《有机化学》课程教学资源（参考书籍）Organic Chemistry, 8th Edition, L . G . WA D E , J R .

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 synthe￾sis 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

Contents vii 5STEREOCHEMISTRY174 5-1 Introduction 174 5-2 Chirality 175 5-3 (R)and(S)Nomenclature of Asymmetric Carbon Atoms 181 5-4 Optical Activity 185 5-5 Biological Discrimination of Enantiomers 189 5-6 Racemic Mixtures 191 5-7 Enantiomeric Excess and Optical Purity 192 5-8 Chirality of Conformationally Mobile Systems 193 5-9 Chiral Compounds without Asymmetric Atoms 195 5-10 Fischer Projections 197 5-11 Summary:Fischer Projections andTheir Use 201 Diastereomers 20 Summary:lypes o me 20 5-12 ules with Two or More 20 5-13 Meso Compounds 205 5-14 Absolute and Relative Configuration 207 5-15 Physical pronerties of diastereomers 208 5.16 Resolution of Enantiomers 209 Essential Terms 213 Study Problems 215 ALKYL HALIDES:NUCLEOPHILIC 6 SUBSTITUTION AND ELIMINATION 218 Introduction 218 ommon Usp kyl Hali kyl Ha 6.5 6-6 rope lides 224 d Halid s22 6-1:Allylic Summ ds for Alkyl Halides 229 6.7 s of alkyl Halides .c. ituti and Eli tion 231 6-8 Second order Nu cleophilic Substitution:The S2 Reac tion 232 Key Mechanism 6-2:The SN2 Reaction 233 6-9 generality of the sn2 reaction 234 Summary:SN2 Reactions of Alkyl Halides 234 6-10 Factors Affecting SN2 Reactions:Strength of the Nucleophile 236 Summary:Trends in Nucleophilicity 237 6-11 Reactivity of the substrate in s2 reactions 240 6-12 Stereochemistry of the SN2 Reaction 244 Mech anism 6-3: nversion of Configuration in the 6-13 ophilic Substitution:The SN1 Reaction 246 e A. on 6-14 6-15 the 25 65.R Reaction 252

Contents vii 5 STEREOCHEMISTRY 174 5-1 Introduction 174 5-2 Chirality 175 5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms 181 5-4 Optical Activity 185 5-5 Biological Discrimination of Enantiomers 189 5-6 Racemic Mixtures 191 5-7 Enantiomeric Excess and Optical Purity 192 5-8 Chirality of Conformationally Mobile Systems 193 5-9 Chiral Compounds without Asymmetric Atoms 195 5-10 Fischer Projections 197 5-11 Summary: Fischer Projections and Their Use 201 Diastereomers 201 Summary: Types of Isomers 203 5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons 204 5-13 Meso Compounds 205 5-14 Absolute and Relative Configuration 207 5-15 Physical Properties of Diastereomers 208 5-16 Resolution of Enantiomers 209 Essential Terms 213 Study Problems 215 6 ALKYL HALIDES: NUCLEOPHILIC SUBSTITUTION AND ELIMINATION 218 6-1 Introduction 218 6-2 Nomenclature of Alkyl Halides 219 6-3 Common Uses of Alkyl Halides 221 6-4 Structure of Alkyl Halides 223 6-5 Physical Properties of Alkyl Halides 224 6-6 Preparation of Alkyl Halides 226 Mechanism 6-1: Allylic Bromination 228 Summary: Methods for Preparing Alkyl Halides 229 6-7 Reactions of Alkyl Halides: Substitution and Elimination 231 6-8 Second-Order Nucleophilic Substitution: The SN2 Reaction 232 Key Mechanism 6-2: The SN2 Reaction 233 6-9 Generality of the SN2 Reaction 234 Summary: SN2 Reactions of Alkyl Halides 234 6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile 236 Summary: Trends in Nucleophilicity 237 6-11 Reactivity of the Substrate in SN2 Reactions 240 6-12 Stereochemistry of the SN2 Reaction 244 Mechanism 6-3: Inversion of Configuration in the SN2 Reaction 244 6-13 First-Order Nucleophilic Substitution: The SN1 Reaction 246 Key Mechanism 6-4:The SN1 Reaction 247 6-14 Stereochemistry of the SN1 Reaction 250 6-15 Rearrangements in the SN1 Reactions 252 Mechanism 6-5: Racemization in the SN1 Reaction 252

viii Contents Mechanism 6-6:Hydride Shift in an s1 Reaction 253 Mechanism 6-7:Methyl Shift in an Sv1 Reaction 254 6-16 Comparison of SN1 and SN2 Reactions 255 Summary:Nucleophilic Substitutions 257 6.17 First-Order e1 reaction 258 Key Mechanism 6-8:The E1 Reaction 258 Mechanism 6-9:Rearrangement in an E1 Reaction 261 Summary:Carbocation Reactions 262 6-18 Positional Orientation of Elimination:Zaitsev's Rule 263 6-19 Second-Order Elimination:The E2 Reaction 265 Key Mechanism 6-10:The E2 Reaction 266 6-20 Stereochemistry of the E2 Reaction 26 6-21 Comparison of E1 and E2 Elimination Mechanisms 269 Strategy:Predicting Su Summary:Elimination Reactions 270 Summary:Reactions of Alkyl Halides 273 EssentialTerms 276 Study Problems 279 7 STRUCTURE AND SYNTHESIS OF ALKENES 285 7-1 Introduction 285 7.2 The Orbital Description of the Alkene Double Bond 286 7.3 Elements of Unsaturation 287 7-4 Nomenclature of Alkenes 289 7.5 Nomenclature of cis-Trans lsomers 291 Summary:Rules for Naming Alkenes 293 76 Commercial Importance of Alkenes 294 7-7 Stability of Alkenes 296 7-8 Physical Properties of Alkenes 302 7-9 Alkene Synthesis by Elimination of Alkyl Halides 304 Mechanism 7-1:Dehydrohalogenation by the E2 Mechanism 304 Stereochemistry of the E2 Reaction 306 E2 Debromination of a V al D bromide 310 7-10 cohol 531 7-11 Alkene Synthesis by High-Temperature Industrial Methods 315 Problem-Solving Strategy:Proposing Reaction Mechanisms 316 Summary:Methods for Synthesis of Alkenes 320 Essential Terms 322 Study Problems 323 8 REACTIONS OF ALKENES 328 8-1 Reactivity of the Carbon-Carbon Double Bond 328 8-2 Electrophilic Addition to Alkenes 329 Key Mechanism 8-1:Electrophilic Addition to Alkenes 330

viii Contents Mechanism 6-6: Hydride Shift in an SN1 Reaction 253 Mechanism 6-7: Methyl Shift in an SN1 Reaction 254 6-16 Comparison of SN1 and SN2 Reactions 255 Summary: Nucleophilic Substitutions 257 6-17 First-Order Elimination: The E1 Reaction 258 Key Mechanism 6-8:The E1 Reaction 258 Mechanism 6-9: Rearrangement in an E1 Reaction 261 Summary: Carbocation Reactions 262 6-18 Positional Orientation of Elimination: Zaitsev’s Rule 263 6-19 Second-Order Elimination: The E2 Reaction 265 Key Mechanism 6-10:The E2 Reaction 266 6-20 Stereochemistry of the E2 Reaction 267 6-21 Comparison of E1 and E2 Elimination Mechanisms 269 Problem-Solving Strategy: Predicting Substitutions and Eliminations 270 Summary: Elimination Reactions 270 Summary: Reactions of Alkyl Halides 273 Essential Terms 276 Study Problems 279 7 STRUCTURE AND SYNTHESIS OF ALKENES 285 7-1 Introduction 285 7-2 The Orbital Description of the Alkene Double Bond 286 7-3 Elements of Unsaturation 287 7-4 Nomenclature of Alkenes 289 7-5 Nomenclature of Cis-Trans Isomers 291 Summary: Rules for Naming Alkenes 293 7-6 Commercial Importance of Alkenes 294 7-7 Stability of Alkenes 296 7-8 Physical Properties of Alkenes 302 7-9 Alkene Synthesis by Elimination of Alkyl Halides 304 Mechanism 7-1: Dehydrohalogenation by the E2 Mechanism 304 Mechanism 7-2: Stereochemistry of the E2 Reaction 306 Mechanism 7-3: E2 Debromination of a Vicinal Dibromide 310 7-10 Alkene Synthesis by Dehydration of Alcohols 312 Key Mechanism 7-4: Acid-Catalyzed Dehydration of an Alcohol 313 7-11 Alkene Synthesis by High-Temperature Industrial Methods 315 Problem-Solving Strategy: Proposing Reaction Mechanisms 316 Summary: Methods for Synthesis of Alkenes 320 Essential Terms 322 Study Problems 323 8 REACTIONS OF ALKENES 328 8-1 Reactivity of the Carbon–Carbon Double Bond 328 8-2 Electrophilic Addition to Alkenes 329 Key Mechanism 8-1: Electrophilic Addition to Alkenes 330

Contents 8-3 Addition of Hydrogen Halides to Alk 331 m83:f 332 cal Additi 8-4 8-4:Acidc 33 f an Alkene 338 8-5 ercuratio curation of an alkene 340 8-6 Alkox ercuration-Demercuration 342 8-7 Hydroboration of Alke Mechanism 8-6:Hydroboration of an Alkene 345 8-8 Addition of Halogens to Alkenes 349 Mechanism 8-7:Addition of Halogens to Alkenes 350 8-9 Formation of Halohydrins 352 Mechanism 8-8:Formation of Halohydrins 352 8-10 Catalytic Hydrogenation of Alkenes 355 8-11 Addition of Carbenes to Alkenes 358 8-12 poxidation of Alkenes 360 Mechanism 8-9:Epoxidation of Alkenes 360 8-13 tion ene 36 anism 8-14 .10. alyzed O ening of Epoxides 362 ylation of lkenes Ken 36 A I 819 nes 36 efin Me 373 nis 811 n Me a Stratea athes376hess370 Summary:Reactions of Alkenes 378 EssentialTerms 383 Study Problems 386 9 △I KYNES3g2 9.1 Introduction 392 02 nes 393 9.3 294 s395 9.5 Electronic Structure of alkynes 396 9-6 Acidity of Alkynes:Formation of Acetylide lons 397 9.7 Synthesis of Alkynes from Acetylides 399 9-8 Synthesis of Alkynes by Elimination Reactions 403 Summary:Syntheses of Alkynes 404 9-g Addition Reactions of Alkynes 405 Mechanism 9-1:Metal-Ammonia Reduction of an Alkyne 407 Mechanism 9-2:Acid-Catalyzed Keto-Enol Tautomerism 411 Mechanism 9-3:Base-Catalyzed Keto-Enol Tautomerism 413 9-10 Oxidation of Alkynes 414 00 Synthesis 416 Summa y:React ns of Alkynes 418 Study Problems

Contents ix 8-3 Addition of Hydrogen Halides to Alkenes 331 Mechanism 8-2: Ionic Addition of HX to an Alkene 332 Mechanism 8-3: Free-Radical Addition of HBr to Alkenes 334 8-4 Addition of Water: Hydration of Alkenes 337 Mechanism 8-4: Acid-Catalyzed Hydration of an Alkene 338 8-5 Hydration by Oxymercuration–Demercuration 340 Mechanism 8-5: Oxymercuration of an Alkene 340 8-6 Alkoxymercuration–Demercuration 342 8-7 Hydroboration of Alkenes 343 Mechanism 8-6: Hydroboration of an Alkene 345 8-8 Addition of Halogens to Alkenes 349 Mechanism 8-7: Addition of Halogens to Alkenes 350 8-9 Formation of Halohydrins 352 Mechanism 8-8: Formation of Halohydrins 352 8-10 Catalytic Hydrogenation of Alkenes 355 8-11 Addition of Carbenes to Alkenes 358 8-12 Epoxidation of Alkenes 360 Mechanism 8-9: Epoxidation of Alkenes 360 8-13 Epoxidation of Alkenes 361 Mechanism 8-10: Acid-Catalyzed Opening of Epoxides 362 8-14 Syn Dihydroxylation of Alkenes 364 8-15 Oxidative Cleavage of Alkenes 366 8-16 Polymerization of Alkenes 369 8-17 Olefin Metathesis 373 Mechanism 8-11: Olefin Metathesis 376 Problem-Solving Strategy: Organic Synthesis 376 Summary: Reactions of Alkenes 378 Essential Terms 383 Study Problems 386 9 ALKYNES 392 9-1 Introduction 392 9-2 Nomenclature of Alkynes 393 9-3 Physical Properties of Alkynes 394 9-4 Commercial Importance of Alkynes 395 9-5 Electronic Structure of Alkynes 396 9-6 Acidity of Alkynes; Formation of Acetylide Ions 397 9-7 Synthesis of Alkynes from Acetylides 399 9-8 Synthesis of Alkynes by Elimination Reactions 403 Summary: Syntheses of Alkynes 404 9-9 Addition Reactions of Alkynes 405 Mechanism 9-1: Metal–Ammonia Reduction of an Alkyne 407 Mechanism 9-2: Acid-Catalyzed Keto–Enol Tautomerism 411 Mechanism 9-3: Base-Catalyzed Keto–Enol Tautomerism 413 9-10 Oxidation of Alkynes 414 Problem-Solving Strategy: Multistep Synthesis 416 Summary: Reactions of Alkynes 418 Essential Terms 421 Study Problems 422

Contents STRUCTURE AND SYNTHESIS 10 OF ALCOHOLS 425 10-1 Introduction 425 10-2 Structure and Classification of Alcohols 425 10-3 Nomenclature of Alcohols and Phenols 427 10-4 Physical Properties of Alcohols 430 10-5 Commercially Important Alcohols 433 10-6 Acidity of Alcohols and Phenols 435 10-7 Synthesis of Alcohols:Introduction and Review 438 Summary:Previous Alcohol Synth 43 188 llic Reagents fo c Reagentst Key Mechanism 10-1 Grianard Reactions 443 Summary:Grignard Reactions 450 Reagents Reduction 10-10 Side Re: 10-11 Carbonyl Group:Synthesis of 1and Mechanism 10-2:Hydride Reduction of a Carbonyl Group 454 Summary:Reactions of LiAlH4 and NaBH4 455 Summary:Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 457 10-12 Thiols(M ercaptans)458 EssentialTerms 46 Study Problems 462 11 REACTIONS OF ALCOHOLS 467 467 Oxidation State hols and Related Functional Groups hols 11-3 11-4 Alcohols 472 cal Oxidation of Alcohols 474 115 Alcohols as Nucleophiles and Electrophiles;Formation ofTosylates 476 Summary:SN2 Reactions OfTosylate Esters 478 11-6 Reduction of Alcohols 478 11-7 Reactions of Alcohols with Hydrohalic Acids 479 Mechanism 11-1:Reaction of aTertiary Alcohol with HBr(SN1)480 c-2:Reaction of a Primary Alcohol with 11-8 Reactic ns of Alcohols with Phospho s Halides 484 ns of alcohols with Th I Chloride 485 11-9 Mechanism 11-3:Reaction of Alcohols with PBr3 485 11-10 hanism 11-4:(Review):Acid-Catalyzed Dehydration of an Alcohol 487 Problem-Solving Strategy:Pr posing Reaction Mechanisms 491 11-11 10s49 Rearrangement 495

x Contents 10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 425 10-1 Introduction 425 10-2 Structure and Classification of Alcohols 425 10-3 Nomenclature of Alcohols and Phenols 427 10-4 Physical Properties of Alcohols 430 10-5 Commercially Important Alcohols 433 10-6 Acidity of Alcohols and Phenols 435 10-7 Synthesis of Alcohols: Introduction and Review 438 Summary: Previous Alcohol Syntheses 438 10-8 Organometallic Reagents for Alcohol Synthesis 440 10-9 Addition of Organometallic Reagents to Carbonyl Compounds 443 Key Mechanism 10-1: Grignard Reactions 443 Summary: Grignard Reactions 450 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 451 10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols 453 Mechanism 10-2: Hydride Reduction of a Carbonyl Group 454 Summary: Reactions of LiAIH4 and NaBH4 455 Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 457 10-12 Thiols (Mercaptans) 458 Essential Terms 461 Study Problems 462 11 REACTIONS OF ALCOHOLS 467 11-1 Oxidation States of Alcohols and Related Functional Groups 467 11-2 Oxidation of Alcohols 469 11-3 Additional Methods for Oxidizing Alcohols 472 11-4 Biological Oxidation of Alcohols 474 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 476 Summary: SN2 Reactions Of Tosylate Esters 478 11-6 Reduction of Alcohols 478 11-7 Reactions of Alcohols with Hydrohalic Acids 479 Mechanism 11-1: Reaction of a Tertiary Alcohol with HBr (SN1) 480 Mechanism 11-2: Reaction of a Primary Alcohol with HBr (SN2) 480 11-8 Reactions of Alcohols with Phosphorus Halides 484 Reactions of Alcohols with Thionyl Chloride 485 11-9 Mechanism 11-3: Reaction of Alcohols with PBr3 485 11-10 Dehydration Reactions of Alcohols 487 Mechanism 11-4: (Review): Acid-Catalyzed Dehydration of an Alcohol 487 Problem-Solving Strategy: Proposing Reaction Mechanisms 491 11-11 Unique Reactions of Diols 494 Mechanism 11-5: The Pinacol Rearrangement 495

Contents 女 11-12 1 497 1-14 sters of Ino ides 50 na stra ien5hersh8ge50 Summary:Reactions of Alcohols 505 EssentialTerms 508 Study Problems 509 12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 513 12-1 Introduction 513 12-2 The Electromagnetic Spectrum 514 ar ons 51 -Activ rared Spe copy of Hyd 522 sorp cohol nd Amines 527 12.10 inds 528 ristic Ab nds 533 12.11 nplified Su of IR Stretch ing Fr 535 1212 ing and Inter 1s537 12.13 to M 5A1 12-14 Determination of the Molecular Formula by Mass Spectrometry 545 12.15 Fragmentation Patterns in Mass Spectrometry 548 Summary:Common Fragmentation Patterns 553 EssentialTerms 555 Study Problems 556 NUCLEAR MAGNETIC RESONANCE 13 SPECTROSCOPY 563 13-1 132 Introduction 563 ar Mac tic Res 13-3 Mag etic Shielding b 13-4 The NMR Spectrometer 567 13-5 The Chemical Shift 568 13.6 The Number of Signals 575 13.7 Areas of the Peaks 577 13-8 Spin-Spin Splitting 580 Problem-Solving Strategy:Drawing An NMR Spectrum 584 13-9 Complex Sitting 588 13-10 Stereochemical Nonequivalence of Protons 591 13-11 Time Dependence of NMR Spectroscopy 594

Contents xi 11-12 Esterification of Alcohols 496 11-13 Esters of Inorganic Acids 497 11-14 Reactions of Alkoxides 500 Key Mechanism 11-6:The Williamson Ether Synthesis 500 Problem-Solving Strategy: Multistep Synthesis 502 Summary: Reactions of Alcohols 505 Essential Terms 508 Study Problems 509 12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 513 12-1 Introduction 513 12-2 The Electromagnetic Spectrum 514 12-3 The Infrared Region 515 12-4 Molecular Vibrations 516 12-5 IR-Active and IR-Inactive Vibrations 518 12-6 Measurement of the IR Spectrum 519 12-7 Infrared Spectroscopy of Hydrocarbons 522 12-8 Characteristic Absorptions of Alcohols and Amines 527 12-9 Characteristic Absorptions of Carbonyl Compounds 528 12-10 Characteristic Absorptions of C—N Bonds 533 12-11 Simplified Summary of IR Stretching Frequencies 535 12-12 Reading and Interpreting IR Spectra (Solved Problems) 537 12-13 Introduction to Mass Spectrometry 541 12-14 Determination of the Molecular Formula by Mass Spectrometry 545 12-15 Fragmentation Patterns in Mass Spectrometry 548 Summary: Common Fragmentation Patterns 553 Essential Terms 555 Study Problems 556 13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 563 13-1 Introduction 563 13-2 Theory of Nuclear Magnetic Resonance 563 13-3 Magnetic Shielding by Electrons 566 13-4 The NMR Spectrometer 567 13-5 The Chemical Shift 568 13-6 The Number of Signals 575 13-7 Areas of the Peaks 577 13-8 Spin-Spin Splitting 580 Problem-Solving Strategy: Drawing An NMR Spectrum 584 13-9 Complex Sitting 588 13-10 Stereochemical Nonequivalence of Protons 591 13-11 Time Dependence of NMR Spectroscopy 594 Problem-Solving Strategy: Interpreting Proton NMR Sectra 597