ORGANIC CHEMISTRY G .WA D E J R
To my students and colleagues at Whitman College About the Author LG.Skip"Wade decided tobecome achemistry majorduring Proop o oral in196 James D.White.While at Harvard,he served as the Head Teaching Fellow for the organic laboratories and was strongly influenced by the teaching RRe点poeKa动 After completing his Ph.D.at Harvard in 1974,Dr.Wade joined the chemistry faculty at Colorado State University.Over the course of fifteer ogy,c stry,human anic synthesis.Since 1989. Dr.Wade has been a chemistry professor at Whitman College,where he emistry and pursues researc erests in organic synth Dr.Wade's interest in forensic science has led him to testify as an expert s worked as 访
To my students and colleagues at Whitman College About the Author L. G. “Skip” Wadedecided to become a chemistry major during his sophomore year at Rice University, while taking organic chemistry from Professor Ronald M. Magid. After receiving his B.A. from Rice in 1969, Wade went on to Harvard University, where he did research with Professor James D. White. While at Harvard, he served as the Head Teaching Fellow for the organic laboratories and was strongly influenced by the teaching methods of two master educators, Professors Leonard K. Nash and Frank H. Westheimer. After completing his Ph.D. at Harvard in 1974, Dr. Wade joined the chemistry faculty at Colorado State University. Over the course of fifteen years at Colorado State, Dr. Wade taught organic chemistry to thousands of students working toward careers in all areas of biology, chemistry, human medicine, veterinary medicine, and environmental studies. He also authored research papers in organic synthesis and in chemical education, as well as eleven books reviewing current research in organic synthesis. Since 1989, Dr. Wade has been a chemistry professor at Whitman College, where he teaches organic chemistry and pursues research interests in organic synthesis and forensic chemistry. Dr. Wade received the A. E. Lange Award for Distinguished Science Teaching at Whitman in 1993. Dr. Wade’s interest in forensic science has led him to testify as an expert witness in court cases involving drugs and firearms, and he has worked as a police firearms instructor, drug consultant, and boating safety officer. He also enjoys repairing and restoring old violins and bows, which he has done professionally for many years. iii
Brief Contents Preface xxv 1 Introduction and Review 1 2 Structure and Properties of Organic Molecules 42 3 Structure and Stereochemistry of Alkanes 87 4 The Study of Chemical Reactions 132 Stereochemistry 174 6 Alkyl Halides:Nucleophilic Substitution and Elimination 218 7 Structure and Synthesis of Alkenes 285 8 Reactions of Alkenes 328 9 Alkynes 392 10 Structure and Synthesis of Alcohols 425 11 Reactions of alcohols 467 12 Infrared Spectroscopy and Mass Spectrometry 513 13 Nuclear Magnetic Resonance Spectroscopy 563 14 Ethers,Epoxides,andThioethers 625 6 Aromatic Compounds 713 17 Reactions of Aromatic Compounds 756 18 Ketones and Aldehydes 816 Amines 879 20 Carboxylic Acids 939 Carboxylic Acid Derivatives 981 22 23 Carbohydrates and Nucleic Acids 1101 24 Amino Acids,Peptides,and Proteins 1155 Lipids 1201 26 Synthetic Polymers 1222 Appendices 1243 Answers A1 Photo Credits PC1 Index 11 iv
Brief Contents Preface xxv 1 Introduction and Review 1 2 Structure and Properties of Organic Molecules 42 3 Structure and Stereochemistry of Alkanes 87 4 The Study of Chemical Reactions 132 5 Stereochemistry 174 6 Alkyl Halides: Nucleophilic Substitution and Elimination 218 7 Structure and Synthesis of Alkenes 285 8 Reactions of Alkenes 328 9 Alkynes 392 10 Structure and Synthesis of Alcohols 425 11 Reactions of Alcohols 467 12 Infrared Spectroscopy and Mass Spectrometry 513 13 Nuclear Magnetic Resonance Spectroscopy 563 14 Ethers, Epoxides, and Thioethers 625 15 Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy 667 16 Aromatic Compounds 713 17 Reactions of Aromatic Compounds 756 18 Ketones and Aldehydes 816 19 Amines 879 20 Carboxylic Acids 939 21 Carboxylic Acid Derivatives 981 22 Condensations and Alpha Substitutions of Carbonyl Compounds 1045 23 Carbohydrates and Nucleic Acids 1101 24 Amino Acids, Peptides, and Proteins 1155 25 Lipids 1201 26 Synthetic Polymers 1222 Appendices 1243 Answers A1 Photo Credits PC1 Index I1 iv
Contents About the Author ii Preface xxv 1 INTRODUCTION AND REVIEW.1. 2monesA8mescnmegv1 1-3 Bond Formation:The Octet Rule 6 1-4 Lewis Structures 7 1-5 Multiple Bonding 8 Summary:Common Bonding Patterns(Uncharged)9 1-6 Electronegativity and Bond Polarity 10 1-7 Formal Charges 11 1-8 lonic Structures 13 ompoary:Common Bonding Patterns in Organic 111 1.12 Arrhenius Acids and Bas 1-14 EssentialTerms 34 Study Problems 36 STRUCTURE AND PROPERTIES 2 OF ORGANIC MOLECULES 42 2-1 Wave Properties of Electrons in Orbitals 42 2-2 Molecular Orbitals 44 2-3 Pi Bonding 47 Hybridization and Molecular Shapes 48 Rfand Gometry53 Bond Rotation 58 ondsand Molecule 62 6 y :ffe 212 人 213 s72 2-14 Organic Cor Study Problems 83
v About the Author iii Preface xxv 1 INTRODUCTION AND REVIEW 1 1-1 The Origins of Organic Chemistry 1 1-2 Principles of Atomic Structure 3 1-3 Bond Formation: The Octet Rule 6 1-4 Lewis Structures 7 1-5 Multiple Bonding 8 Summary: Common Bonding Patterns (Uncharged) 9 1-6 Electronegativity and Bond Polarity 10 1-7 Formal Charges 11 1-8 Ionic Structures 13 Summary: Common Bonding Patterns in Organic Compounds and Ions 13 1-9 Resonance 14 1-10 Structural Formulas 18 1-11 Molecular Formulas and Empirical Formulas 21 1-12 Arrhenius Acids and Bases 22 1-13 Brønsted–Lowry Acids and Bases 23 1-14 Lewis Acids and Bases 31 Essential Terms 34 Study Problems 36 2 STRUCTURE AND PROPERTIES OF ORGANIC MOLECULES 42 2-1 Wave Properties of Electrons in Orbitals 42 2-2 Molecular Orbitals 44 2-3 Pi Bonding 47 2-4 Hybridization and Molecular Shapes 48 2-5 Drawing Three-Dimensional Molecules 52 2-6 General Rules of Hybridization and Geometry 53 2-7 Bond Rotation 58 2-8 Isomerism 60 2-9 Polarity of Bonds and Molecules 62 2-10 Intermolecular Forces 66 2-11 Polarity Effects on Solubilities 70 2-12 Hydrocarbons 72 2-13 Organic Compounds Containing Oxygen 76 2-14 Organic Compounds Containing Nitrogen 78 Essential Terms 81 Study Problems 83 Contents
vi Contents 3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 87 3-1 Classification of Hydrocarbons (Review)87 32 Molecular Formulas of Alkanes 88 Nomenclature of Alkanes 89 Summary:Rules for Naming Alkanes 94 3-4 Physical Properties of Alkanes 95 Uses and Sources of Alkanes 97 Reactions of Alkanes 99 Structure and Co Cgnormationsof ormations of Alkanes 100 Alkanes 106 3 8s107 2.12 nin Cy 3-13 ofyeoang 314 Conformations of Mono substituted Cyclohexanes 117 3-15 Conformations of Disubstituted Cvclohexanes 120 Problem-Solving Strategy:Recognizing Cis and Trans Isomers 122 3-16 Bicyclic Molecules 123 Essential lerms 125 Study Problems 129 4 THE STUDY OF CHEMICAL REACTIONS 132 4-1 Introduction 132 4-2 Chlorination of Methane 132 4-3 The Free-Radical Chain Reaction 134 Key Mechanism 4-1:Free-Radical Halogenation 136 4-4 Equilibrium Constants and Free Energy 138 Enthalpy and Entropy 140 4-6 Bond-Dissociation Enthalpies 142 Enthalpy Changes in Chlorination 143 Kinetics and the Rate Equation 145 4-9 Activation Energy and the Temperature Dependence of Rates 147 419 40 tep r epend logenation 150 414 tulate 157 4-15 61 4-16 162 Summary Reactive ms168 Study Proble ns170
3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 87 3-1 Classification of Hydrocarbons (Review) 87 3-2 Molecular Formulas of Alkanes 88 3-3 Nomenclature of Alkanes 89 Summary: Rules for Naming Alkanes 94 3-4 Physical Properties of Alkanes 95 3-5 Uses and Sources of Alkanes 97 3-6 Reactions of Alkanes 99 3-7 Structure and Conformations of Alkanes 100 3-8 Conformations of Butane 104 3-9 Conformations of Higher Alkanes 106 3-10 Cycloalkanes 107 3-11 Cis-trans Isomerism in Cycloalkanes 109 3-12 Stabilities of Cycloalkanes; Ring Strain 109 3-13 Cyclohexane Conformations 113 Problem-Solving Strategy: Drawing Chair Conformations 116 3-14 Conformations of Monosubstituted Cyclohexanes 117 3-15 Conformations of Disubstituted Cyclohexanes 120 Problem-Solving Strategy: Recognizing Cis and Trans Isomers 122 3-16 Bicyclic Molecules 123 Essential Terms 125 Study Problems 129 4 THE STUDY OF CHEMICAL REACTIONS 132 4-1 Introduction 132 4-2 Chlorination of Methane 132 4-3 The Free-Radical Chain Reaction 134 Key Mechanism 4-1: Free-Radical Halogenation 136 4-4 Equilibrium Constants and Free Energy 138 4-5 Enthalpy and Entropy 140 4-6 Bond-Dissociation Enthalpies 142 4-7 Enthalpy Changes in Chlorination 143 4-8 Kinetics and the Rate Equation 145 4-9 Activation Energy and the Temperature Dependence of Rates 147 4-10 Transition States 148 4-11 Rates of Multistep Reactions 149 4-12 Temperature Dependence of Halogenation 150 4-13 Selectivity in Halogenation 151 4-14 The Hammond Postulate 157 4-15 Radical Inhibitors 161 4-16 Reactive Intermediates 162 Summary: Reactive Intermediates 168 Essential Terms 168 Study Problems 170 vi Contents