Organic Chemistry as a Second Language

CHAPTER 1 AROMATICITY 1

1.1 Introduction to Aromatic Compounds 1

1.2 Nomenclature of Aromatic Compounds 2

1.3 Criteria for Aromaticity 6

1.4 Lone Pairs 9

End-of-Chapter Problems 11

CHAPTER 2 IR SPECTROSCOPY 14

2.1 Vibrational Excitation 14

2.2 IR Spectra 16

2.3 Wavenumber 16

2.4 Signal Intensity 21

2.5 Signal Shape 22

2.6 Analyzing an IR Spectrum 29

End-of-Chapter Problems 36

CHAPTER 3 NMR SPECTROSCOPY 39

3.1 Chemical Equivalence 39

3.2 Chemical Shift (Benchmark Values) 42

3.3 Integration 47

3.4 Multiplicity 50

3.5 Pattern Recognition 52

3.6 Complex Splitting 54

3.7 No Splitting 55

3.8 Hydrogen Deficiency Index (Degrees of Unsaturation) 56

3.9 Analyzing a Proton NMR Spectrum 59

3.10 13C NMR Spectroscopy 63

End-of-Chapter Problems 65

CHAPTER 4 ELECTROPHILIC AROMATIC SUBSTITUTION 78

4.1 Halogenation and the Role of Lewis Acids 79

4.2 Nitration 83

4.3 Friedel–Crafts Alkylation and Acylation 85

4.4 Sulfonation 92

4.5 Activation and Deactivation 96

4.6 Directing Effects 98

4.7 Identifying Activators and Deactivators 107

4.8 Predicting and Exploiting Steric Effects 117

4.9 Synthesis Strategies 124

End-of-Chapter Problems 129

CHAPTER 5 NUCLEOPHILIC AROMATIC SUBSTITUTION 134

5.1 Criteria for Nucleophilic Aromatic Substitution 134

5.2 SNAr Mechanism 136

5.3 Elimination–Addition 142

5.4 Mechanism Strategies 148

End-of-Chapter Problems 151

CHAPTER 6 KETONES AND ALDEHYDES 154

6.1 Preparation of Ketones and Aldehydes 154

6.2 Stability and Reactivity of C=O Bonds 157

6.3 H-Nucleophiles 159

6.4 O-Nucleophiles 164

6.5 S-Nucleophiles 174

6.6 N-Nucleophiles 176

6.7 C-Nucleophiles 184

6.8 Exceptions to the Rule 193

6.9 How to Approach Synthesis Problems 197

End-of-Chapter Problems 203

CHAPTER 7 CARBOXYLIC ACID DERIVATIVES 207

7.1 Reactivity of Carboxylic Acid Derivatives 207

7.2 General Rules 208

7.3 Acid Halides 212

7.4 Acid Anhydrides 220

7.5 Esters 222

7.6 Amides and Nitriles 231

7.7 Synthesis Problems 240

End-of-Chapter Problems 247

CHAPTER 8 ENOLS AND ENOLATES 253

8.1 Alpha Protons 253

8.2 Keto-Enol Tautomerism 255

8.3 Reactions Involving Enols 259

8.4 Making Enolates 262

8.5 Haloform Reaction 265

8.6 Alkylation of Enolates 268

8.7 Aldol Reactions 272

8.8 Claisen Condensation 278

8.9 Decarboxylation 285

8.10 Michael Reactions 292

End-of-Chapter Problems 299

CHAPTER 9 AMINES 303

9.1 Nucleophilicity and Basicity of Amines 303

9.2 Preparation of Amines Through SN2 Reactions 305

9.3 Preparation of Amines Through Reductive Amination 308

9.4 Acylation of Amines 313

9.5 Reactions of Amines with Nitrous Acid 316

9.6 Aromatic Diazonium Salts 319

End-of-Chapter Problems 322

CHAPTER 10 DIELS–ALDER REACTIONS 325

10.1 Introduction and Mechanism 325

10.2 The Dienophile 328

10.3 The Diene 329

10.4 Other Pericyclic Reactions 335

End-of-Chapter Problems 336

Detailed Solutions S-1

Index I-1