THE THEORY OF ORGANIC CHEMISTRY AN ADVANCED COURSEPDF电子书下载

Ⅰ．THE DEVELOPMENT OF STRUCTURAL CHEMISTRY 1

1．Valence 1

2．Structural Isomerism 6

3．The Persistence of Structure 6

4．Structural Analogy 10

5．Structural Iteration 12

6．Tautomerism 14

7．Stereoisomerism 16

8．The Constancy of Valence 20

Ⅱ．ATOMIC STRUCTURE 26

9．The Nuclear Atom 26

10．The Lewis Atom 27

11．The Quantum Theory of the Atom 28

11a．The Bohr atom 28

11b．The wave mechanical atom 29

Ⅲ．MOLECULAR STRUCTURE 38

12．Electronic Structural Formulas 38

12a．Co-ordination number 42

12b．Charge distribution 43

12c．Acids,bases,and free radicals 45

13．The Electron Pair Bond in Quantum Mechanics 46

13a．Methods of approximation 47

13b．The hydrogen molecule 51

13c．The one-electron bond 58

13d．Bond dipole 59

13e．The tetrahedral carbon atom 60

Ⅳ．GROUP INTERACTION 62

14．Group Interactions without Considering Resonance 62

14a．Steric hindrance 62

14b．Negativity 63

14c．Polarity and induction 63

14d．The Hixon-Johns method 65

15．Conjugation 67

Ⅳ．GROUP INTERACTION(Cont．) 70

16．Resonance and Mesomerism 70

16a．Mesomerism as a tautomerism 70

16b．Molecular resonance as an extension of the Lewis theory 73

16c．Molecular resonance as a theorem in quantum mechanics 81

Ⅴ．PHYSICAL PROPERTIES 91

17．Bond Distances and Angles 92

17a．Experimental methods 92

17b．Bond distances 111

17c．The hydrogen bond 116

17d．Bond angles 121

17e．Free rotation 124

18．Dipole Moments 126

18a．Bond moments 129

18b．Sign of dipole moment 132

18c．Vector addition of dipole moments 133

18d．Dipole moment and rotation about a single bond 139

18e．Dipole moment and resonance 144

19．Raman Spectra and Force Constants 151

19a．Force constants 153

20．Color 155

20a．Older theories 157

20b．Quantum mechanical calculations 157

20c．Complexity of spectra 159

20d．Electrons as quantized oscillators 162

20e．Approximately linear oscillators 163

20f．Conjugation,insulation,partials 168

20g．The function of auxochromes 172

20h．Oscillators in more than one direction 174

20i．Acid-base indicators 179

Ⅵ．EQUILIBRIUM—ACID STRENGTH 183

21．Equilibrium 183

22．Acids and Bases 186

23．Acid Strength and Structure 188

23a．Mechanism of comparison of acid strength 188

23b．Mechanism for the description of intramolecular action;division into contributing factors 192

24．Acids without Resonance 201

24a．Discussion of special cases 205

24b．The electrostatic method 216

25．The Fatty Acids 217

26．Unsaturated Acids 233

26s．Cross-conjugation 235

27．The Aromatic Acids 240

27a．Resonance of aromatic nuclei 240

27b．Classification of aromatic acids 242

27c．Meta groups 245

27d．Para groups 249

27e．Ortho groups 257

28．Miscellaneous Acids 265

28a．Ammonia acids 266

28b．Methane acids 268

28c．Generalized acids 269

Ⅶ．ENERGY RELATIONSHIPS IN SOME OTHER REACTIONS 271

29．Ionic Resonance and the Heat of Formation 271

30．Valence Bond Resonance and Heat of Formation 272

30a．The branched-chain effect 274

30b．Ring strain 278

30c．Resonance energies 280

31．Tautomerism 281

31a．Keto-enol equilibria 289

31b．Solvent effect 296

31c．Other tautomeric systems 297

32．Oxidation-Reduction Potentials 303

32a．Homopolar valence bond resonance 305

32b．Ionic resonance and induction 315

33．Free Radicals 317

33a．Trivalent carbon 319

33b．Divalent nitrogen and tetravalent nitrogen 326

33c．Monovalent oxygen 332

33d．Diradicals 333

34．cis-trans Isomerism of Olefins 339

35．Equilibrium in the Addition to the Double Bond 343

Ⅷ．THE RATE FACTOR IN CHEMICAL BEHAVIOR 352

36．The Variation of Rate with Concentration 353

36a．Reversible reactions 354

36b．Simultaneous reaction 356

36c．Successive reactions 357

36d．Catalysis 362

36e．Chain reactions 364

36f．Inhibitors 365

37．The Temperature Coefficient of Reaction Rate 367

37a．Unimolecular reactions 369

37b．Bimolecular reactions 372

37c．The temperature coefficient of a complex reaction 375

38．Transition state 376

39．Molecular association 384

40．The Quantum Mechanical Treatment 387

40a．The Eyring-Polanyi method 390

Ⅸ．THE REACTIONS OF ACIDS AND BASES WITH NEUTRAL SUB-STANCES—THREE-CENTER REACTIONS 393

41．The Mechanisms of the Reactions 394

41a．The Walden inversion 395

41b．The differentiation of rate-determining and preliminary reversible reactions 396

41c．The salt effect 397

41d．Reaction with both hydrogen ion and undissociated acid 399

41e．Reaction of substrate with either acid or base 401

41f．Lowry＇s mechanism 403

41g．Unimolecular and bimolecular hydrolysis 405

41h．Slow and fast reactions 407

42．The Strength of the Reacting Acid or Base(C) 408

42a．Br？nsted＇s equation 409

42b．Hammett＇s equation 416

42c．The relationship between Br？nsted＇s and Hammett＇s equations 420

42d．Acids without hydrogen atoms 420

42e．Charged and neutral bases 421

42f．The polarizability effect 422

43．The Strength of the Product Acid or Base(A) 423

44．The Middle Group(B)in the Three-Center Reaction 426

45．Inductive and Tautomeric Effects 428

46．The Effect of Branching Chains 430

47．The Effect of Resonance on Reaction Rate 434

47a．Effect of resonance in a reacting or product base 435

47b．Resonance of the middle group of the transition state 436

47c．Resonance effects of para substituents 440

48．Steric Effects 443

Ⅹ．REACTIONS OF THE DOUBLE BOND 449

49．The Ethylenic Double Bond 451

49a．Ethylenes as bases or pseudo-bases 451

49b．Stereochemistry of addition reactions 454

49c．Macropolymerization 455

50．The Carbonyl Double Bond 457

50a．Addition of bisulfite ion 458

50b．Oximes,hydrazones,and semicarbazones 459

50c．Addition of organometallic compounds 462

50d．The aldol condensation 463

50e．The Cannizzaro reaction 466

51．Conjugate Systems 467

52．Substitution Reactions of Benzene 470

52a．The directing influence of substituents 471

52b．Application of Hammett＇s equation to para and meta substitution 480

52c．The reaction of benzene as a pseudo-acid 481

52d．The reaction of carbonyl compounds with phenols and anilines 482

52e．The relationship between addition to ethylene and substitution in benzene 483

52f．Condensed-ring systems 484

53．Four-Center Reactions 487

53a．Aromatic rings in the diene condensation 490

AUTHOR INDEX 493

SUBJECT INDEX 499