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More About This Title Organic Chemistry, Eleventh Edition
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English
1 The Basics
BONDING AND MOLECULAR STRUCTURE 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 130
3.12 Organic Compounds as Bases 130
3.13 A Mechanism for an Organic Reaction 132
3.14 Acids and Bases in Nonaqueous Solutions 133
3.15 Acid–Base Reactions and the Synthesis of Deuterium- and Tritium-Labeled Compounds 134
3.16 Applications of Basic Principles 135
4 Nomenclature and Conformations of Alkanes and Cycloalkanes 142
4.1 Introduction to Alkanes and Cycloalkanes 143
4.2 Shapes of Alkanes 144
4.3 HOW TO Name Alkanes, Alkyl Halides, and Alcohols: The IUPAC System 146
4.4 HOW TO Name Cycloalkanes 153
4.5 HOW TO Name Alkenes and Cycloalkenes 156
4.6 HOW TO Name Alkynes 158
4.7 Physical Properties of Alkanes and Cycloalkanes 159
4.8 Sigma Bonds and Bond Rotation 162
4.9 Conformational Analysis of Butane 164
4.10 The Relative Stabilities of Cycloalkanes: Ring Strain 167
4.11 Conformations of Cyclohexane: The Chair and the Boat 168
4.12 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Groups 171
4.13 Disubstituted Cycloalkanes: Cis–Trans Isomerism 175
4.14 Bicyclic and Polycyclic Alkanes 179
4.15 Chemical Reactions of Alkanes 180
4.16 Synthesis of Alkanes and Cycloalkanes 180
4.17 HOW TO Gain Structural Information from Molecular Formulas and the Index of Hydrogen Deficiency 182
4.18 Applications of Basic Principles 184
5 Stereochemistry
CHIRAL MOLECULES 191
5.1 Chirality and Stereochemistry 192
5.2 Isomerism: Constitutional Isomers and Stereoisomers 193
5.3 Enantiomers and Chiral Molecules 195
5.4 Molecules Having One Chirality Center are Chiral 196
5.5 More about the Biological Importance of Chirality 199
5.6 HOW TO Test for Chirality: Planes of Symmetry 201
5.7 Naming Enantiomers: The R,S-System 202
5.8 Properties of Enantiomers: Optical Activity 206
5.9 The Origin of Optical Activity 211
5.10 The Synthesis of Chiral Molecules 213
5.11 Chiral Drugs 215
5.12 Molecules with More than One Chirality Center 217
5.13 Fischer Projection Formulas 223
5.14 Stereoisomerism of Cyclic Compounds 225
5.15 Relating Configurations through Reactions in which No Bonds to the Chirality Center Are Broken 227
5.16 Separation of Enantiomers: Resolution 231
5.17 Compounds with Chirality Centers Other than Carbon 232
5.18 Chiral Molecules That Do Not Possess a Chirality Center 232
6 Ionic Reactions
NUCLEOPHILIC SUBSTITUTION AND ELIMINATION REACTIONS OF ALKYL HALIDES 239
6.1 Alkyl Halides 240
6.2 Nucleophilic Substitution Reactions 241
6.3 Nucleophiles 243
6.4 Leaving Groups 245
6.5 Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction 245
6.6 A Mechanism for the SN2 Reaction 246
6.7 Transition State Theory: Free-Energy Diagrams 248
6.8 The Stereochemistry of SN2 Reactions 251
6.9 The Reaction of Tert-Butyl Chloride with Water: An SN1 Reaction 253
6.10 A Mechanism for the SN1 Reaction 254
6.11 Carbocations 256
6.12 The Stereochemistry of SN1 Reactions 258
6.13 Factors Affecting the Rates of SN1 and SN2 Reactions 261
6.14 Organic Synthesis: Functional Group Transformations Using SN2 Reactions 271
6.15 Elimination Reactions of Alkyl Halides 275
6.16 The E2 Reaction 276
6.17 The E1 Reaction 278
6.18 HOW TO Determine Whether Substitution or Elimination Is Favored 280
6.19 Overall Summary 282
7 Alkenes and Alkynes I
PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES 291
7.1 Introduction 292
7.2 The (E)–(Z) System for Designating Alkene Diastereomers 292
7.3 Relative Stabilities of Alkenes 293
7.4 Cycloalkenes 296
7.5 Synthesis of Alkenes via Elimination Reactions 296
7.6 Dehydrohalogenation of Alkyl Halides 297
7.7 Acid-Catalyzed Dehydration of Alcohols 303
7.8 Carbocation Stability and the Occurrence of Molecular Rearrangements 309
7.9 The Acidity of Terminal Alkynes 313
7.10 Synthesis of Alkynes by Elimination Reactions 314
7.11 Terminal Alkynes Can Be Converted to Nucleophiles for Carbon–Carbon Bond Formation 316
7.12 Hydrogenation of Alkenes 318
7.13 Hydrogenation: The Function of the Catalyst 320
7.14 Hydrogenation of Alkynes 321
7.15 An Introduction to Organic Synthesis 323
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 Nuclear Spin: The Origin of the Signal 401
9.5 Detecting the Signal: Fourier Transform NMR Spectrometers 403
9.6 The Chemical Shift 405
9.7 Shielding and Deshielding of Protons 406
9.8 Chemical Shift Equivalent and Nonequivalent Protons 408
9.9 Signal Splitting: Spin–Spin Coupling 411
9.10 Proton NMR Spectra and Rate Processes 420
9.11 Carbon-13 NMR Spectroscopy 422
9.12 Two-Dimensional (2D) NMR Techniques 428
9.13 An Introduction to Mass Spectrometry 431
9.14 Formation of Ions: Electron Impact Ionization 432
9.15 Depicting the Molecular Ion 432
9.16 Fragmentation 433
9.17 Isotopes in Mass Spectra 440
9.18 GC/MS Analysis 443
9.19 Mass Spectrometry of Biomolecules 444
10 Radical Reactions 457
10.1 Introduction: How Radicals Form and How They React 458
10.2 Homolytic Bond Dissociation Energies (DH) 460
10.3 Reactions of Alkanes with Halogens 463
10.4 Chlorination of Methane: Mechanism of Reaction 465
10.5 Halogenation of Higher Alkanes 468
10.6 The Geometry of Alkyl Radicals 471
10.7 Reactions That Generate Tetrahedral Chirality Centers 471
10.8 Allylic Substitution and Allylic Radicals 475
10.9 Benzylic Substitution and Benzylic Radicals 478
10.10 Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide 481
10.11 Radical Polymerization of Alkenes: Chain-Growth Polymers 483
10.12 Other Important Radical Reactions 487
11 Alcohols and Ethers
SYNTHESIS AND REACTIONS 498
11.1 Structure and Nomenclature 499
11.2 Physical Properties of Alcohols and Ethers 501
11.3 Important Alcohols and Ethers 503
11.4 Synthesis of Alcohols from Alkenes 505
11.5 Reactions of Alcohols 507
11.6 Alcohols as Acids 509
11.7 Conversion of Alcohols into Alkyl Halides 510
11.8 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides 510
11.9 Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl2 513
11.10 Tosylates, Mesylates, and Triflates: Leaving Group Derivatives of Alcohols 514
11.11 Synthesis of Ethers 517
11.12 Reactions of Ethers 522
11.13 Epoxides 523
11.14 Reactions of Epoxides 525
11.15 Anti 1,2-Dihydroxylation of Alkenes via Epoxides 528
11.16 Crown Ethers 531
11.17 Summary of Reactions of Alkenes, Alcohols, and Ethers 532
12 Alcohols from Carbonyl Compounds
OXIDATION–REDUCTION AND ORGANOMETALLIC COMPOUNDS 542
12.1 Structure of the Carbonyl Group 543
12.2 Oxidation–Reduction Reactions in Organic Chemistry 544
12.3 Alcohols by Reduction of Carbonyl Compounds 546
12.4 Oxidation of Alcohols 551
12.5 Organometallic Compounds 556
12.6 Preparation of Organolithium and Organomagnesium Compounds 557
12.7 Reactions of Organolithium and Organomagnesium Compounds 558
12.8 Alcohols from Grignard Reagents 561
12.9 Protecting Groups 570
13 Conjugated Unsaturated Systems 581
13.1 Introduction 582
13.2 The Stability of the Allyl Radical 582
13.3 The Allyl Cation 586
13.4 Resonance Theory Revisited 587
13.5 Alkadienes and Polyunsaturated Hydrocarbons 591
13.6 1,3-Butadiene: Electron Delocalization 592
13.7 The Stability of Conjugated Dienes 595
13.8 Ultraviolet–Visible Spectroscopy 596
13.9 Electrophilic Attack on Conjugated Dienes: 1,4-Addition 604
13.10 The Diels–Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes 608
14 Aromatic Compounds 626
14.1 The Discovery of Benzene 627
14.2 Nomenclature of Benzene Derivatives 628
14.3 Reactions of Benzene 630
14.4 The Kekulé Structure for Benzene 631
14.5 The Thermodynamic Stability of Benzene 632
14.6 Modern Theories of the Structure of Benzene 634
14.7 Hückel’s Rule: The 4n2 p Electron Rule 637
14.8 Other Aromatic Compounds 645
14.9 Heterocyclic Aromatic Compounds 648
14.10 Aromatic Compounds in Biochemistry 650
14.11 Spectroscopy of Aromatic Compounds 652
15 Reactions of Aromatic Compounds 669
15.1 Electrophilic Aromatic Substitution Reactions 670
15.2 A General Mechanism for Electrophilic Aromatic Substitution 671
15.3 Halogenation of Benzene 673
15.4 Nitration of Benzene 674
15.5 Sulfonation of Benzene 675
15.6 Friedel–Crafts Alkylation 676
15.7 Friedel–Crafts Acylation 678
15.8 Limitations of Friedel–Crafts Reactions 680
15.9 Synthetic Applications of Friedel–Crafts Acylations: The Clemmensen and Wolff–Kishner Reductions 683
15.10 Substituents Can Affect Both the Reactivity of the Ring and the Orientation of the Incoming Group 685
15.11 How Substituents Affect Electrophilic Aromatic Substitution: A Closer Look 690
15.12 Reactions of the Side Chain of Alkylbenzenes 699
15.13 Alkenylbenzenes 702
15.14 Synthetic Applications 704
15.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions 708
15.16 Reduction of Aromatic Compounds 710
16 Aldehydes and Ketones
NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 720
16.1 Introduction 721
16.2 Nomenclature of Aldehydes and Ketones 721
16.3 Physical Properties 723
16.4 Synthesis of Aldehydes 724
16.5 Synthesis of Ketones 729
16.6 Nucleophilic Addition to the Carbon–Oxygen Double Bond 732
16.7 The Addition of Alcohols: Hemiacetals and Acetals 735
16.8 The Addition of Primary and Secondary Amines 741
16.9 The Addition of Hydrogen Cyanide: Cyanohydrins 746
16.10 The Addition of Ylides: The Wittig Reaction 747
16.11 Oxidation of Aldehydes 751
16.12 The Baeyer–Villiger Oxidation 751
16.13 Chemical Analyses for Aldehydes and Ketones 753
16.14 Spectroscopic Properties of Aldehydes and Ketones 753
16.15 Summary of Aldehyde and Ketone Addition Reactions 756
17 Carboxylic Acids and Their Derivatives
NUCLEOPHILIC ADDITION–ELIMINATION AT THE ACYL CARBON 771
17.1 Introduction 772
17.2 Nomenclature and Physical Properties 772
17.3 Preparation of Carboxylic Acids 781
17.4 Acyl Substitution: Nucleophilic Addition–Elimination at the Acyl Carbon 784
17.5 Acyl Chlorides 786
17.6 Carboxylic Acid Anhydrides 788
17.7 Esters 789
17.8 Amides 796
17.9 Derivatives of Carbonic Acid 802
17.10 Decarboxylation of Carboxylic Acids 805
17.11 Chemical Tests for Acyl Compounds 807
17.12 Polyesters and Polyamides: Step-Growth Polymers 807
17.13 Summary of the Reactions of Carboxylic Acids and Their Derivatives 809
18 Reactions at the A Carbon of Carbonyl Compounds
ENOLS AND ENOLATES 821
18.1 The Acidity of the a Hydrogens of Carbonyl Compounds: Enolate Anions 822
18.2 Keto and Enol Tautomers 823
18.3 Reactions via Enols and Enolates 825
18.4 Lithium Enolates 831
18.5 Enolates of b-Dicarbonyl Compounds 834
18.6 Synthesis of Methyl Ketones: The Acetoacetic Ester Synthesis 835
18.7 Synthesis of Substituted Acetic Acids: The Malonic Ester Synthesis 840
18.8 Further Reactions of Active Hydrogen Compounds 844
18.9 Synthesis of Enamines: Stork Enamine Reactions 844
18.10 Summary of Enolate Chemistry 847
19 Condensation and Conjugate Addition Reactions of Carbonyl Compounds
MORE CHEMISTRY OF ENOLATES 858
19.1 Introduction 859
19.2 The Claisen Condensation: A Synthesis of b-Keto Esters 859
19.3 b-Dicarbonyl Compounds by Acylation of Ketone Enolates 864
19.4 Aldol Reactions: Addition of Enolates and Enols to Aldehydes and Ketones 865
19.5 Crossed Aldol Condensations 871
19.6 Cyclizations via Aldol Condensations 876
19.7 Additions to a,b-Unsaturated Aldehydes and Ketones 877
19.8 The Mannich Reaction 882
19.9 Summary of Important Reactions 884
20 Amines 897
20.1 Nomenclature 898
20.2 Physical Properties and Structure of Amines 899
20.3 Basicity of Amines: Amine Salts 901
20.4 Preparation of Amines 908
20.5 Reactions of Amines 917
20.6 Reactions of Amines with Nitrous Acid 918
20.7 Replacement Reactions of Arenediazonium Salts 920
20.8 Coupling Reactions of Arenediazonium Salts 924
20.9 Reactions of Amines with Sulfonyl Chlorides 926
20.10 Synthesis of Sulfa Drugs 928
20.11 Analysis of Amines 929
20.12 Eliminations Involving Ammonium Compounds 931
20.13 Summary of Preparations and Reactions of Amines 932
21 Phenols and Aryl Halides
NUCLEOPHILIC AROMATIC SUBSTITUTION 944
21.1 Structure and Nomenclature of Phenols 945
21.2 Naturally Occurring Phenols 946
21.3 Physical Properties of Phenols 947
21.4 Synthesis of Phenols 947
21.5 Reactions of Phenols as Acids 949
21.6 Other Reactions of the OH Group of Phenols 952
21.7 Cleavage of Alkyl Aryl Ethers 952
21.8 Reactions of the Benzene Ring of Phenols 953
21.9 The Claisen Rearrangement 956
21.10 Quinones 957
21.11 Aryl Halides and Nucleophilic Aromatic Substitution 959
21.12 Spectroscopic Analysis of Phenols and Aryl Halides 966
22 Carbohydrates 979
22.1 Introduction 980
22.2 Monosaccharides 982
22.3 Mutarotation 987
22.4 Glycoside Formation 988
22.5 Other Reactions of Monosaccharides 990
22.6 Oxidation Reactions of Monosaccharides 994
22.7 Reduction of Monosaccharides: Alditols 999
22.8 Reactions of Monosaccharides with Phenylhydrazine: Osazones 999
22.9 Synthesis and Degradation of Monosaccharides 1000
22.10 The D Family of Aldoses 1002
22.11 Fischer’s Proof of the Configuration of D-(+)-Glucose 1003
22.12 Disaccharides 1005
22.13 Polysaccharides 1009
22.14 Other Biologically Important Sugars 1013
22.15 Sugars That Contain Nitrogen 1014
22.16 Glycolipids and Glycoproteins of the Cell Surface: Cell Recognition and the Immune System 1016
22.17 Carbohydrate Antibiotics 1018
22.18 Summary of Reactions of Carbohydrates 1019
23 Lipids 1027
23.1 Introduction 1028
23.2 Fatty Acids and Triacylglycerols 1028
23.3 Terpenes and Terpenoids 1037
23.4 Steroids 1040
23.5 Prostaglandins 1049
23.6 Phospholipids and Cell Membranes 1050
23.7 Waxes 1054
24 Amino Acids and Proteins 1060
24.1 Introduction 1061
24.2 Amino Acids 1062
24.3 Synthesis of a-Amino Acids 1068
24.4 Polypeptides and Proteins 1070
24.5 Primary Structure of Polypeptides and Proteins 1073
24.6 Examples of Polypeptide and Protein Primary Structure 1077
24.7 Polypeptide and Protein Synthesis 1080
24.8 Secondary, Tertiary, and Quaternary Structures of Proteins 1086
24.9 Introduction to Enzymes 1090
24.10 Lysozyme: Mode of Action of an Enzyme 1092
24.11 Serine Proteases 1094
24.12 Hemoglobin: A Conjugated Protein 1096
24.13 Purification and Analysis of Polypeptides and Proteins 1098
25 Nucleic Acids and Protein Synthesis 1105
25.1 Introduction 1106
25.2 Nucleotides and Nucleosides 1107
25.3 Laboratory Synthesis of Nucleosides and Nucleotides 1110
25.4 Deoxyribonucleic Acid: DNA 1113
25.5 RNA and Protein Synthesis 1120
25.6 Determining the Base Sequence of DNA: The Chain-Terminating (Dideoxynucleotide) Method 1128
25.7 Laboratory Synthesis of Oligonucleotides 1131
25.8 The Polymerase Chain Reaction 1133
25.9 Sequencing of the Human Genome: An Instruction Book for the Molecules of Life 1135
ANSWERS TO SELECTED PROBLEMS A-1
GLOSSARY GL-1
INDEX I-1
