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Abstract
For courses in Organic Chemistry (2-Semester)
A Student-Centered Approach to Learning and Studying Organic Chemistry
Wade & Simek’s Ninth Edition of Organic Chemistry presents key principles of organic chemistry in the context of fundamental reasoning and problem solving. Authored to complement how students use a textbook today, new Problem Solving Strategies, Partially Solved Problems, Visual Reaction Guides and Reaction Starbursts encourage students to use the text before class as a primary introduction to organic chemistry as well as a comprehensive study tool for working problems and/or preparing for exams. With unparalleled and highly refined pedagogy, this Ninth edition gives students a contemporary overview of organic principles and the tools for organizing and understanding reaction mechanisms and synthetic organic chemistry.
MasteringChemistry™ not included. Students, if MasteringChemistry is a recommended/mandatory component of the course, please ask your instructor for the correct ISBN and course ID. MasteringChemistry should only be purchased when required by an instructor. Instructors, contact your Pearson representative for more information.
MasteringChemistry is an online homework, tutorial, and assessment system, designed to improve results by engaging students before, during, and after class with powerful content. Instructors ensure students arrive ready to learn by assigning educationally effective content before class, and encourage critical thinking and retention with in-class resources such as Learning Catalytics™.
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Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Title Page 1 | 1 | ||
| Copyright Page 2 | 2 | ||
| About the Authors 3 | 3 | ||
| Contents 5 | 5 | ||
| Preface 25 | 25 | ||
| 1 STRUCTURE AND BONDING 37 | 37 | ||
| 1-1 The Origins of Organic Chemistry 37 | 37 | ||
| 1-2 Principles of Atomic Structure 39 | 39 | ||
| 1-3 Bond Formation: The Octet Rule 43\n | 43 | ||
| 1-4 Lewis Structures 44\n | 44 | ||
| 1-5 Multiple Bonding 45\n | 45 | ||
| Summary: Common Bonding Patterns (Uncharged) 45\n | 45 | ||
| 1-6 Electronegativity and Bond Polarity 46\n | 46 | ||
| 1-7 Formal Charges 47\n | 47 | ||
| 1-8 Ionic Structures 49 | 49 | ||
| 1-9 Resonance 50 | 50 | ||
| PROBLEM-SOLVING STRATEGY: Drawing and Evaluating Resonance Forms 54 | 54 | ||
| 1-10 Structural Formulas 58 | 58 | ||
| 1-11 Molecular Formulas and Empirical Formulas 61 | 61 | ||
| 1-12 Wave Properties of Electrons in Orbitals 63 | 63 | ||
| 1-13 Molecular Orbitals 64 | 64 | ||
| 1-14 Pi Bonding 67 | 67 | ||
| 1-15 Hybridization and Molecular Shapes 68 | 68 | ||
| 1-16 Drawing Three-Dimensional Molecules 72 | 72 | ||
| 1-17 General Rules of Hybridization and Geometry 73 | 73 | ||
| Summary: Hybridization and Geometry 73 | 73 | ||
| 1-18 Bond Rotation 78 | 78 | ||
| 1-19 Isomerism 80 | 80 | ||
| Essential Terms 83 | 83 | ||
| Study Problems 86 | 86 | ||
| 2 ACIDS AND BASES; FUNCTIONAL GROUPS 91 | 91 | ||
| 2-1 Polarity of Bonds and Molecules 92 | 92 | ||
| 2-2 Intermolecular Forces 96 | 96 | ||
| 2-3 Polarity Effects on Solubilities 100 | 100 | ||
| 2-4 Arrhenius Acids and Bases 103 | 103 | ||
| 2-5 Brønsted–Lowry Acids and Bases 104 | 104 | ||
| 2-6 Strengths of Acids and Bases 105 | 105 | ||
| 2-7 Equilibrium Positions of Acid–Base Reactions 109 | 109 | ||
| PROBLEM-SOLVING STRATEGY: Predicting Acid–Base Equilibrium Positions 111 | 111 | ||
| 2-8 Solvent Effects on Acidity and Basicity 112 | 112 | ||
| Summary: Acidity and Basicity Limitations in Common Solvents 114 | 91 | ||
| 2-9 Effects of Size and Electronegativity on Acidity 114 | 114 | ||
| 2-10 Inductive Effects on Acidity 116 | 116 | ||
| 2-11 Hybridization Effects on Acidity 117 | 117 | ||
| 2-12 Resonance Effects on Acidity and Basicity 119 | 119 | ||
| 2-13 Lewis Acids and Bases 122 | 122 | ||
| 2-14 The Curved-Arrow Formalism 124 | 124 | ||
| 2-15 Hydrocarbons 126 | 126 | ||
| 2-16 Functional Groups with Oxygen 129 | 129 | ||
| 2-17 Functional Groups with Nitrogen 132 | 132 | ||
| Essential Terms 134 | 134 | ||
| Study Problems 137 | 137 | ||
| 3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 143 | 143 | ||
| 3-1 Classification of Hydrocarbons (Review) 144 | 144 | ||
| 3-2 Molecular Formulas of Alkanes 144 | 144 | ||
| 3-3 Nomenclature of Alkanes 146 | 146 | ||
| Summary: Rules for Naming Alkanes 151 | 151 | ||
| 3-4 Physical Properties of Alkanes 153 | 153 | ||
| 3-5 Uses and Sources of Alkanes 154 | 154 | ||
| 3-6 Reactions of Alkanes 157 | 157 | ||
| 3-7 Structure and Conformations of Alkanes 158 | 158 | ||
| 3-8 Conformations of Butane 162 | 162 | ||
| 3-9 Conformations of Higher Alkanes 165 | 165 | ||
| 3-10 Cycloalkanes 165 | 165 | ||
| 3-11 Cis-trans Isomerism in Cycloalkanes 167 | 167 | ||
| 3-12 Stabilities of Cycloalkanes; Ring Strain 168 | 168 | ||
| 3-13 Cyclohexane Conformations 172 | 172 | ||
| PROBLEM-SOLVING STRATEGY: Drawing Chair Conformations 174 | 174 | ||
| 3-14 Conformations of Monosubstituted Cyclohexanes 176 | 176 | ||
| 3-15 Conformations of Disubstituted Cyclohexanes 179 | 179 | ||
| PROBLEM-SOLVING STRATEGY: Recognizing Cis and Trans Isomers 179 | 179 | ||
| 3-16 Bicyclic Molecules 182 | 182 | ||
| Essential Terms 184 | 184 | ||
| Study Problems 188 | 188 | ||
| 4 THE STUDY OF CHEMICAL REACTIONS 191 | 191 | ||
| 4-1 Introduction 191 | 191 | ||
| 4-2 Chlorination of Methane 192 | 192 | ||
| 4-3 The Free-Radical Chain Reaction 193 | 193 | ||
| 4-4 Equilibrium Constants and Free Energy 197 | 197 | ||
| 4-5 Enthalpy and Entropy 199 | 199 | ||
| 4-6 Bond-Dissociation Enthalpies 201 | 201 | ||
| 4-7 Enthalpy Changes in Chlorination 202 | 202 | ||
| 4-8 Kinetics and the Rate Equation 205 | 205 | ||
| 4-9 Activation Energy and the Temperature Dependence of Rates 207 | 207 | ||
| 4-10 Transition States 208 | 208 | ||
| 4-11 Rates of Multistep Reactions 210 | 210 | ||
| 4-12 Temperature Dependence of Halogenation 211 | 211 | ||
| 4-13 Selectivity in Halogenation 212 | 212 | ||
| 4-14 Hammond’s Postulate 218 | 218 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 219 | 219 | ||
| 4-15 Radical Inhibitors 222 | 222 | ||
| 4-16 Reactive Intermediates 223 | 223 | ||
| Summary: Reactive Intermediates 230 | 230 | ||
| Essential Terms 230 | 230 | ||
| Study Problems 233 | 233 | ||
| 5 STEREOCHEMISTRY 237 | 237 | ||
| 5-1 Introduction 237 | 237 | ||
| 5-2 Chirality 238 | 238 | ||
| 5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms 244 | 244 | ||
| 5-4 Optical Activity 249 | 249 | ||
| 5-5 Biological Discrimination of Enantiomers 254 | 254 | ||
| 5-6 Racemic Mixtures 255 | 255 | ||
| 5-7 Enantiomeric Excess and Optical Purity 256 | 256 | ||
| 5-8 Chirality of Conformationally Mobile Systems 257 | 257 | ||
| 5-9 Chiral Compounds Without Asymmetric Atoms 260 | 260 | ||
| 5-10 Fischer Projections 262 | 262 | ||
| Summary: Fischer Projections and Their Use 266 | 266 | ||
| 5-11 Diastereomers 266 | 266 | ||
| Summary: Types of Isomers 268 | 268 | ||
| 5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons 269 | 269 | ||
| 5-13 Meso Compounds 269 | 269 | ||
| 5-14 Absolute and Relative Configuration 271 | 271 | ||
| 5-15 Physical Properties of Diastereomers 273 | 273 | ||
| 5-16 Resolution of Enantiomers 274 | 274 | ||
| Essential Terms 277 | 277 | ||
| Study Problems 280 | 280 | ||
| 6 ALKYL HALIDES; NUCLEOPHILIC SUBSTITUTION 283 | 283 | ||
| 6-1 Introduction 283 | 283 | ||
| 6-2 Nomenclature of Alkyl Halides 284 | 284 | ||
| 6-3 Common Uses of Alkyl Halides 286 | 286 | ||
| 6-4 Structure of Alkyl Halides 288 | 288 | ||
| 6-5 Physical Properties of Alkyl Halides 289 | 289 | ||
| 6-6 Preparation of Alkyl Halides 291 | 291 | ||
| Summary: Methods for Preparing Alkyl Halides 295 | 295 | ||
| 6-7 Reactions of Alkyl Halides: Substitution and Elimination 296 | 296 | ||
| 6-8 Bimolecular Nucleophilic Substitution: The SN2 Reaction 297 | 297 | ||
| 6-9 Generality of the SN2 Reaction 299 | 299 | ||
| Summary: SN2 Reactions of Alkyl Halides 300 | 300 | ||
| 6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile 301 | 301 | ||
| Summary: Trends in Nucleophilicity 302 | 302 | ||
| 6-11 Reactivity of the Substrate in SN2 Reactions 305 | 305 | ||
| 6-12 Stereochemistry of the SN2 Reaction 309 | 309 | ||
| 6-13 Unimolecular Nucleophilic Substitution: The SN1 Reaction 311 | 311 | ||
| 6-14 Stereochemistry of the SN1 Reaction 315 | 315 | ||
| 6-15 Rearrangements in SN1 Reactions 317 | 317 | ||
| 6-16 Comparison of SN1 and SN2 Reactions 320 | 320 | ||
| Summary: Nucleophilic Substitutions 322 | 322 | ||
| Summary: Reactions of Alkyl Halides 323 | 323 | ||
| Essential Terms 324 | 324 | ||
| Study Problems 327 | 327 | ||
| 7 STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION 332 | 332 | ||
| 7-1 Introduction 332 | 332 | ||
| 7-2 The Orbital Description of the Alkene Double Bond 333 | 333 | ||
| 7-3 Elements of Unsaturation 335 | 335 | ||
| 7-4 Nomenclature of Alkenes 337 | 337 | ||
| 7-5 Nomenclature of Cis-Trans Isomers 339 | 339 | ||
| Summary: Rules for Naming Alkenes 341 | 341 | ||
| 7-6 Commercial Importance of Alkenes 342 | 342 | ||
| 7-7 Physical Properties of Alkenes 344 | 344 | ||
| 7-8 Stability of Alkenes 346 | 346 | ||
| 7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl Halides 354 | 354 | ||
| 7-10 Unimolecular Elimination: The E1 Reaction 355 | 355 | ||
| Summary: Carbocation Reactions 359 | 359 | ||
| 7-11 Positional Orientation of Elimination: Zaitsev’s Rule 360 | 360 | ||
| 7-12 Bimolecular Elimination: The E2 Reaction 362 | 362 | ||
| 7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation 364 | 364 | ||
| 7-14 Stereochemistry of the E2 Reaction 365 | 365 | ||
| 7-15 E2 Reactions in Cyclohexane Systems 368 | 368 | ||
| 7-16 Comparison of E1 and E2 Elimination Mechanisms 370 | 370 | ||
| Summary: Elimination Reactions 371 | 371 | ||
| Summary: Substitution and Elimination Reactions of Alkyl Halides 374 | 374 | ||
| PROBLEM-SOLVING STRATEGY: Predicting Substitutions and Eliminations 376 | 376 | ||
| 7-18 Alkene Synthesis by Dehydration of Alcohols 377 | 377 | ||
| 7-19 Alkene Synthesis by High-Temperature Industrial Methods 380 | 380 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 382 | 382 | ||
| Summary: Methods for Synthesis of Alkenes 385 | 385 | ||
| Essential Terms 386 | 386 | ||
| Study Problems 389 | 389 | ||
| 8 REACTIONS OF ALKENES 395 | 395 | ||
| 8-1 Reactivity of the Carbon–Carbon Double Bond 395 | 395 | ||
| 8-2 Electrophilic Addition to Alkenes 396 | 396 | ||
| 8-3 Addition of Hydrogen Halides to Alkenes 398 | 398 | ||
| 8-4 Addition of Water: Hydration of Alkenes 406 | 406 | ||
| 8-5 Hydration by Oxymercuration–Demercuration 408 | 408 | ||
| 8-6 Alkoxymercuration–Demercuration 411 | 411 | ||
| 8-7 Hydroboration of Alkenes 412 | 412 | ||
| 8-8 Addition of Halogens to Alkenes 418 | 418 | ||
| 8-9 Formation of Halohydrins 421 | 421 | ||
| 8-10 Catalytic Hydrogenation of Alkenes 425 | 425 | ||
| 8-11 Addition of Carbenes to Alkenes 427 | 427 | ||
| 8-12 Epoxidation of Alkenes 429 | 429 | ||
| 8-13 Acid-Catalyzed Opening of Epoxides 431 | 431 | ||
| 8-14 Syn Dihydroxylation of Alkenes 434 | 434 | ||
| 8-15 Oxidative Cleavage of Alkenes 436 | 436 | ||
| 8-16 Polymerization of Alkenes 439 | 439 | ||
| 8-17 Olefin Metathesis 443 | 443 | ||
| PROBLEM-SOLVING STRATEGY: Organic Synthesis 446 | 446 | ||
| Summary: Reactions of Alkenes 448 | 448 | ||
| Summary: Electrophilic Additions to Alkenes 451 | 451 | ||
| Summary: Oxidation and Cyclopropanation Reactions of Alkenes 452 | 452 | ||
| Essential Terms 453 | 453 | ||
| Study Problems 457 | 457 | ||
| 9 ALKYNES 464 | 464 | ||
| 9-1 Introduction 464 | 464 | ||
| 9-2 Nomenclature of Alkynes 465 | 465 | ||
| 9-3 Physical Properties of Alkynes 467 | 467 | ||
| 9-4 Commercial Importance of Alkynes 467 | 467 | ||
| 9-5 Electronic Structure of Alkynes 469 | 469 | ||
| 9-6 Acidity of Alkynes; Formation of Acetylide Ions 470 | 470 | ||
| 9-7 Synthesis of Alkynes from Acetylides 472 | 472 | ||
| 9-8 Synthesis of Alkynes by Elimination Reactions 475 | 475 | ||
| Summary: Syntheses of Alkynes 477 | 477 | ||
| 9-9 Addition Reactions of Alkynes 477 | 477 | ||
| 9-10 Oxidation of Alkynes 486 | 486 | ||
| PROBLEM-SOLVING STRATEGY: Multistep Synthesis 488 | 488 | ||
| Summary: Reactions of Alkynes 490 | 490 | ||
| Summary: Reactions of Terminal Alkynes 491 | 491 | ||
| Essential Terms 492 | 492 | ||
| Study Problems 493 | 493 | ||
| 10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 496 | 496 | ||
| 10-1 Introduction 496 | 496 | ||
| 10-2 Structure and Classification of Alcohols 496 | 496 | ||
| 10-3 Nomenclature of Alcohols and Phenols 497 | 497 | ||
| 10-4 Physical Properties of Alcohols 502 | 502 | ||
| 10-5 Commercially Important Alcohols 504 | 504 | ||
| 10-6 Acidity of Alcohols and Phenols 506 | 506 | ||
| 10-7 Synthesis of Alcohols: Introduction and Review 510 | 510 | ||
| Summary: Previous Alcohol Syntheses 510 | 510 | ||
| 10-8 Organometallic Reagents for Alcohol Synthesis 511 | 511 | ||
| 10-9 Reactions of Organometallic Compounds 514 | 514 | ||
| Summary: Grignard Reactions 520 | 520 | ||
| 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 522 | 522 | ||
| 10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols 525 | 525 | ||
| Summary: Reactions of LiAIH4 and NaBH4 527 | 527 | ||
| Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 528 | 528 | ||
| 10-12 Thiols (Mercaptans) 530 | 530 | ||
| Summary: Synthesis of Alcohols from Carbonyl Compounds 533 | 533 | ||
| Essential Terms 533 | 533 | ||
| Study Problems 535 | 535 | ||
| 11 REACTIONS OF ALCOHOLS 541 | 541 | ||
| 11-1 Oxidation States of Alcohols and Related Functional Groups 542 | 542 | ||
| 11-2 Oxidation of Alcohols 543 | 543 | ||
| 11-3 Additional Methods for Oxidizing Alcohols 547 | 547 | ||
| 11-4 Biological Oxidation of Alcohols 549 | 549 | ||
| 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 551 | 551 | ||
| Summary: SN2 Reactions of Tosylate Esters 553 | 553 | ||
| 11-6 Reduction of Alcohols 554 | 554 | ||
| 11-7 Reactions of Alcohols with Hydrohalic Acids 555 | 555 | ||
| 11-8 Reactions of Alcohols with Phosphorus Halides 560 | 560 | ||
| 11-9 Reactions of Alcohols with Thionyl Chloride 561 | 561 | ||
| 11-10 Dehydration Reactions of Alcohols 563 | 563 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 567 | 567 | ||
| 12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 592 | 592 | ||
| 12-1 Introduction 592 | 592 | ||
| 12-2 The Electromagnetic Spectrum 593 | 593 | ||
| 12-3 The Infrared Region 594 | 594 | ||
| 12-4 Molecular Vibrations 595 | 595 | ||
| 12-5 IR-Active and IR-Inactive Vibrations 597 | 597 | ||
| 12-6 Measurement of the IR Spectrum 598 | 598 | ||
| 12-7 Infrared Spectroscopy of Hydrocarbons 601 | 601 | ||
| 12-8 Characteristic Absorptions of Alcohols and Amines 606 | 606 | ||
| 12-9 Characteristic Absorptions of Carbonyl Compounds 607 | 607 | ||
| 12-10 Characteristic Absorptions of C¬N Bonds 612 | 612 | ||
| 12-11 Simplified Summary of IR Stretching Frequencies 614 | 614 | ||
| 12-12 Reading and Interpreting IR Spectra (Solved Problems) 616 | 616 | ||
| 12-13 Introduction to Mass Spectrometry 620 | 620 | ||
| 12-14 Determination of the Molecular Formula by Mass Spectrometry 623 | 623 | ||
| 12-15 Fragmentation Patterns in Mass Spectrometry 626 | 626 | ||
| Summary: Common Fragmentation Patterns 632 | 632 | ||
| Essential Terms 633 | 633 | ||
| Study Problems 635 | 635 | ||
| 13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 643 | 643 | ||
| 13-1 Introduction 643 | 643 | ||
| 13-2 Theory of Nuclear Magnetic Resonance 644 | 644 | ||
| 13-3 Magnetic Shielding by Electrons 646 | 646 | ||
| 13-4 The NMR Spectrometer 648 | 648 | ||
| 13-5 The Chemical Shift 649 | 649 | ||
| 13-6 The Number of Signals 656 | 656 | ||
| 13-7 Areas of the Peaks 658 | 658 | ||
| 13-8 Spin-Spin Splitting 661 | 661 | ||
| PROBLEM-SOLVING STRATEGY: Drawing an NMR Spectrum 666 | 666 | ||
| 13-9 Complex Splitting 670 | 670 | ||
| 13-10 Stereochemical Nonequivalence of Protons 673 | 673 | ||
| 13-11 Time Dependence of NMR Spectroscopy 676 | 676 | ||
| PROBLEM-SOLVING STRATEGY: Interpreting Proton NMR Spectra 679 | 679 | ||
| 13-12 Carbon-13 NMR Spectroscopy 684 | 684 | ||
| 13-13 Interpreting Carbon NMR Spectra 692 | 692 | ||
| 13-14 Nuclear Magnetic Resonance Imaging 694 | 694 | ||
| PROBLEM-SOLVING STRATEGY: Spectroscopy Problems 695 | 695 | ||
| Essential Terms 699 | 699 | ||
| Study Problems 701 | 701 | ||
| 14 ETHERS, EPOXIDES, AND THIOETHERS 708 | 708 | ||
| 14-1 Introduction 708 | 708 | ||
| 14-2 Physical Properties of Ethers 709 | 709 | ||
| 14-3 Nomenclature of Ethers 713 | 713 | ||
| 14-4 Spectroscopy of Ethers 716 | 716 | ||
| 14-5 The Williamson Ether Synthesis 718 | 718 | ||
| 14-6 Synthesis of Ethers by Alkoxymercuration–Demercuration 720 | 720 | ||
| 14-7 Industrial Synthesis: Bimolecular Condensation of Alcohols 720 | 720 | ||
| Summary: Syntheses of Ethers (Review) 721 | 721 | ||
| 14-8 Cleavage of Ethers by HBr and HI 722 | 722 | ||
| 14-9 Autoxidation of Ethers 724 | 724 | ||
| Summary: Reactions of Ethers 725 | 725 | ||
| 14-10 Thioethers (Sulfides) and Silyl Ethers 725 | 725 | ||
| 14-11 Synthesis of Epoxides 729 | 729 | ||
| Summary: Epoxide Syntheses 732 | 732 | ||
| 14-12 Acid-Catalyzed Ring Opening of Epoxides 732 | 732 | ||
| 14-13 Base-Catalyzed Ring Opening of Epoxides 736 | 736 | ||
| 14-14 Orientation of Epoxide Ring Opening 738 | 738 | ||
| Summary: Orientation of Epoxide Ring Opening 739 | 739 | ||
| 14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 740 | 740 | ||
| 14-16 Epoxy Resins: The Advent of Modern Glues 741 | 741 | ||
| Essential Terms 743 | 743 | ||
| Study Problems 746 | 746 | ||
| Summary: Reactions of Epoxides 743 | 743 | ||
| 15 CONJUGATED SYSTEMS, ORBITAL SYMMETRY, AND ULTRAVIOLET SPECTROSCOPY 752 | 752 | ||
| 15-1 Introduction 752 | 752 | ||
| 15-2 Stabilities of Dienes 753 | 753 | ||
| 15-3 Molecular Orbital Picture of a Conjugated System 754 | 754 | ||
| 15-4 Allylic Cations 759 | 759 | ||
| 15-5 1,2- and 1,4-Addition to Conjugated Dienes 760 | 760 | ||
| 15-6 Kinetic Versus Thermodynamic Control in the Addition of HBr to Buta-1,3-diene 762 | 762 | ||
| 15-7 Allylic Radicals 764 | 764 | ||
| 15-8 Molecular Orbitals of the Allylic System 766 | 766 | ||
| 15-9 Electronic Configurations of the Allyl Radical, Cation, and Anion 768 | 768 | ||
| 15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 769 | 769 | ||
| 15-11 The Diels–Alder Reaction 770 | 770 | ||
| 15-12 The Diels–Alder as an Example of a Pericyclic Reaction 779 | 779 | ||
| 15-13 Ultraviolet Absorption Spectroscopy 782 | 782 | ||
| 15-14 Colored Organic Compounds 788 | 788 | ||
| 15-15 UV-Visible Analysis in Biology and Medicine 790 | 790 | ||
| Essential Terms 792 | 792 | ||
| Study Problems 795 | 795 | ||
| 16 AROMATIC COMPOUNDS 800 | 800 | ||
| 16-1 Introduction: The Discovery of Benzene 800 | 800 | ||
| 16-2 The Structure and Properties of Benzene 801 | 801 | ||
| 16-3 The Molecular Orbitals of Benzene 805 | 805 | ||
| 16-4 The Molecular Orbital Picture of Cyclobutadiene 808 | 808 | ||
| 16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds 809 | 809 | ||
| 16-6 Hückel’s Rule 810 | 810 | ||
| 16-7 Molecular Orbital Derivation of Hückel’s Rule 812 | 812 | ||
| 16-8 Aromatic Ions 813 | 813 | ||
| 16-9 Heterocyclic Aromatic Compounds 819 | 819 | ||
| 16-10 Polynuclear Aromatic Hydrocarbons 823 | 823 | ||
| 16-11 Aromatic Allotropes of Carbon 825 | 825 | ||
| 16-12 Fused Heterocyclic Compounds 827 | 827 | ||
| 16-13 Nomenclature of Benzene Derivatives 828 | 828 | ||
| 16-14 Physical Properties of Benzene and Its Derivatives 830 | 830 | ||
| 16-15 Spectroscopy of Aromatic Compounds 832 | 832 | ||
| Essential Terms 834 | 834 | ||
| Study Problems 836 | 836 | ||
| 17 REACTIONS OF AROMATIC COMPOUNDS 845 | 845 | ||
| 17-1 Electrophilic Aromatic Substitution 845 | 845 | ||
| 17-2 Halogenation of Benzene 847 | 847 | ||
| 17-3 Nitration of Benzene 849 | 849 | ||
| 17-4 Sulfonation of Benzene 850 | 850 | ||
| 17-5 Nitration of Toluene: The Effect of Alkyl Substitution 853 | 853 | ||
| 17-6 Activating, Ortho, Para-Directing Substituents 855 | 855 | ||
| Summary: Activating, Ortho, Para-Directors 858 | 858 | ||
| 17-7 Deactivating, Meta-Directing Substituents 858 | 858 | ||
| Summary: Deactivating, Meta-Directors 861 | 861 | ||
| 17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing 862 | 862 | ||
| Summary: Directing Effects of Substituents 863 | 863 | ||
| 17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 863 | 863 | ||
| 17-10 The Friedel–Crafts Alkylation 866 | 866 | ||
| 17-11 The Friedel–Crafts Acylation 871 | 871 | ||
| Summary: Comparison of Friedel–Crafts Alkylation and Acylation 873 | 873 | ||
| 17-12 Nucleophilic Aromatic Substitution 875 | 875 | ||
| 17-13 Aromatic Substitutions Using Organometallic Reagents 879 | 879 | ||
| 17-14 Addition Reactions of Benzene Derivatives 885 | 885 | ||
| 17-15 Side-Chain Reactions of Benzene Derivatives 888 | 888 | ||
| 17-16 Reactions of Phenols 892 | 892 | ||
| PROBLEM-SOLVING STRATEGY: Synthesis Using Electrophilic Aromatic Substitution 895 | 895 | ||
| Summary: Reactions of Aromatic Compounds 899 | 899 | ||
| Summary: Electrophilic Aromatic Substitution of Benzene 902 | 902 | ||
| Summary: Substitutions of Aryl Halides 902 | 902 | ||
| Essential Terms 903 | 903 | ||
| Study Problems 906 | 906 | ||
| 18 KETONES AND ALDEHYDES 912 | 912 | ||
| 18-1 Carbonyl Compounds 912 | 912 | ||
| 18-2 Structure of the Carbonyl Group 913 | 913 | ||
| 18-3 Nomenclature of Ketones and Aldehydes 914 | 914 | ||
| 18-4 Physical Properties of Ketones and Aldehydes 916 | 916 | ||
| 18-5 Spectroscopy of Ketones and Aldehydes 918 | 918 | ||
| 18-6 Industrial Importance of Ketones and Aldehydes 924 | 924 | ||
| 18-7 Review of Syntheses of Ketones and Aldehydes 925 | 925 | ||
| 18-8 Synthesis of Ketones from Carboxylic Acids 929 | 929 | ||
| 18-9 Synthesis of Ketones and Aldehydes from Nitriles 929 | 929 | ||
| 18-10 Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 931 | 931 | ||
| Summary: Syntheses of Ketones and Aldehydes 933 | 933 | ||
| 18-11 Reactions of Ketones and Aldehydes: Introduction to Nucleophilic Addition 934 | 934 | ||
| 18-12 Hydration of Ketones and Aldehydes 938 | 938 | ||
| 18-13 Formation of Cyanohydrins 940 | 940 | ||
| 18-14 Formation of Imines 942 | 942 | ||
| 18-15 Condensations with Hydroxylamine and Hydrazines 945 | 945 | ||
| Summary: Condensations of Amines with Ketones and Aldehydes 946 | 946 | ||
| 18-16 Formation of Acetals 947 | 947 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 951 | 951 | ||
| 18-17 Use of Acetals as Protecting Groups 952 | 952 | ||
| 18-18 The Wittig Reaction 954 | 954 | ||
| 18-19 Oxidation of Aldehydes 957 | 957 | ||
| 18-20 Reductions of Ketones and Aldehydes 958 | 958 | ||
| Summary: Reactions of Ketones and Aldehydes 961 | 961 | ||
| Summary: Nucleophilic Addition Reactions of Aldehydes and Ketones 963 | 963 | ||
| Essential Terms 964 | 964 | ||
| Study Problems 967 | 967 | ||
| 19 AMINES 977 | 977 | ||
| 19-1 Introduction 977 | 977 | ||
| 19-2 Nomenclature of Amines 978 | 978 | ||
| 19-3 Structure of Amines 981 | 981 | ||
| 19-4 Physical Properties of Amines 983 | 983 | ||
| 19-5 Basicity of Amines 984 | 984 | ||
| 19-6 Factors that Affect Amine Basicity 986 | 986 | ||
| 19-7 Salts of Amines 988 | 988 | ||
| 19-8 Spectroscopy of Amines 990 | 990 | ||
| 19-9 Reactions of Amines with Ketones and Aldehydes (Review) 994 | 994 | ||
| 19-10 Aromatic Substitution of Arylamines and Pyridine 994 | 994 | ||
| 19-11 Alkylation of Amines by Alkyl Halides 998 | 998 | ||
| 19-12 Acylation of Amines by Acid Chlorides 999 | 999 | ||
| 19-13 Formation of Sulfonamides 1001 | 1001 | ||
| 19-14 Amines as Leaving Groups: The Hofmann Elimination 1003 | 1003 | ||
| 19-15 Oxidation of Amines; The Cope Elimination 1006 | 1006 | ||
| 19-16 Reactions of Amines with Nitrous Acid 1009 | 1009 | ||
| 19-17 Reactions of Arenediazonium Salts 1011 | 1011 | ||
| Summary: Reactions of Amines 1014 | 1014 | ||
| 19-18 Synthesis of Amines by Reductive Amination 1016 | 1016 | ||
| 19-19 Synthesis of Amines by Acylation–Reduction 1018 | 1018 | ||
| 19-20 Syntheses Limited to Primary Amines 1020 | 1020 | ||
| Summary: Synthesis of Amines 1024 | 1024 | ||
| Essential Terms 1025 | 1025 | ||
| Study Problems 1028 | 1028 | ||
| 20 CARBOXYLIC ACIDS 1038 | 1038 | ||
| 20-1 Introduction 1038 | 1038 | ||
| 20-2 Nomenclature of Carboxylic Acids 1039 | 1039 | ||
| 20-3 Structure and Physical Properties of Carboxylic Acids 1042 | 1042 | ||
| 20-4 Acidity of Carboxylic Acids 1043 | 1043 | ||
| 20-5 Salts of Carboxylic Acids 1047 | 1047 | ||
| 20-6 Commercial Sources of Carboxylic Acids 1049 | 1049 | ||
| 20-7 Spectroscopy of Carboxylic Acids 1051 | 1051 | ||
| 20-8 Synthesis of Carboxylic Acids 1055 | 1055 | ||
| Summary: Syntheses of Carboxylic Acids 1057 | 1057 | ||
| 20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic AcylSubstitution 1058 | 1058 | ||
| 20-10 Condensation of Acids with Alcohols: The Fischer Esterification 1060 | 1060 | ||
| 20-11 Esterification Using Diazomethane 1064 | 1064 | ||
| 20-12 Condensation of Acids with Amines: Direct Synthesis of Amides 1064 | 1064 | ||
| 20-13 Reduction of Carboxylic Acids 1065 | 1065 | ||
| 20-14 Alkylation of Carboxylic Acids to Form Ketones 1067 | 1067 | ||
| 20-15 Synthesis and Use of Acid Chlorides 1067 | 1067 | ||
| Summary: Reactions of Carboxylic Acids 1070, 1071 | 1070 | ||
| Summary: Reactions of Carboxylic Acids 1070, 1071 | 1071 | ||
| Essential Terms 1072 | 1072 | ||
| Study Problems 1073 | 1073 | ||
| 21 CARBOXYLIC ACID DERIVATIVES 1079 | 1079 | ||
| 21-1 Introduction 1079 | 1079 | ||
| 21-2 Structure and Nomenclature of Acid Derivatives 1080 | 1080 | ||
| 21-3 Physical Properties of Carboxylic Acid Derivatives 1087 | 1087 | ||
| 21-4 Spectroscopy of Carboxylic Acid Derivatives 1089 | 1089 | ||
| 21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 1096 | 1096 | ||
| 21-6 Transesterification 1105 | 1105 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1106 | 1106 | ||
| 21-7 Hydrolysis of Carboxylic Acid Derivatives 1109 | 1109 | ||
| 21-8 Reduction of Acid Derivatives 1114 | 1114 | ||
| 21-9 Reactions of Acid Derivatives with Organometallic Reagents 1117 | 1117 | ||
| 21-10 Summary of the Chemistry of Acid Chlorides 1119 | 1119 | ||
| 21-11 Summary of the Chemistry of Anhydrides 1121 | 1121 | ||
| 21-12 Summary of the Chemistry of Esters 1124 | 1124 | ||
| 21-13 Summary of the Chemistry of Amides 1127 | 1127 | ||
| 21-14 Summary of the Chemistry of Nitriles 1130 | 1130 | ||
| 21-15 Thioesters 1131 | 1131 | ||
| 21-16 Esters and Amides of Carbonic Acid 1133 | 1133 | ||
| Essential Terms 1135 | 1135 | ||
| Summary: Reactions of Acid Chlorides 1136 | 1136 | ||
| Study Problems 1139 | 1139 | ||
| 22 CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL COMPOUNDS 1148 | 1148 | ||
| 22-1 Introduction 1148 | 1148 | ||
| 22-2 Enols and Enolate Ions 1150 | 1150 | ||
| 22-3 Alkylation of Enolate Ions 1153 | 1153 | ||
| 22-4 Formation and Alkylation of Enamines 1155 | 1155 | ||
| 22-5 Alpha Halogenation of Ketones 1157 | 1157 | ||
| 22-6 Alpha Bromination of Acids: The HVZ Reaction 1163 | 1163 | ||
| 22-7 The Aldol Condensation of Ketones and Aldehydes 1164 | 1164 | ||
| 22-8 Dehydration of Aldol Products 1168 | 1168 | ||
| 22-9 Crossed Aldol Condensations 1169 | 1169 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1170 | 1170 | ||
| 22-10 Aldol Cyclizations 1172 | 1172 | ||
| 22-11 Planning Syntheses Using Aldol Condensations 1173 | 1173 | ||
| 22-12 The Claisen Ester Condensation 1175 | 1175 | ||
| 22-13 The Dieckmann Condensation: A Claisen Cyclization 1178 | 1178 | ||
| 22-14 Crossed Claisen Condensations 1179 | 1179 | ||
| 22-15 Syntheses Using b-Dicarbonyl Compounds 1182 | 1182 | ||
| 22-16 The Malonic Ester Synthesis 1184 | 1184 | ||
| 22-17 The Acetoacetic Ester Synthesis 1187 | 1187 | ||
| 22-18 Conjugate Additions: The Michael Reaction 1190 | 1190 | ||
| 22-19 The Robinson Annulation 1194 | 1194 | ||
| PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1195 | 1195 | ||
| Summary: Enolate Additions and Condensations 1197 | 1197 | ||
| Summary: Reactions of Stabilized Carbanions 1199 | 1199 | ||
| Essential Terms 1199 | 1199 | ||
| Study Problems 1202 | 1202 | ||
| 23 CARBOHYDRATES AND NUCLEIC ACIDS 1208 | 1208 | ||
| 23-1 Introduction 1208 | 1208 | ||
| 23-2 Classification of Carbohydrates 1209 | 1209 | ||
| 23-3 Monosaccharides 1210 | 1210 | ||
| 23-4 Cyclic Structures of Monosaccharides 1214 | 1214 | ||
| 23-5 Anomers of Monosaccharides; Mutarotation 1218 | 1218 | ||
| 23-6 Reactions of Monosaccharides: Reduction 1221 | 1221 | ||
| 23-7 Oxidation of Monosaccharides; Reducing Sugars 1222 | 1222 | ||
| 23-8 Nonreducing Sugars: Formation of Glycosides 1224 | 1224 | ||
| 23-9 Ether and Ester Formation 1226 | 1226 | ||
| 23-10 Chain Shortening: The Ruff Degradation 1229 | 1229 | ||
| 23-11 Chain Lengthening: The Kiliani–Fischer Synthesis 1230 | 1230 | ||
| Summary: Reactions of Sugars 1232 | 1232 | ||
| 23-12 Disaccharides 1234 | 1234 | ||
| 23-13 Polysaccharides 1239 | 1239 | ||
| 23-14 Nucleic Acids: Introduction 1242 | 1242 | ||
| 23-15 Ribonucleosides and Ribonucleotides 1244 | 1244 | ||
| 23-16 The Structures of RNA and DNA 1246 | 1246 | ||
| 23-17 Additional Functions of Nucleotides 1250 | 1250 | ||
| Essential Terms 1252 | 1252 | ||
| Study Problems 1255 | 1255 | ||
| 24 AMINO ACIDS, PEPTIDES, AND PROTEINS 1258 | 1258 | ||
| 24-1 Introduction 1258 | 1258 | ||
| 24-2 Structure and Stereochemistry of the a-Amino Acids 1259 | 1259 | ||
| 24-3 Acid–Base Properties of Amino Acids 1263 | 1263 | ||
| 24-4 Isoelectric Points and Electrophoresis 1265 | 1265 | ||
| 24-5 Synthesis of Amino Acids 1267 | 1267 | ||
| Summary: Syntheses of Amino Acids 1270 | 1270 | ||
| 24-6 Resolution of Amino Acids 1270 | 1270 | ||
| 24-7 Reactions of Amino Acids 1271 | 1271 | ||
| Summary: Reactions of Amino Acids 1274 | 1274 | ||
| 24-8 Structure and Nomenclature of Peptides and Proteins 1274 | 1274 | ||
| 24-9 Peptide Structure Determination 1278 | 1278 | ||
| 24-10 Laboratory Peptide Synthesis 1283 | 1283 | ||
| 24-11 Classification of Proteins 1289 | 1289 | ||
| 24-12 Levels of Protein Structure 1290 | 1290 | ||
| 24-13 Protein Denaturation 1292 | 1292 | ||
| Essential Terms 1295 | 1295 | ||
| Study Problems 1297 | 1297 | ||
| 25 LIPIDS 1301 | 1301 | ||
| 25-1 Introduction 1301 | 1301 | ||
| 25-2 Waxes 1302 | 1302 | ||
| 25-3 Triglycerides 1302 | 1302 | ||
| 25-4 Saponification of Fats and Oils: Soaps and Detergents 1306 | 1306 | ||
| 25-5 Phospholipids 1309 | 1309 | ||
| 25-6 Steroids 1311 | 1311 | ||
| 25-7 Prostaglandins 1314 | 1314 | ||
| 25-8 Terpenes 1315 | 1315 | ||
| Essential Terms 1318 | 1318 | ||
| Study Problems 1319 | 1319 | ||
| 26 SYNTHETIC POLYMERS 1322 | 1322 | ||
| 26-1 Introduction 1322 | 1322 | ||
| 26-2 Chain-Growth Polymers 1323 | 1323 | ||
| 26-3 Stereochemistry of Polymers 1329 | 1329 | ||
| 26-4 Stereochemical Control of Polymerization: Ziegler–Natta Catalysts 1330 | 1330 | ||
| 26-5 Natural and Synthetic Rubbers 1331 | 1331 | ||
| 26-6 Copolymers of Two or More Monomers 1333 | 1333 | ||
| 26-7 Step-Growth Polymers 1333 | 1333 | ||
| 26-8 Polymer Structure and Properties 1337 | 1337 | ||
| 26-9 Recycling of Plastics 1339 | 1339 | ||
| Essential Terms 1340 | 1340 | ||
| Study Problems 1342 | 1342 | ||
| APPENDICES 1344 | 1344 | ||
| 1A NMR: Spin-Spin Coupling Constants 1344 | 1344 | ||
| 1B NMR: Proton Chemical Shifts 1345 | 1345 | ||
| 1C NMR: 13C Chemical Shifts in Organic Compounds 1347 | 1347 | ||
| 2A IR: Characteristic Infrared Group Frequencies 1348 | 1348 | ||
| 2B IR: Characteristic Infrared Absorptions of Functional Groups 1351 | 1351 | ||
| 3A Methods and Suggestions for Proposing Mechanisms 1353 | 1353 | ||
| 3B Suggestions for Developing Multistep Syntheses 1355 | 1355 | ||
| 4 pKa Values for Representative Compounds 1356 | 1356 | ||
| 5 Summary of Organic Nomenclature 1358 | 1358 | ||
| Brief Answers to Selected Problems 1368 | 1368 | ||
| Photo Credits 1374 | 1374 | ||
| Index 1375 | 1375 |