Organic KNOWLEDGE TOOLS - pe56d.s3.amazonaws.com · 34 Se Selenium 78.96 35 Br Bromine 79.904 36 Kr...

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ORGANIC CHEMISTRY7e


Organic Chemistry, Seventh EditionJohn McMurry

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iii

Contents in Brief

1 Structure and Bonding 1

2 Polar Covalent Bonds; Acids and Bases 353 Organic Compounds: Alkanes and Their Stereochemistry 734 Organic Compounds: Cycloalkanes and Their Stereochemistry 1075 An Overview of Organic Reactions 1376 Alkenes: Structure and Reactivity 1727 Alkenes: Reactions and Synthesis 2138 Alkynes: An Introduction to Organic Synthesis 2599 Stereochemistry 289

10 Organohalides 33211 Reactions of Alkyl Halides: Nucleophilic Substitutions and

Eliminations 35912 Structure Determination: Mass Spectrometry and Infrared

Spectroscopy 40813 Structure Determination: Nuclear Magnetic Resonance

Spectroscopy 44014 Conjugated Compounds and Ultraviolet Spectroscopy 48215 Benzene and Aromaticity 51616 Chemistry of Benzene: Electrophilic Aromatic Substitution 54717 Alcohols and Phenols 59918 Ethers and Epoxides; Thiols and Sulfides 652> A Preview of Carbonyl Compounds 686

19 Aldehydes and Ketones: Nucleophilic Addition Reactions 69520 Carboxylic Acids and Nitriles 75121 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution

Reactions 78522 Carbonyl Alpha-Substitution Reactions 84123 Carbonyl Condensation Reactions 87724 Amines and Heterocycles 91625 Biomolecules: Carbohydrates 97326 Biomolecules: Amino Acids, Peptides, and Proteins 101627 Biomolecules: Lipids 106028 Biomolecules: Nucleic Acids 110029 The Organic Chemistry of Metabolic Pathways 112530 Orbitals and Organic Chemistry: Pericyclic Reactions 117831 Synthetic Polymers 1206


iv

1 Structure and Bonding 11.1 Atomic Structure: The Nucleus 31.2 Atomic Structure: Orbitals 41.3 Atomic Structure: Electron Configurations 61.4 Development of Chemical Bonding Theory 71.5 The Nature of Chemical Bonds: Valence Bond Theory 101.6 sp3 Hybrid Orbitals and the Structure of Methane 121.7 sp3 Hybrid Orbitals and the Structure of Ethane 141.8 sp2 Hybrid Orbitals and the Structure of Ethylene 151.9 sp Hybrid Orbitals and the Structure of Acetylene 171.10 Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur 191.11 The Nature of Chemical Bonds: Molecular Orbital Theory 211.12 Drawing Chemical Structures 22

Focus On . . . Chemicals, Toxicity, and Risk 25Summary and Key Words 26 � Visualizing Chemistry 28Additional Problems 29

2 Polar Covalent Bonds; Acids and Bases 352.1 Polar Covalent Bonds: Electronegativity 352.2 Polar Covalent Bonds: Dipole Moments 382.3 Formal Charges 402.4 Resonance 432.5 Rules for Resonance Forms 442.6 Drawing Resonance Forms 462.7 Acids and Bases: The Brønsted–Lowry Definition 492.8 Acid and Base Strength 502.9 Predicting Acid–Base Reactions from pKa Values 522.10 Organic Acids and Organic Bases 542.11 Acids and Bases: The Lewis Definition 572.12 Molecular Models 612.13 Noncovalent Interactions 61

Focus On . . . Alkaloids: Naturally Occurring Bases 64Summary and Key Words 65 � Visualizing Chemistry 66Additional Problems 68

Contents

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3 Organic Compounds: Alkanes and Their Stereochemistry 733.1 Functional Groups 733.2 Alkanes and Alkane Isomers 793.3 Alkyl Groups 833.4 Naming Alkanes 863.5 Properties of Alkanes 913.6 Conformations of Ethane 933.7 Conformations of Other Alkanes 95

Focus On . . . Gasoline 99Summary and Key Words 100 � Visualizing Chemistry 101Additional Problems 102

4 Organic Compounds: Cycloalkanes and TheirStereochemistry 1074.1 Naming Cycloalkanes 1084.2 Cis–Trans Isomerism in Cycloalkanes 1104.3 Stability of Cycloalkanes: Ring Strain 1134.4 Conformations of Cycloalkanes 1154.5 Conformations of Cyclohexane 1174.6 Axial and Equatorial Bonds in Cyclohexane 1194.7 Conformations of Monosubstituted Cyclohexanes 1224.8 Conformations of Disubstituted Cyclohexanes 1244.9 Conformations of Polycyclic Molecules 128

Focus On . . . Molecular Mechanics 130Summary and Key Words 131 � Visualizing Chemistry 132Additional Problems 133

5 An Overview of Organic Reactions 1375.1 Kinds of Organic Reactions 1375.2 How Organic Reactions Occur: Mechanisms 1395.3 Radical Reactions 1405.4 Polar Reactions 1425.5 An Example of a Polar Reaction: Addition of HBr to Ethylene 1475.6 Using Curved Arrows in Polar Reaction Mechanisms 1495.7 Describing a Reaction: Equilibria, Rates, and Energy

Changes 1525.8 Describing a Reaction: Bond Dissociation Energies 1555.9 Describing a Reaction: Energy Diagrams and Transition

States 157

Contents v

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vi Contents

5.10 Describing a Reaction: Intermediates 1605.11 A Comparison between Biological Reactions and Laboratory

Reactions 162

Focus On . . . Where Do Drugs Come From? 164Summary and Key Words 165 � Visualizing Chemistry 166Additional Problems 168

6 Alkenes: Structure and Reactivity 1726.1 Industrial Preparation and Use of Alkenes 1736.2 Calculating Degree of Unsaturation 1746.3 Naming Alkenes 1766.4 Cis–Trans Isomerism in Alkenes 1786.5 Sequence Rules: the E,Z Designation 1806.6 Stability of Alkenes 1856.7 Electrophilic Addition Reactions of Alkenes 1886.8 Orientation of Electrophilic Additions: Markovnikov’s Rule 1916.9 Carbocation Structure and Stability 1956.10 The Hammond Postulate 1976.11 Evidence for the Mechanism of Electrophilic Additions:

Carbocation Rearrangements 200

Focus On . . . Terpenes: Naturally Occurring Alkenes 202Summary and Key Words 204 � Visualizing Chemistry 205Additional Problems 206

7 Alkenes: Reactions and Synthesis 2137.1 Preparation of Alkenes: A Preview of Elimination Reactions 2147.2 Addition of Halogens to Alkenes 2157.3 Addition of Hypohalous Acids to Alkenes: Halohydrin

Formation 2187.4 Addition of Water to Alkenes: Oxymercuration 2207.5 Addition of Water to Alkenes: Hydroboration 2237.6 Addition of Carbenes to Alkenes: Cyclopropane Synthesis 2277.7 Reduction of Alkenes: Hydrogenation 2297.8 Oxidation of Alkenes: Epoxidation and Hydroxylation 2337.9 Oxidation of Alkenes: Cleavage to Carbonyl Compounds 2367.10 Radical Additions to Alkenes: Polymers 2397.11 Biological Additions of Radicals to Alkenes 243

Focus On . . . Natural Rubber 245Summary and Key Words 246 � Summary of Reactions 247Visualizing Chemistry 250 � Additional Problems 251

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Contents vii

8 Alkynes: An Introduction to Organic Synthesis 2598.1 Naming Alkynes 2598.2 Preparation of Alkynes: Elimination Reactions of Dihalides 2618.3 Reactions of Alkynes: Addition of HX and X2 2618.4 Hydration of Alkynes 2648.5 Reduction of Alkynes 2688.6 Oxidative Cleavage of Alkynes 2708.7 Alkyne Acidity: Formation of Acetylide Anions 2708.8 Alkylation of Acetylide Anions 2728.9 An Introduction to Organic Synthesis 274

Focus On . . . The Art of Organic Synthesis 278Summary and Key Words 279 � Summary of Reactions 280Visualizing Chemistry 282 � Additional Problems 283

9 Stereochemistry 2899.1 Enantiomers and the Tetrahedral Carbon 2909.2 The Reason for Handedness in Molecules: Chirality 2919.3 Optical Activity 2949.4 Pasteur’s Discovery of Enantiomers 2969.5 Sequence Rules for Specifying Configuration 2979.6 Diastereomers 3029.7 Meso Compounds 3059.8 Racemic Mixtures and the Resolution of Enantiomers 3079.9 A Review of Isomerism 3099.10 Stereochemistry of Reactions: Addition of H2O to an Achiral

Alkene 3119.11 Stereochemistry of Reactions: Addition of H2O to a Chiral

Alkene 3129.12 Chirality at Nitrogen, Phosphorus, and Sulfur 3149.13 Prochirality 3159.14 Chirality in Nature and Chiral Environments 318

Focus On . . . Chiral Drugs 320Summary and Key Words 322 � Visualizing Chemistry 323Additional Problems 324

10 Organohalides 33210.1 Naming Alkyl Halides 33310.2 Structure of Alkyl Halides 33410.3 Preparing Alkyl Halides from Alkanes: Radical Halogenation 335

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10.4 Preparing Alkyl Halides from Alkenes: Allylic Bromination 33910.5 Stability of the Allyl Radical: Resonance Revisited 34110.6 Preparing Alkyl Halides from Alcohols 34410.7 Reactions of Alkyl Halides: Grignard Reagents 34510.8 Organometallic Coupling Reactions 34610.9 Oxidation and Reduction in Organic Chemistry 348

Focus On . . . Naturally Occurring Organohalides 351Summary and Key Words 352 � Summary of Reactions 353Visualizing Chemistry 354 � Additional Problems 355

11 Reactions of Alkyl Halides: Nucleophilic Substitutionsand Eliminations 35911.1 The Discovery of Nucleophilic Substitution Reactions 35911.2 The SN2 Reaction 36211.3 Characteristics of the SN2 Reaction 36511.4 The SN1 Reaction 37211.5 Characteristics of the SN1 Reaction 37611.6 Biological Substitution Reactions 38111.7 Elimination Reactions of Alkyl Halides: Zaitsev’s Rule 38311.8 The E2 Reaction and the Deuterium Isotope Effect 38611.9 The E2 Reaction and Cyclohexane Conformation 38911.10 The E1 and E1cB Reactions 39111.11 Biological Elimination Reactions 39311.12 A Summary of Reactivity: SN1, SN2, E1, E1cB, and E2 393

Focus On . . . Green Chemistry 395Summary and Key Words 397 � Summary of Reactions 398Visualizing Chemistry 399 � Additional Problems 400

12 Structure Determination: Mass Spectrometry and InfraredSpectroscopy 40812.1 Mass Spectrometry of Small Molecules: Magnetic-Sector

Instruments 40912.2 Interpreting Mass Spectra 41112.3 Mass Spectrometry of Some Common Functional Groups 41512.4 Mass Spectrometry in Biological Chemistry: Time-of-Flight (TOF)

Instruments 41712.5 Spectroscopy and the Electromagnetic Spectrum 41812.6 Infrared Spectroscopy 42212.7 Interpreting Infrared Spectra 42312.8 Infrared Spectra of Some Common Functional Groups 426

viii Contents

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Contents ix

Focus On . . . Chromatography: Purifying Organic Compounds 431Summary and Key Words 433 � Visualizing Chemistry 434Additional Problems 434

13 Structure Determination: Nuclear Magnetic ResonanceSpectroscopy 44013.1 Nuclear Magnetic Resonance Spectroscopy 44013.2 The Nature of NMR Absorptions 44213.3 Chemical Shifts 44513.4 13C NMR Spectroscopy: Signal Averaging and FT–NMR 44613.5 Characteristics of 13C NMR Spectroscopy 44813.6 DEPT 13C NMR Spectroscopy 45113.7 Uses of 13C NMR Spectroscopy 45313.8 1H NMR Spectroscopy and Proton Equivalence 45413.9 Chemical Shifts in 1H NMR Spectroscopy 45713.10 Integration of 1H NMR Absorptions: Proton Counting 45913.11 Spin–Spin Splitting in 1H NMR Spectra 46013.12 More Complex Spin–Spin Splitting Patterns 46513.13 Uses of 1H NMR Spectroscopy 467

Focus On . . . Magnetic Resonance Imaging (MRI) 468Summary and Key Words 469 � Visualizing Chemistry 470Additional Problems 471

14 Conjugated Compounds and Ultraviolet Spectroscopy 48214.1 Stability of Conjugated Dienes: Molecular Orbital Theory 48314.2 Electrophilic Additions to Conjugated Dienes: Allylic

Carbocations 48714.3 Kinetic versus Thermodynamic Control of Reactions 49014.4 The Diels–Alder Cycloaddition Reaction 49214.5 Characteristics of the Diels–Alder Reaction 49314.6 Diene Polymers: Natural and Synthetic Rubbers 49814.7 Structure Determination in Conjugated Systems: Ultraviolet

Spectroscopy 50014.8 Interpreting Ultraviolet Spectra: The Effect of Conjugation 50214.9 Conjugation, Color, and the Chemistry of Vision 503

Focus On . . . Photolithography 505Summary and Key Words 507 � Summary of Reactions 507Visualizing Chemistry 508 � Additional Problems 509

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15 Benzene and Aromaticity 51615.1 Sources and Names of Aromatic Compounds 51715.2 Structure and Stability of Benzene: Molecular Orbital Theory 52015.3 Aromaticity and the Hückel 4n � 2 Rule 52315.4 Aromatic Ions 52515.5 Aromatic Heterocycles: Pyridine and Pyrrole 52815.6 Why 4n � 2? 53015.7 Polycyclic Aromatic Compounds 53115.8 Spectroscopy of Aromatic Compounds 534

Focus On . . . Aspirin, NSAIDs, and COX-2 Inhibitors 537Summary and Key Words 538 � Visualizing Chemistry 539Additional Problems 541

16 Chemistry of Benzene: Electrophilic Aromatic Substitution 54716.1 Electrophilic Aromatic Substitution Reactions: Bromination 54816.2 Other Aromatic Substitutions 55016.3 Alkylation and Acylation of Aromatic Rings: The Friedel–Crafts

Reaction 55416.4 Substituent Effects in Substituted Aromatic Rings 56016.5 An Explanation of Substituent Effects 56416.6 Trisubstituted Benzenes: Additivity of Effects 57016.7 Nucleophilic Aromatic Substitution 57216.8 Benzyne 57516.9 Oxidation of Aromatic Compounds 57616.10 Reduction of Aromatic Compounds 57916.11 Synthesis of Trisubstituted Benzenes 581

Focus On . . . Combinatorial Chemistry 585Summary and Key Words 587 � Summary of Reactions 588Visualizing Chemistry 590 � Additional Problems 591

17 Alcohols and Phenols 59917.1 Naming Alcohols and Phenols 60017.2 Properties of Alcohols and Phenols 60217.3 Preparation of Alcohols: A Review 60717.4 Alcohols from Reduction of Carbonyl Compounds 60917.5 Alcohols from Reaction of Carbonyl Compounds with Grignard

Reagents 61317.6 Reactions of Alcohols 61717.7 Oxidation of Alcohols 62317.8 Protection of Alcohols 62617.9 Phenols and Their Uses 628

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17.10 Reactions of Phenols 63117.11 Spectroscopy of Alcohols and Phenols 632

Focus On . . . Ethanol: Chemical, Drug, and Poison 636Summary and Key Words 637 � Summary of Reactions 638Visualizing Chemistry 640 � Additional Problems 642

18 Ethers and Epoxides; Thiols and Sulfides 65218.1 Names and Properties of Ethers 65318.2 Synthesis of Ethers 65418.3 Reactions of Ethers: Acidic Cleavage 65718.4 Reactions of Ethers: Claisen Rearrangement 65918.5 Cyclic Ethers: Epoxides 66018.6 Reactions of Epoxides: Ring-Opening 66218.7 Crown Ethers 66618.8 Thiols and Sulfides 66718.9 Spectroscopy of Ethers 671

Focus On . . . Epoxy Resins and Adhesives 673Summary and Key Words 674 � Summary of Reactions 675Visualizing Chemistry 676 � Additional Problems 677

A Preview of Carbonyl Compounds 686I Kinds of Carbonyl Compounds 686II Nature of the Carbonyl Group 688III General Reactions of Carbonyl Compounds 688IV Summary 694

19 Aldehydes and Ketones: Nucleophilic Addition Reactions 69519.1 Naming Aldehydes and Ketones 69619.2 Preparation of Aldehydes and Ketones 69819.3 Oxidation of Aldehydes and Ketones 70019.4 Nucleophilic Addition Reactions of Aldehydes and Ketones 70219.5 Nucleophilic Addition of H2O: Hydration 70519.6 Nucleophilic Addition of HCN: Cyanohydrin Formation 70719.7 Nucleophilic Addition of Grignard and Hydride Reagents:

Alcohol Formation 70819.8 Nucleophilic Addition of Amines: Imine and Enamine

Formation 71019.9 Nucleophilic Addition of Hydrazine: The Wolff–Kishner

Reaction 71519.10 Nucleophilic Addition of Alcohols: Acetal Formation 717

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19.11 Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction 720

19.12 Biological Reductions 72319.13 Conjugate Nucleophilic Addition to �,�-Unsaturated Aldehydes

and Ketones 72519.14 Spectroscopy of Aldehydes and Ketones 730

Focus On . . . Enantioselective Synthesis 734Summary and Key Words 736 � Summary of Reactions 736Visualizing Chemistry 739 � Additional Problems 740

20 Carboxylic Acids and Nitriles 75120.1 Naming Carboxylic Acids and Nitriles 75220.2 Structure and Properties of Carboxylic Acids 75420.3 Biological Acids and the Henderson–Hasselbalch Equation 75820.4 Substituent Effects on Acidity 75920.5 Preparation of Carboxylic Acids 76220.6 Reactions of Carboxylic Acids: An Overview 76420.7 Chemistry of Nitriles 76520.8 Spectroscopy of Carboxylic Acids and Nitriles 770

Focus On . . . Vitamin C 772Summary and Key Words 774 � Summary of Reactions 775Visualizing Chemistry 776 � Additional Problems 777

21 Carboxylic Acid Derivatives: Nucleophilic AcylSubstitution Reactions 78521.1 Naming Carboxylic Acid Derivatives 78621.2 Nucleophilic Acyl Substitution Reactions 78921.3 Nucleophilic Acyl Substitution Reactions of Carboxylic Acids 79421.4 Chemistry of Acid Halides 80021.5 Chemistry of Acid Anhydrides 80621.6 Chemistry of Esters 80821.7 Chemistry of Amides 81321.8 Chemistry of Thioesters and Acyl Phosphates: Biological

Carboxylic Acid Derivatives 81621.9 Polyamides and Polyesters: Step-Growth Polymers 81821.10 Spectroscopy of Carboxylic Acid Derivatives 822

Focus On . . . �-Lactam Antibiotics 824Summary and Key Words 825 � Summary of Reactions 826Visualizing Chemistry 829 � Additional Problems 830

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22 Carbonyl Alpha-Substitution Reactions 84122.1 Keto–Enol Tautomerism 84222.2 Reactivity of Enols: The Mechanism of Alpha-Substitution

Reactions 84522.3 Alpha Halogenation of Aldehydes and Ketones 84622.4 Alpha Bromination of Carboxylic Acids: The

Hell–Volhard–Zelinskii Reaction 84922.5 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 84922.6 Reactivity of Enolate Ions 85322.7 Alkylation of Enolate Ions 855

Focus On . . . X-Ray Crystallography 864Summary and Key Words 865 � Summary of Reactions 866Visualizing Chemistry 868 � Additional Problems 869

23 Carbonyl Condensation Reactions 87723.1 Carbonyl Condensations: The Aldol Reaction 87723.2 Carbonyl Condensations versus Alpha Substitutions 88023.3 Dehydration of Aldol Products: Synthesis of Enones 88223.4 Using Aldol Reactions in Synthesis 88423.5 Mixed Aldol Reactions 88523.6 Intramolecular Aldol Reactions 88623.7 The Claisen Condensation Reaction 88823.8 Mixed Claisen Condensations 89023.9 Intramolecular Claisen Condensations: The Dieckmann

Cyclization 89223.10 Conjugate Carbonyl Additions: The Michael Reaction 89423.11 Carbonyl Condensations with Enamines: The Stork Reaction 89623.12 The Robinson Annulation Reaction 89923.13 Some Biological Carbonyl Condensation Reactions 901

Focus On . . . A Prologue to Metabolism 903Summary and Key Words 904 � Summary of Reactions 905Visualizing Chemistry 907 � Additional Problems 908

24 Amines and Heterocycles 91624.1 Naming Amines 91624.2 Properties of Amines 91924.3 Basicity of Amines 92124.4 Basicity of Substituted Arylamines 924

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24.5 Biological Amines and the Henderson–Hasselbalch Equation 92524.6 Synthesis of Amines 92724.7 Reactions of Amines 93624.8 Reactions of Arylamines 93924.9 Heterocycles 94524.10 Spectroscopy of Amines 952

Focus On . . . Green Chemistry II: Ionic Liquids 956Summary and Key Words 958 � Summary of Reactions 959Visualizing Chemistry 961 � Additional Problems 963

25 Biomolecules: Carbohydrates 97325.1 Classification of Carbohydrates 97425.2 Depicting Carbohydrate Stereochemistry: Fischer

Projections 97525.3 D,L Sugars 98025.4 Configurations of the Aldoses 98125.5 Cyclic Structures of Monosaccharides: Anomers 98425.6 Reactions of Monosaccharides 98725.7 The Eight Essential Monosaccharides 99625.8 Disaccharides 99725.9 Polysaccharides and Their Synthesis 100025.10 Some Other Important Carbohydrates 100225.11 Cell-Surface Carbohydrates and Carbohydrate Vaccines 1003

Focus On . . . Sweetness 1005Summary and Key Words 1006 � Summary of Reactions 1007Visualizing Chemistry 1008 � Additional Problems 1009

26 Biomolecules: Amino Acids, Peptides, and Proteins 101626.1 Structures of Amino Acids 101726.2 Amino Acids, the Henderson–Hasselbalch Equation, and

Isoelectric Points 102226.3 Synthesis of Amino Acids 102526.4 Peptides and Proteins 102726.5 Amino Acid Analysis of Peptides 103026.6 Peptide Sequencing: The Edman Degradation 103126.7 Peptide Synthesis 103326.8 Automated Peptide Synthesis: The Merrifield Solid-Phase

Method 103626.9 Protein Structure 103826.10 Enzymes and Coenzymes 104026.11 How Do Enzymes Work? Citrate Synthase 1043

Focus On . . . The Protein Data Bank 1048Summary and Key Words 1049 � Summary of Reactions 1050Visualizing Chemistry 1052 � Additional Problems 1053

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27 Biomolecules: Lipids 106027.1 Waxes, Fats, and Oils 106127.2 Soap 106427.3 Phospholipids 106627.4 Prostaglandins and Other Eicosanoids 106727.5 Terpenoids 107027.6 Steroids 107927.7 Biosynthesis of Steroids 1084

Focus On . . . Saturated Fats, Cholesterol, and Heart Disease 1090Summary and Key Words 1091 � Visualizing Chemistry 1092Additional Problems 1093

28 Biomolecules: Nucleic Acids 110028.1 Nucleotides and Nucleic Acids 110028.2 Base Pairing in DNA: The Watson–Crick Model 110328.3 Replication of DNA 110628.4 Transcription of DNA 110728.5 Translation of RNA: Protein Biosynthesis 110928.6 DNA Sequencing 111228.7 DNA Synthesis 111428.8 The Polymerase Chain Reaction 1117

Focus On . . . DNA Fingerprinting 1118Summary and Key Words 1119 � Visualizing Chemistry 1120Additional Problems 1121

29 The Organic Chemistry of Metabolic Pathways 112529.1 An Overview of Metabolism and Biochemical Energy 112629.2 Catabolism of Triacylglycerols: The Fate of Glycerol 113029.3 Catabolism of Triacylglycerols: �-Oxidation 113329.4 Biosynthesis of Fatty Acids 113829.5 Catabolism of Carbohydrates: Glycolysis 114329.6 Conversion of Pyruvate to Acetyl CoA 115029.7 The Citric Acid Cycle 115429.8 Carbohydrate Biosynthesis: Gluconeogenesis 115929.9 Catabolism of Proteins: Transamination 116529.10 Some Conclusions about Biological Chemistry 1169

Focus On . . . Basal Metabolism 1169Summary and Key Words 1170 � Visualizing Chemistry 1171Additional Problems 1172

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30 Orbitals and Organic Chemistry: Pericyclic Reactions 117830.1 Molecular Orbitals and Pericyclic Reactions of Conjugated

Pi Systems 117830.2 Electrocyclic Reactions 118130.3 Stereochemistry of Thermal Electrocyclic Reactions 118330.4 Photochemical Electrocyclic Reactions 118530.5 Cycloaddition Reactions 118630.6 Stereochemistry of Cycloadditions 118830.7 Sigmatropic Rearrangements 119130.8 Some Examples of Sigmatropic Rearrangements 119230.9 A Summary of Rules for Pericyclic Reactions 1196

Focus On . . . Vitamin D, the Sunshine Vitamin 1197Summary and Key Words 1198 � Visualizing Chemistry 1199Additional Problems 1200

31 Synthetic Polymers 120631.1 Chain-Growth Polymers 120731.2 Stereochemistry of Polymerization: Ziegler–Natta Catalysts 120931.3 Copolymers 121031.4 Step-Growth Polymers 121231.5 Polymer Structure and Physical Properties 1215

Focus On . . . Biodegradable Polymers 1218Summary and Key Words 1220 � Visualizing Chemistry 1221Additional Problems 1221

Appendix A Nomenclature of Polyfunctional Organic Compounds A-1

Appendix B Acidity Constants for Some Organic Compounds A-8

Appendix C Glossary A-10

Appendix D Answers to In-Text Problems A-30

Index I-1

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I love to write. I get real pleasure from taking a complicated subject, turning itaround until I see it clearly, and then explaining it in simple words. I write toexplain chemistry to students today the way I wish it had been explained to meyears ago.

The enthusiastic response to the six previous editions has been very gratify-ing and suggests that this book has served students well. I hope you will findthat this seventh edition of Organic Chemistry builds on the strengths of the firstsix and serves students even better. I have made every effort to make this newedition as effective, clear, and readable as possible; to show the beauty and logicof organic chemistry; and to make organic chemistry enjoyable to learn.

Organization and Teaching Strategies This seventh edition, like its predeces-sors, blends the traditional functional-group approach with a mechanisticapproach. The primary organization is by functional group, beginning with thesimple (alkenes) and progressing to the more complex. Most faculty will agreethat students new to the subject and not yet versed in the subtleties of mecha-nism do better this way. In other words, the what of chemistry is generally eas-ier to grasp than the why. Within this primary organization, however, I placeheavy emphasis on explaining the fundamental mechanistic similarities of reac-tions. This emphasis is particularly evident in the chapters on carbonyl-groupchemistry (Chapters 19–23), where mechanistically related reactions like thealdol and Claisen condensations are covered together. By the time studentsreach this material, they have seen all the common mechanisms and the valueof mechanisms as an organizing principle has become more evident.

The Lead-Off Reaction: Addition of HBr to Alkenes Students usually attach greatimportance to a text’s lead-off reaction because it is the first reaction they see andis discussed in such detail. I use the addition of HBr to an alkene as the lead-off toillustrate general principles of organic chemistry for several reasons: the reactionis relatively straightforward; it involves a common but important functionalgroup; no prior knowledge of stereochemistry or kinetics in needed to understandit; and, most important, it is a polar reaction. As such, I believe that electrophilicaddition reactions represent a much more useful and realistic introduction tofunctional-group chemistry than a lead-off such as radical alkane chlorination.

Reaction Mechanisms In the first edition of this book, I introduced an innova-tive format for explaining reaction mechanisms in which the reaction steps areprinted vertically, with the changes taking place in each step described next tothe reaction arrow. This format allows a reader to see easily what is occurring ateach step without having to flip back and forth between structures and text.Each successive edition has seen an increase in the number and quality of thesevertical mechanisms, which are still as fresh and useful as ever.

xvii

Preface


xviii Preface

Organic Synthesis Organic synthesis is treated in this text as a teaching device tohelp students organize and deal with a large body of factual information—thesame skill so critical in medicine. Two sections, the first in Chapter 8 (Alkynes) andthe second in Chapter 16 (Chemistry of Benzene), explain the thought processesinvolved in working synthesis problems and emphasize the value of starting fromwhat is known and logically working backward. In addition, Focus On boxes,including The Art of Organic Synthesis, Combinatorial Chemistry, and Enantiose-lective Synthesis, further underscore the importance and timeliness of synthesis.

Modular Presentation Topics are arranged in a roughly modular way. Thus, cer-tain chapters are grouped together: simple hydrocarbons (Chapters 3–8), spec-troscopy (Chapters 12–14), carbonyl-group chemistry (Chapters 19–23), andbiomolecules (Chapters 25–29). I believe that this organization brings to thesesubjects a cohesiveness not found in other texts and allows the instructor theflexibility to teach in an order different from that presented in the book.

Basic Learning Aids In writing and revising this text, I consistently aim forlucid explanations and smooth transitions between paragraphs and betweentopics. New concepts are introduced only when they are needed, not before, and they are immediately illustrated with concrete examples. Frequent cross-references to earlier material are given, and numerous summaries are providedto draw information together, both within and at the ends of chapters. In addi-tion, the back of this book contains a wealth of material helpful for learningorganic chemistry, including a large glossary, an explanation of how to namepolyfunctional organic compounds, and answers to all in-text problems. For stillfurther aid, an accompanying Study Guide and Solutions Manual gives summariesof name reactions, methods for preparing functional groups, functional-groupreactions, and the uses of important reagents.

Changes and Additions for the Seventh EditionThe primary reason for preparing a new edition is to keep the book up to date,both in its scientific coverage and in its pedagogy. My overall aim is always torefine the features that made earlier editions so successful, while adding new ones.

� The writing has again been revised at the sentence level, streamlining thepresentation, improving explanations, and updating a thousand small details.Several little-used reactions have been deleted (the alkali fusion of arene-sulfonic acids to give phenols, for instance), and a few new ones have beenadded (the Sharpless enantioselective epoxidation of alkenes, for instance).

� Other notable content changes are:

Chapter 2, Polar Covalent Bonds; Acids and Bases—A new Section 2.13 on non-covalent interactions has been added.

Chapter 3, Organic Compounds: Alkanes and Their Stereochemistry—The chap-ter has been revised to focus exclusively on open-chain alkanes.

Chapter 4, Organic Compounds: Cycloalkanes and Their Stereochemistry—Thechapter has been revised to focus exclusively on cycloalkanes.

Chapter 5, An Overview of Organic Reactions—A new Section 5.11 comparingbiological reactions and laboratory reactions has been added.


Preface xix

Chapter 7, Alkenes: Reactions and Synthesis—Alkene epoxidation has beenmoved to Section 7.8, and Section 7.11 on the biological addition of radicalsto alkenes has been substantially expanded.

Chapter 9, Stereochemistry—A discussion of chirality at phosphorus and sulfurhas been added to Section 9.12, and a discussion of chiral environments hasbeen added to Section 9.14.

Chapter 11, Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations—A discussion of the E1cB reaction has been added to Section 11.10,and a new Section 11.11 discusses biological elimination reactions.

Chapter 12, Structure Determination: Mass Spectrometry and Infrared Spectroscopy—A new Section 12.4 discusses mass spectrometry of biologicalmolecules, focusing on time-of-flight instruments and soft ionization meth-ods such as MALDI.

Chapter 20, Carboxylic Acids and Nitriles—A new Section 20.3 discusses bio-logical carboxylic acids and the Henderson–Hasselbalch equation.

Chapter 24, Amines and Heterocycles—This chapter now includes a discussionof heterocycles, and a new Section 24.5 on biological amines and the Hen-derson–Hasselbalch equation has been added.

Chapter 25, Biomolecules: Carbohydrates—A new Section 25.7 on the eightessential carbohydrates has been added, and numerous content revisions havebeen made.

Chapter 26, Biomolecules: Amino Acids, Peptides, and Proteins—The chapter hasbeen updated, particularly in its coverage of solid-phase peptide synthesis.

Chapter 27, Biomolecules: Lipids—The chapter has been extensively revised,with increased detail on prostaglandins (Section 27.4), terpenoid biosynthesis(Section 27.5), and steroid biosynthesis, (Section 27.7).

Chapter 28, Biomolecules: Nucleic Acids—Coverage of heterocyclic chemistryhas been moved to Chapter 24.

Chapter 29, The Organic Chemistry of Metabolic Pathways—The chapter hasbeen reorganized and extensively revised, with substantially increased detailon important metabolic pathways.

Chapter 30, Orbitals and Organic Chemistry: Pericyclic Reactions—All the art inthis chapter has been redone.

� The order of topics remains basically the same but has been changed todevote Chapter 3 entirely to alkanes and Chapter 4 to cycloalkanes. In addi-tion, epoxides are now introduced in Chapter 7 on alkenes, and coverage ofheterocyclic chemistry has been moved to Chapter 24.

� The problems within and at the end of each chapter have been reviewed, andapproximately 100 new problems have been added, many of which focus onbiological chemistry.

� Focus On boxes at the end of each chapter present interesting applications oforganic chemistry relevant to the main chapter subject. Including topics frombiology, industry, and day-to-day life, these applications enliven and reinforcethe material presented within the chapter. The boxes have been updated, and new ones added, including Where Do Drugs Come From? (Chapter 5),


xx Preface

Green Chemistry (Chapter 11), X-Ray Crystallography (Chapter 22), and GreenChemistry II: Ionic Liquids (Chapter 24).

� Biologically important molecules and mechanisms have received particu-lar attention in this edition. Many reactions now show biological counterpartsto laboratory examples, many new problems illustrate reactions and mecha-nisms that occur in living organisms, and enhanced detail is given for majormetabolic pathways.

More Features

NEW! � Why do we have to learn this? I’ve been asked this question so many times bystudents that I thought that it would be appropriate to begin each chapterwith the answer. The Why This Chapter? section is a short paragraph thatappears at the end of the introduction to every chapter and tells students whythe material about to be covered is important.

NEW! � Thirteen Key Ideas are highlighted in the book. These include topics pivotal tostudents’ development in organic chemistry, such as Curved Arrows in Reac-tion Mechanisms (Chapter 5) and Markovnikov’s Rule (Chapter 6). These KeyIdeas are further reinforced in end-of-chapter problems marked with a � icon.A selection of these problems are also assignable in OWL, denoted by a �.

� Worked Examples are now titled to give students a frame of reference. Each Worked Example includes a Strategy and a worked-out Solution, andthen is followed by problems for students to try on their own. This book hasmore than 1800 in-text and end-of-chapter problems.

� An overview chapter, A Preview of Carbonyl Chemistry, follows Chapter 18 andhighlights the author’s belief that studying organic chemistry requires bothsummarizing and looking ahead.

NEW! � Thorough media integration with Organic Knowledge Tools: ThomsonNOWfor Organic Chemistry and Organic OWL are provided to help students prac-tice and test their knowledge of the concepts. ThomsonNOW is an onlineassessment program for self-study with interactive tutorials. Organic OWL isan online homework learning system. Icons throughout the book direct stu-dents to ThomsonNOW at www.thomsonedu.com. A fee-based access code isrequired for Organic OWL.

NEW! � About 15 to 20 end-of-chapter problems per chapter, denoted with a � icon,are assignable in the OWL online homework system. These questions are algo-rithmically generated, allowing students more practice.

� OWL (Online Web-based Learning) for Organic Chemistry, developed at theUniversity of Massachusetts, Amherst; class-tested by thousands of students;and used by more than 50,000 students, provides fully class-tested questionsand tutors in an easy-to-use format. OWL is also customizable and cross-platform. The OWL Online Web-based Learning system provides studentswith instant grading and feedback on homework problems, modeling questions, and animations to accompany this text. With parameterization,OWL for Organic Chemistry offers nearly 6000 different questions as well asMarvinSketch for viewing and drawing chemical structures.



Preface xxi

� A number of the figures are animated in ThomsonNOW. These are designatedas Active Figures in the figure legends.

� The Visualizing Chemistry Problems that begin the exercises at the end of eachchapter offer students an opportunity to see chemistry in a different way byvisualizing molecules rather than by simply interpreting structural formulas.

� Summaries and Key Word lists help students by outlining the key concepts ofthe chapter.

� Summaries of Reactions, at the ends of appropriate chapters, bring togetherthe key reactions from the chapter in one complete list.

Companions to This TextSupporting instructor materials are available to qualified adopters. Please con-sult your local Thomson Brooks/Cole representative for details.

Visit www.thomsonedu.com to:

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Ancillaries for StudentsStudy Guide and Solutions Manual, by Susan McMurry, provides answers andexplanations to all in-text and end-of-chapter exercises. (0-495-11268-2)

ThomsonNOW Website To further student understanding, the text features sen-sible media integration through ThomsonNOW, a powerful online learningcompanion that helps students determine their unique study needs and providesthem with individualized resources. This dynamic learning companion com-bines with the text to provide students with a seamless, integrated learning sys-tem. The access code that is required for ThomsonNOW may be included with anew copy of the text or purchased separately. Visit www.thomsonedu.com toregister for access (or to purchase access) to ThomsonNOW.

OWL for Organic Chemistry, authored by Steve Hixson and Peter Lillya of theUniversity of Massachusetts, Amherst, and William Vining of the State Univer-sity of New York at Oneonta. Class-tested by thousands of students and used bymore than 50,000 students, OWL (Online Web-based Learning) provides fullyclass-tested content in an easy-to-use format. OWL is also customizable andcross-platform. The OWL Online Web-based Learning system provides studentswith instant analysis and feedback on homework problems, modeling ques-tions, and animations to accompany this text. With parameterization, OWL forOrganic Chemistry offers more than 6000 questions as well as MarvinSketch, aJava applet for viewing and drawing chemical structures.

This powerful system maximizes the students’ learning experience and, atthe same time, reduces faculty workload and helps facilitate instruction. OWLalso uses the MDL Chime application to assist students with viewing structuresof organic compounds. New to this edition are 15 to 20 end-of-chapter problemsper chapter, denoted by a � icon, which are assignable in OWL. A fee-basedaccess code is required for OWL.


xxii Preface

Pushing Electrons: A Guide for Students of Organic Chemistry, third edition, byDaniel P. Weeks. A workbook designed to help students learn techniques ofelectron pushing, its programmed approach emphasizes repetition and activeparticipation. (0-03-020693-6)

NEW! Spartan Model Electronic Modeling Kit, A set of easy-to-use builders allow for theconstruction and 3-D manipulation of molecules of any size or complexity—from a hydrogen atom to DNA and everything in between. This kit includes theSpartanModel software on CD-ROM, an extensive molecular database, 3-Dglasses, and a Tutorial and Users Guide that includes a wealth of activities to helpyou get the most out of your course. (0-495-01793-0)

Ancillaries for InstructorsPowerLecture A dual-platform digital library and presentation tool that pro-vides art and tables from the main text in a variety of electronic formats that areeasily exported into other software packages. Also contains simulations, molec-ular models, and QuickTime movies to supplement lectures as well as electronicfiles of various print supplements. Slides use the full power of Microsoft Power-Point® and incorporate videos, animations, and other media assets from Thom-sonNOW. Instructors can customize their lecture presentations by adding theirown slides or by deleting or changing existing slides (0-495-11265-8). Power-Lecture also includes:

� ExamView Testing This easy-to-use software, containing questions andproblems authored specifically for the text, allows professors to create, deliver,and customize tests in minutes.

� JoinIn on Turning Point for Organic Chemistry Book-specific JoinIn™content for Response Systems tailored to Organic Chemistry allows you totransform your classroom and assess your students’ progress with instant in-class quizzes and polls. Our exclusive agreement to offer TurningPoint soft-ware lets you pose book-specific questions and display students’ answersseamlessly within the Microsoft PowerPoint slides of your own lecture, in con-junction with the “clicker” hardware of your choice. Enhance how your stu-dents interact with you, your lecture, and one another. Contact your localThomson representative to learn more.

WebCT/NOW Integration Instructors and students enter ThomsonNOWthrough their familiar Blackboard or WebCT environment without the need fora separate user name or password and can access all of the ThomsonNOWassessments and content. Contact your local Thomson representative to learnmore.

Transparency Acetates Approximately 200 full-color transparency acetatesof key text illustrations, enlarged for use in the classroom and lecture halls.(0-495-11260-7)

Organic Chemistry Laboratory Manuals Brooks/Cole is pleased to offer a choice of organic chemistry laboratory manuals catered to fit individual needs.Visit www.thomsonedu.com. Customizable laboratory manuals also can beassembled—contact your Thomson representative to learn more.


Preface xxiii

AcknowledgmentsI thank all the people who helped to shape this book and its message. AtBrooks/Cole they include: David Harris, publisher; Sandra Kiselica, seniordevelopment editor; Amee Mosley executive marketing manager; Teresa Trego,project manager; Lisa Weber; technology project manager; and Sylvia Krick,assistant editor, along with Suzanne Kastner and Gwen Gilbert at GraphicWorld.

I am grateful to colleagues who reviewed the manuscript for this book andparticipated in a survey about its approach. They include:

Manuscript ReviewersArthur W. Bull, Oakland UniversityRobert Coleman, Ohio State UniversityNicholas Drapela, Oregon State UniversityChristopher Hadad, Ohio State UniversityEric J. Kantorowski, California Polytechnic State UniversityJames J. Kiddle, Western Michigan UniversityJoseph B. Lambert, Northwestern UniversityDominic McGrath, University of ArizonaThomas A. Newton, University of Southern MaineMichael Rathke, Michigan State UniversityLaren M. Tolbert, Georgia Institute of Technology

Reviewers of Previous EditionsWayne Ayers, East Carolina UniversityKevin Belfield, University of Central

Florida-OrlandoByron Bennett, University of Las VegasRobert A. Benkeser, Purdue UniversityDonald E. Bergstrom Purdue UniversityChristine Bilicki, Pasedena City CollegeWeston J. Borden, University of North

TexasSteven Branz, San Jose State UniversityLarry Bray, Miami-Dade Community

CollegeJames Canary, New York UniversityRonald Caple, University of Minnesota-

DuluthJohn Cawley, Villanova UniversityGeorge Clemans, Bowling Green State

UniversityBob Coleman, Ohio State UniversityPaul L. Cook, Albion CollegeDouglas Dyckes, University of

Colorado-DenverKenneth S. Feldman, Pennsylvania

State UniversityMartin Feldman, Howard University

Kent Gates, University of Missouri-Columbia

Warren Gierring, Boston UniversityDaniel Gregory, St. Cloud State

UniversityDavid Hart, Ohio State UniversityDavid Harpp, McGill UniversityNorbert Hepfinger, Rensselaer

Polytechnic InstituteWerner Herz, Florida State UniversityJohn Hogg, Texas A&M UniversityPaul Hopkins, University of

WashingtonJohn Huffman, Clemson UniversityJack Kampmeier, University of RochesterThomas Katz, Columbia UniversityGlen Kauffman, Eastern Mennonite

CollegeAndrew S. Kendle, University of North

Carolina- WilmingtonPaul E. Klinedinst, Jr., California State

University- NorthridgeJoseph Lamber, Northwestern

UniversityJohn T. Landrum, Florida International

University


xxiv Preface

Peter Lillya, University ofMassachusetts

Thomas Livinghouse, Montana StateUniversity

James Long, University of OregonTodd Lowary, University of AlbertaLuis Martinez, University of Texas, El

PasoEugene A. Mash, University of ArizonaFred Matthews, Austin Peay State

UniversityGuy Matson, University of Central

FloridaKeith Mead, Mississippi State

UniversityMichael Montague-Smith, University of

MarylandAndrew Morehead, East Carolina

UniversityHarry Morrison, Purdue UniversityCary Morrow, University of New

MexicoClarence Murphy, East Stroudsburg

UniversityRoger Murray, St. Joseph’s UniversityOliver Muscio, Murray State UniversityEd Neeland, University of British

ColumbiaJacqueline Nikles, University of

AlabamaMike Oglioruso, Virginia Polytechnic

Institute and State UniversityWesley A. Pearson, St. Olaf College

Robert Phillips, University of GeorgiaCarmelo Rizzo, Vanderbilt UniversityWilliam E. Russey, Juniata CollegeNeil E. Schore, University of California-

DavisGerald Selter, California State

University- San JoseEric Simanek, Texas A&M UniversityJan Simek, California Polytechnic State

UniversityErnest Simpson, California State

Polytechnic University- PomonaPeter W. Slade, University College of

Fraser ValleyGary Snyder, University of

MassachusettsRonald Starkey, University of

Wisconsin- Green BayJ. William Suggs, Brown UniversityMichelle Sulikowski, Vanderbilt

UniversityDouglas Taber, University of DelawareDennis Taylor, University of AdelaideMarcus W. Thomsen, Franklin &

Marshall CollegeWalter Trahanovsky, Iowa State

UniversityHarry Ungar, Cabrillo CollegeJoseph J. Villafranca, Pennsylvania

State UniversityBarbara J. Whitlock, University of

Wisconsin-MadisonVera Zalkow, Kennesaw College


What is organic chemistry, and why should you study it? The answers to thesequestions are all around you. Every living organism is made of organic chemi-cals. The proteins that make up your hair, skin, and muscles; the DNA that con-trols your genetic heritage; the foods that nourish you; and the medicines thatheal you are all organic chemicals. Anyone with a curiosity about life and livingthings, and anyone who wants to be a part of the many exciting developmentsnow happening in medicine and the biological sciences, must first understandorganic chemistry. Look at the following drawings for instance, which show thechemical structures of some molecules whose names might be familiar to you.

Benzylpenicillin

Oxycodone

(OxyContin)

H H

H

CH3O

O

OHCH3

CH3

CH3

CO2–

N

OO

N

H

H

S

N

O

HOH

HCH3

CH3 H

H

Cholesterol

H

Sildenafil

(Viagra)

Rofecoxib

(Vioxx)

S

O

O

CH2CH2CH3

CH3CH2O

CH3

CH3

O

OON

N

N

N

N

N

O

O

H

SCH3


Throughout thischapter, there are opportunitiesfor online self-study, linking youto interactive tutorials based onyour level of understanding. Signin at www.thomsonedu.comto view organic chemistrytutorials and simulations,develop problem-solving skills,and test your knowledge withthese interactive self-studyresources.

Online homework for thisand other chapters may beassigned in Organic OWL.

1

Sean

Dug

gan

1 Structure and Bonding


2 CHAPTER 1 Structure and Bonding

Although the drawings may appear unintelligible at this point, don’t worry.Before long they’ll make perfectly good sense and you’ll be drawing similarstructures for any substance you’re interested in.

The foundations of organic chemistry date from the mid-1700s, when chem-istry was evolving from an alchemist’s art into a modern science. At that time,unexplainable differences were noted between substances obtained from livingsources and those obtained from minerals. Compounds obtained from plantsand animals were often difficult to isolate and purify. Even when pure, they wereoften difficult to work with, and they tended to decompose more easily thancompounds obtained from minerals. The Swedish chemist Torbern Bergman in1770 was the first to express this difference between “organic” and “inorganic”substances, and the term organic chemistry soon came to mean the chemistry ofcompounds found in living organisms.

To many chemists of the time, the only explanation for the differences inbehavior between organic and inorganic compounds was that organic com-pounds must contain a peculiar “vital force” as a result of their origin in livingsources. One consequence of this vital force, chemists believed, was that organiccompounds could not be prepared and manipulated in the laboratory as couldinorganic compounds. As early as 1816, however, this vitalistic theory receiveda heavy blow when Michel Chevreul found that soap, prepared by the reactionof alkali with animal fat, could be separated into several pure organic com-pounds, which he termed fatty acids. For the first time, one organic substance(fat) was converted into others (fatty acids plus glycerin) without the interven-tion of an outside vital force.

Little more than a decade later, the vitalistic theory suffered still furtherwhen Friedrich Wöhler discovered in 1828 that it was possible to convert the“inorganic” salt ammonium cyanate into the “organic” substance urea, whichhad previously been found in human urine.

By the mid-1800s, the weight of evidence was clearly against the vitalistictheory. As William Brande wrote in 1848, “No definite line can be drawnbetween organic and inorganic chemistry. . . . Any distinctions . . . must for thepresent be merely considered as matters of practical convenience calculated tofurther the progress of students.” Chemistry today is unified, and the same prin-ciples explain the behaviors of all substances, regardless of origin or complexity.The only distinguishing characteristic of organic chemicals is that all contain theelement carbon.

UreaAmmonium cyanate

CNH2H2N

OHeatNH4

+ –OCN

+Animal fat Soap GlycerinH2O

NaOH

Soap “Fatty acids”H3O+

Michel-Eugène Chevreul(1786–1889) was born in Angers,France. After studies at theCollège de France in Paris, hebecame professor of physics atthe Lycée Charlemagne in 1813and professor of chemistry in1830. Chevreul’s studies of soapsand waxes led him to patent amethod for manufacturingcandles. He also published workon the psychology of color per-ception and of aging. All Francecelebrated his 100th birthday in1886.

Michel-Eugène Chevreul

Friedrich Wöhler (1800–1882)was born in Eschersheim,Germany, and studied at Heidel-berg under Leopold Gmelin. From1836 to 1882, he was professor ofchemistry at Göttingen. Wöhlerdeveloped the first industrialmethod for preparing aluminummetal, and he discovered severalnew elements. In addition, hewrote textbooks about both inor-ganic and organic chemistry.

Friedrich Wöhler

William Thomas Brande(1788–1866) was born in London,England. Trained as an apothe-cary, he became a lecturer inchemistry at the University ofLondon in 1808 and was a profes-sor at the Royal Institution from1813 to 1852. His scientificachievements were modest,although he was the first personto discover naphthalene, nowused in mothballs.

William Thomas Brande


1.1 Atomic Structure: The Nucleus 3

Organic chemistry, then, is the study of carbon compounds. But why iscarbon special? Why, of the more than 30 million presently known chemicalcompounds, do more than 99% of them contain carbon? The answers to thesequestions come from carbon’s electronic structure and its consequent positionin the periodic table (Figure 1.1). As a group 4A element, carbon can share fourvalence electrons and form four strong covalent bonds. Furthermore, carbonatoms can bond to one another, forming long chains and rings. Carbon, aloneof all elements, is able to form an immense diversity of compounds, from thesimple to the staggeringly complex—from methane, with one carbon atom, toDNA, which can have more than 100 hundred million carbons.

Not all carbon compounds are derived from living organisms, of course, andchemists over the years have developed a remarkably sophisticated ability todesign and synthesize new organic compounds. Medicines, dyes, polymers,food additives, pesticides, and a host of other substances are now prepared inthe laboratory. Organic chemistry touches the lives of everyone. Its study is afascinating undertaking.

WHY THIS CHAPTER?

We’ll ease into the study of organic chemistry by first reviewing some ideasabout atoms, bonds, and molecular geometry that you may recall from yourgeneral chemistry course. Much of the material in this chapter and the next islikely to be familiar to you, but it’s nevertheless a good idea to make sure youunderstand it before going on.

1.1 Atomic Structure: The Nucleus

As you probably know, an atom consists of a dense, positively charged nucleus sur-rounded at a relatively large distance by negatively charged electrons (Figure 1.2).The nucleus consists of subatomic particles called neutrons, which are electricallyneutral, and protons, which are positively charged. Because an atom is neutral

OLi

Group1A

H

Na

K

Rb

Cs

Fr

Be

2A

Mg

Ca

Sr

Ba

Ra

B

Al

Ga

In

Tl

Si P

C N

Ge

Sn

Pb

As

Sb

Bi

S

Se

Te

Po

F

Cl

Br

I

At

Ne

Ar

He6A3A 4A 5A 7A

8A

Kr

Xe

Rn

Sc

Y

La

Ti

Zr

Hf

V

Nb

Ta

Cr

Mo

W

Mn

Tc

Re

Fe

Ru

Os

Co

Rh

Ir

Ni

Pd

Pt

Cu

Ag

Au

Zn

Cd

Hg

Ac

Figure 1.1 The position ofcarbon in the periodic table.Other elements commonlyfound in organic com-pounds are shown in thecolors typically used to rep-resent them.


4 CHAPTER 1 Structure and Bonding

overall, the number of positive protons in the nucleus and the number of nega-tive electrons surrounding the nucleus are the same.

Although extremely small—about 10�14 to 10�15 meter (m) in diameter—the nucleus nevertheless contains essentially all the mass of the atom. Electronshave negligible mass and circulate around the nucleus at a distance of approxi-mately 10�10 m. Thus, the diameter of a typical atom is about 2 � 10�10 m, or200 picometers (pm), where 1 pm � 10�12 m. To give you an idea of how smallthis is, a thin pencil line is about 3 million carbon atoms wide. Many organicchemists and biochemists, particularly in the United States, still use the unitangstrom (Å) to express atomic distances, where 1 Å � 10�10 m � 100 pm, butwe’ll stay with the SI unit picometer in this book.

A specific atom is described by its atomic number (Z), which gives the num-ber of protons in the atom’s nucleus, and its mass number (A), which gives thetotal of protons plus neutrons in its nucleus. All the atoms of a given elementhave the same atomic number—1 for hydrogen, 6 for carbon, 15 for phospho-rus, and so on—but they can have different mass numbers, depending on howmany neutrons they contain. Atoms with the same atomic number but differ-ent mass numbers are called isotopes. The weighted average mass in atomicmass units (amu) of an element’s naturally occurring isotopes is called the ele-ment’s atomic mass (or atomic weight)—1.008 amu for hydrogen, 12.011 amu forcarbon, 30.974 amu for phosphorus, and so on.

1.2 Atomic Structure: Orbitals

How are the electrons distributed in an atom? You might recall from your gen-eral chemistry course that, according to the quantum mechanical model, thebehavior of a specific electron in an atom can be described by a mathematicalexpression called a wave equation—the same sort of expression used to describethe motion of waves in a fluid. The solution to a wave equation is called a wavefunction, or orbital, and is denoted by the Greek letter psi, �.

By plotting the square of the wave function, �2, in three-dimensional space,the orbital describes the volume of space around a nucleus that an electron ismost likely to occupy. You might therefore think of an orbital as looking like aphotograph of the electron taken at a slow shutter speed. The orbital wouldappear as a blurry cloud indicating the region of space around the nucleus wherethe electron has been. This electron cloud doesn’t have a sharp boundary, butfor practical purposes we can set the limits by saying that an orbital representsthe space where an electron spends most (90%–95%) of its time.

Nucleus (protons + neutrons)

Volume around nucleusoccupied by orbiting electrons

Figure 1.2 A schematic view ofan atom. The dense, positivelycharged nucleus contains mostof the atom’s mass and is sur-rounded by negatively chargedelectrons. The three-dimensionalview on the right shows calcu-lated electron-density surfaces.Electron density increasessteadily toward the nucleus andis 40 times greater at the bluesolid surface than at the graymesh surface.


1.2 Atomic Structure: Orbitals 5

What do orbitals look like? There are four different kinds of orbitals,denoted s, p, d, and f, each with a different shape. Of the four, we’ll be concernedprimarily with s and p orbitals because these are the most common in organicand biological chemistry. The s orbitals are spherical, with the nucleus at their center; p orbitals are dumbbell-shaped; and four of the five d orbitals arecloverleaf-shaped, as shown in Figure 1.3. The fifth d orbital is shaped like anelongated dumbbell with a doughnut around its middle.

The orbitals in an atom are organized into different layers, or electronshells, of successively larger size and energy. Different shells contain differentnumbers and kinds of orbitals, and each orbital within a shell can be occupiedby two electrons. The first shell contains only a single s orbital, denoted 1s, andthus holds only 2 electrons. The second shell contains one 2s orbital and three2p orbitals and thus holds a total of 8 electrons. The third shell contains a 3s orbital, three 3p orbitals, and five 3d orbitals, for a total capacity of 18 elec-trons. These orbital groupings and their energy levels are shown in Figure 1.4.

The three different p orbitals within a given shell are oriented in spacealong mutually perpendicular directions, denoted px, py, and pz. As shown inFigure 1.5, the two lobes of each p orbital are separated by a region of zero elec-tron density called a node. Furthermore, the two orbital regions separated bythe node have different algebraic signs, � and �, in the wave function. As we’llsee in Section 1.11, the algebraic signs of the different orbital lobes have impor-tant consequences with respect to chemical bonding and chemical reactivity.

3rd shell(capacity—18 electrons)

2nd shell(capacity—8 electrons)

1st shell(capacity—2 electrons)

En

erg

y

3d

3p

2p

3s

2s

1s

Figure 1.4 The energy levels ofelectrons in an atom. The firstshell holds a maximum of 2 elec-trons in one 1s orbital; thesecond shell holds a maximumof 8 electrons in one 2s and three2p orbitals; the third shell holds amaximum of 18 electrons in one3s, three 3p, and five 3d orbitals;and so on. The two electrons ineach orbital are represented byup and down arrows, ↑↓.Although not shown, the energylevel of the 4s orbital fallsbetween 3p and 3d.

An s orbital A p orbital A d orbital

Figure 1.3 Representations ofs, p, and d orbitals. The s orbitalsare spherical, the p orbitals aredumbbell-shaped, and four ofthe five d orbitals are cloverleaf-shaped. Different lobes of p orbitals are often drawn forconvenience as teardrops, buttheir true shape is more like thatof a doorknob, as indicated.

OC7_12585_01_Ch01_0001-0034 11/16/06 2:38 PM Page 5

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