Includes index.

CHAPTER 1 BOND-LINE DRAWINGS 1

1.1 How to Read Bond-Line Drawings 1

1.2 How to Draw Bond-Line Drawings 5

1.3 Mistakes to Avoid 7

1.4 More Exercises 7

1.5 Identifying Formal Charges 9

1.6 Finding Lone Pairs that are Not Drawn 13

CHAPTER 2 RESONANCE 18

2.1 What is Resonance? 18

2.2 Curved Arrows: The Tools for Drawing Resonance Structures 19

2.3 The Two Commandments 21

2.4 Drawing Good Arrows 24

2.5 Formal Charges in Resonance Structures 26

2.6 Drawing Resonance Structures—Step by Step 30

2.7 Drawing Resonance Structures—by Recognizing Patterns 34

2.8 Assessing the Relative Importance of Resonance Structures 43

CHAPTER 3 ACID–BASE REACTIONS 49

3.1 Factor 1—What Atom is the Charge On? 50

3.2 Factor 2—Resonance 53

3.3 Factor 3—Induction 56

3.4 Factor 4—Orbitals 59

3.5 Ranking the Four Factors 60

3.6 Other Factors 63

3.7 Quantitative Measurement (pKa Values) 64

3.8 Predicting the Position of Equilibrium 65

3.9 Showing a Mechanism 66

CHAPTER 4 GEOMETRY 69

4.1 Orbitals and Hybridization States 69

4.2 Geometry 72

4.3 Lone Pairs 76

CHAPTER 5 NOMENCLATURE 77

5.1 Functional Group 78

5.2 Unsaturation 80

5.3 Naming the Parent Chain 81

5.4 Naming Substituents 84

5.5 Stereoisomerism 88

5.6 Numbering 90

5.7 Common Names 95

5.8 Going from a Name to a Structure 96

CHAPTER 6 CONFORMATIONS 97

6.1 How to Draw a Newman Projection 98

6.2 Ranking the Stability of Newman Projections 102

6.3 Drawing Chair Conformations 105

6.4 Placing Groups On the Chair 108

6.5 Ring Flipping 112

6.6 Comparing the Stability of Chairs 119

6.7 Don’t Be Confused by the Nomenclature 122

CHAPTER 7 CONFIGURATIONS 123

7.1 Locating Stereocenters 123

7.2 Determining the Configuration of a Stereocenter 126

7.3 Nomenclature 134

7.4 Drawing Enantiomers 138

7.5 Diastereomers 143

7.6 Meso Compounds 144

7.7 Drawing Fischer Projections 147

7.8 Optical Activity 152

CHAPTER 8 MECHANISMS 154

8.1 Introduction to Mechanisms 154

8.2 Nucleophiles and Electrophiles 154

8.3 Basicity vs. Nucleophilicity 157

8.4 Arrow-Pushing Patterns for Ionic Mechanisms 159

8.5 Carbocation Rearrangements 164

8.6 Information Contained in a Mechanism 169

CHAPTER 9 SUBSTITUTION REACTIONS 173

9.1 The Mechanisms 173

9.2 Factor 1—The Electrophile (Substrate) 175

9.3 Factor 2—The Nucleophile 178

9.4 Factor 3—The Leaving Group 180

9.5 Factor 4—The Solvent 183

9.6 Using All Four Factors 185

9.7 Substitution Reactions Teach Us Some Important Lessons 186

CHAPTER 10 ELIMINATION REACTIONS 188

10.1 The E2 Mechanism 188

10.2 The Regiochemical Outcome of an E2 Reaction 189

10.3 The Stereochemical Outcome of an E2 Reaction 191

10.4 The E1 Mechanism 194

10.5 The Regiochemical Outcome of an E1 Reaction 195

10.6 The Stereochemical Outcome of an E1 Reaction 196

10.7 Substitution vs. Elimination 196

10.8 Determining the Function of the Reagent 197

10.9 Identifying the Mechanism(s) 199

10.10 Predicting the Products 202

CHAPTER 11 ADDITION REACTIONS 206

11.1 Terminology Describing Regiochemistry 206

11.2 Terminology Describing Stereochemistry 208

11.3 Adding H and H 216

11.4 Adding H and X, Markovnikov 219

11.5 Adding H and Br, Anti-Markovnikov 226

11.6 Adding H and OH, Markovnikov 230

11.7 Adding H and OH, Anti-Markovnikov 233

11.8 Synthesis Techniques 238

11.9 Adding Br and Br; Adding Br and OH 245

11.10 Adding OH and OH, anti 250

11.11 Adding OH and OH, syn 253

11.12 Oxidative Cleavage of an Alkene 255

Summary of Reactions 257

CHAPTER 12 ALKYNES 258

12.1 Structure and Properties of Alkynes 258

12.2 Preparation of Alkynes 261

12.3 Alkylation of Terminal Alkynes 262

12.4 Reduction of Alkynes 264

12.5 Hydration of Alkynes 268

12.6 Keto-Enol Tautomerization 273

12.7 Ozonolysis of Alkynes 279

CHAPTER 13 ALCOHOLS 280

13.1 Naming and Designating Alcohols 280

13.2 Predicting Solubility of Alcohols 281

13.3 Predicting Relative Acidity of Alcohols 283

13.4 Preparing Alcohols: A Review 286

13.5 Preparing Alcohols via Reduction 287

13.6 Preparing Alcohols via Grignard Reactions 294

13.7 Summary of Methods for Preparing Alcohols 298

13.8 Reactions of Alcohols: Substitution and Elimination 300

13.9 Reactions of Alcohols: Oxidation 303

13.10 Converting an Alcohol Into an Ether 305

CHAPTER 14 ETHERS AND EPOXIDES 308

14.1 Introduction to Ethers 308

14.2 Preparation of Ethers 310

14.3 Reactions of Ethers 313

14.4 Preparation of Epoxides 314

14.5 Ring-Opening Reactions of Epoxides 316

CHAPTER 15 SYNTHESIS 323

15.1 One-Step Syntheses 324

15.2 Multistep Syntheses 336

15.3 Retrosynthetic Analysis 337

15.4 Creating Your Own Problems 338

Answer Key 339

Index 371

FEATURES