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Leading reference on the theories of organic chemistry, now updated to reflect the most recent literature from 2018 to 2023
Building on the success of the 8th Edition as winner of the Textbook & Academic Authors Association 2021 McGuffey Longevity Award, the revised and updated 9th Edition of March's Advanced Organic Chemistryexplains the theories of organic chemistry, covers new advances in areas of organic chemistry published between 2018 and 2023, and guides readers to plan and execute multi-step synthetic reactions. Detailed examples and descriptions of all reactions are included throughout the text.
As in previous editions, the goal of this edition is to give equal weight to three fundamental aspects of the study of organic chemistry: reactions, mechanisms, and structure. Specific but specialized areas of organic chemistry, such as terpenes, polymerization, and steroids, have been incorporated into primary sections rather than segregated into their own sections.
The first nine chapters cover general organic chemistry with theoretical principles. The next 10 chapters address reactions and mechanistic discussion. Appendix A focuses on literature references and resources. More than 4,400 references are included throughout the text.
March's Advanced Organic Chemistry provides information on:
Localized and delocalized chemical bonding and bonding weaker than covalent
Microwave chemistry, use of ultrasound, mechanochemistry, and reactions done under flow conditions
Acids and bases, irradiation processes, stereochemistry, structure of intermediates, and ordinary and photochemical reactions
Mechanisms and methods of determining carbocations, carbanions, free radicals, carbenes, and nitrenes
Aliphatic, alkenyl, and alkynyl substitution, additions to carbon-carbon and carbon-hetero bonds, eliminations, rearrangements, and oxidations and reductions
This 9th Edition of March's Advanced Organic Chemistry continues to serve as a must-have reference for every student and professional working in organic chemistry or related fields.
Contents
New Reaction Sections Correlation: 8th Edition → 9th Editions xiii
Preface xix
Common Abbreviations xxi
Biographical Statement xxvii
New Features of the 9th Edition xxix
Part I Introduction 1
1. Localized Chemical Bonding 3
1.a. Covalent Bonding 3
1.b. Multiple Valence 6
1.c. Hybridization 6
1.d. Multiple Bonds 7
1.e. Photoelectron Spectroscopy 9
1.f. Electronic Structures of Molecules 11
1.g. Electronegativity 13
1.h. Dipole Moment 15
1.i. Inductive and Field Effects 16
1.j. Bond Distances 19
1.k. Bond Angles 22
1.l. Bond Energies 23
2. Delocalized Chemical Bonding 27
2.a. Molecular Orbitals 28
2.b. Bond Energies and Distances in Compounds Containing Delocalized Bonds 31
2.c. Molecules that have Delocalized Bonds 32
2.d. Cross- Conjugation 35
2.e. The Rules of Resonance 36
2.f. The Resonance Effect 37
2.g. Steric Inhibition of Resonance and the Influences of Strain 37
2.h. pπ-dπ Bonding. Ylids 40
2.i. Aromaticity 42
2.I.i. Six- Membered Rings 45
2.I.ii. Five- , Seven- , and Eight- Membered Rings 48
2.I.iii. Other Systems Containing Aromatic Sextets 52
2.j. Alternant and Nonalternant Hydrocarbons 54
2.k. Aromatic Systems with Electron Numbers other than Six 54
2.K.i. Systems of Two Electrons 55
2.K.ii. Systems of Four Electrons: Antiaromaticity 56
2.K.iii. Systems of Eight Electrons 59
2.K.iv. Systems of Ten Electrons 60
2.K.v. Systems of More than Ten Electrons: 4n + 2 Electrons 62
2.K.vi. Systems of More than Ten Electrons: 4n Electrons 66
2.l. Other Aromatic Compounds 70
2.M. Hyperconjugation 72
2.n. Tautomerism 75
2.N.i. Keto- Enol Tautomerism 75
2.N.ii. Other Proton- Shift Tautomerism 79
3. Bonding Weaker Than Covalent 83
3.a. Hydrogen Bonding 83
3.b. π-π Interactions 90
3.c. Addition Compounds 91
3.C.i. Electron Donor-Acceptor Complexes 92
3.C.ii. Crown Ether Complexes and Cryptates 94
3.C.iii. Inclusion Compounds 99
3.C.iv. Cyclodextrins 102
3.d. Catenanes and Rotaxanes 104
3.e. Cucurbit[n]Uril- Based Gyroscane 107
4. Stereochemistry and Conformation 109
4.a. Optical Activity and Chirality 109
4.b. Dependence of Rotation on Conditions of Measurement 111
4.c. What kinds of Molecules Display Optical Activity? 112
4.d. The Fischer Projection 121
4.e. Absolute Configuration 121
4.E.i. The Cahn-Ingold-Prelog System 122
4.E.ii. Methods of Determining Configuration 125
4.f. Optical Purity 128
4.g. The Cause of Optical Activity 130
4.h. Molecules with more than One Stereogenic Center 131
4.i. Asymmetric Synthesis 134
4.j. Methods of Resolution 137
4.k. Cis-Trans Isomerism 142
4.K.i. Cis-Trans Isomerism Resulting from Double Bonds 142
4.K.ii. Cis-Trans Isomerism of Monocyclic Compounds 145
4.K.iii. Cis-Trans Isomerism of Fused and Bridged Ring Systems 146
4.l. Out-In Isomerism 147
4.M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 149
4.n. Stereospecific and Stereoselective Syntheses 151
4.o. Conformational Analysis 152
4.O.i. Conformation in Open- Chain Systems 153
4.O.ii. Conformation in Six- Membered Rings 158
4.O.iii. Conformation in Six- Membered Rings Containing Heteroatoms 162
4.O.iv. Conformation in Other Rings 164
4.p. Molecular Mechanics 166
4.q. Strain 168
4.Q.i. Strain in Small Rings 168
4.Q.ii. Strain in Other Rings 172
4.Q.iii. Unsaturated Rings 174
4.Q.iv. Strain Due to Unavoidable Crowding 177
5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 181
5.a. Carbocations 182
5.A.i. Nomenclature 182
5.A.ii. Stability and Structure of Carbocations 182
5.A.iii. The Generation and Fate of Carbocations 190
5.b. Carbanions 192
5.B.i. Stability and Structure 192
5.B.ii. The Structure of Grignard Reagents and Organolithium Reagents 198
5.B.iii. The Generation and Fate of Carbanions 201
5.c. Free Radicals 202
5.C.i. Stability and Structure 202
5.C.ii. The Generation and Fate of Free Radicals 212
5.C.iii. Radical Ions 215
5.d. Carbenes 217
5.D.i. Stability and Structure 217
5.D.ii. The Generation and Fate of Carbenes 220
5.D.iii. N- Heterocyclic Carbenes 223
5.e. Nitrenes 225
6. Mechanisms and Methods of Determining Them 229
6.a. Types of Mechanism 229
6.b. Types of Reaction 230
6.c. Thermodynamic Requirements for Reaction 232
6.d. Kinetic Requirements for Reaction 233
6.e. The Baldwin Rules for Ring Closure 236
6.f. Kinetic and Thermodynamic Control 238
6.g. The Hammond Postulate 238
6.h. Microscopic Reversibility 239
6.i. Marcus Theory 239
6.j. Methods of Determining Mechanisms 240
6.J.i. Identification of Products 241
6.J.ii. Determination of the Presence of an Intermediate 241
6.J.iii. The Study of Catalysis 242
6.J.iv. Isotopic Labeling 243
6.J.v. Stereochemical Evidence 243
6.J.vi. Kinetic Evidence 244
6.J.vii. Isotope Effects 250
6.k. Catalyst Development 253
7. Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 257
7.a. Photochemistry 257
7.A.i. Excited States and the Ground State 257
7.A.ii. Singlet and Triplet States: "Forbidden" Transitions 259
7.A.iii. Types of Excitation 260
7.A.iv. Nomenclature and Properties of Excited States 262
7.A.v. Photolytic Cleavage 262
7.A.vi. The Fate of the Excited Molecule: Physical Processes 263
7.A.vii. The Fate of the Excited Molecule: Chemical Processes 267
7.A.viii. The Determination of Photochemical Mechanisms 271
7.b. Sonochemistry 272
7.c. Microwave Chemistry 274
7.d. Flow Chemistry 275
7.e. Mechanochemistry 276
8. Acids and Bases 279
8.a. Brønsted Theory 279
8.A.i. Brønsted Acids 280
8.A.ii. Brønsted Bases 286
8.b. The Mechanism of Proton Transfer Reactions 289
8.c. Measurements of Solvent Acidity 290
8.d. Acid and Base Catalysis 293
8.e. Lewis Acids and Bases 295
8.E.i. Hard-Soft Acids-Bases 296
8.f. The Effects of Structure on the Strengths of Acids and Bases 298
8.g. The Effects of the Medium on Acid and Base Strength 306
9. Effects of Structure and Medium on Reactivity 309
9.a. Resonance and Field Effects 309
9.b. Steric Effects 311
9.c. Quantitative Treatments of the Effect of Structure on Reactivity 313
9.d. Effect of Medium on Reactivity and Rate 320
9.e. High Pressure 321
9.f. Water and other Nonorganic Solvents 321
9.g. Ionic Liquid Solvents 323
9.h. Solventless Reactions 325
Part II Introduction 327
10. Aliphatic Substitution: Nucleophilic and Organometallic 329
10.A. Mechanisms 330
10.A.i. The S N 2 Mechanism 330
10.A.ii. The S N 1 Mechanism 334
10.A.iii. Ion Pairs in the S N 1 Mechanism 338
10.A.iv. Mixed S N 1 and S N 2 Mechanisms 340
10.B. Set Mechanisms 342
10.C. The Neighboring- Group Mechanism 344
10.C.i. Neighboring- Group Participation by π and σ Bonds: Nonclassical Carbocations 347
10.D. The S N I Mechanism 359
10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 360
10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 363
10.G. Reactivity 366
10.G.i. The Effect of Substrate Structure 366
10.G.ii. The Effect of the Attacking Nucleophile 374
10.G.iii. The Effect of the Leaving Group 378
10.G.iv. The Effect of the Reaction Medium 382
10.G.v. Phase- Transfer Catalysis 387
10.G.vi. Influencing Reactivity by External Means 389
10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 390
10.G.viii. Ambident Substrates 393
10.H. Reactions 394
11. Aromatic Substitution: Electrophilic 491
11.A. Mechanisms 491
11.A.i. The Arenium Ion Mechanism 491
11.B. Orientation and Reactivity 496
11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings 496
11.B.ii. The Ortho/Para Ratio 499
11.B.iii. Ipso Attack 500
11.B.iv. Orientation in Benzene Rings with more than one Substituent 501
11.B.v. Orientation in Other Ring Systems 502
11.C. Quantitative Treatments of Reactivity in the Substrate 504
11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 505
11.E. The Effect of the Leaving Group 507
11.F. Reactions 507
12. Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 555
12.A. Mechanisms 555
12.A.i. Bimolecular Mechanisms: S E 2 and S E I 556
12.A.ii. The S E 1 Mechanism 558
12.A.iii. Electrophilic Substitution Accompanied by Double- Bond Shifts 560
12.A.iv. Other Mechanisms 561
12.B. Reactivity 561
12.C. Reactions 562
13. Aromatic Substitution: Nucleophilic and Organometallic 617
13.A. Mechanisms 617
13.A.i. The S N Ar Mechanism 618
13.A.ii. The S N 1 Mechanism 620
13.A.iii. The Benzyne Mechanism 621
13.A.iv. The S RN 1 Mechanism 623
13.A.v. Other Mechanisms 624
13.B. Reactivity 625
13.B.i. The Effect of Substrate Structure 625
13.B.ii. The Effect of the Leaving Group 626
13.B.iii. The Effect of the Attacking Nucleophile 626
13.C. Reactions 627
14. Radical Reactions 677
14.A. Mechanisms 677
14.A.i. Radical Mechanisms in General 677
14.A.ii. Free- Radical Substitution Mechanisms 681
14.A.iii. Mechanisms at an Aromatic Substrate 682
14.A.iv. Neighboring- Group Assistance in Free- Radical Reactions 683
14.B. Reactivity 684
14.B.i. Reactivity for Aliphatic Substrates 684
14.B.ii. Reactivity at a Bridgehead 688
14.B.iii. Reactivity in Aromatic Substrates 689
14.B.iv. Reactivity in the Attacking Radical 690
14.B.v. The Effect of Solvent on Reactivity 690
14.C. Reactions 691
15. Addition to Carbon-Carbon Multiple Bonds 717
15.A. Mechanisms 717
15.A.i. Electrophilic Addition 717
15.A.ii. Nucleophilic Addition 719
15.A.iii. Free- Radical Addition 720
15.A.iv. Cyclic Mechanisms 722
15.A.v. Addition to Conjugated Systems 722
15.B. Orientation and Reactivity 722
15.B.i. Reactivity 722
15.B.ii. Orientation 725
15.B.iii. Stereochemical Orientation 727
15.B.iv. Addition to Cyclopropane Rings 728
15.C. Reactions 729
16. Addition to Carbon-Heteroatom Multiple Bonds 869
16.A. Mechanism and Reactivity 869
16.A.i. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 871
16.B. Reactions 874
17. Elimination Reactions 1001
17.A. Mechanisms and Orientation 1001
17.A.i. The E2 Mechanism 1002
17.A.ii. The E1 Mechanism 1006
17.A.iii. The E1cB Mechanism 1007
17.A.iv. The E1-E2-E1cB Spectrum 1011
17.A.v. The E2C Mechanism 1012
17.B. Regiochemistry of the Double Bond 1013
17.C. Stereochemistry of the Double Bond 1014
17.D. Reactivity 1015
17.D.i. Effect of Substrate Structure 1015
17.D.ii. Effect of the Attacking Base 1017
17.D.iii. Influence of the Leaving Group 1017
17.D.iv. Influence of the Medium 1018
17.E. Mechanisms and Orientation in Pyrolytic Eliminations 1018
17.E.i. Mechanisms 1018
17.E.ii. Orientation in Pyrolytic Eliminations 1020
17.F. Reactions 1021
18. Rearrangements 1047
18.A. Mechanisms 1048
18.A.i. Nucleophilic Rearrangements 1048
18.A.ii. The Actual Nature of the Migration 1049
18.A.iii. Migratory Aptitudes 1051
18.A.iv. Memory Effects 1052
18.B. Longer Nucleophilic Rearrangements 1053
18.C. Free- Radical Rearrangements 1054
18.D. Carbene Rearrangements 1057
18.E. Electrophilic Rearrangements 1057
18.F. Reactions 1057
19. Oxidations and Reductions 1123
19.A. Mechanisms 1125
19.B. Reactions 1126
19.B.i. Oxidations 1126
19.B.ii. Reductions 1172
Appendix A: the Literature of Organic Chemistry 1243
Indexes 1273
Author Index 1273
Subject Index 1501
