有机化学基础 英文版PDF电子书下载

1 Structure and Bonding: Acids and Bases 1

1.1 Atomic Structure 3

1.2 Electron Configuration of Atoms 4

1.3 Development of Chemical Bonding Theory 6

1.4 The Nature of Chemical Bonds: Ionic Bonds 7

1.5 The Nature of Chemical Bonds: Covalent Bonds 8

1.6 Formation of Covalent Bonds 11

1.7 Hybridization: sp3 Orbitals and the Structure of Methane 12

1.8 The Structure of Ethane 14

1.9 Hybridization: sp2 Orbitals and the Structure of Ethylene 16

1.10 Hybridization: sp Orbitals and the Structure of Acetylene 18

1.11 Bond Polarity and Electronegativity 20

1.12 Acids and Bases: The Br?nsted-Lowry Definition 23

1.13 Acids and Bases: The Lewis Definition 26

Interlude—Chemicals, Toxicity, and Risk 29

Summary and Key Words 30

Additional Problems 31

Working Problems 31

2 The Nature of Organic Compounds: Alkanes 36

2.1 Functional Groups 36

2.2 Alkanes and Alkyl Groups: Isomers 41

2.3 Naming Branched-Chain Alkanes 47

2.4 Properties of Alkanes 50

2.5 Conformations of Ethane 51

2.6 Drawing Chemical Structures 55

2.7 Cycloalkanes 57

2.8 Cis-Trans Isomerism in Cycloalkanes 58

2.9 Conformations of Some Common Cycloalkanes 60

2.10 Axial and Equatorial Bonds in Cyclohexane 63

2.11 Conformational Mobility of Cyclohexane 65

Interlude—Petroleum 67

Summary and Key Words 69

Additional Problems 70

3 Alkenes: The Nature of Organic Reactions 76

3.1 Naming Alkenes 77

3.2 Electronic Structure of Alkenes 79

3.3 Cis-Trans Isomers of Alkenes 80

3.4 Sequence Rules: The E,Z Designation 83

3.5 Kinds of Organic Reactions 87

3.6 How Reactions Occur: Mechanisms 88

3.7 An Example of a Polar Reaction: Addition of HCI to Ethylene 91

3.8 The Mechanism of an Organic Reaction: Addition of HCI to Ethylene 92

3.9 Describing a Reaction: Rates and Equilibria 93

3.10 Describing a Reaction: Reaction Energy Diagrams and Transition States 96

3.11 Describing a Reaction: Intermediates 98

Interlude--Carrots, Alkenes, and the Chemistry of Vision 100

Summary and Key Words 102

Additional Problems 103

4 Alkenes and Alkynes 108

4.1 Addition of HX to Alkenes: Hydrohalogenation 109

4.2 Orientation of Alkene Addition Reactions: Markovnikov s Rule 110

4.3 Carbocation Structure and Stability 112

4.4 Addition of H2O to Alkenes: Hydration 114

4.5 Addition of X2 to Alkenes: Halogenation 116

4.6 Addition of H2 to Alkenes: Hydrogenation 118

4.7 Oxidation of Alkenes 120

4.8 Alkene Polymers 122

4.9 Preparation of Alkenes: Elimination Reactions 124

4.10 Conjugated Dienes 127

4.11 Stability of Allylic Carbocations: Resonance 129

4.12 Drawing and Interpreting Resonance Forms 131

4.13 Alkynes 134

4.14 Reactions of Alkynes: Addition of H2, HX, and X2 136

4.15 Addition of H2O to Alkynes 137

4.16 Alkyne Acidity: Formation of Acetylide Anions 138

Interlude—Natural Rubber 140

Summary and Key Words 141

Summary of Reactions 142

Additional Problems 145

5 Aromatic Compounds 150

5.1 Structure of Benzene: The Kekule Proposal 151

5.2 Stability of Benzene 152

5.3 Structure of Benzene: The Resonance Proposal 153

5.4 Naming Aromatic Compounds 154

5.5 Chemistry of Benzene: Electrophilic Aromatic Substitution Reactions 157

5.6 Bromination of Benzene 158

5.7 Other Electrophilic Aromatic Substitution Reactions 160

5.8 The Friedel-Crafts Alkylation and Acylation Reactions 163

5.9 Substituent Effects in Electrophilic Aromatic Substitution 164

5.10 An Explanation of Substituent Effects 166

5.11 Oxidation and Reduction of Aromatic Compounds 170

5.12 Polycyclic Aromatic Hydrocarbons 171

5.13 Organic Synthesis 172

Interlude—Aspirin and Other Aromatic NSAID s 175

Summary and Key Words 176

Summary of Reactions 177

Additional Problems 178

6 Stereochemistry 183

6.1 Stereochemistry and the Tetrahedral Carbon 183

6.2 The Reason for Handedness in Molecules: Chirality 185

6.3 Optical Activity 190

6.4 Specific Rotation 191

6.5 Pasteur s Discovery of Enantiomers 192

6.6 Sequence Rules for Specifying Configuration 193

6.7 Diastereomers 196

6.8 Meso Compounds 198

6.9 Molecules with More Than Two Stereocenters 200

6.10 Racemic Mixtures and the Resolution of Enantiomers 201

6.11 Physical Properties of Stereoisomers 204

6.12 A Brief Review of Isomerism 205

6.13 Stereochemistry of Reactions: Addition of HBr to Alkenes 206

6.14 Chirality in Nature 208

Interlude—Chiral Drugs 209

Summary and Key Words 211

Additional Problems 211

7 Alkyl Halides 217

7.1 Naming Alkyl Halides 218

7.2 Preparation of Alkyl Halides: Radical Chlorination of Alkanes 219

7.3 Alkyl Halides from Alcohols 222

7.4 Reactions of Alkyl Halides: Grignard Reagents 223

7.5 Nucleophilic Substitution Reactions: The Discovery 225

7.6 Kinds of Nucleophilic Substitution Reactions 226

7.7 The SN2 Reaction 228

7.8 The SN1 Reaction 232

7.9 Eliminations: The E2 Reaction 236

7.10 Eliminations: The E1 Reaction 239

7.11 A Summary of Reactivity: SN1, SN2, E1, E2 239

7.12 Substitution Reactions in Living Organisms 242

Interlude—Naturally Occurring Organohalogen Compounds 243

Summary and Key Words 244

Summary of Reactions 245

Additional Problems 246

8 Alcohols,Ethers,and Phenols 251

8.1 Naming Alcohols, Phenols, and Ethers 252

8.2 Properties of Alcohols, Phenols, and Ethers: Hydrogen Bonding 254

8.3 Properties of Alcohols and Phenols: Acidity 256

8.4 Synthesis of Alcohols 258

8.5 Alcohols from Carbonyl Compounds 259

8.6 Ethers from Alcohols: The Williamson Ether Synthesis 261

8.7 Reactions of Alcohols 263

8.8 Synthesis and Reactions of Phenols 265

8.9 Reactions of Ethers: Acidic Cleavage 267

8.10 Cyclic Ethers: Epoxides 268

8.11 Ring-Opening Reactions of Epoxides 269

8.12 Thiols and Sulfides 270

Interlude—Ethanol as Chemical, Drug, and Poison 272

Summary and Key Words 274

Summary of Reactions 275

Additional Problems 276

9 Aldehydes and Ketones: Nucleophilic Addition Reactions 281

9.1 Kinds of Carbonyl Compounds 282

9.2 Structure and Properties of Carbonyl Groups 283

9.3 Naming Aldehydes and Ketones 284

9.4 Synthesis of Aldehydes and Ketones 286

9.5 Oxidation of Aldehydes 287

9.6 Reactions of Aldehydes and Ketones: Nucleophilic Additions 288

9.7 Nucleophilic Addition of Water: Hydration 290

9.8 Nucleophilic Addition of Alcohols: Acetal Formation 293

9.9 Nucleophilic Addition of Amines: Imine Formation 295

9.10 Nucleophilic Addition of Grignard Reagents: Alcohol Formation 296

9.11 Some Biological Nucleophilic Addition Reactions 299

Interlude—Insect Antifeedants 300

Summary and Key Words 301

Summary of Reactions 302

Additional Problems 303

10 Carboxylic Acids and Derivatives 308

10.1 Naming Carboxylic Acids and Derivatives 309

10.2 Occurrence, Structure, and Properties of Carboxylic Acids 313

10.3 Acidity of Carboxylic Acids 313

10.4 Synthesis of Carboxylic Acids 316

10.5 Nucleophilic Acyl Substitution Reactions 318

10.6 Reactions of Carboxylic Acids 321

10.7 Chemistry of Acid Halides 325

10.8 Chemistry of Acid Anhydrides 327

10.9 Chemistry of Esters 329

10.10 Chemistry of Amides 334

10.11 Chemistry of Nitriles 336

10.12 Nylons and Polyesters: Step-Growth Polymers 339

Interlude—β-Lactam Antibiotics 342

Summary and Key Words 343

Summary of Reactions 344

Additional Problems 346

11 Carbonyl Alpha-Substitution Reactions and Condensation Reactions 352

11.1 Keto-Enol Tautomerism 353

11.2 Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions 356

11.3 Alpha Halogenation of Aldehydes and Ketones 356

11.4 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 358

11.5 Reactivity of Enolate Ions 362

11.6 Alkylation of Enolate Ions 362

11.7 Carbonyl Condensation Reactions 365

11.8 Condensations of Aldehydes and Ketones: The Aldol Reaction 366

11.9 Dehydration of Aldol Products: Synthesis of Enones 368

11.10 Condensations of Esters: The Claisen Condensation Reaction 369

Interlude—Carbonyl Compounds in Metabolism 372

Summary and Key Words 373

Summary of Reactions 374

Additional Problems 375

12 Amines 380

12.1 Naming Amines 381

12.2 Structure and Properties of Amines 383

12.3 Amine Basicity 384

12.4 Synthesis of Amines 387

12.5 Reactions of Amines 390

12.6 Heterocyclic Amines 394

Interlude—Naturally Occurring Amines: Morphine Alkaloids 398

Summary and Key Words 400

Summary of Reactions 401

Additional Problems 402

13 Structure Determination 406

13.1 Infrared Spectroscopy and the Electromagnetic Spectrum 407

13.2 Infrared Spectroscopy of Organic Molecules 410

13.3 Ultraviolet Spectroscopy 415

13.4 Interpreting Ultraviolet Spectra: The Effect of Conjugation 416

13.5 Nuclear Magnetic Resonance Spectroscopy 418

13.6 The Nature of NMR Absorptions 419

13.7 Chemical Shifts 421

13.8 Chemical Shifts in 1H NMR Spectra 423

13.9 Integration of 1H NMR Spectra: Proton Counting 424

13.10 Spin-Spin Splitting in 1H NMR Spectra 425

13.11 Uses of 1H NMR Spectra 429

13.12 13C NMR Spectroscopy 430

Interlude—Magnetic Resonance Imaging (MRI) 432

Summary and Key Words 433

Additional Problems 434

14 Biomolecules: Carbohydrates 440

14.1 Classification of Carbohydrates 441

14.2 Configurations of Monosaccharides: Fischer Projections 443

14.3 D,L Sugars 445

14.4 Configurations of Aldoses 447

14.5 Cyclic Structures of Monosaccharides: Hemiacetal Formation 448

14.6 Monosaccharide Anomers: Mutarotation 452

14.8 Reactions of Monosaccharides 454

14.7 Conformations of Monosaccharides 454

14.9 Disaccharides 460

14.10 Polysaccharides 462

14.11 Other Important Carbohydrates 465

14.12 Cell-Surface Carbohydrates 466

Interlude—Sweetness 468

Summary and Key Words 469

Additional Problems 470

15 Biomolecules: Amino Acids,Peptides, and Proteins 474

15.1 Structures of Amino Acids 475

15.2 Dipolar Structure of Amino Acids 478

15.3 Isoelectric Points 480

15.4 Peptides and Proteins 481

15.5 Covalent Bonding in Peptides 484

15.6 Peptide Structure Determination: Amino Acid Analysis 484

15.7 Peptide Sequencing: The Edman Degradation 486

15.8 Peptide Synthesis 488

15.9 Classification of Proteins 491

15.10 Protein Structure 493

15.11 Enzymes 497

15.12 Structure and Classification of Enzymes 497

Interlude—Protein and Nutrition 500

Summary and Key Words 501

Additional Problems 502

16.1 Lipids 507

16 Biomolecules: Lipids and Nucleic Acids 507

16.2 Fats and Oils 508

16.3 Soaps 511

16.4 Phospholipids 513

16.5 Steroids 515

16.6 Nucleic Acids and Nucleotides 517

16.7 Structure of DNA 519

16.8 Base Pairing in DNA: The Watson-Crick Model 522

16.10 Replication of DNA 525

16.9 Nucleic Acids and Heredity 525

16.11 Structure and Synthesis of RNA: Transcription 527

16.12 RNA and Protein Biosynthesis: Translation 528

16.13 Sequencing DNA 532

16.14 The Polymerase Chain Reaction 536

Interlude—Cholesterol and Heart Disease 538

Summary and Key Words 539

Additional Problems 540

17 The Organic Chemistry of Metabolic Pathways 543

17.1 An Overview of Metabolism and Biochemical Energy 543

17.2 Catabolism of Fats: β-Οxidation Pathway 547

17.3 Catabolism of Carbohydretes: Glycolysis 552

17.4 The Citric Acid Cycle 557

17.5 Catabolism of Proteins: Transamination 560

Interlude—Basal Metabolism 562

Summary and Key Words 563

Additional Problems 564