Chapter 1 Bond-Line Drawings 1

1.1 How to Read Bond-Line Drawings 1

1.2 How to Draw Bond-Line Drawings 4

1.3 Mistakes to Avoid 6

1.4 More Exercises 6

1.5 Identifying Formal Charges 8

1.6 Finding Lone Pairs that are Not Drawn 11

Chapter 2 Resonance 15

2.1 What is Resonance? 15

2.2 Curved Arrows: The Tools for Drawing Resonance Structures 16

2.3 The Two Commandments 17

2.4 Drawing Good Arrows 20

2.5 Formal Charges in Resonance Structures 22

2.6 Drawing Resonance Structures—Step by Step 25

2.7 Drawing Resonance Structures—by Recognizing Patterns 29

2.8 Assessing the Relative Importance of Resonance Structures 36

Chapter 3 Acid–Base Reactions 41

3.1 Factor 1—What Atom is the Charge On? 41

3.2 Factor 2—Resonance 44

3.3 Factor 3—Induction 47

3.4 Factor 4—Orbitals 49

3.5 Ranking the Four Factors 50

3.6 Other Factors 53

3.7 Quantitative Measurement (pK_a Values) 54

3.8 Predicting the Position of Equilibrium 54

3.9 Showing a Mechanism 55

Chapter 4 Geometry 57

4.1 Orbitals and Hybridization States 57

4.2 Geometry 60

4.3 Lone Pairs 62

Chapter 5 Nomenclature 64

5.1 Functional Group 65

5.2 Unsaturation 66

5.3 Naming the Parent Chain 67

5.4 Naming Substituents 70

5.5 Stereoisomerism 72

5.6 Numbering 74

5.7 Common Names 78

5.8 Going from a Name to a Structure 79

Chapter 6 Conformations 80

6.1 How to Draw a Newman Projection 80

6.2 Ranking the Stability of Newman Projections 84

6.3 Drawing Chair Conformations 86

6.4 Placing Groups on the Chair 90

6.5 Ring Flipping 93

6.6 Comparing the Stability of Chairs 99

6.7 Don’t Be Confused by the Nomenclature 102

Chapter 7 Configurations 103

7.1 Locating Chiral Centers 103

7.2 Determining the Configuration of a Chiral Center 106

7.3 Nomenclature 113

7.4 Drawing Enantiomers 116

7.5 Diastereomers 120

7.6 Meso Compounds 121

7.7 Drawing Fischer Projections 123

7.8 Optical Activity 127

Chapter 8 Mechanisms 129

8.1 Introduction to Mechanisms 129

8.2 Nucleophiles and Electrophiles 129

8.3 Basicity vs. Nucleophilicity 131

8.4 Arrow-Pushing Patterns for Ionic Mechanisms 133

8.5 Carbocation Rearrangements 138

8.6 Information Contained in a Mechanism 142

Chapter 9 Substitution Reactions 145

9.1 The Mechanisms 145

9.2 Factor 1—The Electrophile (Substrate) 147

9.3 Factor 2—The Nucleophile 149

9.4 Factor 3—The Leaving Group 151

9.5 Factor 4—The Solvent 153

9.6 Using All Four Factors 155

9.7 Substitution Reactions Teach Us Some Important Lessons 156

Chapter 10 Elimination Reactions 157

10.1 The E2 Mechanism 157

10.2 The Regiochemical Outcome of an E2 Reaction 158

10.3 The Stereochemical Outcome of an E2 Reaction 159

10.4 The E1 Mechanism 162

10.5 The Regiochemical Outcome of an E1 Reaction 163

10.6 The Stereochemical Outcome of an E1 Reaction 164

10.7 Substitution vs. Elimination 164

10.8 Determining the Function of the Reagent 165

10.9 Identifying the Mechanism(s) 167

10.10 Predicting the Products 169

Chapter 11 Addition Reactions 172

11.1 Terminology Describing Regiochemistry 172

11.2 Terminology Describing Stereochemistry 174

11.3 Adding H and H 180

11.4 Adding H and X, Markovnikov 183

11.5 Adding H and Br, Anti-Markovnikov 188

11.6 Adding H and OH, Markovnikov 192

11.7 Adding H and OH, Anti-Markovnikov 194

11.8 Synthesis Techniques 198

11.9 Adding Br and Br; Adding Br and OH 204

11.10 Adding OH and OH, Anti 209

11.11 Adding OH and OH, syn 211

11.12 Oxidative Cleavage of an Alkene 213

Summary of Reactions 214

Chapter 12 Alkynes 216

12.1 Structure and Properties of Alkynes 216

12.2 Preparation of Alkynes 218

12.3 Alkylation of Terminal Alkynes 219

12.4 Reduction of Alkynes 221

12.5 Hydration of Alkynes 224

12.6 Keto-Enol Tautomerization 227

12.7 Ozonolysis of Alkynes 232

Chapter 13 Alcohols 234

13.1 Naming and Designating Alcohols 234

13.2 Predicting Solubility of Alcohols 235

13.3 Predicting Relative Acidity of Alcohols 237

13.4 Preparing Alcohols: A Review 239

13.5 Preparing Alcohols via Reduction 240

13.6 Preparing Alcohols via Grignard Reactions 246

13.7 Summary of Methods for Preparing Alcohols 249

13.8 Reactions of Alcohols: Substitution and Elimination 250

13.9 Reactions of Alcohols: Oxidation 253

13.10 Converting an Alcohol into an Ether 255

Chapter 14 Ethers and Epoxides 257

14.1 Introduction to Ethers 257

14.2 Preparation of Ethers 259

14.3 Reactions of Ethers 261

14.4 Preparation of Epoxides 262

14.5 Ring-Opening Reactions of Epoxides 264

Chapter 15 Synthesis 270

15.1 One-Step Syntheses 271

15.2 Multistep Syntheses 283

15.3 Retrosynthetic Analysis 284

15.4 Creating Your Own Problems 285

Detailed Solutions 287

Index 381

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