Readers continue to turn to Klein’s Organic Chemistry as a Second Language: First Semester Topics, 3rd Edition because it enables them to better understand fundamental principles, solve problems, and focus on what they need to know to succeed. This edition explores the major principles in the field and explains why they are relevant. It is written in a way that clearly shows the patterns in organic chemistry so that readers can gain a deeper conceptual understanding of the material. Topics are presented clearly in an accessible writing style along with numerous of hands-on problem solving exercises.

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 10

1.6 Finding Lone Pairs That Are Not Drawn 14

CHAPTER 2 RESONANCE 20

2.1 What Is Resonance? 20

2.2 Curved Arrows: The Tools for Drawing Resonance Structures 21

2.3 The Two Commandments 24

2.4 Drawing Good Arrows 27

2.5 Formal Charges in Resonance Structures 29

2.6 Drawing Resonance Structures—Step by Step 33

2.7 Drawing Resonance Structures—By Recognizing Patterns 38

A Lone Pair Next to a Pi Bond 38

A Lone Pair Next to a Positive Charge 41

A Pi Bond Next to a Positive Charge 43

A Pi Bond Between Two Atoms, Where One of Those Atoms Is Electronegative (N, O, etc.) 44

Pi Bonds Going All the Way Around a Ring 45

2.8 Assessing the Relative Importance of Resonance Structures 47

CHAPTER 3 ACID–BASE REACTIONS 53

3.1 Factor 1—What Atom Is the Charge on? 54

3.2 Factor 2—Resonance 57

3.3 Factor 3—Induction 61

3.4 Factor 4—Orbitals 64

3.5 Ranking the Four Factors 65

3.6 Quantitative Measurement (pKa values) 69

3.7 Predicting the Position of Equilibrium 70

3.8 Showing a Mechanism 71

CHAPTER 4 GEOMETRY 74

4.1 Orbitals and Hybridization States 74

4.2 Geometry 78

4.3 Lone Pairs 81

CHAPTER 5 NOMENCLATURE 83

5.1 Functional Group 84

5.2 Unsaturation 86

5.3 Naming the Parent Chain 88

5.4 Naming Substituents 90

5.5 Stereoisomerism 94

5.6 Numbering 97

5.7 Common Names 102

5.8 Going from a Name to a Structure 103

CHAPTER 6 CONFORMATIONS 104

6.1 How to Draw a Newman Projection 105

6.2 Ranking the Stability of Newman Projections 109

6.3 Drawing Chair Conformations 113

6.4 Placing Groups on the Chair 116

6.5 Ring Flipping 121

6.6 Comparing the Stability of Chairs 127

6.7 Don’t Be Confused by the Nomenclature 131

CHAPTER 7 CONFIGURATIONS 132

7.1 Locating Stereocenters 133

7.2 Determining the Configuration of a Stereocenter 136

7.3 Nomenclature 144

7.4 Drawing Enantiomers 149

7.5 Diastereomers 154

7.6 Meso Compounds 155

7.7 Drawing Fischer Projections 158

7.8 Optical Activity 163

CHAPTER 8 MECHANISMS 165

8.1 Curved Arrows 166

8.2 Arrow Pushing 171

8.3 Drawing Intermediates 173

8.4 Nucleophiles and Electrophiles 176

8.5 Bases Versus Nucleophiles 177

8.6 The Regiochemistry Is Contained Within the Mechanism 180

8.7 The Stereochemistry Is Contained Within the Mechanism 183

8.8 A List of Mechanisms 188

CHAPTER 9 SUBSTITUTION REACTIONS 209

9.1 The Mechanisms 209

9.2 Factor 1—The Electrophile (Substrate) 212

9.3 Factor 2—The Nucleophile 215

9.4 Factor 3—The Leaving Group 217

9.5 Factor 4—The Solvent 220

9.6 Using All Four Factors 223

9.7 Substitution Reactions Teach Us Some Important Lessons 224

CHAPTER 10 ELIMINATION REACTIONS 226

10.1 The E2 Mechanism 226

10.2 The Regiochemical Outcome of an E2 Reaction 227

10.3 The Stereochemical Outcome of an E2 Reaction 229

10.4 The E1 Mechanism 232

10.5 The Regiochemical Outcome of an E1 Reaction 233

10.6 The Stereochemical Outcome of an E1 Reaction 234

10.7 Substitution vs. Elimination 234

10.8 Determining the Function of the Reagent 235

10.9 Identifying the Mechanism(s) 238

10.10 Predicting the Products 241

CHAPTER 11 ADDITION REACTIONS 245

11.1 Terminology Describing Regiochemistry 245

11.2 Terminology Describing Stereochemistry 247

11.3 Adding H and H 256

11.4 Adding H and X, Markovnikov 259

11.5 Adding H and Br, Anti-Markovnikov 266

11.6 Adding H and OH, Markovnikov 271

11.7 Adding H and OH, Anti-Markovnikov 275

11.8 Synthesis Techniques 279

11.9 Adding Br and Br; Adding Br and OH 287

11.10 Adding OH and OH, Anti 293

11.11 Adding OH and OH, Syn 296

11.12 Oxidative Cleavage of an Alkene 298

CHAPTER 12 ALCOHOLS 302

12.1 Naming and Designating Alcohols 302

12.2 Predicting Solubility of Alcohols 303

12.3 Predicting Relative Acidity of Alcohols 306

12.4 Preparing Alcohols: A Review 309

12.5 Preparing Alcohols via Reduction 310

12.6 Preparing Alcohols via Grignard Reactions 317

12.7 Summary of Methods for Preparing Alcohols 322

12.8 Reactions of Alcohols: Substitution and Elimination 323

12.9 Reactions of Alcohols: Oxidation 327

12.10 Converting an Alcohol into an Ether 329

CHAPTER 13 SYNTHESIS 332

13.1 One-step Syntheses 333

13.2 Multistep Syntheses 345

13.3 Retrosynthetic Analysis 346

13.4 Creating Your Own Problems 347

Answer Key 349

Index 375