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Organic Chemistry, Fifth Edition

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An Introduction to the Study of Organic Chemistry

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Organic Chemistry, Fifth Edition

by Paula Yurkanis Bruice

Publisher: Prentice Hall

Copyright Year: 2007

Publishing Date: 2006/03/21

eText ISBN-10: 0-13-604443-3

eText ISBN-13: 978-0-13-604443-7

Print ISBN-10: 0-13-196316-3

Print ISBN-13: 978-0-13-196316-0

Course: Organic Chemistry

Pages: 1440

eTextbook $102.00

(540 day subscription)

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Table of Contents | Description

Instructor Resources | Student Resources

ABOUT THIS TITLE - TABLE OF CONTENTS

For the Student, xxx

About the Author, xxxviii

Part 1. An Introduction to the Study of Organic Chemistry, 1

1. Electronic Structure and Bonding · Acids and Bases, 2

Natural Versus Synthetic, 3

1.1. The Structure of an Atom, 4

1.2. How the Electrons in an Atom Are Distributed, 5

Albert Einstein, 6

Max Karl Ernst Ludwig Planck, 7

1.3. Ionic and Covalent Bonds, 8

1.4. How the Structure of a Compound Is Represented, 15

Problem-Solving Strategy, 17

1.5. Atomic Orbitals, 21

1.6. An Introduction to Molecular Orbital Theory, 22

1.7. How Single Bonds Are Formed in Organic Compounds, 28

1.8. How a Double Bond Is Formed: The Bonds in Ethene, 32

Diamond, Graphite, and Buckminsterfullerene: Substances Containing Only Carbon Atoms, 33

1.9. How a Triple Bond Is Formed: The Bonds in Ethyne, 34

1.10. The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion, 35

1.11. The Bonds in Water, 37

1.12. The Bonds in Ammonia and in the Ammonium Ion, 38

Water—A Unique Compound, 38

1.13. The Bonds in the Hydrogen Halides, 39

1.14. Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles, 40

Problem-Solving Strategy, 42

1.15. The Dipole Moments of Molecules, 43

1.16. An Introduction to Acids and Bases, 44

1.17. pK_a and pH, 45

1.18. Organic Acids and Bases, 47

Problem-Solving Strategy, 47

1.19. How to Predict the Outcome of an Acid–Base Reaction, 50

1.20. How the Structure of an Acid Affects Its Acidity, 51

1.21. How Substituents Affect the Strength of an Acid, 55

Problem-Solving Strategy, 56

1.22. An Introduction to Delocalized Electrons, 57

1.23. A Summary of the Factors That Determine Acid Strength, 58

1.24. How the pH Affects the Structure of an Organic Compound, 60

Derivation of the Henderson–Hasselbalch Equation, 60

Problem-Solving Strategy, 61

1.25. Buffer Solutions, 63

1.26. The Second Definition of Acid and Base: Lewis Acids and Bases, 64

Blood: A Buffered Solution, 64

2. An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure, 71

2.1. How Alkyl Substituents Are Named, 74

2.2. The Nomenclature of Alkanes, 78

2.3. Nomenclature of Cycloalkanes · Skeletal Structures, 82

Problem-Solving Strategy, 83

2.4. Nomenclature of Alkyl Halides, 85

2.5. Nomenclature of Ethers, 86

2.6. Nomenclature of Alcohols, 87

2.7. Nomenclature of Amines, 89

Bad Smelling Compounds, 90

2.8. The Structures of Alkyl Halides, Alcohols, Ethers, and Amines, 92

2.9. The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines, 94

Problem-Solving Strategy, 97

2.10. Rotation Occurs About Carbon–Carbon Bonds, 101

2.11. Some Cycloalkanes Have Angle Strain, 104

Highly Strained Hydrocarbons, 105

von Baeyer and Barbituric Acid, 106

2.12. Conformations of Cyclohexane, 107

Problem-Solving Strategy, 108

2.13. Conformers of Monosubstituted Cyclohexanes, 110

2.14. Conformers of Disubstituted Cyclohexanes, 113

Problem-Solving Strategy, 113

Part 2. Electrophilic Addition Reactions, Stereochemistry, and Electron Delocalization, 123

3. Alkenes: Structure, Nomenclature, and an Introduction to Reactivity · Thermodynamics and Kinetics, 124

3.1. Molecular Formulas and the Degree of Unsaturation, 125

3.2. The Nomenclature of Alkenes, 126

3.3. The Structures of Alkenes, 129

3.4. Alkenes Can Have Cis and Trans Isomers, 130

Cis–Trans Interconversion in Vision, 132

3.5. Naming Alkenes Using the E,Z System, 133

Problem-Solving Strategy, 136

3.6. How Alkenes React · Curved Arrows Show the Flow of Electrons, 137

A Few Words About Curved Arrows, 140

3.7. Thermodynamics and Kinetics, 141

The Difference Between ΔG† and E_a, 151

3.8. Using a Reaction Coordinate Diagram to Describe a Reaction, 152

4. The Reactions of Alkenes, 159

4.1. Addition of a Hydrogen Halide to an Alkene, 160

4.2. Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon, 161

4.3. The Structure of the Transition State Lies Partway Between the Structures of the Reactants and Products, 164

4.4. Electrophilic Addition Reactions Are Regioselective, 166

Problem-Solving Strategy, 167

4.5. Acid-Catalyzed Addition Reactions, 169

4.6. A Carbocation Will Rearrange If It Can Form a More Stable Carbocation, 172

4.7. Addition of a Halogen to an Alkene, 175

4.8. Oxymercuration–Reduction and Alkoxymercuration–Reduction Are Other Ways to Add Water or an Alcohol to an Alkene, 180

4.9. Addition of a Peroxyacid to an Alkene, 182

Problem-Solving Strategy, 183

4.10. Addition of Borane to an Alkene: Hydroboration–Oxidation, 184

Borane and Diborane, 185

4.11. Addition of Hydrogen to an Alkene · The Relative Stabilities of Alkenes, 188

Problem-Solving Strategy, 190

Trans Fats, 190

4.12. Reactions and Synthesis, 192

Pesticides: Natural and Synthetic, 193

Summary of Reactions, 194

5. Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions, 200

5.1. Cis–Trans Isomers Result from Restricted Rotation, 201

5.2. A Chiral Object Has a Nonsuperimposable Mirror Image, 202

5.3. An Asymmetric Center Is a Cause of Chirality in a Molecule, 203

5.4. Isomers with One Asymmetric Center, 204

5.5. Asymmetric Centers and Stereocenters, 205

5.6. How to Draw Enantiomers, 205

5.7. Naming Enantiomers by the R,S System, 206

Problem-Solving Strategy, 210

Problem-Solving Strategy, 211

5.8. Chiral Compounds Are Optically Active, 212

5.9. How Specific Rotation Is Measured, 213

5.10. Enantiomeric Excess, 215

5.11. Isomers with More than One Asymmetric Center, 216

Problem-Solving Strategy, 220

5.12. Meso Compounds Have Asymmetric Centers but Are Optically Inactive, 221

Problem-Solving Strategy, 223

5.13. How to Name Isomers with More than One Asymmetric Center, 225

Problem-Solving Strategy, 227

5.14. Reactions of Compounds That Contain an Asymmetric Center, 229

5.15. The Absolute Configuration of (+)-Glyceraldehyde, 230

5.16. How Enantiomers Can Be Separated, 232

5.17. Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers, 233

5.18. Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions, 234

5.19. The Stereochemistry of Electrophilic Addition Reactions of Alkenes, 235

Cyclic Alkenes, 239

Problem-Solving Strategy, 244

5.20. The Stereochemistry of Enzyme-Catalyzed Reactions, 246

5.21. Enantiomers Can Be Distinguished by Biological Molecules, 247

The Enantiomers of Thalidomide, 249

Chiral Drugs, 250

6. The Reactions of Alkynes: An Introduction to Multistep Synthesis, 258

Ethyne Chemistry or the Forward Pass?, 259

6.1. The Nomenclature of Alkynes, 260

6.2. How to Name a Compound That Has More than One Functional Group, 261

6.3. The Physical Properties of Unsaturated Hydrocarbons, 263

How a Banana Slug Knows What to Eat, 263

6.4. The Structure of Alkynes, 264

6.5. How Alkynes React, 264

6.6. Addition of Hydrogen Halides and Addition of Halogens to an Alkyne, 266

6.7. Addition of Water to an Alkyne, 269

6.8. Addition of Borane to an Alkyne: Hydroboration–Oxidation, 271

6.9. Addition of Hydrogen to an Alkyne, 272

6.10. A Hydrogen Bonded to an sp Carbon Is “Acidic”, 274

Problem-Solving Strategy, 275

Sodium Amide and Sodium, 275

6.11. Synthesis Using Acetylide Ions, 276

6.12. Designing a Synthesis I: An Introduction to Multistep Synthesis, 277

Identifying Compounds, 281

Summary of Reactions, 282

7. Delocalized Electrons and Their Effect on Stability, Reactivity, and pK_a · More About Molecular Orbital Theory, 287

7.1. Benzene Has Delocalized Electrons, 288

Kekulé’s Dream, 290

7.2. The Bonding in Benzene, 291

7.3. Resonance Contributors and the Resonance Hybrid, 291

7.4. How to Draw Resonance Contributors, 293

Peptide Bonds, 295

7.5. The Predicted Stabilities of Resonance Contributors, 296

7.6. Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound, 298

Problem-Solving Strategy, 300

7.7. Examples Illustrating the Effect of Delocalized Electrons on Stability, 301

Problem-Solving Strategy, 304

7.8. A Molecular Orbital Description of Stability, 305

7.9. How Delocalized Electrons Affect pK_a, 312

7.10. Delocalized Electrons Can Affect the Product of a Reaction, 316

7.11. Thermodynamic Versus Kinetic Control of Reactions, 321

7.12. The Diels–Alder Reaction Is a 1,4-Addition Reaction, 326

Problem-Solving Strategy, 334

Summary of Reactions, 336

Part 3. Substitution and Elimination Reactions, 343

8. Substitution Reactions of Alkyl Halides, 344

Survival Compounds, 345

8.1. How Alkyl Halides React, 346

8.2. The Mechanism of an S_N2 Reaction, 346

8.3. Factors That Affect S_N2 Reactions, 352

8.4. The Reversibility of an S_N2 Reaction Depends on the Basicities of the Leaving Groups in the Forward and Reverse Directions, 357

8.5. The Mechanism of an S_N1 Reaction, 361

Why Carbon Instead of Silicon?, 361

8.6. Factors That Affect S_N1 Reactions, 364

8.7. More About the Stereochemistry of S_N2 and S_N1 Reactions, 366

8.8. Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides, 368

Problem-Solving Strategy, 370

8.9. Competition Between S_N2 and S_N1 Reactions, 371

Problem-Solving Strategy, 373

8.10. The Role of the Solvent in S_N2 and S_N1 Reactions, 375

Solvation Effects, 376

Environmental Adaptation, 379

8.11. Intermolecular Versus Intramolecular Reactions, 381

8.12. Biological Methylating Reagents Have Good Leaving Groups, 382

Eradicating Termites, 383

S-Adenosylmethionine: A Natural Antidepressant, 384

Summary of Reactions, 385

9. Elimination Reactions of Alkyl Halides · Competition Between Substitution and Elimination, 389

9.1. The E2 Reaction, 390

Investigating Naturally Occurring Organohalides, 390

9.2. An E2 Reaction Is Regioselective, 391

9.3. The E1 Reaction, 398

Problem-Solving Strategy, 401

9.4. Competition Between E2 and E1 Reactions, 402

9.5. E2 and E1 Reactions Are Stereoselective, 403

9.6. Elimination from Substituted Cyclohexanes, 408

9.7. A Kinetic Isotope Effect Can Help Determine a Mechanism, 412

9.8. Competition Between Substitution and Elimination, 413

9.9. Substitution and Elimination Reactions in Synthesis, 418

9.10. Consecutive E2 Elimination Reactions, 420

9.11. Designing a Synthesis II: Approaching the Problem, 421

Summary of Reactions, 424

10. Reactions of Alcohols, Amines, Ethers, Epoxides, and Sulfur-Containing Compounds · Organometallic Compounds, 429

10.1. Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides, 430

The Lucas Test, 432

10.2. Other Methods for Converting Alcohols into Alkyl Halides, 434

Grain Alcohol and Wood Alcohol, 434

10.3. Converting Alcohols into Sulfonate Esters, 435

10.4. Elimination Reactions of Alcohols: Dehydration, 438

Problem-Solving Strategy, 443

Biological Dehydrations, 443

10.5. Oxidation of Alcohols, 445

10.6. Amines Do Not Undergo Substitution or Elimination Reactions but Are the Most Common Organic Bases, 447

Blood Alcohol Content, 447

10.7. Nucleophilic Substitution Reactions of Ethers, 449

Anesthetics, 451

10.8. Nucleophilic Substitution Reactions of Epoxides, 452

10.9. Arene Oxides, 455

Benzo[a]pyrene and Cancer, 459

10.10. Crown Ethers, 460

Chimney Sweeps and Cancer, 460

10.11. Thiols, Sulfides, and Sulfonium Salts, 462

An Ionophorous Antibiotic, 462

Mustard—A Chemical Warfare Agent, 464

Antidote to a Chemical Warfare Agent, 464

10.12. Organometallic Compounds, 465

10.13. Coupling Reactions, 469

Summary of Reactions, 473

11. Radicals · Reactions of Alkanes, 481

Octane Number, 482

Fossil Fuels: A Problematic Energy Source, 482

11.1. Alkanes Are Unreactive Compounds, 483

11.2. Chlorination and Bromination of Alkanes, 483

11.3. Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron, 485

11.4. The Distribution of Products Depends on Probability and Reactivity, 486

11.5. The Reactivity–Selectivity Principle, 489

Problem-Solving Strategy, 491

11.6. Addition of Radicals to an Alkene, 493

11.7. Stereochemistry of Radical Substitution and Addition Reactions, 496

11.8. Radical Substitution of Benzylic and Allylic Hydrogens, 497

11.9. Designing a Synthesis III: More Practice with Multistep Synthesis, 500

Cyclopropane, 500

11.10. Radical Reactions Occur in Biological Systems, 502

Decaffeinated Coffee and the Cancer Scare, 503

Food Preservatives, 504

11.11. Radicals and Stratospheric Ozone, 505

Artificial Blood, 506

Summary of Reactions, 507

Part 4. Identification of Organic Compounds, 511

12. Mass Spectrometry, Infrared Spectroscopy, and Ultraviolet/Visible Spectroscopy, 512

12.1. Mass Spectrometry, 513

12.2. The Mass Spectrum · Fragmentation, 515

12.3. Isotopes in Mass Spectrometry, 518

12.4. High-Resolution Mass Spectrometry Can Reveal Molecular Formulas, 520

12.5. Fragmentation Patterns of Functional Groups, 520

Mass Spectrometry in Forensics, 526

12.6. Spectroscopy and the Electromagnetic Spectrum, 528

12.7. Infrared Spectroscopy, 530

12.8. Characteristic Infrared Absorption Bands, 533

12.9. The Intensity of Absorption Bands, 534

12.10. The Position of Absorption Bands, 535

The Originator of Hooke’s Law, 535

12.11. The Position of an Absorption Band Is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding, 536

Problem-Solving Strategy, 539

12.12. The Shape of Absorption Bands, 544

12.13. The Absence of Absorption Bands, 544

12.14. Some Vibrations Are Infrared Inactive, 545

12.15. A Lesson in Interpreting Infrared Spectra, 546

12.16. Ultraviolet and Visible Spectroscopy, 549

12.17. The Beer–Lambert Law, 551

Ultraviolet Light and Sunscreens, 551

12.18. The Effect of Conjugation on λ_max, 552

12.19. The Visible Spectrum and Color, 554

12.20. Some Uses of UV/Vis Spectroscopy, 555

Anthocyanins: A Colorful Class of Compounds, 555

13. NMR Spectroscopy, 569

13.1. An Introduction to NMR Spectroscopy, 569

13.2. Fourier Transform NMR, 572

Nikola Tesla (1856–1943), 572

13.3. Shielding Causes Different Hydrogens to Show Signals at Different Frequencies, 573

13.4. The Number of Signals in an ^1H NMR Spectrum, 574

Problem-Solving Strategy, 575

13.5. The Chemical Shift Tells How Far the Signal Is from the Reference Signal, 577

13.6. The Relative Positions of ^1H NMR Signals, 578

13.7. Characteristic Values of Chemical Shifts, 579

13.8. Diamagnetic Anisotropy, 582

13.9. The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal, 584

13.10. Splitting of the Signals Is Desribed by the N + 1 Rule, 586

13.11. More Examples of ^1H NMR Spectra, 591

13.12. Coupling Constants Identify Coupled Protons, 597

Problem-Solving Strategy, 599

13.13. Splitting Diagrams Explain the Multiplicity of a Signal, 600

13.14. Diastereotopic Hydrogens Are Not Chemically Equivalent, 603

13.15. The Time Dependence of NMR Spectroscopy, 604

13.16. Protons Bonded to Oxygen and Nitrogen, 605

13.17. The Use of Deuterium in ^1H NMR Spectroscopy, 607

13.18. The Resolution of ^1H NMR Spectra, 608

13.19. ^13C NMR Spectroscopy, 610

Problem-Solving Strategy, 614

13.20. DEPT ^13C NMR Spectra, 616

13.21. Two-Dimensional NMR Spectroscopy, 616

13.22. NMR Used in Medicine Is Called Magnetic Resonance Imaging, 619

Part 5. Aromatic Compounds, 639

14. Aromaticity · Reactions of Benzene, 640

14.1. Aromatic Compounds Are Unusually Stable, 640

14.2. The Two Criteria for Aromaticity, 642

14.3. Applying the Criteria for Aromaticity, 643

Buckyballs and AIDS, 644

14.4. Aromatic Heterocyclic Compounds, 646

14.5. Some Chemical Consequences of Aromaticity, 647

14.6. Antiaromaticity, 649

Problem-Solving Strategy, 649

14.7. A Molecular Orbital Description of Aromaticity and Antiaromaticity, 650

14.8. Nomenclature of Monosubstituted Benzenes, 651

The Toxicity of Benzene, 652

14.9. How Benzene Reacts, 653

14.10. The General Mechanism for Electrophilic Aromatic Substitution Reactions, 654

14.11. Halogenation of Benzene, 655

14.12. Nitration of Benzene, 657

14.13. Sulfonation of Benzene, 658

14.14. Friedel–Crafts Acylation of Benzene, 660

14.15. Friedel–Crafts Alkylation of Benzene, 661

Incipient Primary Carbocations, 663

14.16. Alkylation of Benzene by Acylation–Reduction, 664

14.17. Using Coupling Reactions to Alkylate Benzene, 665

14.18. It Is Important to Have More Than One Way to Carry Out a Reaction, 665

14.19. How Some Substituents on a Benzene Ring Can Be Chemically Changed, 666

Summary of Reactions, 671

15. Reactions of Substituted Benzenes, 677

15.1. Nomenclature of Disubstituted and Polysubstituted Benzenes, 678

Measuring Toxicity, 679

15.2. Some Substituents Increase the Reactivity of a Benzene Ring and Some Decrease Its Reactivity, 681

15.3. The Effect of Substituents on Orientation, 687

15.4. The Effect of Substituents on pK_a, 691

15.5. The Ortho–Para Ratio, 693

Problem-Solving Strategy, 693

15.6. Additional Considerations Regarding Substituent Effects, 694

15.7. Designing a Synthesis IV: Synthesis of Monosubstituted and Disubstituted Benzenes, 696

15.8. Synthesis of Trisubstituted Benzenes, 698

15.9. Synthesis of Substituted Benzenes Using Arenediazonium Salts, 699

15.10. The Arenediazonium Ion as an Electrophile, 703

15.11. The Mechanism for the Reaction of Amines with Nitrous Acid, 704

Nitrosamines and Cancer, 706

15.12. Nucleophilic Aromatic Substitution: An Addition–Elimination Mechanism, 707

15.13. Nucleophilic Aromatic Substitution: An Elimination–Addition Mechanism That Forms a Benzyne Intermediate, 709

15.14. Polycyclic Benzenoid Hydrocarbons, 711

Summary of Reactions, 712

Part 6. Carbonyl Compounds, 721

16. Carbonyl Compounds I: Nucleophilic Acyl Substitution, 722

16.1. Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives, 724

16.2. Structures of Carboxylic Acids and Carboxylic Acid Derivatives, 729

16.3. Physical Properties of Carbonyl Compounds, 730

16.4. Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives, 731

The Discovery of Penicillin, 732

16.5. How Class I Carbonyl Compounds React, 733

Dalmatians: The High Cost of Black Spots, 733

Problem-Solving Strategy, 736

16.6. Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives, 737

16.7. General Mechanism for Nucleophilic Acyl Substitution Reactions, 738

16.8. Reactions of Acyl Halides, 739

16.9. Reactions of Acid Anhydrides, 742

16.10. Reactions of Esters, 743

16.11. Acid-Catalyzed Ester Hydrolysis and Transesterification, 746

16.12. Hydroxide-Ion-Promoted Ester Hydrolysis, 751

16.13. How the Mechanism for Nucleophilic Acyl Substitution Reactions Was Confirmed, 752

16.14. Soaps, Detergents, and Micelles, 754

Making Soap, 756

16.15. Reactions of Carboxylic Acids, 757

16.16. Reactions of Amides, 758

Problem-Solving Strategy, 758

16.17. The Hydrolysis of Amides Is Catalyzed by Acids, 760

Nature’s Sleeping Pill, 760

Penicillin and Drug Resistance, 762

Penicillins in Clinical Use, 762

16.18. The Hydrolysis of an Imide: A Way to Synthesize Primary Amines, 763

16.19. The Hydrolysis of Nitriles, 764

16.20. Designing a Synthesis V: The Synthesis of Cyclic Compounds, 765

16.21. How Chemists Activate Carboxylic Acids, 767

16.22. How Cells Activate Carboxylic Acids, 768

Nerve Impulses, Paralysis, and Insecticides, 771

16.23. Dicarboxylic Acids and Their Derivatives, 772

Synthetic Polymers, 774

Dissolving Sutures, 774

Summary of Reactions, 776

17. Carbonyl Compounds II: Reactions of Aldehydes and Ketones · More Reactions of Carboxylic Acid Derivatives · Reactions of α,β-Unsaturated Carbonyl Compounds, 788

17.1. Nomenclature of Aldehydes and Ketones, 790

Butanedione: An Unpleasant Compound, 792

17.2. Relative Reactivities of Carbonyl Compounds, 793

17.3. How Aldehydes and Ketones React, 795

17.4. Reactions of Carbonyl Compounds with Grignard Reagents, 796

Problem-Solving Strategy, 799

17.5. Reactions of Carbonyl Compounds with Acetylide Ions, 800

17.6. Reactions of Carbonyl Compounds with Hydride Ion, 800

17.7. Reactions of Aldehydes and Ketones with Hydrogen Cyanide, 805

17.8. Reactions of Aldehydes and Ketones with Amines and Derivatives of Amines, 806

Identifying of Aldehydes and Ketones without Using Spectroscopy, 811

17.9. Reactions of Aldehydes and Ketones with Water, 814

Preserving Biological Specimens, 815

17.10. Reactions of Aldehydes and Ketones with Alcohols, 816

Problem-Solving Strategy, 818

17.11. Protecting Groups, 819

17.12. Addition of Sulfur Nucleophiles, 822

17.13. The Wittig Reaction Forms an Alkene, 822

β-Carotene, 825

17.14. Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces, 826

17.15. Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents, 827

Enyzme-Catalyzed Carbonyl Additions, 827

Synthesizing Organic Compounds, 829

17.16. Nucleophilic Addition to α,β-Unsaturated Aldehydes and Ketones, 830

Semisynthetic Drugs, 830

Cancer Chemotherapy, 833

17.17. Nucleophilic Addition to α,β-Unsaturated Carboxylic Acid Derivatives, 834

17.18. Enzyme-Catalyzed Additions to α,β-Unsaturated Carbonyl Compounds, 835

Enzyme-Catalyzed Cis-Trans Interconversion, 835

Summary of Reactions, 836

18. Carbonyl Compounds III: Reactions at the α-Carbon, 850

18.1. The Acidity of an α-Hydrogen, 851

Problem-Solving Strategy, 854

18.2. Keto–Enol Tautomers, 855

18.3. Enolization, 856

18.4. How Enols and Enolate Ions React, 857

18.5. Halogenation of the α-Carbon of Aldehydes and Ketones, 859

18.6. Halogenation of the α-Carbon of Carboxylic Acids: The Hell–Volhard–Zelinski Reaction, 861

18.7. α-Halogenated Carbonyl Compounds Are Useful in Synthesis, 862

18.8. Using LDA to Form an Enolate Ion, 863

18.9. Alkylation of the α-Carbon of Carbonyl Compounds, 864

The Synthesis of Aspirin, 865

Problem-Solving Strategy, 866

18.10. Alkylation and Acylation of the α-Carbon Using an Enamine Intermediate, 867

18.11. Alkylation of the β-Carbon: The Michael Reaction, 869

18.12. An Aldol Addition Forms β-Hydroxyaldehydes or β-Hydroxyketones, 871

18.13. Dehydration of Aldol Addition Products Forms α,β-Unsaturated Aldehydes and Ketones, 873

18.14. The Mixed Aldol Addition, 874

18.15. A Claisen Condensation Forms a β-Keto Ester, 876

18.16. The Mixed Claisen Condensation, 878

18.17. Intramolecular Condensation and Addition Reactions, 880

Problem-Solving Strategy, 883

18.18. 3-Oxocarboxylic Acids Can Be Decarboxylated, 884

18.19. The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid, 886

18.20. The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone, 888

18.21. Designing a Synthesis VII: Making New Carbon–Carbon Bonds, 889

18.22. Reactions at the α-Carbon in Biological Systems, 891

Summary of Reactions, 896

Part 7. More About Oxidation–Reduction Reactions and Amines, 907

19. More About Oxidation–Reduction Reactions, 908

19.1. Reduction Reactions, 911

19.2. Oxidation of Alcohols, 917

The Role of Hydrates in the Oxidation of Primary Alcohols, 918

Treating Alcoholism with Antabuse, 919

Fetal Alcohol Syndrome, 919

19.3. Oxidation of Aldehydes and Ketones, 919

19.4. Designing a Synthesis VIII: Controlling Stereochemistry, 922

19.5. Hydroxylation of Alkenes, 923

19.6. Oxidative Cleavage of 1,2-Diols, 925

Problem-Solving Strategy, 925

19.7. Oxidative Cleavage of Alkenes, 926

19.8. Oxidative Cleavage of Alkynes, 931

19.9. Designing a Synthesis IX: Functional Group Interconversion, 932

Summary of Reactions, 934

20. More About Amines · Heterocyclic Compounds, 943

20.1. More About Amine Nomenclature, 944

20.2. More About the Acid–Base Properties of Amines, 945

20.3. Amines React as Bases and as Nucleophiles, 946

20.4. Quaternary Ammonium Hydroxides Undergo Elimination Reactions, 947

A Useful Bad-Tasting Compound, 950

20.5. Phase-Transfer Catalysis, 951

20.6. Oxidation of Amines · The Cope Elimination Reaction, 952

20.7. Synthesis of Amines, 953

20.8. Aromatic Five-Membered-Ring Heterocycles, 955

20.9. Aromatic Six-Membered-Ring Heterocycles, 960

20.10. Amine Heterocycles Have Important Roles in Nature, 966

Porphyrin, Bilirubin, and Jaundice, 968

Summary of Reactions, 969

Part 8. Bioorganic Compounds, 977

21. Carbohydrates, 978

21.1. Classification of Carbohydrates, 979

21.2. The D and L Notation, 980

21.3. The Configurations of Aldoses, 982

21.4. The Configurations of Ketoses, 983

21.5. Reactions of Monosaccharides in Basic Solutions, 984

21.6. Redox Reactions of Monosaccharides, 985

21.7. Monosaccharides Form Crystalline Osazones, 987

Measuring the Blood Glucose Levels in Diabetes, 988

21.8. Lengthening the Chain: The Kiliani–Fischer Synthesis, 989

21.9. Shortening the Chain: The Wohl Degradation, 990

21.10. Stereochemistry of Glucose: The Fischer Proof, 990

21.11. Monosaccharides Form Cyclic Hemiacetals, 992

Glucose/Dextrose, 992

21.12. Glucose Is the Most Stable Aldohexose, 995

21.13. Formation of Glycosides, 997

21.14. The Anomeric Effect, 999

21.15. Reducing and Nonreducing Sugars, 999

21.16. Disaccharides, 1000

Lactose Intolerance, 1002

Galactosemia, 1002

21.17. Polysaccharides, 1003

Why the Dentist Is Right, 1004

21.18. Some Naturally Occurring Products Derived from Carbohydrates, 1006

Controlling Fleas, 1006

Vitamin C, 1008

21.19. Carbohydrates on Cell Surfaces, 1008

21.20. Synthetic Sweeteners, 1010

The Wonder of Discovery, 1011

Acceptable Daily Intake, 1011

Summary of Reactions, 1012

Key Terms, 1014

22. Amino Acids, Peptides, and Proteins, 1017

22.1. Classification and Nomenclature of Amino Acids, 1018

Proteins and Nutrition, 1022

22.2. Configuration of the Amino Acids, 1023

Amino Acids and Disease, 1023

A Peptide Antibiotic, 1024

22.3. Acid–Base Properties of Amino Acids, 1024

22.4. The Isoelectric Point, 1026

22.5. Separation of Amino Acids, 1028

22.6. Synthesis of Amino Acids, 1032

Water Softeners: Examples of Cation-Exchange Chromatography, 1032

22.7. Resolution of Racemic Mixtures of Amino Acids, 1035

22.8. Peptide Bonds and Disulfide Bonds, 1035

Hair: Straight or Curly?, 1038

22.9. Some Interesting Peptides, 1039

22.10. The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation, 1040

22.11. Automated Peptide Synthesis, 1043

22.12. An Introduction to Protein Structure, 1045

22.13. How to Determine the Primary Structure of a Peptide or a Protein, 1046

Primary Structure and Evolution, 1046

Problem-Solving Strategy, 1048

22.14. Secondary Structure of Proteins, 1052

22.15. Tertiary Structure of Proteins, 1055

β-Peptides: An Attempt to Improve on Nature, 1055

22.16. Quaternary Structure of Proteins, 1057

22.17. Protein Denaturation, 1058

Key Terms, 1059

23. Catalysis, 1063

23.1. Catalysis in Organic Reactions, 1065

The Nobel Prize, 1065

23.2. Acid Catalysis, 1066

23.3. Base Catalysis, 1069

23.4. Nucleophilic Catalysis, 1070

23.5. Metal-Ion Catalysis, 1072

23.6. Intramolecular Reactions, 1074

23.7. Intramolecular Catalysis, 1076

23.8. Catalysis in Biological Reactions, 1079

23.9. Enzyme-Catalyzed Reactions, 1081

Key Terms, 1094

24. The Organic Mechanisms of the Coenzymes, 1098

Vitamin B_1, 1100

“Vitamine”—An Amine Required for Life, 1100

24.1. An Introduction to Metabolism, 1101

24.2. The Vitamin Needed for Many Redox Reactions: Vitamin B_3, 1101

Niacin Deficiency, 1102

24.3. Flavin Adenine Dinucleotide and Flavin Mononucleotide: Vitamin B_2, 1107

24.4. Thiamine Pyrophosphate: Vitamin B_1, 1110

24.5. Biotin: Vitamin H, 1115

24.6. Pyridoxal Phosphate: Vitamin B_6, 1117

Assessing the Damage After a Heart Attack, 1121

24.7. Coenzyme B12: Vitamin B_12, 1124

24.8. Tetrahydrofolate: Folic Acid, 1126

24.9. Vitamin KH_2: Vitamin K, 1131

The First Antibiotics, 1131

Too Much Broccoli, 1133

Key Terms, 1134

25. The Chemistry of Metabolism, 1137

25.1. The Four Stages of Catabolism, 1138

Differences in Metabolism, 1138

25.2. ATP Is the Carrier of Chemical Energy, 1139

25.3. There Are Three Mechanisms for Phosphoryl Transfer Reactions, 1141

25.4. The “High-Energy” Character of Phosphoanhydride Bonds, 1144

25.5. Why ATP Is Kinetically Stable in a Cell, 1145

25.6. The Catabolism of Fats, 1146

25.7. The Catabolism of Carbohydrates, 1149

25.8. The Fates of Pyruvate, 1152

Problem-Solving Strategy, 1152

25.9. The Catabolism of Proteins, 1153

25.10. The Citric Acid Cycle, 1155

Phenylketonuria: An Inborn Error of Metabolism, 1155

Alcaptonuria, 1155

25.11. Oxidative Phosphorylation, 1158

25.12. Anabolism, 1159

Basal Metabolic Rate, 1159

Key Terms, 1160

26. Lipids, 1162

26.1. Fatty Acids Are Long-Chain Carboxylic Acids, 1163

26.2. Waxes Are High-Molecular-Weight Esters, 1165

26.3. Fats and Oils, 1165

Omega Fatty Acids, 1165

Olestra: Nonfat with Flavor, 1169

Whales and Echolocation, 1169

26.4. Phospholipids and Sphingolipids Are Components of Membranes, 1170

Snake Venom, 1172

Is Chocolate a Health Food?, 1172

26.5. Prostaglandins Regulate Physiological Responses, 1173

Multiple Sclerosis and the Myelin Sheath, 1173

26.6. Terpenes Contain Carbon Atoms in Multiples of Five, 1177

26.7. Vitamin A Is a Diterpene, 1179

26.8. How Terpenes Are Biosynthesized, 1180

26.9. Steroids Are Chemical Messengers, 1186

Cholesterol and Heart Disease, 1189

Clinical Treatment of High Cholesterol, 1190

26.10. How Nature Synthesizes Cholesterol, 1190

26.11. Synthetic Steroids, 1192

Key Terms, 1193

27. Nucleosides, Nucleotides, and Nucleic Acids, 1197

27.1. Nucleosides and Nucleotides, 1198

The Structure of DNA: Watson, Crick, Franklin, and Wilkins, 1199

27.2. Other Important Nucleotides, 1202

27.3. Nucleic Acids Are Composed of Nucleotide Subunits, 1202

27.4. DNA Is Stable but RNA Is Easily Cleaved, 1207

27.5. Biosynthesis of DNA Is Called Replication, 1207

27.6. Biosynthesis of RNA Is Called Transcription, 1209

27.7. There Are Three Kinds of RNA, 1210

27.8. Biosynthesis of Proteins Is Called Translation, 1212

27.9. Why DNA Contains Thymine Instead of Uracil, 1216

Sickle Cell Anemia, 1216

Antibiotics That Act by Inhibiting Translation, 1216

27.10. How the Base Sequence of DNA Is Determined, 1217

27.11. Polymerase Chain Reaction (PCR), 1220

27.12. Genetic Engineering, 1221

DNA Fingerprinting, 1221

27.13. Laboratory Synthesis of DNA Strands, 1222

Resisting Herbicides, 1222

Key Terms, 1228

Part 9. Special Topics in Organic Chemistry, 1231

28. Synthetic Polymers, 1232

28.1. There Are Two Major Classes of Synthetic Polymers, 1233

28.2. Chain-Growth Polymers, 1234

Recycling Symbols, 1239

28.3. Stereochemistry of Polymerization · Ziegler–Natta Catalysts, 1245

28.4. Polymerization of Dienes · The Manufacture of Rubber, 1246

28.5. Copolymers, 1248

28.6. Step–Growth Polymers, 1249

28.7. Physical Properties of Polymers, 1254

Designing a Polymer, 1255

Key Terms, 1258

29. Pericyclic Reactions, 1262

29.1. Three Kinds of Pericyclic Reations, 1263

29.2. Molecular Orbitals and Orbital Symmetry, 1265

29.3. Electrocyclic Reactions, 1269

29.4. Cycloaddition Reactions, 1275

Luminescence, 1278

29.5. Sigmatropic Rearrangements, 1279

29.6. Pericyclic Reactions in Biological Systems, 1284

The Sunshine Vitamin, 1286

29.7. Summary of the Selection Rules for Pericyclic Reactions, 1287

Key Terms, 1288

30. The Organic Chemistry of Drugs: Discovery and Design, 1293

30.1. Naming Drugs, 1297

30.2. Lead Compounds, 1297

30.3. Molecular Modification, 1298

30.4. Random Screening, 1300

30.5. Serendipity in Drug Development, 1302

Drug Safety, 1302

30.6. Receptors, 1304

30.7. Drugs as Enzyme Inhibitors, 1307

30.8. Designing a Suicide Substrate, 1311

30.9. Quantitative Structure–Activity Relationships (QSAR), 1312

30.10. Molecular Modeling, 1314

30.11. Combinatorial Organic Synthesis, 1314

30.12. Antiviral Drugs, 1316

30.13. Economics of Drugs · Governmental Regulations, 1317

Orphan Drugs, 1317

Key Terms, 1318

Appendices, A-1

I. Physical Properties of Organic Compounds, A-1

II. pK_a Values, A-8

III. Derivations of Rate Laws, A-10

IV. Summary of Methods Used to Synthesize a Particular Functional Group, A-13

V. Summary of Methods Employed to Form Carbon–Carbon Bonds, A-17

VI. Spectroscopy Tables, A-18

Answers to Selected Problems, A-24

Photo Credits, P-1

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This innovative text is organized in a way that discourages rote memorization, by emphasizing what functional groups do rather than how they are made, highlighting mechanistic similarities and tying synthesis and reactivity together. Bruice's writing has been praised for anticipating students' questions, appealing to their visual and problem solving needs. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.
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