March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure / Edition 8 available in Hardcover
March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure / Edition 8
- ISBN-10:
- 1119371805
- ISBN-13:
- 9781119371809
- Pub. Date:
- 02/19/2020
- Publisher:
- Wiley
March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure / Edition 8
Hardcover
Buy New
$190.75Buy Used
$115.36-
SHIP THIS ITEM— Not Eligible for Free Shipping
-
SHIP THIS ITEM
Temporarily Out of Stock Online
Please check back later for updated availability.
-
Overview
The revised and updated 8th edition of March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure explains the theories of organic chemistry with examples and reactions. This book is the most comprehensive resource about organic chemistry available. Readers are guided on the planning and execution of multi-step synthetic reactions, with detailed descriptions of all the reactions
The opening chapters of March's Advanced Organic Chemistry, 8th Edition deal with the structure of organic compounds and discuss important organic chemistry bonds, fundamental principles of conformation, and stereochemistry of organic molecules, and reactive intermediates in organic chemistry. Further coverage concerns general principles of mechanism in organic chemistry, including acids and bases, photochemistry, sonochemistry and microwave irradiation. The relationship between structure and reactivity is also covered. The final chapters cover the nature and scope of organic reactions and their mechanisms. This edition:
- Provides revised examples and citations that reflect advances in areas of organic chemistry published between 2011 and 2017
- Includes appendices on the literature of organic chemistry and the classification of reactions according to the compounds prepared
- Instructs the reader on preparing and conducting multi-step synthetic reactions, and provides complete descriptions of each reaction
The 8th edition of March's Advanced Organic Chemistry proves once again that it is a must-have desktop reference and textbook for every student and professional working in organic chemistry or related fields.Winner of the Textbook & Acadmic Authors Association 2021 McGuffey Longevity Award.
Product Details
| ISBN-13: | 9781119371809 |
|---|---|
| Publisher: | Wiley |
| Publication date: | 02/19/2020 |
| Edition description: | 8th ed. |
| Pages: | 2144 |
| Product dimensions: | 7.20(w) x 10.20(h) x 2.90(d) |
About the Author
Read an Excerpt
Table of Contents
New Reaction Sections Correlation: 7th Edition → 8th Edition xvPreface xxi
Common Abbreviations xxv
Biographical Statement xxxi
New Features of the 8th Edition xxxiii
Part I Introduction 1
1. Localized Chemical Bonding 3
1.A. Covalent Bonding 3
1.B. Multiple Valence 7
1.C. Hybridization 7
1.D. Multiple Bonds 9
1.E. Photoelectron Spectroscopy 12
1.F. Electronic Structures of Molecules 15
1.G. Electronegativity 17
1.H. Dipole Moment 19
1.I. Inductive and Field Effects 20
1.J. Bond Distances 23
1.K. Bond Angles 27
1.L. Bond Energies 29
2. Delocalized Chemical Bonding 33
2.A. Molecular Orbitals 34
2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds 37
2.C. Molecules that have Delocalized Bonds 39
2.D. Cross Conjugation 44
2.E. The Rules of Resonance 46
2.F. The Resonance Effect 48
2.G. Steric Inhibition of Resonance and the Influences of Strain 48
2.H. pπ–dπ Bonding: Ylids 52
2.I. Aromaticity 54
2.I.i. Six-Membered Rings 58
2.I.ii. Five-, Seven-, and Eight-Membered Rings 62
2.I.iii. Other Systems Containing Aromatic Sextets 67
2.J. Alternant and Nonalternant Hydrocarbons 68
2.K. Aromatic Systems with Electron Numbers Other Than Six 70
2.K.i. Systems of Two Electrons 72
2.K.ii. Systems of Four Electrons: Antiaromaticity 73
2.K.iii. Systems of Eight Electrons 76
2.K.iv. Systems of Ten Electrons 77
2.K.v. Systems of More than Ten Electrons: 4n + 2 Electrons 80
2.K.vi. Systems of More Than Ten Electrons: 4n Electrons 85
2.L. Other Aromatic Compounds 89
2.M. Hyperconjugation 92
2.N. Tautomerism 96
2.N.i. Keto–Enol Tautomerism 97
2.N.ii. Other Proton-Shift Tautomerism 100
3. Bonding Weaker Than Covalent 105
3.A. Hydrogen Bonding 105
3.B. π–π Interactions 113
3.C. Addition Compounds 114
3.C.i. Electron Donor–Acceptor (EDA) Complexes 114
3.C.ii. Crown Ether Complexes and Cryptates 117
3.C.iii. Inclusion Compounds 122
3.C.iv. Cyclodextrins 125
3.D. Catenanes and Rotaxanes 127
3.E. Cucurbit[n]Uril-Based Gyroscane 131
4. Stereochemistry and Conformation 133
4.A. Optical Activity and Chirality 133
4.B. Dependence of Rotation on Conditions of Measurement 135
4.C. What Kinds of Molecules Display Optical Activity? 136
4.D. The Fischer Projection 147
4.E. Absolute Configuration 148
4.E.i. The Cahn-Ingold-Prelog System 150
4.E.ii. Methods of Determining Configuration 152
4.F. The Cause of Optical Activity 156
4.G. Molecules with More Than One Stereogenic Center 157
4.H. Asymmetric Synthesis 161
4.I. Methods of Resolution 166
4.J. Optical Purity 173
4.K. Cis–Trans Isomerism 175
4.K.i. Cis–Trans Isomerism Resulting from Double Bonds 175
4.K.ii. Cis–Trans Isomerism of Monocyclic Compounds 179
4.K.iii. Cis–Trans Isomerism of Fused and Bridged Ring Systems 180
4.L. Out–In Isomerism 181
4.M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 183
4.N. Stereospecific and Stereoselective Syntheses 186
4.O. Conformational Analysis 187
4.O.i. Conformation in Open-Chain Systems 188
4.O.ii. Conformation in Six-Membered Rings 194
4.O.iii. Conformation in Six-Membered Rings Containing Heteroatoms 199
4.O.iv. Conformation in Other Rings 202
4.P. Molecular Mechanics 204
4.Q. Strain 206
4.Q.i. Strain in Small Rings 207
4.Q.ii. Strain in Other Rings 213
4.Q.iii. Unsaturated Rings 215
4.Q.iv. Strain Due to Unavoidable Crowding 218
5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 223
5.A. Carbocations 224
5.A.i. Nomenclature 224
5.A.ii. Stability and Structure of Carbocations 224
5.A.iii. The Generation and Fate of Carbocations 234
5.B. Carbanions 237
5.B.i. Stability and Structure 237
5.B.ii. The Structure of Organometallic Compounds 244
5.B.iii. The Generation and Fate of Carbanions 249
5.C. Free Radicals 250
5.C.i. Stability and Structure 250
5.C.ii. The Generation and Fate of Free Radicals 261
5.C.iii. Radical Ions 265
5.D. Carbenes 266
5.D.i. Stability and Structure 266
5.D.ii. The Generation and Fate of Carbenes 269
5.D.iii. N-Heterocyclic Carbenes (NHCs) 274
5.E. Nitrenes 276
6. Mechanisms and Methods of Determining Them 279
6.A. Types of Mechanism 279
6.B. Types of Reaction 280
6.C. Thermodynamic Requirements for Reaction 283
6.D. Kinetic Requirements for Reaction 284
6.E. The Baldwin Rules for Ring Closure 288
6.F. Kinetic and Thermodynamic Control 290
6.G. The Hammond Postulate 291
6.H. Microscopic Reversibility 291
6.I. Marcus Theory 292
6.J. Methods of Determining Mechanisms 293
6.J.i. Identification of Products 293
6.J.ii. Determination of the Presence of an Intermediate 294
6.J.iii. The Study of Catalysis 295
6.J.iv. Isotopic Labeling 296
6.J.v. Stereochemical Evidence 296
6.J.vi. Kinetic Evidence 297
6.J.vii. Isotope Effects 304
6.K. Catalyst Development 308
7. Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 313
7.A. Photochemistry 314
7.A.i. Excited States and the Ground State 314
7.A.ii. Singlet and Triplet States: “Forbidden” Transitions 316
7.A.iii. Types of Excitation 317
7.A.iv. Nomenclature and Properties of Excited States 318
7.A.v. Photolytic Cleavage 319
7.A.vi. The Fate of the Excited Molecule: Physical Processes 320
7.A.vii. The Fate of the Excited Molecule: Chemical Processes 325
7.A.viii. The Determination of Photochemical Mechanisms 330
7.B. Sonochemistry 331
7.C. Microwave Chemistry 334
7.D. Flow Chemistry 336
7.E. Mechanochemistry 338
8. Acids and Bases 339
8.A. Brønsted Theory 339
8.A.i. Brønsted Acids 340
8.A.ii. Brønsted Bases 347
8.B. The Mechanism of Proton Transfer Reactions 350
8.C. Measurements of Solvent Acidity 352
8.D. Acid and Base Catalysis 355
8.E. Lewis Acids and Bases 357
8.E.i. Hard–Soft Acids–Bases 359
8.F. The Effects of Structure on the Strengths of Acids and Bases 361
8.G. The Effects of the Medium on Acid and Base Strength 370
9. Effects of Structure and Medium on Reactivity 375
9.A. Resonance and Field Effects 375
9.B. Steric Effects 377
9.C. Quantitative Treatments of the Effect of Structure on Reactivity 380
9.D. Effect of Medium on Reactivity and Rate 390
9.E. High Pressure 390
9.F. Water and Other Nonorganic Solvents 391
9.G. Ionic Liquid Solvents 393
9.H. Solventless Reactions 395
Part II Introduction 397
10. Aliphatic Substitution, Nucleophilic and Organometallic 403
10.A. Mechanisms 404
10.A.i. The SN2 Mechanism 404
10.A.ii. The SN1 Mechanism 410
10.A.iii. Ion Pairs in the SN1 Mechanism 414
10.A.iv. Mixed SN1 and SN2 Mechanisms 418
10.B. SET Mechanisms 420
10.C. The Neighboring-Group Mechanism 422
10.C.i. Neighboring-Group Participation by π and σ Bonds: Nonclassical Carbocations 425
10.D. The SNi Mechanism 440
10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 441
10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 445
10.G. Reactivity 449
10.G.i. The Effect of Substrate Structure 449
10.G.ii. The Effect of the Attacking Nucleophile 457
10.G.iii. The Effect of the Leaving Group 464
10.G.iv. The Effect of the Reaction Medium 469
10.G.v. Phase-Transfer Catalysis 474
10.G.vi. Influencing Reactivity by External Means 477
10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 478
10.G.viii. Ambident Substrates 481
10.H. Reactions 483
10.H.i. Oxygen Nucleophiles 483
10.H.ii. Sulfur Nucleophiles 506
10.H.iii. Nitrogen Nucleophiles 512
10.H.iv. Halogen Nucleophiles 534
10.H.v. Carbon Nucleophiles 545
11. Aromatic Substitution, Electrophilic 607
11.A. Mechanisms 607
11.A.i. The Arenium Ion Mechanism 608
11.A.ii. The SE1 Mechanism 613
11.B. Orientation and Reactivity 614
11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings 614
11.B.ii. The Ortho/Para Ratio 618
11.B.iii. Ipso Attack 620
11.B.iv. Orientation in Benzene Rings with More Than One Substituent 621
11.B.v. Orientation in Other Ring Systems 622
11.C. Quantitative Treatments of Reactivity in the Substrate 624
11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 626
11.E. The Effect of the Leaving Group 628
11.F. Reactions 629
11.F.i. Hydrogen as the Leaving Group in Simple Substitution Reactions 629
11.F.ii. Hydrogen as the Leaving Group in Rearrangement Reactions 675
11.F.iii. Other Leaving Groups 680
12. Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 687
12.A. Mechanisms 687
12.A.i. Bimolecular Mechanisms. SE2 and SEi 688
12.A.ii. The SE1 Mechanism 691
12.A.iii. Electrophilic Substitution Accompanied by Double-Bond Shifts 694
12.A.iv. Other Mechanisms 695
12.B. Reactivity 695
12.C. Reactions 697
12.C.i. Hydrogen as Leaving Group 697
12.C.ii. Metals as Leaving Groups 733
12.C.iii. Halogen as Leaving Group 746
12.C.iv. Carbon Leaving Groups 751
12.C.v. Electrophilic Substitution At Nitrogen 760
13. Aromatic Substitution: Nucleophilic and Organometallic 767
13.A. Mechanisms 768
13.A.i. The SNAr Mechanism 768
13.A.ii. The SN1 Mechanism 771
13.A.iii. The Benzyne Mechanism 772
13.A.iv. The SRN1 Mechanism 774
13.A.v. Other Mechanisms 776
13.B. Reactivity 776
13.B.i. The Effect of Substrate Structure 776
13.B.ii. The Effect of the Leaving Group 778
13.B.iii. The Effect of the Attacking Nucleophile 779
13.C. Reactions 779
13.C.i. All Leaving Groups Except Hydrogen and N2+ 779
13.C.ii. Hydrogen as Leaving Group 823
13.C.iii. Nitrogen as Leaving Group 824
13.C.iv. Rearrangements 834
14. Radical Reactions 839
14.A. Mechanisms 839
14.A.i. Radical Mechanisms in General 839
14.A.ii. Free-Radical Substitution Mechanisms 844
14.A.iii. Mechanisms at an Aromatic Substrate 845
14.A.iv. Neighboring-Group Assistance in Free-Radical Reactions 847
14.B. Reactivity 848
14.B.i. Reactivity for Aliphatic Substrates 848
14.B.ii. Reactivity at a Bridgehead 853
14.B.iii. Reactivity in Aromatic Substrates 854
14.B.iv. Reactivity in the Attacking Radical 855
14.B.v. The Effect of Solvent on Reactivity 856
14.C. Reactions 856
14.C.i. Hydrogen as Leaving Group 856
14.C.ii. Metals as Leaving Groups 880
14.C.iii. Halogen as Leaving Group 883
14.C.iv. Sulfur as Leaving Group 883
14.C.v. Carbon as Leaving Group 885
15. Addition to Carbon–Carbon Multiple Bonds 891
15.A. Mechanisms 892
15.A.i. Electrophilic Addition 892
15.A.ii. Nucleophilic Addition 895
15.A.iii. Free-Radical Addition 896
15.A.iv. Cyclic Mechanisms 898
15.A.v. Addition to Conjugated Systems 898
15.B. Orientation and Reactivity 899
15.B.i. Reactivity 899
15.B.ii. Orientation 902
15.B.iii. Stereochemical Orientation 904
15.B.iv. Addition to Cyclopropane Rings 906
15.C. Reactions 908
15.C.i. Isomerization of Double and Triple Bonds 908
15.C.ii. Reactions in Which Hydrogen Adds to One Side 910
15.C.iii. Reactions in Which Hydrogen Adds to Neither Side 992
15.C.iv. Cycloaddition Reactions 1027
16. Addition to Carbon–Heteroatom Multiple Bonds 1087
16.A. Mechanism and Reactivity 1087
16.A.i. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 1089
16.B. Reactions 1094
16.B.i. Reactions in Which Hydrogen or a Metallic Ion Adds to the Heteroatom 1095
16.B.ii. Acyl Substitution Reactions 1218
16.B.iii. Reactions in Which Carbon Adds to the Heteroatom 1257
16.B.iv. Addition to Isocyanides 1264
16.B.v. Nucleophilic Substitution at a Sulfonyl Sulfur Atom 1266
17. Elimination Reactions 1273
17.A. Mechanisms and Orientation 1273
17.A.i. The E2 Mechanism 1274
17.A.ii. The E1 Mechanism 1280
17.A.iii. The E1cB Mechanism 1281
17.A.iv. The E1-E2-E1cB Spectrum 1286
17.A.v. The E2C Mechanism 1287
17.B. Regiochemistry of the Double Bond 1288
17.C. Stereochemistry of the Double Bond 1290
17.D. Reactivity 1291
17.D.i. Effect of Substrate Structure 1291
17.D.ii. Effect of the Attacking Base 1293
17.D.iii. Effect of the Leaving Group 1294
17.D.iv. Effect of the Medium 1294
17.E. Mechanisms and Orientation in Pyrolytic Eliminations 1295
17.E.i. Mechanisms 1295
17.E.ii. Orientation in Pyrolytic Eliminations 1298
17.E.iii. 1,4 Conjugate Eliminations 1298
17.F. Reactions 1299
17.F.i. Reactions in Which C C and C≡C Bonds are Formed 1299
17.F.ii. Fragmentations 1321
17.F.iii. Reactions in Which C≡N or C N Bonds are Formed 1325
17.F.iv. Reactions in Which C O Bonds are Formed 1328
17.F.v. Reactions in Which N N Bonds are Formed 1329
17.F.vi. Extrusion Reactions 1329
18. Rearrangements 1335
18.A. Mechanisms 1336
18.A.i. Nucleophilic Rearrangements 1336
18.A.ii. The Actual Nature of the Migration 1337
18.A.iii. Migratory Aptitudes 1340
18.A.iv. Memory Effects 1343
18.B. Longer Nucleophilic Rearrangements 1344
18.C. Free-Radical Rearrangements 1345
18.D. Carbene Rearrangements 1349
18.E. Electrophilic Rearrangements 1349
18.F. Reactions 1350
18.F.i. 1,2-Rearrangements 1350
18.F.ii. Non 1,2-Rearrangements 1389
19. Oxidations and Reductions 1439
19.A. Mechanisms 1440
19.B. Reactions 1442
19.B.i. Oxidations 1442
19.B.ii. Reductions 1510
Appendix A: The Literature of Organic Chemistry 1607
Appendix B: Classification of Reactions by Type of Compounds Synthesized 1645
Indexes
Author Index 1669
Subject Index 1917
Preface
The goal, as in previous editions, is to give equal weight to the three fundamental aspects of the study of organic chemistry: reactions, mechanisms, and structure. A student who has completed a course based on this book should be able to approach the literature directly, with a sound knowledge of modern basic organic chemistry. Major special areas of organic chemistry (terpenes, carbohydrates, proteins, many organometallic reagents, combinatorial chemistry, polymerization and electrochemical reactions, steroids, etc.) have been treated lightly or ignored completely. I share Professor March's opinion that these topics are best approached after the first year of graduate study, when the fundamentals have been mastered, either in advanced courses, or directly, by consulting the many excellent books and review articles available on these subjects. In addition, many of these topics are so vast, they are beyond the scope of this book.
The organization is based on reaction types, so the student can be shown that despite the large number of organic reactions, a relatively few principles suffice to explain nearly all of them. Accordingly, the reactions-mechanisms section of this book (Part 2) is divided into 10 chapters (10-19), each concerned with a different type of reaction. In the first part of each chapter, the appropriate basic mechanisms are discussed along with considerations of reactivity and orientation, while the second part consists of numbered sections devoted to individual reactions, where the scope and the mechanism of each reaction are discussed. Numbered sections are used for the reactions. For a further discussion of the arrangement of Part 2, see page 382. Since the methods for the preparation of individual classes of compounds (e.g., ketones and nitriles) are not treated all in one place, an index has been provided (Appendix B) by use of which all methods for the preparation of a given type of compound will be found. For each reaction, a list of Organic Syntheses references is given when that is possible. Thus for most reactions the student can consult actual examples in Organic Syntheses. It is important to note that the numbers for each reaction differ from one edition to the other, and many of the sections in the Fifth Edition do not correlate with the Fourth. Hydroboration was found in Section 15-12 in the Fourth Edition, for example, but it appears in Section 15-16 in the Fifth.
The structure of organic compounds is discussed in the first five chapters of Part 1. This section provides a necessary background for understanding mechanisms and is also important in its own right. The discussion begins with chemical bonding and ends with a chapter on stereochemistry. There follow two chapters on reaction mechanisms in general, one for ordinary reactions and the other for photochemical reactions. Part 1 concludes with two more chapters that give further background to the study of mechanisms.
In addition to reactions, mechanisms, and structure, the student should have some familiarity with the literature of organic chemistry. A chapter devoted to this topic has been placed in Appendix A, though many teachers may wish to cover this material at the beginning of the course.
The IUPAC names for organic transformations, first introduced in the Third Edition, is included. Since then the rules have been broadened to cover additional cases; hence more such names are given in this edition. Furthermore, IUPAC has now published a new system for designating reaction mechanisms (see p. 384), and some of the simpler designations are included.
In treating a subject as broad as the basic structures, reactions, and mechanisms of organic chemistry, it is obviously not possible to cover each topic in great depth. Nor would this be desirable even if possible. Nevertheless, students will often wish to pursue individual topics further. An effort has therefore been made to guide the reader to pertinent review articles and books published since about 1965. In this respect, this book is intended to be a guide to the secondary literature (since about 1965) of the areas it covers. Furthermore, in a graduate course, students should be encouraged to consult primary sources. To this end, more than 12,000 references to original papers have been included.
Although basically designed for a one-year course on the graduate level, this book can also be used in advanced undergraduate courses but a one-year course in organic chemistry prior to this is essential, and a one-year course in physical chemistry is strongly recommended. It can also be adapted, by the omission of a large part of its contents, to a one-semester course. Indeed, even for a one-year course, more is included than can be conveniently covered. Many individual sections can be easily omitted without disturbing continuity.
The reader will observe that this text contains much material that is included in first-year organic and physical chemistry courses, though in most cases it goes more deeply into each subject and, of course, provides references, which first-year texts do not. It has been my experience that students who have completed the first-year courses often have a hazy recollection of the material and greatly profit from a representation of the material if it is organized in a different way. It is hoped that the organization of the material on reactions and mechanisms will greatly aid the memory and the understanding. In any given course, the teacher may want to omit some chapters because his students already have an adequate knowledge of the material, or because there are other graduate courses that cover the areas more thoroughly. Chapters 1, 4, and 7 especially may fall into one of these categories.
Although this is a textbook, it has been designed to have reference value also. Students preparing for qualifying examinations and practicing organic chemists will find that Part 2 contains a survey of what is known about the mechanism and scope of about 580 reactions, arranged in an orderly manner based on reaction type and on which bonds are broken and formed. Also valuable for reference purposes are the previously mentioned lists of reactions classified by type of compound prepared (Appendix B) and of all of the Organic Syntheses references to each reaction.
Anyone who writes a book such as this, where international rules mandate one system, but published papers use another is faced with the question of which units to use. Two instances are the units used for energies and for bond distances. For energies, IUPAC mandates joules, and many journals do use this unit exclusively. However, organic chemists who publish in United States journals overwhelmingly use calories, and this situation shows no signs of changing in the near future. Since previous editions of this book have been used extensively both in this country and abroad, I have now adopted the practice of giving virtually all energy values in both calories and joules. The question of units for bond distances is easier to answer. Although IUPAC does not recommend angstrom units, nearly all bond distances published in the literature anywhere in the world, whether in organic or in crystallographic journals, are in these units, though a few papers do use picometers. Therefore, I continue to use only angstrom units.
I acknowledge the contributions of those chemists cited and thanked by Professor March in the previous four editions.
Special thanks are due to the STM division of John Wiley & Sons, Dr. Darla Henderson, Shirley Thomas, and Jeannette Stiefel and the other editors at Wiley for their fine work in turning the manuscript into the finished book. I gratefully acknowledge the contribution of Ted Hoffman, the editor who worked with Professor March to make sure there was a Fifth Edition. I am also grateful to those readers who wrote to tell Professor March about errors they discovered in the preceding editions or to make other comments. Such letters are always welcome.
I encourage those who read and use the Fifth Edition to contact me directly with comments, errors, and with publications that might be appropriate for future editions. I hope that this new edition will carry on the tradition that Professor March began with the first edition.
Micheal B. Smith
Storrs, Connecticut