Ann Fabirkiewicz, PhD, is Professor of Chemistry at Randolph College where she teaches organic chemistry and biochemistry, including one on Intermediate Organic Chemistry.

John Stowell, PhD, was Professor of Chemistry at the University of New Orleans. His previous books include the first two editions of Intermediate Organic Chemistry and Carbanions in Organic Synthesis, published by Wiley.

Preface to the Third Edition xi

Preface to the Second Edition xiii

Preface to the First Edition xv

1 Reading Nomenclature 1

1.1 Acyclic Polyfunctional Molecules 2

1.2 Monocyclic Aliphatic Compounds 3

1.3 Bridged Polycyclic Structures 4

1.4 Fused Polycyclic Compounds 6

1.5 Spiro Compounds 10

1.6 Monocyclic Heterocyclic Compounds 12

1.7 Fused]Ring Heterocyclic Compounds 14

1.8 Bridged and Spiro Heterocyclic Compounds 19

Resources 20

Problems 21

References 22

2 Accessing Chemical Information 25

2.1 Databases 25

2.2 Chemical Literature 26

2.3 Synthetic Procedures 29

2.4 Health and Safety Information 30

Problems 32

References 33

3 Stereochemistry 35

3.1 Representations 35

3.2 Vocabulary 37

3.3 Property Differences Among Stereoisomers 40

3.4 Resolution of Enantiomers 44

3.5 Enantioselective Synthesis 47

3.6 Reactions at a Stereogenic Atom 49

3.6.1 Racemization 49

3.6.2 Epimerization 50

3.6.3 Inversion 51

3.6.4 Retention 51

3.6.5 Transfer 52

3.7 Relative and Absolute Configuration 53

3.8 Topism 56

Resources 59

Problems 60

References 65

4 Mechanisms and Predictions 69

4.1 Reaction Coordinate Diagrams and Mechanisms 69

4.2 The Hammond Postulate 71

4.3 Methods for Determining Mechanisms 72

4.3.1 Identification of Products and Intermediates 72

4.3.2 Isotope Tracing 73

4.3.3 Stereochemical Determination 74

4.3.4 Concentration Dependence of Kinetics 75

4.3.5 Isotope Effects in Kinetics 85

4.3.6 Temperature Effects on Kinetics 87

4.3.7 Substituent Effects on Kinetics 90

4.4 Representative Mechanisms 95

4.4.1 Reactions in Basic Solution 96

4.4.2 Reactions in Acidic Solution 100

4.4.3 Free]Radical Reactions 103

4.4.4 Molecular Rearrangements 106

Resources 108

Problems 109

References 120

5 Electron Delocalization, Aromatic Character, and Pericyclic Reactions 123

5.1 Molecular Orbitals 124

5.2 Aromatic Character 130

5.3 Pericyclic Reactions 135

5.3.1 Cycloaddition Reactions 137

5.3.2 Electrocyclic Reactions 142

5.3.3 Sigmatropic Reactions 147

Resources 152

Problems 152

References 158

6 Functional Group Transformations 163

6.1 Carboxylic Acids and Related Derivatives 164

6.1.1 Carboxylic Acids 164

6.1.2 Carboxylic Esters 166

6.1.3 Carboxylic Amides 168

6.1.4 Carboxylic Acid Halides 168

6.1.5 Carboxylic Anhydrides 169

6.1.6 Nitriles 169

6.1.7 O rtho Esters 170

6.2 Aldehydes, Ketones, and Derivatives 171

6.2.1 Aldehydes 171

6.2.2 Ketones 174

6.2.3 Imines and Enamines 175

6.2.4 Acetals 175

6.2.5 Vinyl Ethers 177

6.3 Alcohols 179

6.4 Ethers 179

6.5 Alkyl Halides 181

6.5.1 Alkyl Chlorides and Alkyl Bromides 182

6.5.2 Alkyl Iodides 184

6.5.3 Alkyl Fluorides 184

6.6 Amines 185

6.7 Isocyanates 187

6.8 Alkenes 187

6.9 Reductive Removal of Functionality 190

Resources 191

Problems 191

References 198

7 Carbon–Carbon Bond Formation 205

7.1 Carbon–Carbon Single Bond Formation 206

7.1.1 Reactions in Basic Solution 206

7.1.2 Reactions in Acidic Solution 214

7.1.3 O rganometallic Coupling Reactions 217

7.2 Carbon–Carbon Double]Bond Formation 218

7.3 Multibond Processes 222

Resources 224

Problems 224

References 230

8 Planning Multistep Syntheses 235

8.1 Retrosynthetic Analysis 235

8.2 Disconnection at a Functional Group or Branch Point 236

8.3 Cooperation for Difunctionality 244

8.4 Ring Closure 250

8.5 Acetylide Alkylation and Addition 253

8.6 T he Diels–Alder Reaction 255

8.7 T he Claisen Rearrangement 259

8.8 Synthetic Strategies 263

8.9 Final Note 265

Resources 266

Problems 266

References 271

9 Physical Influences on Reactions 277

9.1 Unimolecular Reactions 278

9.2 Homogenous Two]Component Reactions 279

9.3 Temperature Effects 280

9.4 Pressure Effects 281

9.5 Solvent Effects 282

9.6 Biphasic Reactions 283

9.6.1 Phase Transfer Catalysis 283

9.6.2 Increasing Solubility 286

9.6.3 Increasing Surface Area 287

9.6.4 Ultrasound 287

9.7 Reactions on Chemical Supports 288

9.8 Using Unfavorable Equilibria 291

9.9 Green Chemistry 293

Resources 294

Problems 294

References 295

10 Survey of Organic Spectroscopy 299

10.1 Electromagnetic Radiation 299

10.2 Ultraviolet Spectroscopy 300

10.2.1 Origin of the Signals 300

10.2.2 Interpretation 302

10.2.3 Visible Spectroscopy 302

10.3 Infrared Spectroscopy 303

10.3.1 Origin of the Signals 304

10.3.2 Interpretation 304

10.4 Mass Spectrometry 305

10.4.1 Origin of the Signals 306

10.4.2 Interpretation 307

10.5 N MR Spectroscopy 309

10.5.1 Origin of the Signals 309

10.5.2 Interpretation of Proton NMR Spectra 311

10.6 Carbon NMR Spectra 323

10.6.1 General Characteristics 323

10.6.2 Interpretation of 13C NMR Spectra 325

10.7 Correlation of 1H and 13C NMR Spectra 327

Resources 329

Problems 329

References 333

Appendix A 337

Appendix B 341

Index 347

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