Organic Chemistry (missing pages)

Cover......Page 1
Title Page 1......Page 2
Copyright Page 2......Page 3
About the Authors 3......Page 4
Contents 5......Page 6
Preface 25......Page 26
 1-1 The Origins of Organic Chemistry 37......Page 38
 1-2 Principles of Atomic Structure 39......Page 40
 1-3 Bond Formation: The Octet Rule 43......Page 44
 1-4 Lewis Structures 44......Page 45
  Summary: Common Bonding Patterns (Uncharged) 45......Page 46
 1-6 Electronegativity and Bond Polarity 46......Page 47
 1-7 Formal Charges 47......Page 48
 1-8 Ionic Structures 49......Page 50
 1-9 Resonance 50......Page 51
  PROBLEM-SOLVING STRATEGY: Drawing and Evaluating Resonance Forms 54......Page 55
 1-10 Structural Formulas 58......Page 59
 1-11 Molecular Formulas and Empirical Formulas 61......Page 62
 1-12 Wave Properties of Electrons in Orbitals 63......Page 64
 1-13 Molecular Orbitals 64......Page 65
 1-14 Pi Bonding 67......Page 68
 1-15 Hybridization and Molecular Shapes 68......Page 69
 1-16 Drawing Three-Dimensional Molecules 72......Page 73
  Summary: Hybridization and Geometry 73......Page 74
 1-18 Bond Rotation 78......Page 79
 1-19 Isomerism 80......Page 81
  Essential Terms 83......Page 84
  Study Problems 86......Page 87
  Summary: Acidity and Basicity Limitations in Common Solvents 114......Page 92
 2-1 Polarity of Bonds and Molecules 92......Page 93
 2-2 Intermolecular Forces 96......Page 97
 2-3 Polarity Effects on Solubilities 100......Page 101
 2-4 Arrhenius Acids and Bases 103......Page 104
 2-5 Brønsted–Lowry Acids and Bases 104......Page 105
 2-6 Strengths of Acids and Bases 105......Page 106
 2-7 Equilibrium Positions of Acid–Base Reactions 109......Page 110
  PROBLEM-SOLVING STRATEGY: Predicting Acid–Base Equilibrium Positions 111......Page 112
 2-8 Solvent Effects on Acidity and Basicity 112......Page 113
 2-9 Effects of Size and Electronegativity on Acidity 114......Page 115
 2-10 Inductive Effects on Acidity 116......Page 117
 2-11 Hybridization Effects on Acidity 117......Page 118
 2-12 Resonance Effects on Acidity and Basicity 119......Page 120
 2-13 Lewis Acids and Bases 122......Page 123
 2-14 The Curved-Arrow Formalism 124......Page 125
 2-15 Hydrocarbons 126......Page 127
 2-16 Functional Groups with Oxygen 129......Page 130
 2-17 Functional Groups with Nitrogen 132......Page 133
  Essential Terms 134......Page 135
  Study Problems 137......Page 138
3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 143......Page 144
 3-2 Molecular Formulas of Alkanes 144......Page 145
 3-3 Nomenclature of Alkanes 146......Page 147
  Summary: Rules for Naming Alkanes 151......Page 152
 3-4 Physical Properties of Alkanes 153......Page 154
 3-5 Uses and Sources of Alkanes 154......Page 155
 3-6 Reactions of Alkanes 157......Page 158
 3-7 Structure and Conformations of Alkanes 158......Page 159
 3-8 Conformations of Butane 162......Page 163
 3-10 Cycloalkanes 165......Page 166
 3-11 Cis-trans Isomerism in Cycloalkanes 167......Page 168
 3-12 Stabilities of Cycloalkanes; Ring Strain 168......Page 169
 3-13 Cyclohexane Conformations 172......Page 173
  PROBLEM-SOLVING STRATEGY: Drawing Chair Conformations 174......Page 175
 3-14 Conformations of Monosubstituted Cyclohexanes 176......Page 177
  PROBLEM-SOLVING STRATEGY: Recognizing Cis and Trans Isomers 179......Page 180
 3-16 Bicyclic Molecules 182......Page 183
  Essential Terms 184......Page 185
  Study Problems 188......Page 189
 4-1 Introduction 191......Page 192
 4-2 Chlorination of Methane 192......Page 193
 4-3 The Free-Radical Chain Reaction 193......Page 194
 4-4 Equilibrium Constants and Free Energy 197......Page 198
 4-5 Enthalpy and Entropy 199......Page 200
 4-6 Bond-Dissociation Enthalpies 201......Page 202
 4-7 Enthalpy Changes in Chlorination 202......Page 203
 4-8 Kinetics and the Rate Equation 205......Page 206
 4-9 Activation Energy and the Temperature Dependence of Rates 207......Page 208
 4-10 Transition States 208......Page 209
 4-11 Rates of Multistep Reactions 210......Page 211
 4-12 Temperature Dependence of Halogenation 211......Page 212
 4-13 Selectivity in Halogenation 212......Page 213
 4-14 Hammond’s Postulate 218......Page 219
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 219......Page 220
 4-15 Radical Inhibitors 222......Page 223
 4-16 Reactive Intermediates 223......Page 224
  Essential Terms 230......Page 231
  Study Problems 233......Page 234
 5-1 Introduction 237......Page 238
 5-2 Chirality 238......Page 239
 5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms 244......Page 245
 5-4 Optical Activity 249......Page 250
 5-5 Biological Discrimination of Enantiomers 254......Page 255
 5-6 Racemic Mixtures 255......Page 256
 5-7 Enantiomeric Excess and Optical Purity 256......Page 257
 5-8 Chirality of Conformationally Mobile Systems 257......Page 258
 5-9 Chiral Compounds Without Asymmetric Atoms 260......Page 261
 5-10 Fischer Projections 262......Page 263
 5-11 Diastereomers 266......Page 267
  Summary: Types of Isomers 268......Page 269
 5-13 Meso Compounds 269......Page 270
 5-14 Absolute and Relative Configuration 271......Page 272
 5-15 Physical Properties of Diastereomers 273......Page 274
 5-16 Resolution of Enantiomers 274......Page 275
  Essential Terms 277......Page 278
  Study Problems 280......Page 281
 6-1 Introduction 283......Page 284
 6-2 Nomenclature of Alkyl Halides 284......Page 285
 6-3 Common Uses of Alkyl Halides 286......Page 287
 6-4 Structure of Alkyl Halides 288......Page 289
 6-5 Physical Properties of Alkyl Halides 289......Page 290
 6-6 Preparation of Alkyl Halides 291......Page 292
  Summary: Methods for Preparing Alkyl Halides 295......Page 296
 6-7 Reactions of Alkyl Halides: Substitution and Elimination 296......Page 297
 6-8 Bimolecular Nucleophilic Substitution: The SN2 Reaction 297......Page 298
 6-9 Generality of the SN2 Reaction 299......Page 300
  Summary: SN2 Reactions of Alkyl Halides 300......Page 301
 6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile 301......Page 302
  Summary: Trends in Nucleophilicity 302......Page 303
 6-11 Reactivity of the Substrate in SN2 Reactions 305......Page 306
 6-12 Stereochemistry of the SN2 Reaction 309......Page 310
 6-13 Unimolecular Nucleophilic Substitution: The SN1 Reaction 311......Page 312
 6-14 Stereochemistry of the SN1 Reaction 315......Page 316
 6-15 Rearrangements in SN1 Reactions 317......Page 318
 6-16 Comparison of SN1 and SN2 Reactions 320......Page 321
  Summary: Nucleophilic Substitutions 322......Page 323
  Summary: Reactions of Alkyl Halides 323......Page 324
  Essential Terms 324......Page 325
  Study Problems 327......Page 328
 7-1 Introduction 332......Page 333
 7-2 The Orbital Description of the Alkene Double Bond 333......Page 334
 7-3 Elements of Unsaturation 335......Page 336
 7-4 Nomenclature of Alkenes 337......Page 338
 7-5 Nomenclature of Cis-Trans Isomers 339......Page 340
  Summary: Rules for Naming Alkenes 341......Page 342
 7-6 Commercial Importance of Alkenes 342......Page 343
 7-7 Physical Properties of Alkenes 344......Page 345
 7-8 Stability of Alkenes 346......Page 347
 7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl Halides 354......Page 355
 7-10 Unimolecular Elimination: The E1 Reaction 355......Page 356
  Summary: Carbocation Reactions 359......Page 360
 7-11 Positional Orientation of Elimination: Zaitsev’s Rule 360......Page 361
 7-12 Bimolecular Elimination: The E2 Reaction 362......Page 363
 7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation 364......Page 365
 7-14 Stereochemistry of the E2 Reaction 365......Page 366
 7-15 E2 Reactions in Cyclohexane Systems 368......Page 369
 7-16 Comparison of E1 and E2 Elimination Mechanisms 370......Page 371
  Summary: Elimination Reactions 371......Page 372
  Summary: Substitution and Elimination Reactions of Alkyl Halides 374......Page 375
  PROBLEM-SOLVING STRATEGY: Predicting Substitutions and Eliminations 376......Page 377
 7-18 Alkene Synthesis by Dehydration of Alcohols 377......Page 378
 7-19 Alkene Synthesis by High-Temperature Industrial Methods 380......Page 381
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 382......Page 383
  Summary: Methods for Synthesis of Alkenes 385......Page 386
  Essential Terms 386......Page 387
  Study Problems 389......Page 390
 8-1 Reactivity of the Carbon–Carbon Double Bond 395......Page 396
 8-2 Electrophilic Addition to Alkenes 396......Page 397
 8-3 Addition of Hydrogen Halides to Alkenes 398......Page 399
 8-4 Addition of Water: Hydration of Alkenes 406......Page 407
 8-5 Hydration by Oxymercuration–Demercuration 408......Page 409
 8-6 Alkoxymercuration–Demercuration 411......Page 412
 8-7 Hydroboration of Alkenes 412......Page 413
 8-8 Addition of Halogens to Alkenes 418......Page 419
 8-9 Formation of Halohydrins 421......Page 422
 8-10 Catalytic Hydrogenation of Alkenes 425......Page 426
 8-11 Addition of Carbenes to Alkenes 427......Page 428
 8-12 Epoxidation of Alkenes 429......Page 430
 8-13 Acid-Catalyzed Opening of Epoxides 431......Page 432
 8-14 Syn Dihydroxylation of Alkenes 434......Page 435
 8-15 Oxidative Cleavage of Alkenes 436......Page 437
 8-16 Polymerization of Alkenes 439......Page 440
 8-17 Olefin Metathesis 443......Page 444
  PROBLEM-SOLVING STRATEGY: Organic Synthesis 446......Page 447
  Summary: Reactions of Alkenes 448......Page 449
  Summary: Electrophilic Additions to Alkenes 451......Page 452
  Summary: Oxidation and Cyclopropanation Reactions of Alkenes 452......Page 453
  Essential Terms 453......Page 454
  Study Problems 457......Page 458
 9-1 Introduction 464......Page 465
 9-2 Nomenclature of Alkynes 465......Page 466
 9-4 Commercial Importance of Alkynes 467......Page 468
 9-5 Electronic Structure of Alkynes 469......Page 470
 9-6 Acidity of Alkynes; Formation of Acetylide Ions 470......Page 471
 9-7 Synthesis of Alkynes from Acetylides 472......Page 473
 9-8 Synthesis of Alkynes by Elimination Reactions 475......Page 476
 9-9 Addition Reactions of Alkynes 477......Page 478
 9-10 Oxidation of Alkynes 486......Page 487
  PROBLEM-SOLVING STRATEGY: Multistep Synthesis 488......Page 489
  Summary: Reactions of Alkynes 490......Page 491
  Summary: Reactions of Terminal Alkynes 491......Page 492
  Essential Terms 492......Page 493
  Study Problems 493......Page 494
 10-2 Structure and Classification of Alcohols 496......Page 497
 10-3 Nomenclature of Alcohols and Phenols 497......Page 498
 10-4 Physical Properties of Alcohols 502......Page 503
 10-5 Commercially Important Alcohols 504......Page 505
 10-6 Acidity of Alcohols and Phenols 506......Page 507
  Summary: Previous Alcohol Syntheses 510......Page 511
 10-8 Organometallic Reagents for Alcohol Synthesis 511......Page 512
 10-9 Reactions of Organometallic Compounds 514......Page 515
  Summary: Grignard Reactions 520......Page 521
 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 522......Page 523
 10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols 525......Page 526
  Summary: Reactions of LiAIH4 and NaBH4 527......Page 528
  Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 528......Page 529
 10-12 Thiols (Mercaptans) 530......Page 531
  Essential Terms 533......Page 534
  Study Problems 535......Page 536
11 REACTIONS OF ALCOHOLS 541......Page 542
 11-1 Oxidation States of Alcohols and Related Functional Groups 542......Page 543
 11-2 Oxidation of Alcohols 543......Page 544
 11-3 Additional Methods for Oxidizing Alcohols 547......Page 548
 11-4 Biological Oxidation of Alcohols 549......Page 550
 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 551......Page 552
  Summary: SN2 Reactions of Tosylate Esters 553......Page 554
 11-6 Reduction of Alcohols 554......Page 555
 11-7 Reactions of Alcohols with Hydrohalic Acids 555......Page 556
 11-8 Reactions of Alcohols with Phosphorus Halides 560......Page 561
 11-9 Reactions of Alcohols with Thionyl Chloride 561......Page 562
 11-10 Dehydration Reactions of Alcohols 563......Page 564
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 567......Page 568
 11-11 Unique Reactions of Diols 570......Page 571
 11-12 Esterification of Alcohols 572......Page 573
 11-13 Esters of Inorganic Acids 573......Page 574
 11-14 Reactions of Alkoxides 576......Page 577
  PROBLEM-SOLVING STRATEGY: Multistep Synthesis 579......Page 580
  Summary: Reactions of Alcohols 582......Page 583
  Summary: Reactions of Alcohols: C¬O Cleavage 584......Page 585
  Essential Terms 585......Page 586
  Study Problems 587......Page 588
 12-1 Introduction 592......Page 593
 12-2 The Electromagnetic Spectrum 593......Page 594
 12-3 The Infrared Region 594......Page 595
 12-4 Molecular Vibrations 595......Page 596
 12-5 IR-Active and IR-Inactive Vibrations 597......Page 598
 12-6 Measurement of the IR Spectrum 598......Page 599
 12-7 Infrared Spectroscopy of Hydrocarbons 601......Page 602
 12-8 Characteristic Absorptions of Alcohols and Amines 606......Page 607
 12-9 Characteristic Absorptions of Carbonyl Compounds 607......Page 608
 12-10 Characteristic Absorptions of C¬N Bonds 612......Page 613
 12-11 Simplified Summary of IR Stretching Frequencies 614......Page 615
 12-12 Reading and Interpreting IR Spectra (Solved Problems) 616......Page 617
 12-13 Introduction to Mass Spectrometry 620......Page 621
 12-14 Determination of the Molecular Formula by Mass Spectrometry 623......Page 624
 12-15 Fragmentation Patterns in Mass Spectrometry 626......Page 627
  Summary: Common Fragmentation Patterns 632......Page 633
  Essential Terms 633......Page 634
  Study Problems 635......Page 636
 13-1 Introduction 643......Page 644
 13-2 Theory of Nuclear Magnetic Resonance 644......Page 645
 13-3 Magnetic Shielding by Electrons 646......Page 647
 13-4 The NMR Spectrometer 648......Page 649
 13-5 The Chemical Shift 649......Page 650
 13-6 The Number of Signals 656......Page 657
 13-7 Areas of the Peaks 658......Page 659
 13-8 Spin-Spin Splitting 661......Page 662
  PROBLEM-SOLVING STRATEGY: Drawing an NMR Spectrum 666......Page 667
 13-9 Complex Splitting 670......Page 671
 13-10 Stereochemical Nonequivalence of Protons 673......Page 674
 13-11 Time Dependence of NMR Spectroscopy 676......Page 677
  PROBLEM-SOLVING STRATEGY: Interpreting Proton NMR Spectra 679......Page 680
 13-12 Carbon-13 NMR Spectroscopy 684......Page 685
 13-13 Interpreting Carbon NMR Spectra 692......Page 693
 13-14 Nuclear Magnetic Resonance Imaging 694......Page 695
  PROBLEM-SOLVING STRATEGY: Spectroscopy Problems 695......Page 696
 Essential Terms 699......Page 700
 Study Problems 701......Page 702
 14-1 Introduction 708......Page 709
 14-2 Physical Properties of Ethers 709......Page 710
 14-3 Nomenclature of Ethers 713......Page 714
 14-4 Spectroscopy of Ethers 716......Page 717
 14-5 The Williamson Ether Synthesis 718......Page 719
 14-7 Industrial Synthesis: Bimolecular Condensation of Alcohols 720......Page 721
  Summary: Syntheses of Ethers (Review) 721......Page 722
 14-8 Cleavage of Ethers by HBr and HI 722......Page 723
 14-9 Autoxidation of Ethers 724......Page 725
 14-10 Thioethers (Sulfides) and Silyl Ethers 725......Page 726
 14-11 Synthesis of Epoxides 729......Page 730
 14-12 Acid-Catalyzed Ring Opening of Epoxides 732......Page 733
 14-13 Base-Catalyzed Ring Opening of Epoxides 736......Page 737
 14-14 Orientation of Epoxide Ring Opening 738......Page 739
  Summary: Orientation of Epoxide Ring Opening 739......Page 740
 14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 740......Page 741
 14-16 Epoxy Resins: The Advent of Modern Glues 741......Page 742
  Summary: Reactions of Epoxides 743......Page 744
  Study Problems 746......Page 747
 15-1 Introduction 752......Page 753
 15-2 Stabilities of Dienes 753......Page 754
 15-3 Molecular Orbital Picture of a Conjugated System 754......Page 755
 15-4 Allylic Cations 759......Page 760
 15-5 1,2- and 1,4-Addition to Conjugated Dienes 760......Page 761
 15-6 Kinetic Versus Thermodynamic Control in the Addition of HBr to Buta-1,3-diene 762......Page 763
 15-7 Allylic Radicals 764......Page 765
 15-8 Molecular Orbitals of the Allylic System 766......Page 767
 15-9 Electronic Configurations of the Allyl Radical, Cation, and Anion 768......Page 769
 15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 769......Page 770
 15-11 The Diels–Alder Reaction 770......Page 771
 15-12 The Diels–Alder as an Example of a Pericyclic Reaction 779......Page 780
 15-13 Ultraviolet Absorption Spectroscopy 782......Page 783
 15-14 Colored Organic Compounds 788......Page 789
 15-15 UV-Visible Analysis in Biology and Medicine 790......Page 791
  Essential Terms 792......Page 793
  Study Problems 795......Page 796
 16-1 Introduction: The Discovery of Benzene 800......Page 801
 16-2 The Structure and Properties of Benzene 801......Page 802
 16-3 The Molecular Orbitals of Benzene 805......Page 806
 16-4 The Molecular Orbital Picture of Cyclobutadiene 808......Page 809
 16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds 809......Page 810
 16-6 Hückel’s Rule 810......Page 811
 16-7 Molecular Orbital Derivation of Hückel’s Rule 812......Page 813
 16-8 Aromatic Ions 813......Page 814
 16-9 Heterocyclic Aromatic Compounds 819......Page 820
 16-10 Polynuclear Aromatic Hydrocarbons 823......Page 824
 16-11 Aromatic Allotropes of Carbon 825......Page 826
 16-12 Fused Heterocyclic Compounds 827......Page 828
 16-13 Nomenclature of Benzene Derivatives 828......Page 829
 16-14 Physical Properties of Benzene and Its Derivatives 830......Page 831
 16-15 Spectroscopy of Aromatic Compounds 832......Page 833
 Essential Terms 834......Page 835
 Study Problems 836......Page 837
 17-1 Electrophilic Aromatic Substitution 845......Page 846
 17-2 Halogenation of Benzene 847......Page 848
 17-3 Nitration of Benzene 849......Page 850
 17-4 Sulfonation of Benzene 850......Page 851
 17-5 Nitration of Toluene: The Effect of Alkyl Substitution 853......Page 854
 17-6 Activating, Ortho, Para-Directing Substituents 855......Page 856
 17-7 Deactivating, Meta-Directing Substituents 858......Page 859
  Summary: Deactivating, Meta-Directors 861......Page 862
 17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing 862......Page 863
 17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 863......Page 864
 17-10 The Friedel–Crafts Alkylation 866......Page 867
 17-11 The Friedel–Crafts Acylation 871......Page 872
  Summary: Comparison of Friedel–Crafts Alkylation and Acylation 873......Page 874
 17-12 Nucleophilic Aromatic Substitution 875......Page 876
 17-13 Aromatic Substitutions Using Organometallic Reagents 879......Page 880
 17-14 Addition Reactions of Benzene Derivatives 885......Page 886
 17-15 Side-Chain Reactions of Benzene Derivatives 888......Page 889
 17-16 Reactions of Phenols 892......Page 893
 PROBLEM-SOLVING STRATEGY: Synthesis Using Electrophilic Aromatic Substitution 895......Page 896
 Summary: Reactions of Aromatic Compounds 899......Page 900
 Summary: Substitutions of Aryl Halides 902......Page 903
 Essential Terms 903......Page 904
 Study Problems 906......Page 907
 18-1 Carbonyl Compounds 912......Page 913
 18-2 Structure of the Carbonyl Group 913......Page 914
 18-3 Nomenclature of Ketones and Aldehydes 914......Page 915
 18-4 Physical Properties of Ketones and Aldehydes 916......Page 917
 18-5 Spectroscopy of Ketones and Aldehydes 918......Page 919
 18-6 Industrial Importance of Ketones and Aldehydes 924......Page 925
 18-7 Review of Syntheses of Ketones and Aldehydes 925......Page 926
 18-9 Synthesis of Ketones and Aldehydes from Nitriles 929......Page 930
 18-10 Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 931......Page 932
  Summary: Syntheses of Ketones and Aldehydes 933......Page 934
 18-11 Reactions of Ketones and Aldehydes: Introduction to Nucleophilic Addition 934......Page 935
 18-12 Hydration of Ketones and Aldehydes 938......Page 939
 18-13 Formation of Cyanohydrins 940......Page 941
 18-14 Formation of Imines 942......Page 943
 18-15 Condensations with Hydroxylamine and Hydrazines 945......Page 946
  Summary: Condensations of Amines with Ketones and Aldehydes 946......Page 947
 18-16 Formation of Acetals 947......Page 948
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 951......Page 952
 18-17 Use of Acetals as Protecting Groups 952......Page 953
 18-18 The Wittig Reaction 954......Page 955
 18-19 Oxidation of Aldehydes 957......Page 958
 18-20 Reductions of Ketones and Aldehydes 958......Page 959
  Summary: Reactions of Ketones and Aldehydes 961......Page 962
  Summary: Nucleophilic Addition Reactions of Aldehydes and Ketones 963......Page 964
 Essential Terms 964......Page 965
 Study Problems 967......Page 968
 19-1 Introduction 977......Page 978
 19-2 Nomenclature of Amines 978......Page 979
 19-3 Structure of Amines 981......Page 982
 19-4 Physical Properties of Amines 983......Page 984
 19-5 Basicity of Amines 984......Page 985
 19-6 Factors that Affect Amine Basicity 986......Page 987
 19-7 Salts of Amines 988......Page 989
 19-8 Spectroscopy of Amines 990......Page 991
 19-10 Aromatic Substitution of Arylamines and Pyridine 994......Page 995
 19-11 Alkylation of Amines by Alkyl Halides 998......Page 999
 19-12 Acylation of Amines by Acid Chlorides 999......Page 1000
 19-13 Formation of Sulfonamides 1001......Page 1002
 19-14 Amines as Leaving Groups: The Hofmann Elimination 1003......Page 1004
 19-15 Oxidation of Amines; The Cope Elimination 1006......Page 1007
 19-16 Reactions of Amines with Nitrous Acid 1009......Page 1010
 19-17 Reactions of Arenediazonium Salts 1011......Page 1012
  Summary: Reactions of Amines 1014......Page 1015
 19-18 Synthesis of Amines by Reductive Amination 1016......Page 1017
 19-19 Synthesis of Amines by Acylation–Reduction 1018......Page 1019
 19-20 Syntheses Limited to Primary Amines 1020......Page 1021
  Summary: Synthesis of Amines 1024......Page 1025
 Essential Terms 1025......Page 1026
 Study Problems 1028......Page 1029
 20-1 Introduction 1038......Page 1039
 20-2 Nomenclature of Carboxylic Acids 1039......Page 1040
 20-3 Structure and Physical Properties of Carboxylic Acids 1042......Page 1043
 20-4 Acidity of Carboxylic Acids 1043......Page 1044
 20-5 Salts of Carboxylic Acids 1047......Page 1048
 20-6 Commercial Sources of Carboxylic Acids 1049......Page 1050
 20-7 Spectroscopy of Carboxylic Acids 1051......Page 1052
 20-8 Synthesis of Carboxylic Acids 1055......Page 1056
  Summary: Syntheses of Carboxylic Acids 1057......Page 1058
 20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic AcylSubstitution 1058......Page 1059
 20-10 Condensation of Acids with Alcohols: The Fischer Esterification 1060......Page 1061
 20-12 Condensation of Acids with Amines: Direct Synthesis of Amides 1064......Page 1065
 20-13 Reduction of Carboxylic Acids 1065......Page 1066
 20-15 Synthesis and Use of Acid Chlorides 1067......Page 1068
  Summary: Reactions of Carboxylic Acids 1070, 1071......Page 1071
  Summary: Reactions of Carboxylic Acids 1070, 1071......Page 1072
 Essential Terms 1072......Page 1073
 Study Problems 1073......Page 1074
 21-1 Introduction 1079......Page 1080
 21-2 Structure and Nomenclature of Acid Derivatives 1080......Page 1081
 21-3 Physical Properties of Carboxylic Acid Derivatives 1087......Page 1088
 21-4 Spectroscopy of Carboxylic Acid Derivatives 1089......Page 1090
 21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 1096......Page 1097
 21-6 Transesterification 1105......Page 1106
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1106......Page 1107
 21-7 Hydrolysis of Carboxylic Acid Derivatives 1109......Page 1110
 21-8 Reduction of Acid Derivatives 1114......Page 1115
 21-9 Reactions of Acid Derivatives with Organometallic Reagents 1117......Page 1118
 21-10 Summary of the Chemistry of Acid Chlorides 1119......Page 1120
 21-11 Summary of the Chemistry of Anhydrides 1121......Page 1122
 21-12 Summary of the Chemistry of Esters 1124......Page 1125
 21-13 Summary of the Chemistry of Amides 1127......Page 1128
 21-14 Summary of the Chemistry of Nitriles 1130......Page 1131
 21-15 Thioesters 1131......Page 1132
 21-16 Esters and Amides of Carbonic Acid 1133......Page 1134
 Essential Terms 1135......Page 1136
 Summary: Reactions of Acid Chlorides 1136......Page 1137
 Study Problems 1139......Page 1140
 22-1 Introduction 1148......Page 1149
 22-2 Enols and Enolate Ions 1150......Page 1151
 22-3 Alkylation of Enolate Ions 1153......Page 1154
 22-4 Formation and Alkylation of Enamines 1155......Page 1156
 22-5 Alpha Halogenation of Ketones 1157......Page 1158
 22-6 Alpha Bromination of Acids: The HVZ Reaction 1163......Page 1164
 22-7 The Aldol Condensation of Ketones and Aldehydes 1164......Page 1165
 22-8 Dehydration of Aldol Products 1168......Page 1169
 22-9 Crossed Aldol Condensations 1169......Page 1170
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1170......Page 1171
 22-10 Aldol Cyclizations 1172......Page 1173
 22-11 Planning Syntheses Using Aldol Condensations 1173......Page 1174
 22-12 The Claisen Ester Condensation 1175......Page 1176
 22-13 The Dieckmann Condensation: A Claisen Cyclization 1178......Page 1179
 22-14 Crossed Claisen Condensations 1179......Page 1180
 22-15 Syntheses Using b-Dicarbonyl Compounds 1182......Page 1183
 22-16 The Malonic Ester Synthesis 1184......Page 1185
 22-17 The Acetoacetic Ester Synthesis 1187......Page 1188
 22-18 Conjugate Additions: The Michael Reaction 1190......Page 1191
 22-19 The Robinson Annulation 1194......Page 1195
  PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1195......Page 1196
 Summary: Enolate Additions and Condensations 1197......Page 1198
 Essential Terms 1199......Page 1200
 Study Problems 1202......Page 1203
 23-1 Introduction 1208......Page 1209
 23-2 Classification of Carbohydrates 1209......Page 1210
 23-3 Monosaccharides 1210......Page 1211
 23-4 Cyclic Structures of Monosaccharides 1214......Page 1215
 23-5 Anomers of Monosaccharides; Mutarotation 1218......Page 1219
 23-6 Reactions of Monosaccharides: Reduction 1221......Page 1222
 23-7 Oxidation of Monosaccharides; Reducing Sugars 1222......Page 1223
 23-8 Nonreducing Sugars: Formation of Glycosides 1224......Page 1225
 23-9 Ether and Ester Formation 1226......Page 1227
 23-10 Chain Shortening: The Ruff Degradation 1229......Page 1230
 23-11 Chain Lengthening: The Kiliani–Fischer Synthesis 1230......Page 1231
  Summary: Reactions of Sugars 1232......Page 1233
 23-12 Disaccharides 1234......Page 1235
 23-13 Polysaccharides 1239......Page 1240
 23-14 Nucleic Acids: Introduction 1242......Page 1243
 23-15 Ribonucleosides and Ribonucleotides 1244......Page 1245
 23-16 The Structures of RNA and DNA 1246......Page 1247
 23-17 Additional Functions of Nucleotides 1250......Page 1251
 Essential Terms 1252......Page 1253
 Study Problems 1255......Page 1256
 24-1 Introduction 1258......Page 1259
 24-2 Structure and Stereochemistry of the a-Amino Acids 1259......Page 1260
 24-3 Acid–Base Properties of Amino Acids 1263......Page 1264
 24-4 Isoelectric Points and Electrophoresis 1265......Page 1266
 24-5 Synthesis of Amino Acids 1267......Page 1268
 24-6 Resolution of Amino Acids 1270......Page 1271
 24-7 Reactions of Amino Acids 1271......Page 1272
 24-8 Structure and Nomenclature of Peptides and Proteins 1274......Page 1275
 24-9 Peptide Structure Determination 1278......Page 1279
 24-10 Laboratory Peptide Synthesis 1283......Page 1284
 24-11 Classification of Proteins 1289......Page 1290
 24-12 Levels of Protein Structure 1290......Page 1291
 24-13 Protein Denaturation 1292......Page 1293
 Essential Terms 1295......Page 1296
 Study Problems 1297......Page 1298
 25-1 Introduction 1301......Page 1302
 25-3 Triglycerides 1302......Page 1303
 25-4 Saponification of Fats and Oils: Soaps and Detergents 1306......Page 1307
 25-5 Phospholipids 1309......Page 1310
 25-6 Steroids 1311......Page 1312
 25-7 Prostaglandins 1314......Page 1315
 25-8 Terpenes 1315......Page 1316
 Essential Terms 1318......Page 1319
 Study Problems 1319......Page 1320
 26-1 Introduction 1322......Page 1323
 26-2 Chain-Growth Polymers 1323......Page 1324
 26-3 Stereochemistry of Polymers 1329......Page 1330
 26-4 Stereochemical Control of Polymerization: Ziegler–Natta Catalysts 1330......Page 1331
 26-5 Natural and Synthetic Rubbers 1331......Page 1332
 26-7 Step-Growth Polymers 1333......Page 1334
 26-8 Polymer Structure and Properties 1337......Page 1338
 26-9 Recycling of Plastics 1339......Page 1340
 Essential Terms 1340......Page 1341
 Study Problems 1342......Page 1343
 1A NMR: Spin-Spin Coupling Constants 1344......Page 1345
 1B NMR: Proton Chemical Shifts 1345......Page 1346
 1C NMR: 13C Chemical Shifts in Organic Compounds 1347......Page 1348
 2A IR: Characteristic Infrared Group Frequencies 1348......Page 1349
 2B IR: Characteristic Infrared Absorptions of Functional Groups 1351......Page 1352
 3A Methods and Suggestions for Proposing Mechanisms 1353......Page 1354
 3B Suggestions for Developing Multistep Syntheses 1355......Page 1356
 4 pKa Values for Representative Compounds 1356......Page 1357
 5 Summary of Organic Nomenclature 1358......Page 1359
 Brief Answers to Selected Problems 1368......Page 1369
 Photo Credits 1374......Page 1375
 Index 1375......Page 1376