Solomons' Organic Chemistry

The 12th edition of Organic Chemistry continues Solomons, Fryhle & Snyder's tradition of excellence in teaching and preparing students for success in the organic classroom and beyond. A central theme of the authors' approach to organic chemistry is to emphasize the relationship between structure and reactivity. To accomplish this, the content is organized in a way that combines the most useful features of a functional group approach with one largely based on reaction mechanisms. The authors' philosophy is to emphasize mechanisms and their common aspects as often as possible, and at the same time, use the unifying features of functional groups as the basis for most chapters. The structural aspects of the authors' approach show students what organic chemistry is. Mechanistic aspects of their approach show students how it works. And wherever an opportunity arises, the authors' show students what it does in living systems and the physical world around us.

Contents:

1 The Basics BONDING ANDMOLECULARSTRUCTURE 1
1.1 Life and the Chemistry of Carbon Compounds—We Are Stardust 2
1.2 Atomic Structure 3
1.3 Chemical Bonds: The Octet Rule 5
1.4 HOW TO Write Lewis Structures 7
1.5 Formal Charges and HOW TO Calculate Them 12
1.6 Isomers: Different Compounds that Have the Same Molecular Formula 14
1.7 HOW TO Write and Interpret Structural Formulas 15
1.8 Resonance Theory 22
1.9 Quantum Mechanics and Atomic Structure 27
1.10 Atomic Orbitals and Electron Configuration 28
1.11 Molecular Orbitals 30
1.12 The Structure of Methane and Ethane: sp3 Hybridization 32
1.13 The Structure of Ethene (Ethylene): Sp2 Hybridization 36
1.14 The Structure of Ethyne (Acetylene): sp Hybridization 40
1.15 A Summary of Important Concepts that Come from Quantum Mechanics 43
1.16 HOW TO Predict Molecular Geometry:The Valence Shell Electron Pair Repulsion Model 44
1.17 Applications of Basic Principles 47
2 Families of Carbon Compounds FUNCTIONAL GROUPS, INTERMOLECULAR FORCES, AND INFRARED (IR) SPECTROSCOPY 55
2.1 Hydrocarbons: Representative Alkanes, Alkenes, Alkynes, and Aromatic Compounds 56
2.2 Polar Covalent Bonds 59
2.3 Polar and Nonpolar Molecules 61
2.4 Functional Groups 64
2.5 Alkyl Halides or Haloalkanes 65
2.6 Alcohols and Phenols 67
2.7 Ethers 69
2.8 Amines 70
2.9 Aldehydes and Ketones 71
2.10 Carboxylic Acids, Esters, and Amides 73
2.11 Nitriles 75
2.12 Summary of Important Families of Organic Compounds 76
2.13 Physical Properties and Molecular Structure 77
2.14 Summary of Attractive Electric Forces 85
2.15 Infrared Spectroscopy: An Instrumental Method for Detecting Functional Groups 86
2.16 Interpreting IR Spectra 90
2.17 Applications of Basic Principles 97
3 Acids and Bases AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS 104
3.1 Acid–Base Reactions 105
3.2 HOW TO Use Curved Arrows in Illustrating Reactions 107
3.3 Lewis Acids and Bases 109
3.4 Heterolysis of Bonds to Carbon: Carbocations and Carbanions 111
3.5 The Strength of Brønsted–Lowry Acids and Bases: Ka and pKa 113
3.6 HOW TO Predict the Outcome of Acid–Base Reactions 118
3.7 Relationships between Structure and Acidity 120
3.8 Energy Changes 123
3.9 The Relationship between the Equilibrium Constant and the Standard Free-Energy Change, ΔG ° 125
3.10 Acidity: Carboxylic Acids versus Alcohols 126
3.11 The Effect of the Solvent on Acidity 132
3.12 Organic Compounds as Bases 132
3.13 A Mechanism for an Organic Reaction 134
3.14 Acids and Bases in Nonaqueous Solutions 135
3.15 Acid–Base Reactions and the Synthesis of Deuterium- and Tritium-Labeled Compounds 136
3.16 Applications of Basic Principles 137
4 Nomenclature and Conformations of Alkanes and Cycloalkanes 144
4.1 Introduction to Alkanes and Cycloalkanes 145
4.2 Shapes of Alkanes 146
4.3 HOW TO Name Alkanes, Alkyl Halides, and Alcohols: The IUPAC System 148
4.4 HOW TO Name Cycloalkanes 155
4.5 HOW TO Name Alkenes and Cycloalkenes 158
4.6 HOW TO Name Alkynes 160
4.7 Physical Properties of Alkanes and Cycloalkanes 161
4.8 Sigma Bonds and Bond Rotation 164
4.9 Conformational Analysis of Butane 166
4.10 The Relative Stabilities of Cycloalkanes: Ring Strain 168
4.11 Conformations of Cyclohexane: The Chair and the Boat 170
4.12 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Groups 173
4.13 Disubstituted Cycloalkanes: Cis–Trans Isomerism 177
4.14 Bicyclic and Polycyclic Alkanes 181
4.15 Chemical Reactions of Alkanes 182
4.16 Synthesis of Alkanes and Cycloalkanes 182
4.17 HOW TO Gain Structural Information from Molecular Formulas and the Index of Hydrogen Deficiency 184
4.18 Applications of Basic Principles 186
5 Stereochemistry CHIRAL MOLECULES 193
5.1 Chirality and Stereochemistry 194
5.2 Isomerism: Constitutional Isomers and Stereoisomers 195
5.3 Enantiomers and Chiral Molecules 197
5.4 Molecules Having One Chirality Center are Chiral 198
5.5 More about the Biological Importance of Chirality 201
5.6 HOW TO Test for Chirality: Planes of Symmetry 203
5.7 Naming Enantiomers: The R,S-System 204
5.8 Properties of Enantiomers: Optical Activity 208
5.9 Racemic Forms 213
5.10 The Synthesis of Chiral Molecules 214
5.11 Chiral Drugs 216
5.12 Molecules with More than One Chirality Center 218
5.13 Fischer Projection Formulas 224
5.14 Stereoisomerism of Cyclic Compounds 226
5.15 Relating Configurations through Reactions in Which No Bonds to the Chirality Center Are Broken 228
5.16 Separation of Enantiomers: Resolution 232
5.17 Compounds with Chirality Centers Other than Carbon 233
5.18 Chiral Molecules that Do Not Possess a Chirality Center 233
6 Nucleophilic Reactions PROPERTIES AND SUBSTITUTION REACTIONS OF ALKYL HALIDES 240
6.1 Alkyl Halides 241
6.2 Nucleophilic Substitution Reactions 242
6.3 Nucleophiles 244
6.4 Leaving Groups 246
6.5 Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction 246
6.6 A Mechanism for the SN2 Reaction 247
6.7 Transition State Theory: Free-Energy Diagrams 249
6.8 The Stereochemistry of SN2 Reactions 252
6.9 The Reaction of tert-Butyl Chloride with Water: An SN1 Reaction 254
6.10 A Mechanism for the SN1 Reaction 255
6.11 Carbocations 257
6.12 The Stereochemistry of SN1 Reactions 259
6.13 Factors Affecting the Rates of SN1 and SN2 Reactions 262
6.14 Organic Synthesis: Functional Group Transformations Using SN2 Reactions 272
7 Alkenes and Alkynes I PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES 282
7.1 Introduction 283
7.2 The (E )–(Z ) System for Designating Alkene Diastereomers 283
7.3 Relative Stabilities of Alkenes 284
7.4 Cycloalkenes 287
7.5 Synthesis of Alkenes: Elimination Reactions 287
7.6 Dehydrohalogenation 288
7.7 The E2 Reaction 289
7.8 The E1 Reaction 297
7.9 Elimination and Substitution Reactions Compete With Each Other 299
7.10 Elimination of Alcohols: Acid-Catalyzed Dehydration 303
7.11 Carbocation Stability and the Occurrence of Molecular Rearrangements 308
7.12 The Acidity of Terminal Alkynes 312
7.13 Synthesis of Alkynes by Elimination Reactions 313
7.14 Terminal Alkynes Can Be Converted to Nucleophiles for Carbon–Carbon Bond Formation 315
7.15 Hydrogenation of Alkenes 317
7.16 Hydrogenation: The Function of the Catalyst 319
7.17 Hydrogenation of Alkynes 320
7.18 An Introduction to Organic Synthesis 322
8 Alkenes and Alkynes II ADDITION REACTIONS 337
8.1 Addition Reactions of Alkenes 338
8.2 Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikov’s Rule 340
8.3 Stereochemistry of the Ionic Addition to an Alkene 345
8.4 Addition of Water to Alkenes: Acid-Catalyzed Hydration 346
8.5 Alcohols from Alkenes through Oxymercuration–Demercuration: Markovnikov Addition 349
8.6 Alcohols from Alkenes through Hydroboration–Oxidation: Anti-Markovnikov Syn Hydration 352
8.7 Hydroboration: Synthesis of Alkylboranes 353
8.8 Oxidation and Hydrolysis of Alkylboranes 355
8.9 Summary of Alkene Hydration Methods 358
8.10 Protonolysis of Alkylboranes 359
8.11 Electrophilic Addition of Bromine and Chlorine to Alkenes 359
8.12 Stereospecific Reactions 363
8.13 Halohydrin Formation 364
8.14 Divalent Carbon Compounds: Carbenes 366
8.15 Oxidation of Alkenes: Syn 1,2-Dihydroxylation 368
8.16 Oxidative Cleavage of Alkenes 371
8.17 Electrophilic Addition of Bromine and Chlorine to Alkynes 374
8.18 Addition of Hydrogen Halides to Alkynes 374
8.19 Oxidative Cleavage of Alkynes 375
8.20 HOW TO Plan a Synthesis: Some Approaches and Examples 376
9 Nuclear Magnetic Resonance and Mass Spectrometry TOOLS FOR STRUCTURE DETERMINATION 391
9.1 Introduction 392
9.2 Nuclear Magnetic Resonance (NMR) Spectroscopy 392
9.3 HOW TO Interpret Proton NMR Spectra 398
9.4 Shielding and Deshielding of Protons: More about Chemical Shift 401
9.5 Chemical Shift Equivalent and Nonequivalent Protons 403
9.6 Spin–Spin Coupling: More about Signal Splitting and Nonequivalent or Equivalent Protons 407
9.7 Proton NMR Spectra and Rate Processes 412
9.8 Carbon-13 NMR Spectroscopy 414
9.9 Two-Dimensional (2D) NMR Techniques 420
9.10 An Introduction to Mass Spectrometry 423
9.11 Formation of Ions: Electron Impact Ionization 424
9.12 Depicting the Molecular Ion 424
9.13 Fragmentation 425
9.14 Isotopes in Mass Spectra 432
9.15 GC/MS Analysis 435
9.16 Mass Spectrometry of Biomolecules 436
10 Radical Reactions 448
10.1 Introduction: How Radicals Form and How They React 449
10.2 Homolytic Bond Dissociation Energies (DH °) 451
10.3 Reactions of Alkanes with Halogens 454
10.4 Chlorination of Methane: Mechanism of Reaction 456
10.5 Halogenation of Higher Alkanes 459
10.6 The Geometry of Alkyl Radicals 462
10.7 Reactions that Generate Tetrahedral Chirality Centers 462
10.8 Allylic Substitution and Allylic Radicals 466
10.9 Benzylic Substitution and Benzylic Radicals 469
10.10 Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide 472
10.11 Radical Polymerization of Alkenes: Chain-Growth Polymers 474
10.12 Other Important Radical Reactions 478
11 Alcohols and Ethers SYNTHESIS AND REACTIONS 489
11.1 Structure and Nomenclature 490
11.2 Physical Properties of Alcohols and Ethers 492
11.3 Important Alcohols and Ethers 494
11.4 Synthesis of Alcohols from Alkenes 496
11.5 Reactions of Alcohols 498
11.6 Alcohols as Acids 500
11.7 Conversion of Alcohols into Alkyl Halides 501
11.8 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides 501
11.9 Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl2 504
11.10 Tosylates, Mesylates, and Triflates: Leaving Group Derivatives of Alcohols 505
11.11 Synthesis of Ethers 507
11.12 Reactions of Ethers 513
11.13 Epoxides 514
11.14 Reactions of Epoxides 516
11.15 Anti 1,2-Dihydroxylation of Alkenes via Epoxides 519
11.16 Crown Ethers 522
11.17 Summary of Reactions of Alkenes, Alcohols, and Ethers 523
12 Alcohols from Carbonyl Compounds OXIDATION–REDUCTION AND ORGANOMETALLIC COMPOUNDS 534
12.1 Structure of the Carbonyl Group 535
12.2 Oxidation–Reduction Reactions in Organic Chemistry 536
12.3 Alcohols by Reduction of Carbonyl Compounds 537
12.4 Oxidation of Alcohols 542
12.5 Organometallic Compounds 547
12.6 Preparation of Organolithium and Organomagnesium Compounds 548
12.7 Reactions of Organolithium and Organomagnesium Compounds 549
12.8 Alcohols from Grignard Reagents 552
12.9 Protecting Groups 561
13 Conjugated Unsaturated Systems 572
13.1 Introduction 573
13.2 The Stability of the Allyl Radical 573
13.3 The Allyl Cation 577
13.4 Resonance Theory Revisited 578
13.5 Alkadienes and Polyunsaturated Hydrocarbons 582
13.6 1,3-Butadiene: Electron Delocalization 583
13.7 The Stability of Conjugated Dienes 586
13.8 Ultraviolet–Visible Spectroscopy 587
13.9 Electrophilic Attack on Conjugated Dienes: 1,4-Addition 595
13.10 The Diels–Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes 599
14 Aromatic Compounds 617
14.1 The Discovery of Benzene 618
14.2 Nomenclature of Benzene Derivatives 619
14.3 Reactions of Benzene 621
14.4 The Kekulé Structure for Benzene 622
14.5 The Thermodynamic Stability of Benzene 623
14.6 Modern Theories of the Structure of Benzene 625
14.7 Hückel’s Rule: The 4n + 2 π Electron Rule 628
14.8 Other Aromatic Compounds 636
14.9 Heterocyclic Aromatic Compounds 639
14.10 Aromatic Compounds in Biochemistry 641
14.11 Spectroscopy of Aromatic Compounds 644
15 Reactions of Aromatic Compounds 660
15.1 Electrophilic Aromatic Substitution Reactions 661
15.2 A General Mechanism for Electrophilic Aromatic Substitution 662
15.3 Halogenation of Benzene 664
15.4 Nitration of Benzene 665
15.5 Sulfonation of Benzene 666
15.6 Friedel–Crafts Reactions 668
15.7 Synthetic Applications of Friedel–Crafts Acylations: The Clemmensen and Wolff–Kishner Reductions 673
15.8 Existing Substituents Direct the Position of Electrophilic Aromatic Substitution 677
15.9 Activating and Deactivating Effects: How Electron-Donating and Electron-Withdrawing Groups Affect the Rate of an EAS Reaction 684
15.10 Directing Effects in Disubstituted Benzenes 685
15.11 Reactions of Benzene Ring Carbon Side Chains 686
15.12 Synthetic Strategies 689
15.13 The SNAr Mechanism: Nucleophilic Aromatic Substitution by Addition-Elimination 691
15.14 Benzyne: Nucleophilic Aromatic Substitution by Elimination–Addition 694
15.15 Reduction of Aromatic Compounds 697
16 Aldehydes and Ketones NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 711
16.1 Introduction 712
16.2 Nomenclature of Aldehydes and Ketones 712
16.3 Physical Properties 714
16.4 Synthesis of Aldehydes 715
16.5 Synthesis of Ketones 720
16.6 Nucleophilic Addition to the Carbon–Oxygen Double Bond: Mechanistic Themes 723
16.7 The Addition of Alcohols: Hemiacetals and Acetals 726
16.8 The Addition of Primary and Secondary Amines 731
16.9 The Addition of Hydrogen Cyanide: Cyanohydrins 736
16.10 The Addition of Ylides: The Wittig Reaction 737
16.11 Oxidation of Aldehydes 741
16.12 The Baeyer–Villiger Oxidation 741
16.13 Chemical Analyses for Aldehydes and Ketones 743
16.14 Spectroscopic Properties of Aldehydes and Ketones 743
16.15 Summary of Aldehyde and Ketone Addition Reactions 746
17 Carboxylic Acids and Their Derivatives NUCLEOPHILIC ADDITION– ELIMINATION AT THE ACYL CARBON 761
17.1 Introduction 762
17.2 Nomenclature and Physical Properties 762
17.3 Preparation of Carboxylic Acids 770
17.4 Acyl Substitution: Nucleophilic Addition–Elimination at the Acyl Carbon 773
17.5 Acyl Chlorides 775
17.6 Carboxylic Acid Anhydrides 777
17.7 Esters 778
17.8 Amides 784
17.9 Derivatives of Carbonic Acid 792
17.10 Decarboxylation of Carboxylic Acids 795
17.11 Polyesters and Polyamides: Step-Growth Polymers 797
17.12 Summary of the Reactions of Carboxylic Acids and Their Derivatives 798
18 Reactions at the α Carbon of Carbonyl Compounds ENOLS AND ENOLATES 811
18.1 The Acidity of the α Hydrogens of Carbonyl Compounds: Enolate Anions 812
18.2 Keto and Enol Tautomers 813
18.3 Reactions via Enols and Enolates 815
18.4 Lithium Enolates 821
18.5 Enolates of β-Dicarbonyl Compounds 824
18.6 Synthesis of Methyl Ketones: The Acetoacetic Ester Synthesis 825
18.7 Synthesis of Substituted Acetic Acids: The Malonic Ester Synthesis 830
18.8 Further Reactions of Active Hydrogen Compounds 833
18.9 Synthesis of Enamines: Stork Enamine Reactions 834
18.10 Summary of Enolate Chemistry 837
19 Condensation and Conjugate Addition Reactions of Carbonyl Compounds MORE CHEMISTRY OF ENOLATES 849
19.1 Introduction 850
19.2 The Claisen Condensation: A Synthesis of β-Keto Esters 850
19.3  β-Dicarbonyl Compounds by Acylation of Ketone Enolates 855
19.4 Aldol Reactions: Addition of Enolates and Enols to Aldehydes and Ketones 856
19.5 Crossed Aldol Condensations 861
19.6 Cyclizations via Aldol Condensations 867
19.7 Additions to  α,β-Unsaturated Aldehydes and Ketones 869
19.8 The Mannich Reaction 874
19.9 Summary of Important Reactions 876
20 Amines 890
20.1 Nomenclature 891
20.2 Physical Properties and Structure of Amines 892
20.3 Basicity of Amines: Amine Salts 894
20.4 Preparation of Amines 901
20.5 Reactions of Amines 909
20.6 Reactions of Amines with Nitrous Acid 911
20.7 Replacement Reactions of Arenediazonium Salts 913
20.8 Coupling Reactions of Arenediazonium Salts 917
20.9 Reactions of Amines with Sulfonyl Chlorides 919
20.10 Synthesis of Sulfa Drugs 921
20.11 Analysis of Amines 921
20.12 Eliminations Involving Ammonium Compounds 923
20.13 Summary of Preparations and Reactions of Amines 924
21 Transition Metal Complexes PROMOTERS OF KEY BOND-FORMING REACTIONS 938
21.1 Organometallic Compounds in Previous Chapters 939
21.2 Transition Metal Elements and Complexes 939
21.3 HOW TO Count Electrons in a Metal Complex 940
21.4 Mechanistic Steps in the Reactions of Some Transition Metal Complexes 942
21.5 Homogeneous Hydrogenation: Wilkinson’s Catalyst 944
21.6 Cross-Coupling Reactions 947
21.7 Olefin Metathesis 955
21.8 Transition Metals in Nature: Vitamin B12 and Vanadium Haloperoxidases 958
22 Carbohydrates 965
22.1 Introduction 966
22.2 Monosaccharides 968
22.3 Mutarotation 973
22.4 Glycoside Formation 974
22.5 Other Reactions of Monosaccharides 976
22.6 Oxidation Reactions of Monosaccharides 979
22.7 Reduction of Monosaccharides: Alditols 984
22.8 Reactions of Monosaccharides with Phenylhydrazine: Osazones 984
22.9 Synthesis and Degradation of Monosaccharides 986
22.10 The d Family of Aldoses 988
22.11 Fischer’s Proof of the Configuration of d-(+)-Glucose 988
22.12 Disaccharides 990
22.13 Polysaccharides 994
22.14 Other Biologically Important Sugars 998
22.15 Sugars that Contain Nitrogen 999
22.16 Glycolipids and Glycoproteins of the Cell Surface: Cell Recognition and the Immune System 1001
22.17 Carbohydrate Antibiotics 1003
22.18 Summary of Reactions of Carbohydrates 1004
23 Lipids 1011
23.1 Introduction 1012
23.2 Fatty Acids and Triacylglycerols 1012
23.3 Terpenes and Terpenoids 1021
23.4 Steroids 1026
23.5 Prostaglandins 1035
23.6 Phospholipids and Cell Membranes 1036
23.7 Waxes 1040
24 Amino Acids and Proteins 1045
24.1 Introduction 1046
24.2 Amino Acids 1047
24.3 Synthesis of α-Amino Acids 1053
24.4 Polypeptides and Proteins 1055
24.5 Primary Structure of Polypeptides and Proteins 1058
24.6 Examples of Polypeptide and Protein Primary Structure 1062
24.7 Polypeptide and Protein Synthesis 1065
24.8 Secondary, Tertiary, and Quaternary Structures of Proteins 1071
24.9 Introduction to Enzymes 1075
24.10 Lysozyme: Mode of Action of an Enzyme 1077
24.11 Serine Proteases 1079
24.12 Hemoglobin: A Conjugated Protein 1081
24.13 Purification and Analysis of Polypeptides and Proteins 1083
24.14 Proteomics 1085
25 Nucleic Acids and Protein Synthesis 1090
25.1 Introduction 1091
25.2 Nucleotides and Nucleosides 1092
25.3 Laboratory Synthesis of Nucleosides and Nucleotides 1095
25.4 Deoxyribonucleic Acid: DNA 1098
25.5 RNA and Protein Synthesis 1105
25.6 Determining the Base Sequence of DNA: The Chain-Terminating (Dideoxynucleotide) Method 1113
25.7 Laboratory Synthesis of Oligonucleotides 1116
25.8 Polymerase Chain Reaction 1118
25.9 Sequencing of the Human Genome: An Instruction Book for the Molecules of Life 1120
ANSWERS TO SELECTED PROBLEMS A-1
GLOSSARY GL-1
INDEX I-1