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Chapter 1 Introduction 1

1.1 The Shape of Molecules 2

1.2 Atomic and Molecular Orbitals 5

1.3 Structure＆Bonding 10

1.4 Chemical Bonding and Valence 13

1.5 Covalent Bonding 14

1.6 Valence 17

1.7 Charge Distribution 17

1.8 Functional Groups 21

Chapter 2 Alkanes 25

2.1 Alkane Nomenclature 25

2.1.1 IUPAC Rules for Alkane Nomenclature 27

2.2 Conformational Stereoisomers 28

2.2.1 Ethane Conformations 29

2.2.2 Butane Conformations 31

2.3 Physical Properties of Alkanes 33

2.4 Chemical Properties of Alkanes 36

Chapter 3 Alkenes 40

3.1 Alkene and Cycloalkene Nomenclature 40

3.1.1 IUPAC Rules 40

3.1.2 Stereoisomers 41

3.1.3 Configurational Stereoisomers ofAlkenes 42

3.1.4 Nomenclature of Alkene Stereoisomers 44

3.1.5 The Sequence Rule forAssignment of Alkene Configurations 45

3.2 Physical Properties of Alkenes 46

3.3 Reactions of Alkenes 47

3.3.1 Addition Reactions of Alkenes 47

a．Addition of Strong Br？nsted Acids 47

b．Regioselectivity and the Markovnikov Rule 49

c．Rearrangement of Carbocations 54

d．Addition of Lewis Acids（Electrophilic Reagents） 55

e．Stereoselectivity in Addition Reactions to Double Bonds 60

f．Br？nsted Acid Additions 61

g．Addition Reactions Initiated by Electrophilic Halogen 61

h．Addition Reactions Involving Other Cyclic Onium Intermediates 63

3.3.2 Hydrogenation 66

3.3.3 Oxidations 68

（i）Hydroxylation 68

（ii）Epoxidation 69

（iii）Oxidative Cleavage of Double Bonds 71

3.3.4 Free Radical Reactions of Alkenes 74

a．Addition of Radicals to Alkenes 74

b．Allylic Substitution 75

Chapter 4 Alkynes 79

4.1 IUPAC Rules for Alkyne Nomenclature 79

4.2 Reactions of Alkynes 80

4.2.1 Adclition Reactions of Alkynes 80

a．Catalytic Hydrogenation 80

b．Addition by Electrophilic Reagents 82

c．Hydration of Alkynes and Tautomerism 86

d．Hydroboration Reactions 88

e．Oxidations 89

4.2.2 Nucleophilic Addition Reactions＆Reduction 90

4.2.3 Acidity of Terminal Alkynes 91

4.3 Physical Properties of Alkynes 93

Chapter 5 Dienes 96

5.1 Properties of Dienes 96

5.1.1 Addition Reactions of Dienes 98

5.1.2 Diels-Alder Cycloaddition 101

5.1.3 Stereospecificity 103

5.2 Properties of Cumulated Dienes 107

5.2.1 Addition Reactions of Allenes 109

Chapter 6 Cycloalkanes 115

6.1 IUPAC Rules for Cycloalkane Nomenclature 116

6.2 Ring Conformations 118

6.2.1 Substituted Cyclohexane Compounds 122

6.2.2 Conformational Structures of Disubstituted Cyclohexanes 123

6.2.3 Configurational Stereoisomers of Cycloalkanes 125

6.3 Cycloalkanes reactions 126

Chapter 7 Alkyl Halide 130

7.1 Naming 130

7.2 Alkyl Halide Reactions 131

7.3 Mechanisms of Nucleophilic Substitution Reactions 143

7.3.1 The SN2 Mechanism 143

7.3.2 The SN1 Mechanism 144

7.3.3 Activation by Electrophilic Cations 147

7.3.4 The E2 Reaction 148

7.3.5 Stereochemistry of the E2 Reaction 154

7.3.6 The E1 Reaction 157

7.3.7 Summary of Factors Influencing Alkyl Halide Reactions 159

7.4 Organometallic Compounds 161

7.4.1 Reactions of Alkyl Halides with Reducing Metals 161

7.5 Reactions of Dihalides 164

7.5.1 Preparation ofAlkynes by Dehydrohalogenation 167

Chapter 8 Aromatic compounds 171

8.1 Benzene Derivatives 171

8.2 Aromaticity 174

8.3 Aromatic Substitution Reactions 179

8.3.1 Substitution Reactions of Benzene and Other Aromatic Compounds 179

8.3.2 A Mechanism for Electrophilic Substitution Reactions of Benzene 181

8.3.3 Substitution Reactions of Benzene Derivatives 183

8.3.4 Characteristics of Specific Substitution Reactions 191

8.3.5 Electrophilic Substitution of Disubstituted Benzene Rings 195

8.4 Reactions of Substituent Groups 198

8.5 Reactions of Fused Benzene Rings 204

8.6 Nucleophilic Substitution,Elimination＆Addition Reactions of Benzene Derivatives 206

8.6.1 Substitution 206

8.6.2 Elimination 207

8.6.3 Addition 209

8.7 Fused Benzene Ring Compounds 210

8.8 Other Aromatic Systems 213

Chapter 9 Alcohol Phenol and Ethers 220

9.1 Alcohol 220

9.1.1 Alcohol Nomenclature 220

9.1.2 Alcohol Reactions 222

a．Electrophilic Substitution at Oxygen 223

b．Nucleophilic Substitution of the Hydroxyl Group 226

c．Elimination Reactions of Alcohols 232

d．Oxidation Reactions of Alcohols 235

9.2 Phenols 239

9.2.1 Phenols Nomenclature 239

9.2.2 Reactions of Phenols 240

a．Acidity of Phenols 241

b．Substitution of the Hydroxyl Hydrogen 243

c．Electrophilic Substitution of the Phenol Aromatic Ring 243

d．Oxidation of Phenols 244

9.3 Ethers 246

9.3.1 Ether Nomenclature 246

9.3.2 Preparation of Ethers 247

9.3.3 Reactions of Ethers 249

9.3.4 Reactions of Epoxides 251

9.4 Sulfur and Phosphorus Compounds 252

9.4.1 Nucleophilicity of Sulfur Compounds 252

9.4.2 Oxidation States of Sulfur Compounds 253

9.4.3 Oxidation of Alcohols by DMSO 255

9.4.4 Nucleophilicity of Phosphorus Compounds 257

9.4.5 Oxidation States of Phosphorus Compounds 258

9.4.6 Phosphorus Compounds as Reducing Agents 259

Chapter 10 Aldehydes and Ketones 265

10.1 Nomenclature of Aldehydes and Ketones 265

10.2 Synthetic Preparation of Aldehydes and Ketones 270

10.3 Properties of Aldehydes and Ketones 272

10.3.1 Reactions of Aldehydes and Ketones 274

a．Reversible Addition Reactions 274

b．Irreversible Addition Reactions 281

10.3.2 Other Carbonyl Group Reactions 288

a．Reduction 288

b．Oxidation 291

10.3.3 Reactions at the α-Carbon 292

a．Mechanism of Electrophilic α-Substitution 293

b．The Aldol Reaction 296

c．Dehydration of Aldol Products 297

d．Mixed A1dol Condensations 300

10.3.4 Irreversible Substitution Reactions 302

a．The Ambident Character of Enolate Anions 302

b．Alkylation Reactions of Enolate Anions 305

Chapter 11 Carboxylic Acids 312

11.1 Nomenclature of Carboxylic Acids 312

11.2 Carboxylic Acid Natural Products 314

11.3 Related Carbonyl Derivatives 316

11.4 Properties of Carboxylic Acids 318

11.4.1 Physical Properties ofCarboxylic Acids 318

11.4.2 Acidity of Carboxylic Acids 320

11.5 Preparation of Carboxylic Acids 324

11.6 Reactions of Carboxylic Acids 326

11.6.1 Salt Formation 326

11.6.2 Substitution of the Hydroxyl Hydrogen 326

11.6.3 Substitution of the Hydroxyl Group 328

11.7 Reductions＆Oxidations of Carboxylic Acids 331

11.7.1 Reduction 331

11.7.2 Oxidation 332

Chapter 12 Derivatives of Carboxylic Acids 336

12.1 Background and Properties 336

12.2 Nomenclature 337

12.3 Reactions ofCarboxylic Acid Derivatives 339

12.3.1 Acyl Group Substitution 339

12.3.2 Reduction 345

12.3.3 Reactions with Organometallic Reagents 354

12.3.4 Other Reactions 356

12.3.5 Reactions at the α-Carbon 357

a．Enolate Intermediates 359

b．Claisen Condensation 361

12.4 Condensation Reactions in Synthesis 365

a．Carbon-Carbon Bond Formation 366

b．Modification of Condensation Products 367

12.5 Fatty Acid Derivatives 372

12.5.1 Fatty Acids 372

12.5.2 Fats and Oils 374

12.5.3 Waxes 377

12.5.4 Terpenes 377

12.6 Biosynthetic Pathways 380

Chapter 13 Chemistry of Amines 389

13.1 Nomenclature and Structure ofAmines 389

13.2 A Structure Formula Relationship 393

13.3 Properties of Amines 394

13.3.1 Boiling Point and Water Solubility 394

13.3.2 Basicity of Amines 395

13.3.3 Acidity of Amines 398

13.3.4 Important Reagent Bases 399

13.4 Amine Reactions 400

13.4.1 Electrophilic Substitution at Nitrogen 400

13.4.2 Preparation of 1°-Amines 403

13.4.3 Preparation of 2°＆3°-Amines 407

13.4.4 Reaction of Amines with Nitrous Acid 409

13.4.5 Reactions of Aryl Diazonium Salts 413

13.4.6 Substitution and Elimination Reactions of Amines 417

13.4.7 Oxidation States of Nitrogen 423