CONTENTS

Dedication and Preace 1

CHAPTER 1
Structure and Bonding 7
Why This Chapter? 7
1.1 Atomic Structure: The Nucleus 9
1.2 Atomic Structure: Orbitals 9
1.3 Atomic Structure: Electron Confgurations 11
1.4 Development o Chemical Bonding Theory 12
1.5 Describing Chemical Bonds: Valence Bond Theory 15
3
1.6 sp Hybrid Orbitals and the Structure o Methane 17
1.7 sp3 Hybrid Orbitals and the Structure o Ethane 18
1.8 sp2 Hybrid Orbitals and the Structure o Ethylene 19
1.9 sp Hybrid Orbitals and the Structure o Acetylene 21
1.10 Hybridization o Nitrogen, Oxygen, Phosphorus, and Sulur 22
1.11 Describing Chemical Bonds: Molecular Orbital Theory 24
1.12 Drawing Chemical Structures 25
Chemistry Matters—Organic Foods: Risk versus Beneft 28
Key Terms 29
Summary 29
Additional Problems 30

CHAPTER 2
Polar Covalent Bonds; Acids and Bases 37
Why This Chapter? 37
2.1 Polar Covalent Bonds and Electronegativity 38
2.2 Polar Covalent Bonds and Dipole Moments 40
2.3 Formal Charges 42
2.4 Resonance 44
2.5 Rules or Resonance Forms 45
2.6 Drawing Resonance Forms 46
2.7 Acids and Bases: The Brønsted–Lowry Defnition 48
2.8 Acid and Base Strength 49
2.9 Predicting Acid–Base Reactions rom pKa Values 51
2.10 Organic Acids and Organic Bases 53
2.11 Acids and Bases: The Lewis Defnition 55
2.12 Noncovalent Interactions between Molecules 58
Chemistry Matters—Alkaloids: From Cocaine to Dental Anesthetics 61
Key Terms 62
Summary 62
Additional Problems 63

CHAPTER 3
Organic Compounds: Alkanes and Their Stereochemistry 71
Why This Chapter? 71
3.1 Functional Groups 72
3.2 Alkanes and Alkane Isomers 78
3.3 Alkyl Groups 81
3.4 Naming Alkanes 84
3.5 Properties o Alkanes 89
3.6 Conormations o Ethane 90
3.7 Conormations o Other Alkanes 92
Chemistry Matters—Gasoline 97
Key Terms 98
Summary 98
Additional Problems 99

CHAPTER 4
Organic Compounds: Cycloalkanes and Their Stereochemistry 105

Why This Chapter? 105

4.1 Naming Cycloalkanes 106
4.2 Cis–Trans Isomerism in Cycloalkanes 108
4.3 Stability o Cycloalkanes: Ring Strain 110
4.4 Conormations o Cycloalkanes 112
4.5 Conormations o Cyclohexane 113
4.6 Axial and Equatorial Bonds in Cyclohexane 115
4.7 Conormations o Monosubstituted Cyclohexanes 118
4.8 Conormations o Disubstituted Cyclohexanes 120
4.9 Conormations o Polycyclic Molecules 123
Chemistry Matters—Molecular Mechanics 126
Key Terms 127
Summary 127
Additional Problems 128

CHAPTER 5
Stereochemistry at Tetrahedral Centers 135
Why This Chapter? 135
5.1 Enantiomers and the Tetrahedral Carbon 136
5.2 The Reason or Handedness in Molecules: Chirality 137
5.3 Optical Activity 140
5.4 Pasteur’s Discovery o Enantiomers 142
5.5 Sequence Rules or Speciying Confguration 143
5.6 Diastereomers 147
5.7 Meso Compounds 150
5.8 Racemic Mixtures and the Resolution o Enantiomers 152
5.9 A Review o Isomerism 154
5.10 Chirality at Nitrogen, Phosphorus, and Sulur 155
5.11 Prochirality 156
5.12 Chirality in Nature and Chiral Environments 159
Chemistry Matters—Chiral Drugs 161
Key Terms 162
Summary 162
Additional Problems 163

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CHAPTER 6
An Overview of Organic Reactions 171
Why This Chapter? 171
6.1 Kinds o Organic Reactions 172
6.2 How Organic Reactions Occur: Mechanisms 173
6.3 Polar Reactions 174
6.4 An Example o a Polar Reaction: Addition o HBr to Ethylene 178
6.5 Using Curved Arrows in Polar Reaction Mechanisms 181
6.6 Radical Reactions 183
6.7 Describing a Reaction: Equilibria, Rates, and Energy Changes 185
6.8 Describing a Reaction: Bond Dissociation Energies 187
6.9 Describing a Reaction: Energy Diagrams and Transition States 189
6.10 Describing a Reaction: Intermediates 192
6.11 A Comparison Between Biological Reactions and Laboratory Reactions 194
Chemistry Matters—Where Do Drugs Come From? 197
Key Terms 198
Summary 199
Additional Problems 199

CHAPTER 7
Alkenes: Structure and Reactivity 207
Why This Chapter? 207
7.1 Industrial Preparation and Use o Alkenes 208
7.2 Calculating the Degree o Unsaturation 209
7.3 Naming Alkenes 211
7.4 Cis–Trans Isomerism in Alkenes 213
7.5 Alkene Stereochemistry and the E,Z Designation 214
7.6 Stability o Alkenes 217
7.7 Electrophilic Addition Reactions o Alkenes 219
7.8 Orientation o Electrophilic Additions: Markovnikov’s Rule 222
7.9 Carbocation Structure and Stability 226
7.10 The Hammond Postulate 228
7.11 Evidence or the Mechanism o Electrophilic Additions: Carbocation Rearrangements 230
Chemistry Matters—Bioprospecting: Hunting or Natural Products 233
Key Terms 234
Summary 234
Additional Problems 235

CHAPTER 8
Alkenes: Reactions and Synthesis 243
Why This Chapter? 243
8.1 Preparing Alkenes: A Preview o Elimination Reactions 244
8.2 Halogenation o Alkenes: Addition o X2 245
8.3 Halohydrins rom Alkenes: Addition o HO-X 247
8.4 Hydration o Alkenes: Addition o H2O by Oxymercuration 249
8.5 Hydration o Alkenes: Addition o H2O by Hydroboration 252
8.6 Reduction o Alkenes: Hydrogenation 255
8.7 Oxidation o Alkenes: Epoxidation and Hydroxylation 259
8.8 Oxidation o Alkenes: Cleavage to Carbonyl Compounds 261
8.9 Addition o Carbenes to Alkenes: Cyclopropane Synthesis 263
8.10 Radical Additions to Alkenes: Chain-Growth Polymers 265
8.11 Biological Additions o Radicals to Alkenes 269
8.12 Reaction Stereochemistry: Addition o H2O to an Achiral Alkene 270
8.13 Reaction Stereochemistry: Addition o H2O to a Chiral Alkene 272
Chemistry Matters—Terpenes: Naturally Occurring Alkenes 273
Key Terms 274
Summary 275
Summary o Reactions 275
Additional Problems 277

CHAPTER 9
Alkynes: An Introduction to Organic Synthesis 287
Why This Chapter? 287
9.1 Naming Alkynes 288
9.2 Preparation o Alkynes: Elimination Reactions o Dihalides 289
9.3 Reactions o Alkynes: Addition o HX and X2 289
9.4 Hydration o Alkynes 291
9.5 Reduction o Alkynes 295
9.6 Oxidative Cleavage o Alkynes 297
9.7 Alkyne Acidity: Formation o Acetylide Anions 298
9.8 Alkylation o Acetylide Anions 299
9.9 An Introduction to Organic Synthesis 301
Chemistry Matters—The Art o Organic Synthesis 305
Key Terms 306
Summary 306
Summary o Reactions 307
Additional Problems 308

CHAPTER 10
Organohalides 317
Why This Chapter? 317
10.1 Names and Structures o Alkyl Halides 318
10.2 Preparing Alkyl Halides rom Alkanes: Radical Halogenation 320
10.3 Preparing Alkyl Halides rom Alkenes: Allylic Bromination 322
10.4 Stability o the Allyl Radical: Resonance Revisited 323
10.5 Preparing Alkyl Halides rom Alcohols 326
10.6 Reactions o Alkyl Halides: Grignard Reagents 327
10.7 Organometallic Coupling Reactions 328
10.8 Oxidation and Reduction in Organic Chemistry 330
Chemistry Matters—Naturally Occurring Organohalides 333
Key Terms 334
Summary 334
Summary o Reactions 334
Additional Problems 335

CHAPTER 11
Reactions of Alkyl Halides: Nucleophilic Substitutions and
Eliminations 341
Why This Chapter? 341
11.1 The Discovery o Nucleophilic Substitution Reactions 342
11.2 The SN2 Reaction 344

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11.3 Characteristics o the SN2 Reaction 346
11.4 The SN1 Reaction 352
11.5 Characteristics o the SN1 Reaction 356
11.6 Biological Substitution Reactions 360
11.7 Elimination Reactions: Zaitsev’s Rule 362
11.8 The E2 Reaction and the Deuterium Isotope Eect 364
11.9 The E2 Reaction and Cyclohexane Conormation 367
11.10 The E1 and E1cB Reactions 369
11.11 Biological Elimination Reactions 370
11.12 A Summary o Reactivity: SN1, SN2, E1, E1cB, and E2 371
Chemistry Matters—Green Chemistry 373
Key Terms 374
Summary 374
Summary o Reactions 375
Additional Problems 375

CHAPTER 12
Structure Determination: Mass Spectrometry and Infrared
Spectroscopy 385
Why This Chapter? 385
12.1 Mass Spectrometry o Small Molecules: Magnetic-Sector Instruments 386
12.2 Interpreting Mass Spectra 388
12.3 Mass Spectrometry o Some Common Functional Groups 391
12.4 Mass Spectrometry in Biological Chemistry: Time-o-Flight (TOF) Instruments 396
12.5 Spectroscopy and the Electromagnetic Spectrum 397
12.6 Inrared Spectroscopy 399
12.7 Interpreting Inrared Spectra 400
12.8 Inrared Spectra o Some Common Functional Groups 404
Chemistry Matters—X-Ray Crystallography 410
Key Terms 411
Summary 412
Additional Problems 412

Appendix A Nomenclature o Polyunctional Organic Compounds 419

Appendix B Acidity Constants or Some Organic Compounds 425
Appendix C Periodic Table 433
Answer Key 435
Index 453

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page for Organic Chemistry: A Tenth Edition on [Link].