View Author Bio
John E. McMurry received his B.A. from Harvard University and his Ph.D. at Columbia University. He is a Fellow of the American Association for the Advancement of Science, and an Alfred P. Sloan Research Foundation Fellow. He has received several awards, which include the National Institutes of Health Career Development Award, the Alexander von Humboldt Senior Scientist Award, and the Max Planck Research Award. In addition to ORGANIC CHEMISTRY, he is also the author or coauthor of ORGANIC CHEMISTRY: A BIOLOGICAL APPROACH, FUNDAMENTALS OF ORGANIC CHEMISTRY, THE ORGANIC CHEMISTRY OF BIOLOGICAL PATHWAYS.
A new co-author, Eric Simanek of Texas A&M University, has expertise in both biochemistry and organic chemistry. Dr. Simanek received his B.S. Chemistry from the University of Illinois at Urbana-Champaign, and his M.S. and Ph.D. in chemistry from Harvard University, where his advisor was George M. Whitesides. He was most recently featured in the Journal of Chemical Education's October edition with an article on dendrimers. Dendrimers are polymers named for trees that show snowflake-like perfection. In 2000, Eric's group introduced dendrimers based on melamine. These architectures are unique in a variety of ways and subsequent reports from his group have addressed synthetic aspects of these architectures. He is also involved in improving science education the state of Texas.
View Table of Contents
Preface xvi
A Note for Students xxi
1 Structure and Bonding; Acids and Bases 1
1.1 Atomic Structure 3
1.2 Electron Configuration of Atoms 5
1.3 Development of Chemical Bonding Theory 6
1.4 The Nature of Chemical Bonds 7
1.5 Forming Covalent Bonds: Valence Bond Theory 10
1.6 Hybridization: sp[superscript 3] Orbitals and the Structure of Methane 11
1.7 Hybridization: sp[superscript 3] Orbitals and the Structure of Ethane 12
1.8 Hybridization: sp[subscript 2] Orbitals and the Structure of Ethylene 13
1.9 Hybridization: sp Orbitals and the Structure of Acetylene 16
1.10 Polar Covalent Bonds: Electronegativity 17
1.11 Acids and Bases: The Bronsted--Lowry Definition 20
1.12 Acids and Bases: The Lewis Definition 24
2 The Nature of Organic Compounds: Alkanes 34
2.1 Functional Groups 35
2.2 Alkanes and Alkyl Groups: Isomers 41
2.3 Naming Branched-Chain Alkanes 46
2.4 Properties of Alkanes 49
2.5 Conformations of Ethane 50
2.6 Drawing Chemical Structures 53
2.7 Cycloalkanes 54
2.8 Cis--Trans Isomerism in Cycloalkanes 55
2.9 Conformations of Some Cycloalkanes 57
2.10 Axial and Equatorial Bonds in Cyclohexane 60
2.11 Conformational Mobility of Cyclohexane 61
3 The Nature of Organic Reactions: Alkenes 74
3.1 Naming Alkenes 75
3.2 Electronic Structure of Alkenes 78
3.3 Cis--Trans Isomers of Alkenes 79
3.4 Sequence Rules: The E,Z Designation 81
3.5 Kinds of Organic Reactions 84
3.6 How Reactions Occur: Mechanisms 86
3.7 The Mechanism of an Organic Reaction: Addition of HCl to Ethylene 89
3.8 Describing a Reaction: Reaction Energy Diagrams and Transition States 92
3.9 Describing a Reaction: Intermediates 94
4 Reactions of Alkenes and Alkynes 105
4.1 Addition of HX to Alkenes: Hydrohalogenation 106
4.2 Orientation of Alkene Addition Reactions: Markovnikov's Rule 106
4.3 Carbocation Structure and Stability 109
4.4 Addition of H[subscript 2]O to Alkenes: Hydration 111
4.5 Addition of X[subscript 2] to Alkenes: Halogenation 113
4.6 Addition of H[subscript 2] to Alkenes: Hydrogenation 115
4.7 Oxidation of Alkenes: Hydroxylation and Cleavage 116
4.8 Biological Addition Reactions of Alkenes 118
4.9 Addition of Radicals to Alkenes: Polymers 119
4.10 Conjugated Dienes 122
4.11 Stability of Allylic Carbocations: Resonance 124
4.12 Drawing and Interpreting Resonance Forms 126
4.13 Alkynes and Their Reactions 128
5 Aromatic Compounds 143
5.1 Structure of Benzene: The Kekule Proposal 144
5.2 Structure of Benzene: The Resonance Proposal 145
5.3 Naming Aromatic Compounds 146
5.4 Electrophilic Aromatic Substitution Reactions: Bromination 149
5.5 Other Electrophilic Aromatic Substitution Reactions 153
5.6 The Friedel--Crafts Alkylation and Acylation Reactions 154
5.7 Substituent Effects in Electrophilic Aromatic Substitution 156
5.8 An Explanation of Substituent Effects 158
5.9 Oxidation and Reduction of Aromatic Compounds 162
5.10 Polycyclic Aromatic Hydrocarbons 163
5.11 Organic Synthesis 164
6 Stereochemistry 177
6.1 Stereochemistry and the Tetrahedral Carbon 178
6.2 The Reason for Handedness in Molecules: Chirality 180
6.3 Optical Activity 183
6.4 Specific Rotation 184
6.5 Pasteur's Discovery of Enantiomers 186
6.6 Sequence Rules for Specifying Configuration 187
6.7 Diastereomers 191
6.8 Meso Compounds 193
6.9 Molecules with More Than Two Stereocenters 195
6.10 Racemic Mixtures and the Resolution of Enantiomers 196
6.11 Physical Properties of Stereoisomers 199
6.12 A Brief Review of Isomerism 199
6.13 Chirality in Nature 201
7 Alkyl Halides 211
7.1 Naming Alkyl Halides 212
7.2 Preparing Alkyl Halides 213
7.3 Reactions of Alkyl Halides: Grignard Reagents 215
7.4 Nucleophilic Substitution Reactions 217
7.5 The S[subscript N]2 Reaction 220
7.6 The S[subscript N]1 Reaction 224
7.7 Eliminations: The E2 Reaction 228
7.8 Eliminations: The E1 Reaction 230
7.9 A Summary of Reactivity: S[subscript N]1, S[subscript N]2, E1, E2 232
7.10 Substitution Reactions in Living Organisms 233
8 Alcohols, Phenols, and Ethers 243
8.1 Naming Alcohols, Phenols, and Ethers 244
8.2 Properties of Alcohols, Phenols, and Ethers: Hydrogen Bonding 246
8.3 Properties of Alcohols and Phenols: Acidity 248
8.4 Synthesis of Alcohols 250
8.5 Reactions of Alcohols 253
8.6 Synthesis and Reactions of Phenols 258
8.7 Synthesis and Reactions of Ethers 261
8.8 Cyclic Ethers: Epoxides 262
8.9 Thiols and Sulfides 264
9 Aldehydes and Ketones: Nucleophilic Addition Reactions 276
9.1 The Nature of Carbonyl Compounds 277
9.2 Naming Aldehydes and Ketones 279
9.3 Synthesis of Aldehydes and Ketones 281
9.4 Oxidation of Aldehydes 282
9.5 Nucleophilic Addition Reactions of Aldehydes and Ketones: Reduction 283
9.6 Nucleophilic Addition of Water: Hydration 285
9.7 Nucleophilic Addition of Alcohols: Acetal Formation 288
9.8 Nucleophilic Addition of Amines: Imine Formation 290
9.9 Nucleophilic Addition of Grignard Reagents: Alcohol Formation 291
9.10 Conjugate Nucleophilic Addition Reactions 294
9.11 Some Biological Nucleophilic Addition Reactions 295
10 Carboxylic Acids and Derivatives 305
10.1 Naming Carboxylic Acids and Derivatives 306
10.2 Occurrence and Properties of Carboxylic Acids 310
10.3 Synthesis of Carboxylic Acids 313
10.4 Nucleophilic Acyl Substitution Reactions 314
10.5 Reactions of Carboxylic Acids 317
10.6 Chemistry of Acid Halides 320
10.7 Chemistry of Acid Anhydrides 322
10.8 Chemistry of Esters 324
10.9 Chemistry of Amides 329
10.10 Chemistry of Nitriles 331
10.11 Polymers from Carbonyl Compounds: Nylons and Polyesters 334
11 Carbonyl Alpha-Substitution Reactions and Condensation Reactions 347
11.1 Keto--Enol Tautomerism 348
11.2 Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions 352
11.3 Alpha Halogenation of Aldehydes and Ketones 353
11.4 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 355
11.5 Reactivity of Enolate Ions 358
11.6 Alkylation of Enolate Ions 359
11.7 Carbonyl Condensation Reactions 362
11.8 Condensations of Aldehydes and Ketones: The Aldol Reaction 362
11.9 Dehydration of Aldol Products: Synthesis of Enones 364
11.10 Condensations of Esters: The Claisen Condensation Reaction 366
11.11 Biological Carbonyl Reactions 368
12 Amines 379
12.1 Naming Amines 380
12.2 Structure and Properties of Amines 383
12.3 Basicity of Amines 383
12.4 Synthesis of Amines 386
12.5 Reactions of Amines 392
12.6 Heterocyclic Amines 393
12.7 Alkaloids: Naturally Occurring Amines 397
13 Structure Determination 406
13.1 Infrared Spectroscopy and the Electromagnetic Spectrum 407
13.2 Infrared Spectroscopy of Organic Molecules 410
13.3 Ultraviolet Spectroscopy 415
13.4 Interpreting Ultraviolet Spectra: The Effect of Conjugation 416
13.5 Nuclear Magnetic Resonance Spectroscopy 418
13.6 The Nature of NMR Absorptions 419
13.7 Chemical Shifts 422
13.8 Chemical Shifts in [superscript 1]H NMR Spectra 423
13.9 Integration of [superscript 1]H NMR Spectra: Proton Counting 425
13.10 Spin--Spin Splitting in [superscript 1]H NMR Spectra 426
13.11 Uses of [superscript 1]H NMR Spectra 430
13.12 [superscript 13]C NMR Spectroscopy 430
14 Biomolecules: Carbohydrates 441
14.1 Classification of Carbohydrates 442
14.2 Configurations of Monosaccharides: Fischer Projections 444
14.3 D,L Sugars 446
14.4 Configurations of Aldoses 448
14.5 Cyclic Structures of Monosaccharides: Hemiacetal Formation 450
14.6 Monosaccharide Anomers: Mutarotation 452
14.7 Reactions of Monosaccharides 454
14.9 Polysaccharides 460
14.10 Other Important Carbohydrates 463
14.11 Cell-Surface Carbohydrates and Carbohydrate Vaccines 463
15 Biomolecules: Amino Acids, Peptides, and Proteins 472
15.1 Structures of Amino Acids 473
15.2 Isoelectric Points 478
15.3 Peptides and Proteins 481
15.4 Covalent Bonding in Peptides 482
15.5 Peptide Structure Determination: Amino Acid Analysis 484
15.6 Peptide Sequencing: The Edman Degradation 484
15.7 Peptide Synthesis 487
15.8 Classification of Proteins 490
15.9 Protein Structure 491
15.10 Enzymes 494
15.11 How Do Enzymes Work? Citrate Synthase 497
16 Biomolecules: Lipids and Nucleic Acids 507
16.1 Lipids 508
16.2 Fats and Oils 508
16.3 Soaps 511
16.4 Phospholipids 513
16.5 Steroids 515
16.6 Nucleic Acids and Nucleotides 517
16.7 Structure of DNA 520
16.8 Base Pairing in DNA: The Watson--Crick Model 521
16.9 Nucleic Acids and Heredity 524
16.10 Replication of DNA 524
16.11 Structure and Synthesis of RNA: Transcription 526
16.12 RNA and Protein Biosynthesis: Translation 527
16.13 Sequencing DNA 530
16.14 The Polymerase Chain Reaction 532
17 The Organic Chemistry of Metabolic Pathways 540
17.1 An Overview of Metabolism and Biochemical Energy 541
17.2 Catabolism of Fats: [beta]-Oxidation Pathway 544
17.3 Catabolism of Carbohydrates: Glycolysis 549
17.4 The Citric Acid Cycle 554
17.5 Catabolism of Proteins: Transamination 557
17.6 The Organic Chemistry of Metabolic Pathways: A Summary 559
Appendixes
A Nomenclature of Polyfunctional Organic Compounds 1
B Glossary 8
C Answers to Selected In-Chapter Problems 18
Index 1
