids with a Five-Membered Heterocycle Containing One Nitrogen Atom 357

22.2. Alkaloids with a System of Two Condensed Five-Membered Rings Containing One Common Nitrogen Atom 359

22.3. Alkaloids with a Five-Membered Heterocycle Containing Two Nitrogen Atoms 360

22.4. Alkaloids with a Six-Membered Heterocycle Containing One Nitrogen Atom 363

22.5. Alkaloids with a System of Two Condensed Six-Membered Rings Containing One Common Nitrogen Atom 371

22.6. Alkaloids with Condensed Five- and Six-Membered Heterocycles and One Nitrogen Atom 372

22.7. Alkaloids with Two Condensed Six-Membered Heterocycles Containing One Nitrogen Atom 377

22.8. Alkaloids with Two Isolated Heterocycles Containing Two Nitrogen Atoms 379

22.9. Alkaloids with Two Condensed Six-Membered Heterocycles Containing One Common Nitrogen Atom and One Isolated Heterocycle 384

22.10. Alkaloids with Three Condensed Heterocycles Containing Two Nitrogen Atoms 389

Chapter 23. Proteins 401

23.1. Isolation and Purification of Proteins 408

23.2. Elucidation of Protein Structure 409

23.3. Synthesis of Peptides and Proteins 410

23.4. The Secondary and Tertiary Structures of Proteins 411

Chapter 24. Nucleotides and Polynucleotides 427

24.1. Protein Biosynthesis 427

24.2. Synthesis of Nucleotides 432

24.3. Polynucleotides 433

Chapter 25. Enzymes 458

25.1. Classification of Enzymes 461

 A. Hydrolases 461

 B. Transferases 465

 C. Oxidoreductases 469

 D. Lyases 474

 E. Isomerases 476

 F. Synthetases 476

Author Index 478

Subject Index 484