Preface xi
Acknowledgments xiii
Introduction xv
Chapter 1 Fundamental Concepts of Organic Chemistry 1
1.1 Atoms and Molecules 1
1.2 Heats of Formation and Reaction 8
1.3 Bonding Models 19
1.4 Complementary Descriptions of the Double Bond 42
1.5 Choosing Models in Organic Chemistry 48
Chapter 2 Stereochemistry 53
2.1 Introduction 53
2.2 Stereoisomerism 56
2.3 Manifestations of Stereoisomerism 86
2.4 Stereotopicity 94
Chapter 3 Conformational Analysis and Molecular Mechanics
113
3.1 Molecular Conformation 113
3.2 Conformational Analysis 119
3.3 Molecular Mechanics 135
3.4 Molecular Strain and Limits to Molecular Stability 155
Chapter 4 Applications of Molecular Orbital Theory and
Valence Bond Theory 175
4.1 Introduction to Molecular Orbital Theory 175
4.2 Aromaticity 199
4.3 Contemporary Computational Methods 220
4.4 Valence Bond Theory 237
Chapter 5 Reactive Intermediates 253
5.1 Reaction Coordinate Diagrams 253
5.2 Radicals 256
5.3 Carbenes 278
5.4 Carbocations 289
5.5 Carbanions 310
5.6 Choosing Models of Reactive Intermediates 320
Chapter 6 Methods of Studying Organic Reactions 327
6.1 Molecular Change and Reaction Mechanisms 327
6.2 Methods to Determine Reaction Mechanisms 327
6.3 Applications of Kinetics in Studying Reaction Mechanisms
341
6.4 Arrhenius Theory and Transition-State Theory 348
6.5 Reaction Barriers and Potential Energy Surfaces 360
6.6 Kinetic Isotope Effects 370
6.7 Substituent Effects 385
6.8 Linear Free Energy Relationships 389
Chapter 7 Acid and Base Catalysis of Organic Reactions
413
7.1 Acidity and Basicity of Organic Compounds 413
7.2 Acid and Base Catalysis of Chemical Reactions 433
7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds
and Carboxylic Acid Derivatives 439
Chapter 8 Substitution Reactions 469
8.1 Introduction 469
8.2 Nucleophilic Aliphatic Substitution 472
8.3 Electrophilic Aromatic Substitution 518
8.4 Nucleophilic Aromatic and Vinylic Substitution 527
Chapter 9 Addition Reactions 551
9.1 Introduction 551
9.2 Addition of Halogens to Alkenes 553
9.3 Other Addition Reactions 585
Chapter 10 Elimination Reactions 633
10.1 Introduction 633
10.2 Dehydrohalogenation and Related 1,2-Elimination Reactions
638
10.3 Other 1,2-Elimination Reactions 665
Chapter 11 Pericyclic Reactions 697
11.1 Introduction 697
11.2 Electrocyclic Transformations 702
11.3 Sigmatropic Reactions 715
11.4 Cycloaddition Reactions 731
11.5 Other Concerted Reactions 747
11.6 A General Selection Rule for Pericyclic Reactions 753
11.7 Alternative Conceptual Models for Concerted Reactions
756
Chapter 12 Photochemistry 787
12.1 Photophysical Processes 787
12.2 Fundamentals of Photochemical Kinetics 804
12.3 Physical Properties of Excited States 810
12.4 Representative Photochemical Reactions 818
12.5 Some Applications of Organic Photochemistry 853
Problems 862
References for Selected Problems 871
Permissions 883
Author Index 895
Subject Index 927
