Table of contents for Organic chemistry.

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Contents
Chapter 1 Carbon Compounds and Chemical Bonds 1
?We Are Stardust? 1
 (Molecular graphic: Glycine, an organic molecule found in space)
1.1 Introduction 2
1.2 The Development of Organic Chemistry as a Science 3
1.3 The Structural Theory of Organic Chemistry 4
1.4 Chemical Bonds: The Octet Rule 6
1.5 Writing Lewis Structures 8
1.6 Exceptions to the Octet Rule 10
1.7 Formal Charge 11
1.8 Resonance 14
1.9 Quantum Mechanics 19
1.10 Atomic Orbitals 20
1.11 Molecular Orbitals 22
1.12 The Structure of Methane and Ethane: sp3 Hybridization 25
The Chemistry of...Calculated Molecular Models: Electron Density Surfaces 29
1.13 The Structure of Ethene (Ethylene): sp2 Hybridization 29
1.14 The Structure of Ethyne (Acetylene): sp Hybridization 34
1.15 A Summary of Important Concepts that Come From Quantum Mechanics 36
1.16 Molecular Geometry: The Valence Shell Electron Pair Repulsion Model 38
1.17 Representation of Structural Formulas 41
Chapter 2 Representative Carbon Compounds: Functional Groups, Intermolecular Forces, and Infrared (IR) Spectroscopy 52
Structure and Function: Organic Chemistry, Nanotechnology, and Bioengineering 52
_ (Molecular graphic: A molecular template for bone growth}
2.1 Carbon?Carbon Covalent Bonds 53
2.2 Hydrocarbons: Representative Alkanes, Alkenes, Alkynes, and Aromatic Compounds 53
2.3 Polar Covalent Bonds 56
The Chemistry of? Calculated Molecular Models: Maps of Electrostatic Potential 58
2.4 Polar and Nonpolar Molecules 59
2.5 Functional Groups 61
2.6 Alkyl Halides or Haloalkanes 63
2.7 Alcohols 63
2.8 Ethers 65
2.9 Amines 66
2.10 Aldehydes and Ketones 67
2.11 Carboxylic Acids, Esters, and Amides 68
2.12 Nitriles 69
2.13 Summary of Important Families of Organic Compounds 70
2.14 Physical Properties and Molecular Structure 70
2.15 Summary of Attractive Electric Forces 78
The Chemistry of? Organic Templates Engineered to Mimic Bone Growth 78
2.16 Infrared Spectroscopy: An Instrumental Method for Detecting Functional Groups 79
Chapter 3 An Introduction to Organic Reactions: Acids and Bases 94
Shuttling the Protons 94
_ (Molecular graphic: Diamox, a drug that prevents altitude sickness)
3.1 Reactions and Their Mechanisms 95
3.2 Acid?Base Reactions 97
The Chemistry of... HOMOs and LUMOs in Reactions 101
3.3 Heterolysis of Bonds to Carbon: Carbocations and Carbanions 101
3.4 The Use of Curved Arrows in Illustrating Reactions 102
3.5 The Strength of Acids and Bases: Ka and pKa 104
3.6 Predicting the Outcome of Acid?Base Reactions 107
3.7 The Relationship Between Structure and Acidity 109
3.8 Energy Changes 113
3.9 The Relationship Between the Equilibrium Constant and the Standard Free-Energy
Change, _Gø 114
3.10 The Acidity of Carboxylic Acids 115
3.11 The Effect of the Solvent on Acidity 120
3.12 Organic Compounds as Bases 121
3.13 A Mechanism for an Organic Reaction 122
The Chemistry of? Carbonic Anhydrase 124
3.14 Acids and Bases in Nonaqueous Solutions 124
3.15 Acid?Base Reactions and the Synthesis of Deuteriumand
Tritium-Labeled Compounds 126
Chapter 4 Alkanes: Nomenclature, Conformational Analysis, and an Introduction to Synthesis 134
To Be Flexible or Inflexible ? Molecular Structure Makes the Difference 134
_ (Molecular graphic: A portion of the structure of diamond, an exceptionally
rigid molecule)
4.1 Introduction to Alkanes and Cycloalkanes 135
4.2 Shapes of Alkanes 137
4.3 IUPAC Nomenclature of Alkanes, Alkyl Halides, and Alcohols 139
4.4 Nomenclature of Cycloalkanes 147
4.5 Nomenclature of Alkenes and Cycloalkenes 150
4.6 Nomenclature of Alkynes 152
4.7 Physical Properties of Alkanes and Cycloalkanes 152
4.8 Sigma Bonds and Bond Rotation 154
4.9 Conformational Analysis of Butane 157
4.10 The Relative Stabilities of Cycloalkanes: Ring Strain 159
4.11 The Origin of Ring Strain in Cyclopropane and Cyclobutane: Angle Strain and Torsional
Strain 162
4.12 Conformations of Cyclohexane 163
The Chemistry of? Nanoscale Motors and Molecular Switches 166
4.13 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Atoms 167
4.14 Disubstituted Cycloalkanes: Cis?Trans Isomerism 171
4.15 Bicyclic and Polycyclic Alkanes 175
The Chemistry of? Pheromones: Communication by Means of Chemicals 177
4.16 Chemical Reactions of Alkanes 177
4.17 Synthesis of Alkanes and Cycloalkanes 178
4.18 Some General Principles of Structure and Reactivity: A Look toward Synthesis 180
4.19 An Introduction to Organic Synthesis 181
The Chemistry of? From the Inorganic to the Organic 185
Chapter 5 Stereochemistry: Chiral Molecules 193
The Handedness of Life 193
_ (Molecular graphic: The mirror-image stereoisomers of alanine,
a chiral amino acid)
5.1 The Biological Significance of Chirality 194
5.2 Isomerism: Constitutional Isomers and Stereoisomers 195
5.4 More about the Biological Importance of Chirality 200
5.5 Historical Origin of Stereochemistry 201
5.6 Tests for Chirality: Planes of Symmetry 202
5.7 Nomenclature of Enantiomers: The R,S-System 203
5.8 Properties of Enantiomers: Optical Activity 208
5.9 The Origin of Optical Activity 212
5.10 The Synthesis of Chiral Molecules 215
5.11 Chiral Drugs 217
The Chemistry of? Selective Binding of Drug Enantiomers to Left- and Right-Hand
Coiled DNA 218
5.12 Molecules with More than One Stereogenic Center 219
5.13 Fischer Projection Formulas 223
5.14 Stereoisomerism of Cyclic Compounds 224
5.15 Relating Configurations Through Reactions in Which No Bonds to the Stereogenic Carbon
Are Broken 227
5.16 Separation of Enantiomers: Resolution 230
5.17 Compounds with Stereogenic Centers Other than Carbon 231
5.18 Chiral Molecules that Do Not Possess a Tetrahedral Atom with Four Different Groups 231
Chapter 6 Ionic Reactions?Nucleophilic Substitution and Elimination Reactions of Alkyl Halides 238
Breaking Bacterial Cell Walls with Organic Chemistry 238
_ (Molecular graphic: The SN2 transition state resulting from collision
of a hydroxide anion with chloromethane)
6.1 Introduction 239
6.2 Nucleophilic Substitution Reactions 241
6.3 Nucleophiles 241
6.4 Leaving Groups 242
6.5 Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction 243
6.6 A Mechanism for the SN2 Reaction 244
6.7 Transition State Theory: Free-Energy Diagrams 245
6.8 The Stereochemistry of SN2 Reactions 249
6.9 The Reaction of tert-Butyl Chloride with Hydroxide Ion: An SN1 Reaction 251
6.10 A Mechanism for the SN1 Reaction 252
6.11 Carbocations 254
6.12 The Stereochemistry of SN1 Reactions 256
6.13 Factors Affecting the Rates of SN1 and SN2 Reactions 258
6.14 Organic Synthesis: Functional Group Transformations Using SN2 Reactions 267
The Chemistry of? Biological Methylation: A Biological Nucleophilic Substitution
Reaction 268
6.15 Elimination Reactions of Alkyl Halides 271
6.16 The E2 Reaction 273
6.17 The E1 Reaction 274
6.18 Substitution versus Elimination 275
6.19 Overall Summary 278
Chapter 7 Alkenes and Alkynes I: Properties and Synthesis. Elimination Reactions of Alkyl Halides 287
Cell Membrane Fluidity 287
_ (Molecular graphic: cis-9-Octadecenoic acid, an unsaturated fatty
acid incorporated into cell membrane phospholipids)
7.1 Introduction 288
7.2 The (E)?(Z) System for Designating Alkene Diastereomers 288
7.3 Relative Stabilities of Alkenes 290
7.4 Cycloalkenes 292
7.5 Synthesis of Alkenes via Elimination Reactions 292
7.6 Dehydrohalogenation of Alkyl Halides 293
7.7 Acid-Catalyzed Dehydration of Alcohols 298
7.8 Carbocation Stability and the Occurrence of Molecular Rearrangements 303
7.9 Synthesis of Alkynes by Elimination Reactions 307
7.10 The Acidity of Terminal Alkynes 308
7.11 Replacement of the Acetylenic Hydrogen Atom of Terminal Alkynes 309
7.12 Hydrogenation of Alkenes 310
The Chemistry of?Hydrogenation in the Food Industry 311
7.13 Hydrogenation: The Function of the Catalyst 312
The Chemistry of?Homogeneous Asymmetric Catalytic Hydrogenation: Examples Involving
L-DOPA, (S)-Naproxen, and Aspartame 313
7.14 Hydrogenation of Alkynes 315
7.15 Structural Information from Molecular Formulas and the Index of Hydrogen Deficiency 317
Chapter 8 Alkenes and Alkynes II: Addition Reactions 328
The Sea: A Treasury of Biologically Active Natural Products 328
_ (Molecular graphic: Dactylyne, a halogenated marine natural product)
8.1 Introduction: Addition to Alkenes 329
8.2 Addition of Hydrogen Halides to Alkenes: Markovnikov's Rule 331
8.3 Stereochemistry of the Ionic Addition to an Alkene 336
8.4 Addition of Sulfuric Acid to Alkenes 337
8.5 Addition of Water to Alkenes: Acid-Catalyzed Hydration 338
8.6 Alcohols from Alkenes through Oxymercuration?Demercuration:
Markovnikov Addition 340
8.7 Alcohols from Alkenes through Hydroboration?Oxidation:
Anti-Markovnikov Syn Hydration 343
8.8 Hydroboration: Synthesis of Alkylboranes 343
8.9 Oxidation and Hydrolysis of Alkyboranes 346
8.10 Summary of Alkene Hydration Methods 348
8.11 Protonolysis of Alkyboranes 348
8.12 Addition of Bromine and Chlorine to Alkenes 349
8.13 Stereochemistry of the Addition of Halogens to Alkenes 351
8.14 Halohydrin Formation 354
The Chemistry of? Regiospecificity in Unsymmetrically Substituted Bromonium Ions:
Bromonium Ions of Ethene, Propene, and 2-Methlypropene 355
8.15 Divalent Carbon Compounds: Carbenes 357
8.16 Oxidations of Alkenes: Syn 1, 2-Dihydroxylation 359
The Chemistry of? Catalytic Asymmetric Dihydroxylation 361
8.17 Oxidative Cleavage of Alkenes 362
8.18 Addition of Bromine and Chlorine to Alkynes 365
8.19 Addition of Hydrogen Halides to Alkynes 366
8.20 Oxidative Cleavage of Alkynes 367
8.21 Synthetic Strategies Revisited 367
The Chemistry of? Cholesterol Biosynthesis: Elegant and Familiar Reactions in Nature 370
Chapter 9 Nuclear Magnetic Resonance and Mass Spectrometry: Tools for Structure Determination 383
A Thermos? of Liquid Helium 383
_ (Molecular graphic: 1-Chloro-2-propanol)
9.1 Introduction 384
9.2 The Electromagnetic Spectrum 384
9.3 Nuclear Magnetic Resonance Spectroscopy 386
9.4 Nuclear Spin: The Origin of the Signal 390
9.5 Shielding and Deshielding of Protons 392
9.6 The Chemical Shift 394
9.7 Chemical Shift Equivalent and Nonequivalent Protons 395
9.8 Signal Splitting: Spin?Spin Coupling 397
9.9 Proton NMR Spectra and Rate Processes 406
9.10 Carbon-13 NMR Spectroscopy 409
9.11 Two-Dimensional (2D) NMR Techniques 414
The Chemistry of? Magnetic Resonance Imaging in Medicine 417
9.12 An Introduction to Mass Spectrometry 418
9.13 The Mass Spectrometer 418
9.14 The Mass Spectrum 421
9.15 Determination of Molecular Formulas and Molecular Weights 423
9.16 Fragmentation 428
9.17 GC/MS Analysis 434
9.18 Mass Spectrometry of Biomolecules 435
Chapter 10 Radical Reactions 447
Calicheamicin _1
I: A Radical Device for Slicing the Backbone of DNA 447
_ (Molecular graphic: Calicheamicin _1
I, a molecule capable of double-strand
DNA cleavage, bound to DNA)
10.1 Introduction 449
The Chemistry of? Radicals in Biology, Medicine, and Industry 450
10.2 Homolytic Bond Dissociation Energies 450
10.3 The Reactions of Alkanes with Halogens 454
10.4 Chlorination of Methane: Mechanism of Reaction 456
10.5 Chlorination of Methane: Energy Changes 459
10.6 Halogenation of Higher Alkanes 466
10.7 The Geometry of Alkyl Radicals 469
10.8 Reactions that Generate Tetrahedral Stereogenic Carbons 469
10.9 Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide 472
10.10 Radical Polymerization of Alkenes: Chain-Growth Polymers 474
10.11 Other Important Radical Reactions 476
Special Topic A: Chain-Growth Polymers 485
Chapter 11 Alcohols and Ethers 492
Molecular Hosts 492
_ (Molecular graphic: Monensin sodium salt, an antibiotic that transports
ions across cell membranes)
11.1 Structure and Nomenclature 493
11.2 Physical Properties of Alcohols and Ethers 495
11.3 Important Alcohols and Ethers 497
11.4 Synthesis of Alcohols from Alkenes 499
11.5 Reactions of Alcohols 501
11.6 Alcohols as Acids 502
11.7 Conversion of Alcohols into Alkyl Halides 503
11.8 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides 503
11.9 Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl2 506
11.10 Tosylates, Mesylates, and Triflates: Leaving Group Derivatives of Alcohols 507
The Chemistry of? Alkyl Phosphates 510
11.11 Synthesis of Ethers 510
11.12 Reactions of Ethers 515
11.13 Epoxides 516
The Chemistry of? The Sharpless Asymmetric Epoxidation 517
11.14 Reactions of Epoxides 519
The Chemistry of? Epoxides, Carcinogens, and Biological Oxidation 521
11.15 Anti 1,2-Dihydroxylation of Alkenes via Epoxides 523
The Chemistry of? Environmentally Friendly Alkene Oxidation Methods 525
11.16 Crown Ethers: Nucleophilic Substitution Reactions in Relatively Nonpolar Aprotic
Solvents by Phase-Transfer Catalysis 526
11.17 Summary of Reactions of Alkenes, Alcohols, and Ethers 529
Chapter 12 Alcohols from Carbonyl Compounds. Oxidation ? Reduction
and Organometallic Compounds 537
The Two Aspects of the Coenzyme NADH 537
_ (Molecular graphic: Nicotinamide [niacin])
12.1 Introduction 538
12.2 Oxidation?Reduction Reactions in Organic Chemistry 539
12.3 Alcohols by Reduction of Carbonyl Compounds 541
The Chemistry of? Alcohol Dehydrogenase 544
The Chemistry of? Stereoselective Reductions of Carbonyl Groups 544
12.4 Oxidation of Alcohols 546
12.5 Organometallic Compounds 550
12.6 Preparation of Organolithium and Organomagnesium Compounds 551
12.7 Reactions of Organolithium and Organomagnesium Compounds 553
12.8 Alcohols from Grignard Reagents 556
12.9 Lithium Dialkylcuprates: The Corey?Posner,Whitesides?House Synthesis 564
12.10 Protecting Groups 566
First Review Problem Set 573
Chapter 13 Conjugated Unsaturated Systems 577
Molecules with the Nobel Prize in Their Synthetic Lineage 577
_ (Molecular graphic: Morphine, the synthesis of which involved
the Diels?Alder reaction)
13.1 Introduction 578
13.2 Allylic Substitution and the Allyl Radical 578
13.3 The Stability of the Allyl Radical 582
13.4 The Allyl Cation 586
13.5 Summary of Rules for Resonance 587
13.6 Alkadienes and Polyunsaturated Hydrocarbons 591
13.7 1,3-Butadiene: Electron Delocalization 593
13.8 The Stability of Conjugated Dienes 595
13.9 Ultraviolet?Visible Spectroscopy 596
The Chemistry of? The Photochemistry of Vision 600
13.10 Electrophilic Attack on Conjugated Dienes: 1,4 Addition 604
13.11 The Diels?Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes 607
Chapter 14 Aromatic Compounds 622
Green Chemistry 622
_ (Molecular graphic: Benzene, parent molecule in the family
of aromatic hydrocarbons)
14.1 Introduction 623
14.2 Nomenclature of Benzene Derivatives 624
14.3 Reactions of Benzene 626
14.4 The Kekul¿ Structure for Benzene 627
14.5 The Stability of Benzene 628
14.6 Modern Theories of the Structure of Benzene 629
14.7 H¿ckel?s Rule: The 4n _ 2 _ Electron Rule 632
14.8 Other Aromatic Compounds 640
The Chemistry of? Nanotubes 643
14.9 Heterocylic Aromatic Compounds 644
14.10 Aromatic Compounds in Biochemistry 645
14.11 Spectroscopy of Aromatic Compounds 648
The Chemistry of... Sunscreens (Catching the Sun?s Rays and What Happens to Them) 652
Chapter 15 Reactions of Aromatic Compounds 664
Biosynthesis of Thyroxine: Aromatic Substitution Involving Iodine 664
_ (Molecular graphic: Thyroxine, an aromatic iodine-containing hormone
associated with regulation of metabolic rate)
15.1 Electrophilic Aromatic Substitution Reactions 665
15.2 A General Mechanism for Electrophilic Aromatic Substitution: Arenium Ions 666
15.3 Halogenation of Benzene 668
15.4 Nitration of Benzene 669
15.5 Sulfonation of Benzene 670
15.6 Friedel?Crafts Alkylation 671
15.7 Friedel?Crafts Acylation 673
15.8 Limitations of Friedel?Crafts Reactions 675
15.9 Synthetic Applications of Friedel?Crafts Acylations: The Clemmensen Reduction 677
15.10 Effect of Substituents on Reactivity and Orientation 679
15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution 681
The Chemistry of? Iodine Incorporation in Thyroxine Biosynthesis 691
15.12 Reactions of the Side Chain of Alkylbenzenes 693
The Chemistry of? Industrial Styrene Synthesis 694
15.13 Alkenylbenzenes 697
15.14 Synthetic Applications 699
15.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions 703
15.16 Reduction of Aromatic Compounds 705
Answers to Selected Problems A-1
Glossary G-1
Photo and Illustration Credits C-1
Index I-1

Library of Congress Subject Headings for this publication:

Chemistry, Organic -- Textbooks.