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Book Details
Abstract
For courses in Organic Chemistry (2-Semester)
A framework for organic chemistry built around the similarities in reaction types
Paula Bruice’s presentation in Organic Chemistry, Eighth Edition provides mixed-science majors with the conceptual foundations, chemical logic, and problem-solving skills they need to reason their way to solutions for diverse problems in synthetic organic chemistry, biochemistry, and medicine. The Eighth Edition builds a strong framework for thinking about organic chemistry by unifying principles of reactivity that students will apply throughout the course, discouraging memorization. With more applications than any other textbook, Dr. Bruice consistently relates structure and reactivity to what occurs in our own cells and reinforces the fundamental reason for all chemical reactions–electrophiles react with nucleophiles. New streamlined coverage of substitution and elimination, updated problem-solving strategies, synthesis skill-building applications and tutorials guide students throughout fundamental and complex content in both the first and second semesters of the course.
MasteringChemistry™ is not included. Students, if MasteringChemistry is a recommended/mandatory component of the course, please ask your instructor for the correct ISBN. MasteringChemistry should only be purchased when required by an instructor. Instructors, contact your Pearson representative for more information.
MasteringChemistry an online homework, tutorial, and assessment program designed to work with this text to engage students and improve results. Interactive, self-paced tutorials provide individualized coaching to help students stay on track. With a wide range of activities available, students can actively learn, understand, and retain even the most difficult concepts.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Title Page | 3 | ||
| Copyright Page | 4 | ||
| Preface | 24 | ||
| ACKNOWLEDGMENTS | 34 | ||
| About the Author | 36 | ||
| Contents | 10 | ||
| PART ONE: An Introduction to the Study of Organic Chemistry | 37 | ||
| 1 Remembering General Chemistry: Electronic Structure and Bonding | 38 | ||
| CHEMICAL CONNECTION: Natural versus Synthetic Organic Compounds | 39 | ||
| 1.1 The Structure of an Atom | 40 | ||
| 1.2 How the Electrons in an Atom are Distributed | 41 | ||
| 1.3 Covalent Bonds | 43 | ||
| 1.4 How the Structure of a Compound is Represented | 49 | ||
| PROBLEM-SOLVING STRATEGY | 51 | ||
| 1.5 Atomic Orbitals | 55 | ||
| 1.6 An Introduction to Molecular Orbital Theory | 57 | ||
| 1.7 How Single Bonds are Formed in Organic Compounds | 61 | ||
| 1.8 How a Double Bond is Formed: The Bonds in Ethene | 65 | ||
| CHEMICAL CONNECTION: Diamond, Graphite, Graphene, and Fullerenes: Substances that Contain Only Carbon Atoms | 67 | ||
| 1.9 How a Triple Bond is Formed: The Bonds in Ethyne | 67 | ||
| 1.10 The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion | 69 | ||
| 1.11 The Bonds in Ammonia and in the Ammonium Ion | 71 | ||
| 1.12 The Bonds in Water | 72 | ||
| CHEMICAL CONNECTION: Water—A Unique Compound | 73 | ||
| 1.13 The Bond in a Hydrogen Halide | 74 | ||
| 1.14 Hybridization and Molecular Geometry | 75 | ||
| PROBLEM-SOLVING STRATEGY | 75 | ||
| 1.15 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles | 76 | ||
| PROBLEM-SOLVING STRATEGY | 80 | ||
| 1.16 Dipole Moments of Molecules | 80 | ||
| ESSENTIAL CONCEPTS | 82 | ||
| PROBLEMS | 83 | ||
| 2 Acids and Bases: Central to Understanding Organic Chemistry | 86 | ||
| 2.1 An Introduction to Acids and Bases | 86 | ||
| 2.2 pK[Sub(a)] and pH | 88 | ||
| PROBLEM-SOLVING STRATEGY | 90 | ||
| CHEMICAL CONNECTION: Acid Rain | 90 | ||
| 2.3 Organic Acids and Bases | 91 | ||
| BIOLOGICAL CONNECTION: Poisonous Amines | 92 | ||
| PROBLEM-SOLVING STRATEGY | 94 | ||
| 2.4 How to Predict the Outcome of an Acid-Base Reaction | 94 | ||
| 2.5 How to Determine the Position of Equilibrium | 95 | ||
| 2.6 How the Structure of an Acid Affects its pK[Sub(a)] Value | 96 | ||
| 2.7 How Substituents Affect the Strength of an Acid | 100 | ||
| PROBLEM-SOLVING STRATEGY | 100 | ||
| 2.8 An Introduction to Delocalized Electrons | 102 | ||
| PROBLEM-SOLVING STRATEGY | 104 | ||
| MEDICAL CONNECTION: Fosamax Prevents Bones from Being Nibbled Away | 103 | ||
| 2.9 A Summary of the Factors that Determine Acid Strength | 105 | ||
| 2.10 How pH Affects the Structure of an Organic Compound | 106 | ||
| PROBLEM-SOLVING STRATEGY | 107 | ||
| CHEMICAL CONNECTION: Derivation of the Henderson-Hasselbalch Equation | 108 | ||
| MEDICAL CONNECTION: Aspirin Must Be in its Basic Form to be Physiologically Active | 110 | ||
| 2.11 Buffer Solutions | 110 | ||
| MEDICAL CONNECTION: Blood: A Buffered Solution | 111 | ||
| 2.12 Lewis Acids and Bases | 112 | ||
| ESSENTIAL CONCEPTS | 113 | ||
| PROBLEMS | 113 | ||
| TUTORIAL Acids and Bases | 116 | ||
| 3 An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Structure | 124 | ||
| 3.1 Alkyl Groups | 128 | ||
| 3.2 The Nomenclature of Alkanes | 131 | ||
| INDUSTRIAL CONNECTION: How is the Octane Number of Gasoline Determined? | 134 | ||
| 3.3 The Nomenclature of Cycloalkanes | 135 | ||
| PROBLEM-SOLVING STRATEGY | 137 | ||
| 3.4 The Nomenclature of Alkyl Halides | 137 | ||
| 3.5 The Nomenclature of Ethers | 139 | ||
| 3.6 The Nomenclature of Alcohols | 140 | ||
| 3.7 The Nomenclature of Amines | 142 | ||
| CHEMICAL CONNECTION: Bad-Smelling Compounds | 145 | ||
| 3.8 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines | 145 | ||
| 3.9 Noncovalent Interactions | 146 | ||
| PROBLEM-SOLVING STRATEGY | 150 | ||
| MEDICAL CONNECTION: Drugs Bind to Their Receptors | 150 | ||
| 3.10 The Solubility of Organic Compounds | 152 | ||
| BIOLOGICAL CONNECTION: Cell Membranes | 154 | ||
| 3.11 Rotation Occurs about Carbon–Carbon Single Bonds | 154 | ||
| 3.12 Some Cycloalkanes Have Angle Strain | 158 | ||
| CHEMICAL CONNECTION: Von Baeyer, Barbituric Acid, and Blue Jeans | 159 | ||
| PROBLEM-SOLVING STRATEGY | 159 | ||
| 3.13 Conformers of Cyclohexane | 160 | ||
| 3.14 Conformers of Monosubstituted Cyclohexanes | 163 | ||
| CHEMICAL CONNECTION: Starch and Cellulose—Axial and Equatorial | 164 | ||
| 3.15 Conformers of Disubstituted Cyclohexanes | 165 | ||
| PROBLEM-SOLVING STRATEGY | 166 | ||
| PROBLEM-SOLVING STRATEGY | 168 | ||
| 3.16 Fused Cyclohexane Rings | 170 | ||
| MEDICAL CONNECTION: Cholesterol and Heart Disease | 170 | ||
| MEDICAL CONNECTION: How High Cholesterol is Treated Clinically | 171 | ||
| ESSENTIAL CONCEPTS | 171 | ||
| PROBLEMS | 172 | ||
| PART TWO: Electrophilic Addition Reactions, Stereochemistry, and Electron Delocalization | 177 | ||
| TUTORIAL Using Molecular Models | 178 | ||
| 4 Isomers: The Arrangement of Atoms in Space | 179 | ||
| 4.1 Cis–Trans Isomers Result from Restricted Rotation | 181 | ||
| CHEMICAL CONNECTION: Cis-Trans Interconversion in Vision | 183 | ||
| 4.2 Using the E,Z System to Distinguish Isomers | 183 | ||
| PROBLEM-SOLVING STRATEGY | 186 | ||
| 4.3 A Chiral Object Has a Nonsuperimposable Mirror Image | 186 | ||
| 4.4 An Asymmetric Center is a Cause of Chirality in a Molecule | 187 | ||
| 4.5 Isomers with One Asymmetric Center | 188 | ||
| 4.6 Asymmetric Centers and Stereocenters | 189 | ||
| 4.7 How to Draw Enantiomers | 189 | ||
| 4.8 Naming Enantiomers by the R,S System | 190 | ||
| PROBLEM-SOLVING STRATEGY | 193 | ||
| PROBLEM-SOLVING STRATEGY | 194 | ||
| 4.9 Chiral Compounds Are Optically Active | 195 | ||
| 4.10 How Specific Rotation Is Measured | 197 | ||
| 4.11 Enantiomeric Excess | 199 | ||
| 4.12 Compounds with More than One Asymmetric Center | 200 | ||
| 4.13 Stereoisomers of Cyclic Compounds | 202 | ||
| PROBLEM-SOLVING STRATEGY | 204 | ||
| 4.14 Meso Compounds Have Asymmetric Centers but Are Optically Inactive | 205 | ||
| PROBLEM-SOLVING STRATEGY | 207 | ||
| 4.15 How to Name Isomers with More than One Asymmetric Center | 208 | ||
| PROBLEM-SOLVING STRATEGY | 211 | ||
| 4.16 Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers | 213 | ||
| 4.17 Receptors | 214 | ||
| MEDICAL CONNECTION: The Enantiomers of Thalidomide | 215 | ||
| 4.18 How Enantiomers Can Be Separated | 215 | ||
| PHARMACEUTICAL CONNECTION: Chiral Drugs | 216 | ||
| ESSENTIAL CONCEPTS | 217 | ||
| PROBLEMS | 217 | ||
| TUTORIAL Interconverting Structural Representations | 223 | ||
| 5 Alkenes: Structure, Nomenclature, and an Introduction to Reactivity • Thermodynamics and Kinetics | 226 | ||
| ENVIRONMENTAL CONNECTION: Pheromones | 227 | ||
| 5.1 Molecular Formulas and the Degree of Unsaturation | 227 | ||
| 5.2 The Nomenclature of Alkenes | 228 | ||
| 5.3 The Structure of Alkenes | 231 | ||
| PROBLEM-SOLVING STRATEGY | 232 | ||
| 5.4 How An Organic Compound Reacts Depends on Its Functional Group | 233 | ||
| 5.5 How Alkenes React • Curved Arrows Show the Flow of Electrons | 234 | ||
| GENERAL CONNECTION: A Few Words About Curved Arrows | 236 | ||
| 5.6 Thermodynamics: How Much Product is Formed? | 238 | ||
| 5.7 Increasing the Amount of Product Formed in a Reaction | 241 | ||
| 5.8 Calculating & | 242 | ||
| 5.9 Using & | 243 | ||
| PROBLEM-SOLVING STRATEGY | 244 | ||
| NUTRITIONAL CONNECTION: Trans Fats | 247 | ||
| 5.10 Kinetics: How Fast is the Product Formed? | 247 | ||
| 5.11 The Rate of a Chemical Reaction | 249 | ||
| CHEMICAL CONNECTION: The Difference between 5.11 The Rate of a Chemical Reaction & | 251 | ||
| 5.12 A Reaction Coordinate Diagram Describes the Energy Changes That Take Place During a Reaction | 251 | ||
| 5.13 Catalysis | 254 | ||
| 5.14 Catalysis by Enzymes | 255 | ||
| ESSENTIAL CONCEPTS | 256 | ||
| PROBLEMS | 257 | ||
| CHEMICAL CONNECTION: Calculating Kinetic Parameters | 260 | ||
| TUTORIAL Drawing Curved Arrows | 261 | ||
| 6 The Reactions of Alkenes • The Stereochemistry of Addition Reactions | 271 | ||
| 6.1 The Addition of a Hydrogen Halide to an Alkene | 272 | ||
| 6.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon | 273 | ||
| 6.3 What Does the Structure of the Transition State Look Like? | 275 | ||
| 6.4 Electrophilic Addition Reactions Are Regioselective | 277 | ||
| PROBLEM-SOLVING STRATEGY | 279 | ||
| 6.5 The Addition of Water to an Alkene | 281 | ||
| 6.6 The Addition of an Alcohol to an Alkene | 282 | ||
| 6.7 A Carbocation Will Rearrange if It Can Form a More Stable Carbocation | 284 | ||
| 6.8 The Addition of Borane to an Alkene: Hydroboration–Oxidation | 286 | ||
| CHEMICAL CONNECTION: Borane and Diborane | 287 | ||
| 6.9 The Addition of a Halogen to an Alkene | 290 | ||
| PROBLEM-SOLVING STRATEGY | 293 | ||
| 6.10 The Addition of a Peroxyacid to an Alkene | 293 | ||
| 6.11 The Addition of Ozone to an Alkene: Ozonolysis | 295 | ||
| PROBLEM-SOLVING STRATEGY | 297 | ||
| 6.12 Regioselective, Stereoselective, And Stereospecific Reactions | 299 | ||
| 6.13 The Stereochemistry of Electrophilic Addition Reactions | 300 | ||
| CHEMICAL CONNECTION: Cyclic Alkenes | 305 | ||
| PROBLEM-SOLVING STRATEGY | 310 | ||
| 6.14 The Stereochemistry of Enzyme-Catalyzed Reactions | 312 | ||
| 6.15 Enantiomers Can Be Distinguished by Biological Molecules | 313 | ||
| CHEMICAL CONNECTION: Chiral Catalysts | 314 | ||
| 6.16 Reactions and Synthesis | 314 | ||
| ENVIRONMENTAL CONNECTION: Which are More Harmful: Natural Pesticides or Synthetic Pesticides? | 316 | ||
| ESSENTIAL CONCEPTS | 316 | ||
| SUMMARY OF REACTIONS | 317 | ||
| PROBLEMS | 318 | ||
| 7 The Reactions of Alkynes • An Introduction to Multistep Synthesis | 324 | ||
| MEDICAL CONNECTION: Synthetic Alkynes Are Used to Treat Parkinson's Disease | 325 | ||
| PHARMACEUTICAL CONNECTION: Why Are Drugs so Expensive? | 326 | ||
| 7.1 The Nomenclature of Alkynes | 326 | ||
| MEDICAL CONNECTION: Synthetic Alkynes Are Used for Birth Control | 327 | ||
| 7.2 How to Name a Compound That Has More than One Functional Group | 328 | ||
| 7.3 The Structure of Alkynes | 329 | ||
| BIOLOGICAL CONNECTION: How a Banana Slug Knows What to Eat | 329 | ||
| 7.4 The Physical Properties of Unsaturated Hydrocarbons | 330 | ||
| 7.5 The Reactivity of Alkynes | 331 | ||
| 7.6 The Addition of Hydrogen Halides and the Addition of Halogens to an Alkyne | 332 | ||
| 7.7 The Addition of Water to an Alkyne | 335 | ||
| 7.8 The Addition of Borane to an Alkyne: Hydroboration–Oxidation | 337 | ||
| 7.9 The Addition of Hydrogen to an Alkyne | 338 | ||
| 7.10 A Hydrogen Bonded to an sp Carbon Is \"Acidic | 340 | ||
| CHEMICAL CONNECTION: Sodium Amide and Sodium in Ammonia | 341 | ||
| PROBLEM-SOLVING STRATEGY | 341 | ||
| 7.11 Synthesis Using Acetylide Ions | 342 | ||
| 7.12 DESIGNING A SYNTHESIS I: An Introduction to Multistep Synthesis | 343 | ||
| ENVIRONMENTAL CONNECTION: Green Chemistry: Aiming for Sustainability | 348 | ||
| ESSENTIAL CONCEPTS | 348 | ||
| SUMMARY OF REACTIONS | 349 | ||
| PROBLEMS | 350 | ||
| 8 Delocalized Electrons: Their Effect on Stability, pK[Sub(a)] , and the Products of a Reaction • Aromaticity and Electronic Effects: An Introduction to the Reactions of Benzene | 354 | ||
| 8.1 Delocalized Electrons Explain Benzene's Structure | 355 | ||
| HISTORICAL CONNECTION: Kekule's Dream | 357 | ||
| 8.2 The Bonding in Benzene | 357 | ||
| 8.3 Resonance Contributors and the Resonance Hybrid | 358 | ||
| 8.4 How to Draw Resonance Contributors | 359 | ||
| BIOLOGICAL CONNECTION: Electron Delocalization Affects the Three-Dimensional Shape of Proteins | 362 | ||
| 8.5 The Predicted Stabilities of Resonance Contributors | 362 | ||
| PROBLEM-SOLVING STRATEGY | 364 | ||
| 8.6 Delocalization Energy is the Additional Stability Delocalized Electrons Give to a Compound | 365 | ||
| 8.7 Delocalized Electrons Increase Stability | 366 | ||
| INDUSTRIAL CONNECTION: Organic Compounds That Conduct Electricity | 369 | ||
| 8.8 A Molecular Orbital Description of Stability | 371 | ||
| 8.9 Delocalized Electrons Affect pK[Sub(a)] Values | 375 | ||
| PROBLEM-SOLVING STRATEGY | 378 | ||
| 8.10 Electronic Effects | 378 | ||
| 8.11 Delocalized Electrons Can Affect the Product of a Reaction | 382 | ||
| 8.12 Reactions of Dienes | 383 | ||
| 8.13 Thermodynamic Versus Kinetic Control | 386 | ||
| 8.14 The Diels–Alder Reaction is a 1,4-Addition Reaction | 391 | ||
| 8.15 Retrosynthetic Analysis of the Diels–Alder Reaction | 397 | ||
| 8.16 Benzene is an Aromatic Compound | 398 | ||
| 8.17 The Two Criteria for Aromaticity | 399 | ||
| 8.18 Applying the Criteria for Aromaticity | 400 | ||
| CHEMICAL CONNECTION: Buckyballs | 401 | ||
| PROBLEM-SOLVING STRATEGY | 402 | ||
| 8.19 A Molecular Orbital Description of Aromaticity | 403 | ||
| 8.20 Aromatic Heterocyclic Compounds | 404 | ||
| 8.21 How Benzene Reacts | 406 | ||
| 8.22 Organizing What We Know About the Reactions of Organic Compounds (Group I) | 408 | ||
| ESSENTIAL CONCEPTS | 409 | ||
| SUMMARY OF REACTIONS | 410 | ||
| PROBLEMS | 411 | ||
| TUTORIAL Drawing Resonance Contributors | 418 | ||
| PART THREE: Substitution and Elimination Reactions | 426 | ||
| 9 Substitution and Elimination Reactions of Alkyl Halides | 427 | ||
| ENVIRONMENTAL CONNECTION: The Birth of the Environmental Movement | 428 | ||
| 9.1 The S[Sub(N)]2 Reaction | 429 | ||
| 9.2 Factors That Affect S[Sub(N)]2 Reactions | 434 | ||
| CHEMICAL CONNECTION: Why Are Living Organisms Composed of Carbon Instead of Silicon? | 441 | ||
| 9.3 The S[Sub(N)]1 Reaction | 442 | ||
| 9.4 Factors That Affect S[Sub(N)]1 Reactions | 445 | ||
| 9.5 Competition Between S[Sub(N)]2 and S[Sub(N)]1 Reactions | 446 | ||
| PROBLEM-SOLVING STRATEGY | 447 | ||
| BIOLOGICAL CONNECTION: Naturally Occurring Alkyl Halides That Defend Against Predators | 448 | ||
| 9.6 Elimination Reactions of Alkyl Halides | 448 | ||
| 9.7 The E2 Reaction | 449 | ||
| 9.8 The E1 Reaction | 455 | ||
| PROBLEM-SOLVING STRATEGY | 457 | ||
| 9.9 Competition Between E2 and E1 Reactions | 458 | ||
| 9.10 E2 and E1 Reactions are Stereoselective | 459 | ||
| PROBLEM-SOLVING STRATEGY | 461 | ||
| 9.11 Elimination from Substituted Cyclohexanes | 463 | ||
| 9.12 Predicting the Products of the Reaction of an Alkyl Halide with a Nucleophile/Base | 465 | ||
| 9.13 Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides | 469 | ||
| PROBLEM-SOLVING STRATEGY | 470 | ||
| PROBLEM-SOLVING STRATEGY | 473 | ||
| 9.14 Solvent Effects | 474 | ||
| CHEMICAL CONNECTION: Solvation Effects | 474 | ||
| ENVIRONMENTAL CONNECTION: Environmental Adaptation | 477 | ||
| 9.15 Substitution and Elimination Reactions in Synthesis | 478 | ||
| 9.16 Intermolecular Versus Intramolecular Reactions | 480 | ||
| PROBLEM-SOLVING STRATEGY | 482 | ||
| 9.17 DESIGNING A SYNTHESIS II: Approaching the Problem | 482 | ||
| ESSENTIAL CONCEPTS | 485 | ||
| SUMMARY OF REACTIONS | 486 | ||
| PROBLEMS | 487 | ||
| 10 Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing Compounds | 494 | ||
| 10.1 Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides | 495 | ||
| CHEMICAL CONNECTION: The Lucas Test | 497 | ||
| GENERAL CONNECTION: Grain Alcohol and Wood Alcohol | 498 | ||
| 10.2 Other Methods Used to Convert Alcohols into Alkyl Halides | 499 | ||
| 10.3 Converting an Alcohol Into a Sulfonate Ester | 501 | ||
| 503 | |||
| 10.4 Elimination Reactions of Alcohols: Dehydration | 504 | ||
| PROBLEM-SOLVING STRATEGY | 507 | ||
| BIOLOGICAL CONNECTION: Biological Dehydrations | 509 | ||
| 10.5 Oxidation of Alcohols | 510 | ||
| GENERAL CONNECTION: Blood Alcohol Concentration | 512 | ||
| MEDICAL CONNECTION: Treating Alcoholism with Antabuse | 512 | ||
| MEDICAL CONNECTION: Methanol Poisoning | 513 | ||
| 10.6 Nucleophilic Substitution Reactions of Ethers | 513 | ||
| MEDICAL CONNECTION: Anesthetics | 514 | ||
| 10.7 Nucleophilic Substitution Reactions of Epoxides | 516 | ||
| CHEMICAL CONNECTION: Crown Ethers—Another Example of Molecular Recognition | 520 | ||
| CHEMICAL CONNECTION: Crown Ethers Can be Used to Catalyze SN[Sub(2)] Reactions | 521 | ||
| 10.8 Arene Oxides | 521 | ||
| ENVIRONMENTAL CONNECTION: Benzo[a]pyrene and Cancer | 524 | ||
| ENVIRONMENTAL CONNECTION: Chimney Sweeps and Cancer | 525 | ||
| 10.9 Amines Do Not Undergo Substitution or Elimination Reactions | 526 | ||
| BIOLOGICAL CONNECTION: Alkaloids | 527 | ||
| PHARMACEUTICAL CONNECTION: Lead Compounds for the Development of Drugs | 527 | ||
| 10.10 Quaternary Ammonium Hydroxides Undergo Elimination Reactions | 528 | ||
| 10.11 Thiols, Sulfides, and Sulfonium Ions | 530 | ||
| HISTORICAL CONNECTION: Mustard Gas–A Chemical Warfare Agent | 531 | ||
| MEDICAL CONNECTION: Alkylating Agents as Cancer Drugs | 532 | ||
| 10.12 Methylating Agents Used by Chemists versus Those Used by Cells | 532 | ||
| CHEMICAL CONNECTION: Eradicating Termites | 533 | ||
| MEDICAL CONNECTION: S-Adenosylmethionine: A Natural Antidepressant | 534 | ||
| 10.13 Organizing What We Know About the Reactions of Organic Compounds (Group II) | 535 | ||
| ESSENTIAL CONCEPTS | 536 | ||
| SUMMARY OF REACTIONS | 537 | ||
| PROBLEMS | 539 | ||
| 11 Organometallic Compounds | 544 | ||
| 11.1 Organolithium and Organomagnesium Compounds | 545 | ||
| 11.2 Transmetallation | 547 | ||
| 11.3 Organocuprates | 548 | ||
| 11.4 Palladium-Catalyzed Coupling Reactions | 551 | ||
| PROBLEM-SOLVING STRATEGY | 557 | ||
| 11.5 Alkene Metathesis | 558 | ||
| HISTORICAL CONNECTION: Grubbs, Schrock, Suzuki, and Heck Receive the Nobel Prize | 562 | ||
| HISTORICAL CONNECTION: The Nobel Prize | 562 | ||
| ESSENTIAL CONCEPTS | 563 | ||
| SUMMARY OF REACTIONS | 563 | ||
| PROBLEMS | 564 | ||
| 12 Radicals | 568 | ||
| 12.1 Alkanes are Unreactive Compounds | 568 | ||
| GENERAL CONNECTION: Natural Gas and Petroleum | 569 | ||
| GENERAL CONNECTION: Fossil Fuels: A Problematic Energy Source | 569 | ||
| 12.2 The Chlorination and Bromination of Alkanes | 570 | ||
| HISTORICAL CONNECTION: Why Radicals No Longer Have to Be Called Free Radicals | 572 | ||
| 12.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron | 572 | ||
| 12.4 The Distribution of Products Depends on Probability and Reactivity | 573 | ||
| 12.5 The Reactivity–Selectivity Principle | 575 | ||
| PROBLEM-SOLVING STRATEGY | 577 | ||
| 12.6 Formation of Explosive Peroxides | 578 | ||
| 12.7 The Addition of Radicals to an Alkene | 579 | ||
| 12.8 The Stereochemistry of Radical Substitution and Radical Addition Reactions | 582 | ||
| 12.9 Radical Substitution of Allylic and Benzylic Hydrogens | 583 | ||
| CHEMICAL CONNECTION: Cyclopropane | 586 | ||
| 12.10 DESIGNING A SYNTHESIS III: More Practice with Multistep Synthesis | 586 | ||
| 12.11 Radical Reactions in Biological Systems | 588 | ||
| NUTRITIONAL CONNECTION: Decaffeinated Coffee and the Cancer Scare | 589 | ||
| NUTRITIONAL CONNECTION: Food Preservatives | 591 | ||
| NUTRITIONAL CONNECTION: Is Chocolate a Health Food? | 592 | ||
| 12.12 Radicals and Stratospheric Ozone | 592 | ||
| MEDICAL CONNECTION: Artificial Blood | 594 | ||
| ESSENTIAL CONCEPTS | 594 | ||
| SUMMARY OF REACTIONS | 595 | ||
| PROBLEMS | 595 | ||
| TUTORIAL Drawing Curved Arrows in Radical Systems | 599 | ||
| PART FOUR: Identification of Organic Compounds | 602 | ||
| 13 Mass Spectrometry; Infrared Spectroscopy; UV/Vis Spectroscopy | 603 | ||
| 13.1 Mass Spectrometry | 605 | ||
| 13.2 The Mass Spectrum • Fragmentation | 606 | ||
| 13.3 Using The m/z Value of the Molecular Ion to Calculate the Molecular Formula | 608 | ||
| PROBLEM-SOLVING STRATEGY | 609 | ||
| 13.4 Isotopes in Mass Spectrometry | 610 | ||
| 13.5 High-Resolution Mass Spectrometry Can Reveal Molecular Formulas | 611 | ||
| 13.6 The Fragmentation Patterns of Functional Groups | 611 | ||
| 13.7 Other Ionization Methods | 619 | ||
| 13.8 Gas Chromatography–Mass Spectrometry | 619 | ||
| GENERAL CONNECTION: Mass Spectrometry in Forensics | 619 | ||
| 13.9 Spectroscopy and the Electromagnetic Spectrum | 619 | ||
| 13.10 Infrared Spectroscopy | 621 | ||
| 13.11 Characteristic Infrared Absorption Bands | 624 | ||
| 13.12 The Intensity of Absorption Bands | 625 | ||
| 13.13 The Position of Absorption Bands | 626 | ||
| GENERAL CONNECTION: The Originator of Hooke's Law | 626 | ||
| 13.14 The Position and Shape of an Absorption Band is Affected by Electron Delocalization and Hydrogen Bonding | 627 | ||
| PROBLEM-SOLVING STRATEGY | 629 | ||
| 13.15 C-H Absorption Bands | 631 | ||
| 13.16 The Absence of Absorption Bands | 634 | ||
| 13.17 Some Vibrations are Infrared Inactive | 635 | ||
| 13.18 How to Interpret an Infrared Spectrum | 636 | ||
| 13.19 Ultraviolet and Visible Spectroscopy | 638 | ||
| GENERAL CONNECTION: Ultraviolet Light and Sunscreens | 639 | ||
| 13.20 The Beer–Lambert Law | 640 | ||
| 13.21 The Effect of Conjugation on & | 641 | ||
| 13.22 The Visible Spectrum and Color | 642 | ||
| CHEMICAL CONNECTION: What Makes Blueberries Blue and Strawberries Red? | 643 | ||
| 13.23 Some Uses of UV/Vis Spectroscopy | 644 | ||
| ESSENTIAL CONCEPTS | 646 | ||
| PROBLEMS | 647 | ||
| 14 NMR Spectroscopy | 656 | ||
| 14.1 An Introduction to NMR Spectroscopy | 656 | ||
| HISTORICAL CONNECTION: Nikola Tesla (1856–1943) | 658 | ||
| 14.2 Fourier Transform NMR | 659 | ||
| 14.3 Shielding Causes Different Nuclei to Show Signals at Different Frequencies | 659 | ||
| 14.4 The Number of Signals in an [Sup(1)]H NMR Spectrum | 660 | ||
| PROBLEM-SOLVING STRATEGY | 661 | ||
| 14.5 The Chemical Shift Tells How Far the Signal Is from the Reference Signal | 662 | ||
| 14.6 The Relative Positions of [Sup(1)]H NMR Signals | 664 | ||
| 14.7 The Characteristic Values of Chemical Shifts | 665 | ||
| 14.8 Diamagnetic Anisotropy | 667 | ||
| 14.9 The Integration of NMR Signals Reveals the Relative Number of Protons Causing Each Signal | 668 | ||
| 14.10 The Splitting of Signals Is Described by the N + 1 Rule | 670 | ||
| 14.11 What Causes Splitting? | 673 | ||
| 14.12 More Examples of [Sup(1)]H NMR Spectra | 675 | ||
| 14.13 Coupling Constants Identify Coupled Protons | 680 | ||
| PROBLEM-SOLVING STRATEGY | 682 | ||
| 14.14 Splitting Diagrams Explain the Multiplicity of a Signal | 683 | ||
| 14.15 Enantiotopic and Diastereotopic Hydrogens | 686 | ||
| 14.16 The Time Dependence of NMR Spectroscopy | 688 | ||
| 14.17 Protons Bonded to Oxygen and Nitrogen | 688 | ||
| 14.18 The Use of Deuterium in [Sup(1)]H NMR Spectroscopy | 690 | ||
| 14.19 The Resolution of [Sup(1)]H NMR Spectra | 691 | ||
| 14.20 [Sup(13)]C NMR Spectroscopy | 693 | ||
| PROBLEM-SOLVING STRATEGY | 696 | ||
| 14.21 Dept [Sup(13)]C NMR Spectra | 698 | ||
| 14.22 Two-Dimensional NMR Spectroscopy | 698 | ||
| 14.23 NMR Used in Medicine is Called Magnetic Resonance Imaging | 701 | ||
| 14.24 X-Ray Crystallography | 702 | ||
| GENERAL CONNECTION: Structural Databases | 703 | ||
| ESSENTIAL CONCEPTS | 704 | ||
| PROBLEMS | 705 | ||
| PART FIVE: Carbonyl Compounds | 721 | ||
| 15 Reactions of Carboxylic Acids and Carboxylic Acid Derivatives | 722 | ||
| 15.1 The Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives | 724 | ||
| MEDICAL CONNECTION: Nature's Sleeping Pill | 727 | ||
| 15.2 The Structures of Carboxylic Acids and Carboxylic Acid Derivatives | 728 | ||
| 15.3 The Physical Properties of Carbonyl Compounds | 729 | ||
| 15.4 How Carboxylic Acids and Carboxylic Acid Derivatives React | 730 | ||
| PROBLEM-SOLVING STRATEGY | 732 | ||
| 15.5 The Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives | 732 | ||
| 15.6 Reactions of Acyl Chlorides | 734 | ||
| 15.7 Reactions of Esters | 737 | ||
| 15.8 Acid-Catalyzed Ester Hydrolysis and Transesterification | 738 | ||
| 15.9 Hydroxide-Ion-Promoted Ester Hydrolysis | 742 | ||
| PHARMACEUTICAL CONNECTION: Aspirin, NSAIDs, and COX-2 Inhibitors | 743 | ||
| 15.10 Reactions of Carboxylic Acids | 745 | ||
| PROBLEM-SOLVING STRATEGY | 746 | ||
| 15.11 Reactions of Amides | 747 | ||
| BIOLOGICAL CONNECTION: Dalmatians: Do Not Fool with Mother Nature | 747 | ||
| 15.12 Acid-Catalyzed Amide Hydrolysis and Alcoholysis | 748 | ||
| HISTORICAL CONNECTION: The Discovery of Penicillin | 749 | ||
| MEDICAL CONNECTION: Penicillin and Drug Resistance | 749 | ||
| PHARMACEUTICAL CONNECTION: Penicillins in Clinical Use | 750 | ||
| BIOLOGICAL CONNECTION: A Semisynthetic Penicillin | 750 | ||
| 15.13 Hydroxide-Ion-Promoted Hydrolysis of Amides | 751 | ||
| INDUSTRIAL CONNECTION: Synthetic Polymers | 751 | ||
| MEDICAL CONNECTION: Dissolving Sutures | 752 | ||
| 15.14 Hydrolysis of an Imide: a Way to Synthesize a Primary Amine | 752 | ||
| 15.15 Nitriles | 753 | ||
| 15.16 Acid Anhydrides | 755 | ||
| GENERAL CONNECTION: What Drug-Enforcement Dogs Are Really Detecting | 757 | ||
| 15.17 Dicarboxylic Acids | 757 | ||
| 15.18 How Chemists Activate Carboxylic Acids | 759 | ||
| 15.19 How Cells Activate Carboxylic Acids | 760 | ||
| CHEMICAL CONNECTION: Nerve Impulses, Paralysis, and Insecticides | 763 | ||
| ESSENTIAL CONCEPTS | 764 | ||
| SUMMARY OF REACTIONS | 765 | ||
| PROBLEMS | 767 | ||
| 16 Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives | 775 | ||
| 16.1 The Nomenclature of Aldehydes and Ketones | 776 | ||
| GENERAL CONNECTION: Butanedione: An Unpleasant Compound | 778 | ||
| 16.2 The Relative Reactivities of Carbonyl Compounds | 779 | ||
| 16.3 How Aldehydes and Ketones React | 780 | ||
| 16.4 Reactions of Carbonyl Compounds with Carbon Nucleophiles | 781 | ||
| CHEMICAL CONNECTION: Enzyme-Catalyzed Carbonyl Additions | 783 | ||
| PROBLEM-SOLVING STRATEGY | 785 | ||
| 16.5 Reactions of Carbonyl Compounds with Hydride Ion | 788 | ||
| 16.6 More About Reduction Reactions | 793 | ||
| 16.7 Chemoselective Reactions | 795 | ||
| 16.8 Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles | 796 | ||
| PHARMACEUTICAL CONNECTION: Serendipity in Drug Development | 801 | ||
| 16.9 Reactions of Aldehydes and Ketones with Oxygen Nucleophiles | 802 | ||
| BIOLOGICAL CONNECTION: Preserving Biological Specimens | 804 | ||
| CHEMICAL CONNECTION: Carbohydrates | 806 | ||
| PROBLEM-SOLVING STRATEGY | 807 | ||
| 16.10 Protecting Groups | 808 | ||
| 16.11 Reactions of Aldehydes and Ketones with Sulfur Nucleophiles | 810 | ||
| 16.12 Reactions of Aldehydes and Ketones with a Peroxyacid | 810 | ||
| 16.13 The Wittig Reaction Forms an Alkene | 812 | ||
| CHEMICAL CONNECTION: & | 813 | ||
| 16.14 DESIGNING A SYNTHESIS IV: Disconnections, Synthons, and Synthetic Equivalents | 815 | ||
| CHEMICAL CONNECTION: Synthesizing Organic Compounds | 817 | ||
| PHARMACEUTICAL CONNECTION: Semisynthetic Drugs | 817 | ||
| 16.15 Nucleophilic Addition to & | 817 | ||
| 16.16 Nucleophilic Addition to & | 821 | ||
| CHEMICAL CONNECTION: Enzyme-Catalyzed Cis-Trans Interconversion | 821 | ||
| 16.17 Conjugate Addition Reactions in Biological Systems | 822 | ||
| MEDICAL CONNECTION: Cancer Chemotherapy | 822 | ||
| ESSENTIAL CONCEPTS | 823 | ||
| SUMMARY OF REACTIONS | 824 | ||
| PROBLEMS | 827 | ||
| 17 Reactions at the & | 837 | ||
| 17.1 The Acidity of an & | 838 | ||
| PROBLEM-SOLVING STRATEGY | 840 | ||
| 17.2 Keto–Enol Tautomers | 841 | ||
| 17.3 Keto–Enol Interconversion | 842 | ||
| 17.4 Halogenation of the & | 843 | ||
| 17.5 Halogenation of the & | 845 | ||
| 17.6 Forming an Enolate Ion | 846 | ||
| 17.7 Alkylating the & | 847 | ||
| PROBLEM-SOLVING STRATEGY | 849 | ||
| INDUSTRIAL CONNECTION: The Synthesis of Aspirin | 849 | ||
| 17.8 Alkylating and Acylating the & | 850 | ||
| 17.9 Alkylating the & | 851 | ||
| 17.10 An Aldol Addition Forms a & | 853 | ||
| 17.11 The Dehydration of Aldol Addition Products Forms & | 855 | ||
| 17.12 A Crossed Aldol Addition | 857 | ||
| MEDICAL CONNECTION: Breast Cancer and Aromatase Inhibitors | 859 | ||
| 17.13 A Claisen Condensation Forms a & | 860 | ||
| 17.14 Other Crossed Condensations | 863 | ||
| 17.15 Intramolecular Condensations and Intramolecular Aldol Additions | 863 | ||
| 17.16 The Robinson Annulation | 866 | ||
| PROBLEM-SOLVING STRATEGY | 866 | ||
| 17.17 CO[Sub(2)] Can be Removed from a Carboxylic Acid that has a Carbonyl Group at the 3-Position | 867 | ||
| 17.18 The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid | 869 | ||
| 17.19 The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone | 870 | ||
| 17.20 DESIGNING A SYNTHESIS V: Making New Carbon–Carbon Bonds | 872 | ||
| 17.21 Reactions at the & | 874 | ||
| 17.22 Organizing What We Know About the Reactions of Organic Compounds (Group III) | 877 | ||
| ESSENTIAL CONCEPTS | 879 | ||
| SUMMARY OF REACTIONS | 880 | ||
| PROBLEMS | 882 | ||
| TUTORIAL Synthesis and Retrosynthetic Analysis | 890 | ||
| PART SIX: Aromatic Compounds | 903 | ||
| 18 Reactions of Benzene and Substituted Benzenes | 904 | ||
| GENERAL CONNECTION: Measuring Toxicity | 905 | ||
| 18.1 The Nomenclature of Monosubstituted Benzenes | 906 | ||
| GENERAL CONNECTION: The Toxicity of Benzene | 907 | ||
| 18.2 The General Mechanism for Electrophilic Aromatic Substitution Reactions | 907 | ||
| 18.3 Halogenation of Benzene | 908 | ||
| MEDICAL CONNECTION: Thyroxine | 910 | ||
| 18.4 Nitration of Benzene | 910 | ||
| 18.5 Sulfonation of Benzene | 911 | ||
| 18.6 Friedel–Crafts Acylation of Benzene | 912 | ||
| 18.7 Friedel–Crafts Alkylation of Benzene | 913 | ||
| CHEMICAL CONNECTION: Incipient Primary Carbocations | 915 | ||
| BIOLOGICAL CONNECTION: A Biological Friedel-Crafts Alkylation | 915 | ||
| 18.8 Alkylation of Benzene by Acylation–Reduction | 916 | ||
| 18.9 Using Coupling Reactions to Alkylate Benzene | 917 | ||
| 18.10 How Some Substituents on a Benzene Ring Can Be Chemically Changed | 918 | ||
| 18.11 The Nomenclature of Disubstituted and Polysubstituted Benzenes | 920 | ||
| 18.12 The Effect of Substituents on Reactivity | 922 | ||
| 18.13 The Effect of Substituents on Orientation | 926 | ||
| 18.14 The Ortho–Para Ratio | 930 | ||
| 18.15 Additional Considerations Regarding Substituent Effects | 930 | ||
| 18.16 DESIGNING A SYNTHESIS VI: The Synthesis of Monosubstituted and Disubstituted Benzenes | 932 | ||
| 18.17 The Synthesis of Trisubstituted Benzenes | 934 | ||
| 18.18 Synthesizing Substituted Benzenes Using Arenediazonium Salts | 936 | ||
| 18.19 Azobenzenes | 939 | ||
| HISTORICAL CONNECTION: Discovery of the First Antibiotic | 940 | ||
| PHARMACEUTICAL CONNECTION: Drug Safety | 940 | ||
| 18.20 The Mechanism for the Formation of a Diazonium Ion | 941 | ||
| MEDICAL CONNECTION: A New Cancer-Fighting Drug | 941 | ||
| NUTRITIONAL CONNECTION: Nitrosamines and Cancer | 942 | ||
| 18.21 Nucleophilic Aromatic Substitution | 943 | ||
| 18.22 DESIGNING A SYNTHESIS VII: The Synthesis of Cyclic Compounds | 945 | ||
| ESSENTIAL CONCEPTS | 946 | ||
| SUMMARY OF REACTIONS | 947 | ||
| PROBLEMS | 949 | ||
| 19 More About Amines • Reactions of Heterocyclic Compounds | 960 | ||
| 19.1 More About Nomenclature | 961 | ||
| 19.2 More About the Acid–Base Properties of Amines | 962 | ||
| MEDICAL CONNECTION: Atropine | 963 | ||
| 19.3 Amines React as Bases and as Nucleophiles | 963 | ||
| 19.4 Synthesis of Amines | 965 | ||
| 19.5 Aromatic Five-Membered-Ring Heterocycles | 965 | ||
| PROBLEM-SOLVING STRATEGY | 967 | ||
| 19.6 Aromatic Six-Membered-Ring Heterocycles | 970 | ||
| 19.7 Some Heterocyclic Amines Have Important Roles in Nature | 975 | ||
| PHARMACEUTICAL CONNECTION: Searching for Drugs: An Antihistamine, a Nonsedating Antihistamine, and a Drug for Ulcers | 976 | ||
| MEDICAL CONNECTION: Porphyrin, Bilirubin, and Jaundice | 979 | ||
| 19.8 Organizing What We Know About the Reactions of Organic Compounds (Group IV) | 979 | ||
| ESSENTIAL CONCEPTS | 980 | ||
| SUMMARY OF REACTIONS | 981 | ||
| PROBLEMS | 982 | ||
| PART SEVEN: Bioorganic Compounds | 985 | ||
| 20 The Organic Chemistry of Carbohydrates | 986 | ||
| 20.1 Classifying Carbohydrates | 987 | ||
| 20.2 The D and L Notation | 988 | ||
| 20.3 The Configurations of Aldoses | 989 | ||
| 20.4 The Configurations of Ketoses | 991 | ||
| 20.5 The Reactions of Monosaccharides in Basic Solutions | 992 | ||
| 20.6 Oxidation–Reduction Reactions of Monosaccharides | 993 | ||
| 20.7 Lengthening the Chain: The Kiliani–Fischer Synthesis | 994 | ||
| 20.8 Shortening the Chain: The Wohl Degradation | 995 | ||
| MEDICAL CONNECTION: Measuring the Blood Glucose Levels in Diabetes | 996 | ||
| 20.9 The Stereochemistry of Glucose: The Fischer Proof | 996 | ||
| GENERAL CONNECTION: Glucose/Dextrose | 998 | ||
| 20.10 Monosaccharides Form Cyclic Hemiacetals | 998 | ||
| 20.11 Glucose is the Most Stable Aldohexose | 1001 | ||
| 20.12 Formation of Glycosides | 1003 | ||
| 20.13 The Anomeric Effect | 1004 | ||
| 20.14 Reducing and Nonreducing Sugars | 1005 | ||
| 20.15 Disaccharides | 1005 | ||
| NUTRITIONAL CONNECTION: Lactose Intolerance | 1007 | ||
| MEDICAL CONNECTION: Galactosemia | 1007 | ||
| BIOLOGICAL CONNECTION: A Toxic Disaccharid | 1008 | ||
| 20.16 Polysaccharides | 1009 | ||
| MEDICAL CONNECTION: Why the Dentist is Right | 1010 | ||
| BIOLOGICAL CONNECTION: Controlling Fleas | 1011 | ||
| 20.17 Some Naturally Occurring Compounds Derived from Carbohydrates | 1012 | ||
| MEDICAL CONNECTION: Resistance to Antibiotics | 1012 | ||
| MEDICAL CONNECTION: Heparin–A Natural Anticoagulant | 1013 | ||
| HISTORICAL CONNECTION: Vitamin C | 1014 | ||
| 20.18 Carbohydrates on Cell Surfaces | 1014 | ||
| 20.19 Artificial Sweeteners | 1015 | ||
| NUTRITIONAL CONNECTION: Acceptable Daily Intake | 1017 | ||
| ESSENTIAL CONCEPTS | 1017 | ||
| SUMMARY OF REACTIONS | 1018 | ||
| PROBLEMS | 1019 | ||
| 21 Amino Acids, Peptides, and Proteins | 1022 | ||
| 21.1 The Nomenclature of Amino Acids | 1023 | ||
| NUTRITIONAL CONNECTION: Proteins and Nutrition | 1027 | ||
| 21.2 The Configuration of Amino Acids | 1027 | ||
| MEDICAL CONNECTION: Amino Acids and Disease | 1028 | ||
| PHARMACEUTICAL CONNECTION: A Peptide Antibiotic | 1028 | ||
| 21.3 Acid–Base Properties of Amino Acids | 1029 | ||
| 21.4 The Isoelectric Point | 1031 | ||
| 21.5 Separating Amino Acids | 1032 | ||
| GENERAL CONNECTION: Water Softeners: Examples of Cation-Exchange Chromatography | 1036 | ||
| 21.6 Synthesis of Amino Acids | 1036 | ||
| 21.7 Resolution of Racemic Mixtures of Amino Acids | 1038 | ||
| 21.8 Peptide Bonds and Disulfide Bonds | 1039 | ||
| MEDICAL CONNECTION: Diabetes | 1042 | ||
| CHEMICAL CONNECTION: Hair: Straight or Curly? | 1042 | ||
| 21.9 Some Interesting Peptides | 1042 | ||
| 21.10 The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation | 1043 | ||
| 21.11 Automated Peptide Synthesis | 1046 | ||
| 21.12 An Introduction to Protein Structure | 1049 | ||
| BIOLOGICAL CONNECTION: Primary Structure and Taxonomic Relationship | 1049 | ||
| 21.13 How to Determine the Primary Structure of a Polypeptide or a Protein | 1049 | ||
| PROBLEM-SOLVING STRATEGY | 1051 | ||
| 21.14 Secondary Structure | 1055 | ||
| CHEMICAL CONNECTION: Right-Handed and Left-Handed Helices | 1056 | ||
| CHEMICAL CONNECTION: & | 1058 | ||
| 21.15 Tertiary Structure | 1058 | ||
| MEDICAL CONNECTION: Diseases Caused by a Misfolded Protein | 1060 | ||
| 21.16 Quaternary Structure | 1060 | ||
| 21.17 Protein Denaturation | 1061 | ||
| ESSENTIAL CONCEPTS | 1061 | ||
| PROBLEMS | 1062 | ||
| 22 Catalysis in Organic Reactions and in Enzymatic Reactions | 1066 | ||
| 22.1 Catalysis in Organic Reactions | 1068 | ||
| 22.2 Acid Catalysis | 1068 | ||
| 22.3 Base Catalysis | 1071 | ||
| 22.4 Nucleophilic Catalysis | 1073 | ||
| 22.5 Metal-Ion Catalysis | 1074 | ||
| 22.6 Intramolecular Reactions | 1076 | ||
| 22.7 Intramolecular Catalysis | 1078 | ||
| 22.8 Catalysis in Biological Reactions | 1080 | ||
| 22.9 An Enzyme-Catalyzed Reaction That Is Reminiscent of Acid-Catalyzed Amide Hydrolysis | 1082 | ||
| 22.10 Another Enzyme-Catalyzed Reaction That Is Reminiscent of Acid-Catalyzed Amide Hydrolysis | 1085 | ||
| 22.11 An Enzyme-Catalyzed Reaction That Involves Two Sequential S[Sub(N)]2 Reactions | 1088 | ||
| MEDICAL CONNECTION: How Tamiflu Works | 1091 | ||
| 22.12 An Enzyme-Catalyzed Reaction That Is Reminiscent of the Base-Catalyzed Enediol Rearrangement | 1092 | ||
| 22.13 An Enzyme Catalyzed-Reaction That Is Reminiscent of a Retro-Aldol Addition | 1093 | ||
| ESSENTIAL CONCEPTS | 1095 | ||
| PROBLEMS | 1096 | ||
| 23 The Organic Chemistry of the Coenzymes, Compounds Derived from Vitamins | 1099 | ||
| HISTORICAL CONNECTION: Vitamin B[Sub(1)] | 1101 | ||
| 23.1 Niacin: The Vitamin Needed for Many Redox Reactions | 1102 | ||
| HISTORICAL CONNECTION: Niacin Deficiency | 1103 | ||
| 23.2 Riboflavin: Another Vitamin Used in Redox Reactions | 1107 | ||
| 23.3 Vitamin B[Sub(1)] : The Vitamin Needed for Acyl Group Transfer | 1111 | ||
| GENERAL CONNECTION: Curing a Hangover with Vitamin B[Sub(1)] | 1114 | ||
| 23.4 Biotin: The Vitamin Needed for Carboxylation of an & | 1115 | ||
| 23.5 Vitamin B[Sub(6)] : The Vitamin Needed for Amino Acid Transformations | 1117 | ||
| MEDICAL CONNECTION: Assessing the Damage After a Heart Attack | 1121 | ||
| 23.6 Vitamin B[Sub(12)] : The Vitamin Needed for Certain Isomerizations | 1122 | ||
| 23.7 Folic Acid: The Vitamin Needed for One-Carbon Transfer | 1124 | ||
| HISTORICAL CONNECTION: The First Antibiotics | 1125 | ||
| MEDICAL CONNECTION: Cancer Drugs and Side Effects | 1128 | ||
| BIOLOGICAL CONNECTION: Competitive Inhibitors | 1128 | ||
| 23.8 Vitamin K: The Vitamin Needed for Carboxylation of Glutamate | 1129 | ||
| MEDICAL CONNECTION: Anticoagulants | 1131 | ||
| NUTRITIONAL CONNECTION: Too Much Broccoli | 1131 | ||
| ESSENTIAL CONCEPTS | 1131 | ||
| PROBLEMS | 1132 | ||
| 24 The Organic Chemistry of the Metabolic Pathways | 1135 | ||
| NUTRITIONAL CONNECTION: Differences in Metabolism | 1136 | ||
| 24.1 ATP is Used for Phosphoryl Transfer Reactions | 1136 | ||
| CHEMICAL CONNECTION: Why Did Nature Choose Phosphates? | 1138 | ||
| 24.2 Why ATP is Kinetically Stable in a Cell | 1138 | ||
| 24.3 The \"High-Energy\" Character of Phosphoanhydride Bonds | 1138 | ||
| 24.4 The Four Stages of Catabolism | 1140 | ||
| 24.5 The Catabolism of Fats: Stages 1 and 2 | 1141 | ||
| 24.6 The Catabolism of Carbohydrates: Stages 1 and 2 | 1144 | ||
| PROBLEM-SOLVING STRATEGY | 1147 | ||
| NUTRITIONAL CONNECTION: Fats Versus Carbohydrates as a Source of Energy | 1148 | ||
| 24.7 The Fate of Pyruvate | 1148 | ||
| 24.8 The Catabolism of Proteins: Stages 1 and 2 | 1149 | ||
| MEDICAL CONNECTION: Phenylketonuria (PKU): An Inborn Error of Metabolism | 1150 | ||
| MEDICAL CONNECTION: Alcaptonuria | 1151 | ||
| 24.9 The Citric Acid Cycle: Stage 3 | 1151 | ||
| 24.10 Oxidative Phosphorylation: Stage 4 | 1154 | ||
| NUTRITIONAL CONNECTION: Basal Metabolic Rate | 1155 | ||
| 24.11 Anabolism | 1155 | ||
| 24.12 Gluconeogenesis | 1156 | ||
| 24.13 Regulating Metabolic Pathways | 1158 | ||
| 24.14 Amino Acid Biosynthesis | 1159 | ||
| ESSENTIAL CONCEPTS | 1160 | ||
| PROBLEMS | 1161 | ||
| 25 The Organic Chemistry of Lipids | 1163 | ||
| 25.1 Fatty Acids Are Long-Chain Carboxylic Acids | 1164 | ||
| NUTRITIONAL CONNECTION: Omega Fatty Acids | 1165 | ||
| 25.2 Waxes Are High-Molecular-Weight Esters | 1166 | ||
| 25.3 Fats and Oils Are Triglycerides | 1166 | ||
| NUTRITIONAL CONNECTION: Olestra: Nonfat with Flavor | 1168 | ||
| BIOLOGICAL CONNECTION: Whales and Echolocation | 1168 | ||
| 25.4 Soaps and Micelles | 1168 | ||
| 25.5 Phospholipids Are Components of Cell Membranes | 1170 | ||
| BIOLOGICAL CONNECTION: Snake Venom | 1172 | ||
| MEDICAL CONNECTION: Multiple Sclerosis and the Myelin Sheath | 1173 | ||
| 25.6 Prostaglandins Regulate Physiological Responses | 1173 | ||
| 25.7 Terpenes Contain Carbon Atoms in Multiples of Five | 1175 | ||
| 25.8 How Terpenes Are Biosynthesized | 1177 | ||
| MEDICAL CONNECTION: How Statins Lower Cholesterol Levels | 1178 | ||
| PROBLEM-SOLVING STRATEGY | 1180 | ||
| CHEMICAL CONNECTION: Protein Prenylation | 1182 | ||
| 25.9 How Nature Synthesizes Cholesterol | 1183 | ||
| 25.10 Steroids | 1184 | ||
| MEDICAL CONNECTION: One Drug—Two Effects | 1185 | ||
| 25.11 Synthetic Steroids | 1186 | ||
| ESSENTIAL CONCEPTS | 1187 | ||
| PROBLEMS | 1188 | ||
| 26 The Chemistry of the Nucleic Acids | 1191 | ||
| 26.1 Nucleosides and Nucleotides | 1191 | ||
| HISTORICAL CONNECTION: The Structure of DNA: Watson, Crick, Franklin, and Wilkins | 1194 | ||
| BIOLOGICAL CONNECTION: Cyclic AMP | 1195 | ||
| 26.2 Nucleic Acids Are Composed of Nucleotide Subunits | 1195 | ||
| 26.3 The Secondary Structure of DNA | 1197 | ||
| 26.4 Why DNA Does Not Have A 2'-OH Group | 1199 | ||
| 26.5 The Biosynthesis of DNA Is Called Replication | 1199 | ||
| 26.6 DNA and Heredity | 1200 | ||
| PHARMACEUTICAL CONNECTION: Natural Products That Modify DNA | 1201 | ||
| 26.7 The Biosynthesis of RNA Is Called Transcription | 1201 | ||
| BIOLOGICAL CONNECTION: There Are More Than Four Bases in DNA | 1202 | ||
| 26.8 The RNAs Used for Protein Biosynthesis | 1203 | ||
| 26.9 The Biosynthesis of Proteins Is Called Translation | 1205 | ||
| MEDICAL CONNECTION: Sickle Cell Anemia | 1207 | ||
| MEDICAL CONNECTION: Antibiotics That Act by Inhibiting Translation | 1208 | ||
| 26.10 Why DNA Contains Thymine Instead of Uracil | 1209 | ||
| MEDICAL CONNECTION: Antibiotics Act by a Common Mechanism | 1210 | ||
| 26.11 Antiviral Drugs | 1210 | ||
| HISTORICAL CONNECTION: Influenza Pandemics | 1211 | ||
| 26.12 How the Base Sequence of DNA Is Determined | 1211 | ||
| 26.13 Genetic Engineering | 1213 | ||
| ENVIRONMENTAL CONNECTION: Resisting Herbicides | 1213 | ||
| PHARMACEUTICAL CONNECTION: Using Genetic Engineering to Treat the Ebola Virus | 1213 | ||
| ESSENTIAL CONCEPTS | 1214 | ||
| PROBLEMS | 1214 | ||
| PART EIGHT: Special Topics in Organic Chemistry | 1217 | ||
| 27 Synthetic Polymers | 1218 | ||
| 27.1 There Are Two Major Classes of Synthetic Polymers | 1219 | ||
| 27.2 An Introduction To Chain-Growth Polymers | 1220 | ||
| 27.3 Radical Polymerization | 1220 | ||
| INDUSTRIAL CONNECTION: Teflon: An Accidental Discovery | 1223 | ||
| ENVIRONMENTAL CONNECTION: Recycling Symbols | 1225 | ||
| 27.4 Cationic Polymerization | 1225 | ||
| 27.5 Anionic Polymerization | 1228 | ||
| 27.6 Ring-Opening Polymerizations | 1229 | ||
| 27.7 Stereochemistry of Polymerization • Ziegler–Natta Catalysts | 1231 | ||
| 27.8 Polymerization of Dienes | 1232 | ||
| 27.9 Copolymers | 1234 | ||
| PHARMACEUTICAL CONNECTION: Nanocontainers | 1234 | ||
| 27.10 An Introduction to Step-Growth Polymers | 1235 | ||
| 27.11 Classes of Step-Growth Polymers | 1236 | ||
| MEDICAL CONNECTION: Health Concerns: Bisphenol A and Phthalates | 1238 | ||
| INDUSTRIAL CONNECTION: Designing a Polymer | 1239 | ||
| 27.12 Physical Properties of Polymers | 1240 | ||
| NUTRITIONAL CONNECTION: Melamine Poisoning | 1241 | ||
| 27.13 Recycling Polymers | 1242 | ||
| 27.14 Biodegradable Polymers | 1243 | ||
| ESSENTIAL CONCEPTS | 1244 | ||
| PROBLEMS | 1244 | ||
| 28 Pericyclic Reactions | 1248 | ||
| 28.1 There Are Three Kinds of Pericyclic Reactions | 1249 | ||
| 28.2 Molecular Orbitals and Orbital Symmetry | 1251 | ||
| 28.3 Electrocyclic Reactions | 1254 | ||
| 28.4 Cycloaddition Reactions | 1260 | ||
| 28.5 Sigmatropic Rearrangements | 1263 | ||
| 28.6 Pericyclic Reactions in Biological Systems | 1268 | ||
| CHEMICAL CONNECTION: Bioluminescence | 1269 | ||
| NUTRITIONAL CONNECTION: The Sunshine Vitamin | 1270 | ||
| NUTRITIONAL CONNECTION: Animals, Birds, Fish—And Vitamin D | 1271 | ||
| 28.7 Summary of the Selection Rules for Pericyclic Reactions | 1271 | ||
| ESSENTIAL CONCEPTS | 1272 | ||
| PROBLEMS | 1272 | ||
| Appendices | 1277 | ||
| I: PK[Sub(A)] VALUES | 1277 | ||
| II: KINETICS | 1279 | ||
| III: SUMMARY OF METHODS USED TO SYNTHESIZE A PARTICULAR FUNCTIONAL GROUP | 1284 | ||
| IV: SUMMARY OF METHODS EMPLOYED TO FORM CARBON-CARBON BONDS | 1287 | ||
| V: SPECTROSCOPY TABLES | 1288 | ||
| VI: PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS | 1294 | ||
| ANSWERS TO SELECTED PROBLEMS | 1297 | ||
| GLOSSARY | 1307 | ||
| A | 1307 | ||
| B | 1308 | ||
| C | 1308 | ||
| D | 1308 | ||
| E | 1310 | ||
| F | 1310 | ||
| G | 1310 | ||
| H | 1311 | ||
| I | 1312 | ||
| K | 1312 | ||
| L | 1312 | ||
| M | 1312 | ||
| N | 1313 | ||
| O | 1313 | ||
| P | 1314 | ||
| Q | 1314 | ||
| R | 1314 | ||
| S | 1315 | ||
| T | 1316 | ||
| U | 1317 | ||
| V | 1317 | ||
| W | 1317 | ||
| X | 1317 | ||
| Z | 1317 | ||
| CREDITS | 1319 | ||
| INDEX | 1321 | ||
| A | 1321 | ||
| B | 1322 | ||
| C | 1324 | ||
| D | 1325 | ||
| E | 1326 | ||
| F | 1327 | ||
| G | 1327 | ||
| H | 1328 | ||
| I | 1329 | ||
| J | 1329 | ||
| K | 1329 | ||
| L | 1329 | ||
| M | 1329 | ||
| N | 1331 | ||
| O | 1331 | ||
| P | 1332 | ||
| Q | 1333 | ||
| R | 1333 | ||
| S | 1334 | ||
| T | 1335 | ||
| U | 1336 | ||
| V | 1336 | ||
| W | 1336 | ||
| X | 1336 | ||
| Y | 1336 | ||
| Z | 1336 |