Perspectives on Structure and Mechanism in Organic Chemistry (eBook)

FELIX A. CARROLL, PhD, is the Joseph R. Morton Professor of Chemistry at Davidson College. His research focuses on organic photochemistry and photophysics, kinetics, the synthesis and characterization of insect pheromone analogues, the correlation of molecular structure with physical properties, and the combustion characteristics of organic compounds. Dr. Carroll has published extensively in the peer-reviewed literature and was awarded a patent in the field of insect pheromones.

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

"With its emphasis on complementary models and independent problem-solving, this text is ideal for upper-level undergraduate and graduate courses in organic chemistry." (Forbes.com, 28 October 2010)