March's Advanced Organic Chemistry

March's Advanced Organic Chemistry


Author:
Michael B. Smith
Published in: John Wiley & Sons
Release Year: 2013
ISBN: 978-0-470-46259-1
Pages: 2075
Edition: Seventh Edition
File Size: 22 MB
File Type: pdf
Language: English



Description of March's Advanced Organic Chemistry


March's Advanced Organic Chemistry seventh edition of March’s Advanced Organic Chemistry has been thoroughly updated to include new advances in areas of Organic chemistry published between 2005 and 2010. Every topic retained from the sixth edition has been brought up to date if there was activity in that area during that five year period. Changes also include a significant rewrite of most of the book. More than 5500 new references have been added for work published since 2005. As with the sixth edition, many older references were deleted to make room for new ones, and in cases where a series of papers by the same principal author were cited, all but the most recent were deleted. 
The older citations are usually found by referring to the more recent publication(s). Many of the figures relating to molecular orbitals dated to the 1960s. In all cases possible, they have been replaced by molecular orbitals drawings using Spartan software from Wavefunction, Inc. The fundamental structure of the seventh edition is essentially the same as that of all previous ones.
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 March's Advanced Organic Chemistry book should be able to approach the literature directly,
with a sound knowledge of modern organic chemistry. Major special areas of organic chemistry: terpenes, carbohydrates, proteins, many organometallic reagents, combinatorial chemistry, polymerization and electrochemical reactions, steroids, and so on, have been treated lightly or ignored completely. 
The use of March's Advanced Organic Chemistry book in the first year of graduate study should help master the fundamentals. It is hoped that March's Advanced Organic Chemistry book will lead a student to consult the many excellent books and review articles cited for various topics in order to understand the subject in more detail. Indeed, many of these topics are so vast, they cannot be explained completely in March's Advanced Organic Chemistry book.

Content of March's Advanced Organic Chemistry


PART I INTRODUCTION 1

1. Localized Chemical Bonding 3
1.A. Covalent Bonding 3
1.B. Multiple Valence 6
1.C. Hybridization 7
1.D. Multiple Bonds 9
1.E. Photoelectron Spectroscopy 11
1.F. Electronic Structures of Molecules 14
1.G. Electronegativity 15
1.H. Dipole Moment 18
1.I. Inductive and Field Effects 19
1.J. Bond Distances 21
1.K. Bond Angles 25
1.L. Bond Energies 27
2. Delocalized Chemical Bonding 31
2.A. Molecular Orbitals 32
2.B. Bond Energies and Distances in Compounds Containing
Delocalized Bonds 35
2.C. Molecules that have Delocalized Bonds 37
2.D. Cross-Conjugation 42
2.E. The Rules of Resonance 43
2.F. The Resonance Effect 45
2.G. Steric Inhibition of Resonance and the Influences of Strain 46
2.H. pp–DP Bonding. Ylids 49
2.I. Aromaticity 50
2.I.i. Six-Membered Rings 54
2.I.ii. Five, Seven, and Eight-Membered Rings 57
2.I.iii. Other Systems Containing Aromatic Sextets 62
2.J. Alternant and Nonalternant Hydrocarbons 63
2.K. Aromatic Systems with Electron Numbers other than Six 65
2.K.i. Systems of Two Electrons 66
2.K.ii. Systems of Four Electrons: Antiaromaticity 67
2.K.iii. Systems of Eight Electrons 71
2.K.iv. Systems of Ten Electrons 72
2.K.v. Systems of more than Ten Electrons: 4n þ 2 Electrons 74
2.K.vi. Systems of more than 10 Electrons: 4n Electrons 79
2.L. Other Aromatic Compounds 82
2.M. Hyperconjugation 85
2.N. Tautomerism 89
2.N.i. Keto–Enol Tautomerism 89
2.N.ii. Other Proton-Shift Tautomerism 92
3. Bonding Weaker Than Covalent 96
3.A. Hydrogen Bonding 96
3.B. p–p Interactions 103
3.C. Addition Compounds 104
3.C.i. Electron Donor-Acceptor Complexes 104
3.C.ii. Crown Ether Complexes and Cryptates 108
3.C.iii. Inclusion Compounds 113
3.C.iv. Cyclodextrins 116
3.D. Catenanes and Rotaxanes 118
3.E. Cucurbit[n]Uril-Based Gyroscane 121
4. Stereochemistry and Conformation 122
4.A. Optical Activity and Chirality 122
4.A.i. Dependence of Rotation on Conditions of Measurement 124
4.B. What Kinds of Molecules Display Optical Activity? 125
4.C. The Fischer Projection 136
4.D. Absolute Configuration 137
4.D.i. The CAHN–INGOLD–PRELOG System 138
4.D.ii. Methods of Determining Configuration 141
4.E. The Cause of Optical Activity 145
4.F. Molecules with more than One Stereogenic Center 146
4.G. Asymmetric Synthesis 149
4.H. Methods of Resolution 154
4.I. Optical Purity 160
4.J. cis-trans Isomerism 162
4.J.i. cis-trans Isomerism Resulting from Double Bonds 162
4.J.ii. cis-trans Isomerism of Monocyclic Compounds 165
4.J.iii. cis-trans Isomerism of Fused and Bridged Ring Systems 167
4.K. Out–In Isomerism 168
4.L. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 170
4.M. Stereospecific and Stereoselective Syntheses 173
4.N. Conformational Analysis 173
4.N.i. Confirmation in Open-Chain Systems 175
4.N.ii. Confirmation in Six-Membered Rings 180
4.N.iii. Confirmation in Six-Membered Rings Containing Heteroatoms 186
4.N.iv. Confirmation in Other Rings 188
4.O. Molecular Mechanics 190
4.P. STRAIN 192
4.P.i. Strain in Small Rings 193
4.P.ii. Strain in Other Rings 199
4.P.iii. Unsaturated Rings 201
4.P.iv. Strain Due to Unavoidable Crowding 204
5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 208
5.A. Carbocations 208
5.A.i. Nomenclature 208
5.A.ii. Stability and Structure of Carbocations 209
5.A.iii. The Generation and Fate of Carbocations 218
5.B. Carbanions 221
5.B.i. Stability and Structure 221
5.B.ii. The Structure of Organometallic Compounds 228
5.B.iii. The Generation and Fate of Carbanions 233
5.C. Free Radicals 234
5.C.i. Stability and Structure 234
5.C.ii. The Generation and Fate of Free Radicals 245
5.C.iii. Radical Ions 248
5.D. Carbenes 249
5.D.i. Stability and Structure 249
5.D.ii. The Generation and Fate of Carbenes 253
5.E. Nitrenes 257
6. Mechanisms and Methods of Determining them 261
6.A. Types of Mechanism 261
6.B. Types of Reaction 262
6.C. Thermodynamic Requirements for Reaction 264
6.D. Kinetic Requirements for Reaction 266
6.E. The Baldwin Rules for Ring Closure 270
6.F. Kinetic and Thermodynamic Control 271
6.G. The Hammond Postulate 272
6.H. Microscopic Reversibility 273
6.I. Marcus Theory 273
6.J. Methods of Determining Mechanisms 275
6.J.i. Identification of Products 275
6.J.ii. Determination of the Presence of an Intermediate 275
6.J.iii. The Study of Catalysis 277
6.J.iv. Isotopic Labeling 277
6.J.v. Stereochemical Evidence 278
6.J.vi. Kinetic Evidence 278
6.J.vii. Isotope Effects 285
7. Irradiation Processes in Organic Chemistry 289
7.A. Photochemistry 289
7.A.i. The excited States and the Ground State 289
7.A.ii. Singlet and Triplet States: “Forbidden” Transitions 291
7.A.iii. Types of Excitation 292
7.A.iv. Nomenclature and Properties of Excited States 294
7.A.v. Photolytic Cleavage 295
7.A.vi. The Fate of the Excited Molecule: Physical Processes 296
7.A.vii. The Fate of the Excited Molecule: Chemical Processes 301
7.A.viii. The Determination of Photochemical Mechanisms 306
7.B. Sonochemistry 307
7.C. Microwave Chemistry 309
8. Acids and Bases 312
8.A. Brønsted Theory 312
8.A.i. Brønsted Acids 313
8.A.ii. Brønsted Bases 320
8.B. The Mechanism of Proton-Transfer Reactions 323
8.C. Measurements of Solvent Acidity 324
8.D. Acid and Base Catalysis 327
8.E. Lewis Acids and Bases 330
8.E.i. Hard–Soft Acids–Bases 331
8.F. The Effects of Structure on the Strengths of Acids and Bases 334
8.G. The Effects of the Medium on Acid and Base Strength 343
9. Effects of Structure and Medium on Reactivity 347
9.A. Resonance and Field Effects 347
9.B. Steric Effects 349
9.C. Quantitative Treatments of the Effect of Structure on Reactivity 352
9.D. Effect of Medium on Reactivity and Rate 361
9.D.i. High Pressure 362
9.D.ii. Water and Other Non-Organic Solvents 363
9.D.iii. Ionic Solvents 364
9.D.iv. Solventless Reactions 366

PART II INTRODUCTION 367

10. Aliphatic Substitution, Nucleophilic and Organometallic 373
10.A. Mechanisms 373
10.A.i. The SN2 Mechanism 374
10.A.ii. The SN1 Mechanism 379
10.A.iii. Ion Pairs in the SN1 Mechanism 383
10.A.iv. Mixed SN1 and SN2 Mechanisms 387
10.B. SET Mechanisms 389
10.C. The Neighboring-Group Mechanism 391
10.C.i. Neighboring-Group Participation by p and s Bonds:
Nonclassical Carbocations 394
10.D. The Sri Mechanism 408
10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic
Rearrangements 409
10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon:
The Tetrahedral Mechanism 413
10.G. Reactivity 417
10.G.i. The Effect of Substrate Structure 417
10.G.ii. The Effect of the Attacking Nucleophile 426
10.G.iii. The Effect of the Leaving Group 432
10.G.iv. The Effect of the Reaction Medium 435
10.G.v. Phase-Transfer Catalysis 442
10.G.vi. Influencing Reactivity by External Means 445
10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 446
10.G.viii. Ambident Substrates 450
10.H. Reactions 451
10.H.i. Oxygen Nucleophiles 451
10.H.ii. Attack by OR at an Alkyl Carbon 459
10.H.iii. Sulfur Nucleophiles 475
10.H.iv. Nitrogen Nucleophiles 481
10.H.v. Halogen Nucleophiles 498
10.H.vi. Carbon Nucleophiles 510
11. Aromatic Substitution, Electrophilic 569
11.A. Mechanisms 569
11.A.i. The Arenium Ion Mechanism 570
11.A.ii. The SE1 Mechanism 576
11.B. Orientation and Reactivity 576
11.B.i. Orientation and Reactivity in Monosubstituted
Benzene Rings 576
11.B.ii. The Ortho/Para Ratio 580
11.B.iii. Ipso Attack 581
11.B.iv. Orientation in Benzene Rings with More Than One Substituent 583
11.B.v. Orientation in Other Ring Systems 584
11.C. Quantitative Treatments of Reactivity in the Substrate 586
11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity
Relationship 588
11.E. The Effect of the Leaving Group 591
11.F. Reactions 591
11.F.i. Hydrogen as the Leaving Group in Simple
Substitution Reactions 592
11.F.ii. Hydrogen as the Leaving Group in Rearrangement
Reactions 635
11.F.iii. Other Leaving Groups 641
12. Aliphatic, Alkenyl, and Alkynyl Substitution, Electrophilic
and Organometallic 649
12.A. Mechanisms 650
12.A.i. Bimolecular Mechanisms: SE2 and SEi 650
12.A.ii. The SE1 Mechanism 654
12.A.iii. Electrophilic Substitution Accompanied by Double-Bond Shifts 657
12.A.iv. Other Mechanisms 658
12.B. Reactivity 658
12.C. Reactions 660
12.C.i. Hydrogen as Leaving Group 660
12.C.ii. Metals as Leaving Groups 698
12.C.iii. Halogen as Leaving Group 713
12.C.iv. Carbon Leaving Groups 718
12.C.v. Electrophilic Substitution at Nitrogen 727
13. Aromatic Substitution: Nucleophilic and Organometallic 732
13.A. Mechanisms 732
13.A.i. The SNAr Mechanism 732
13.A.ii. The SN1 Mechanism 735
13.A.iii. The Benzyne Mechanism 737
13.A.iv. The SRN1 Mechanism 739
13.A.v. Other Mechanisms 740
13.B. Reactivity 741
13.B.i. The Effect of Substrate Structure 741
13.B.ii. The Effect of the Leaving Group 744
13.B.iii. The Effect of the Attacking Nucleophile 745
13.C. Reactions 745
13.C.i. All Leaving Groups Except Hydrogen and N2þ 746
13.C.ii. Hydrogen as Leaving Group 784
13.C.iii. Nitrogen as Leaving Group 788
13.C.iv. Rearrangements 797
14. Substitution Reactions: Radical 803
14.A. Mechanisms 803
14.A.i. Radical Mechanisms in General 803
14.A.ii. Free Radical Substitution Mechanisms 807
14.A.iii. Mechanisms at an Aromatic Substrate 809
14.A.iv. Neighboring-Group Assistance in Free Radical Reactions 810
14.B. Reactivity 812
14.B.i. Reactivity for Aliphatic Substrates 812
14.B.ii. Reactivity at a Bridgehead 817
14.B.iii. Reactivity in Aromatic Substrates 818
14.B.iv. Reactivity in the Attacking Radical 819
14.B.v. The Effect of Solvent on Reactivity 820
14.C. Reactions 821
14.C.i. Hydrogen as a Leaving Group 821
14.C.ii. N2 as Leaving Group 846
14.C.iii. Metals as Leaving Groups 849
14.C.iv. Halogen as Leaving Group 851
14.C.v. Sulfur as Leaving Group 851
14.C.vi. Carbon as Leaving Group 853
15. Addition to Carbon-Carbon Multiple Bonds 859
15.A. Mechanisms 859
15.A.i. Electrophilic Addition 859
15.A.ii. Nucleophilic Addition 865
15.A.iii. Free Radical Addition 867
15.A.iv. Cyclic Mechanisms 869
15.A.v. Addition to Conjugated Systems 869
15.B. Orientation and Reactivity 871
15.B.i. Reactivity 871
15.B.ii. Orientation 874
15.B.iii. Stereochemical Orientation 877
15.B.iv. Addition to Cyclopropane Rings 879
15.C. Reactions 881
15.C.i. Isomerization of Double and Triple Bonds 881
15.C.ii. Reactions in which Hydrogen Adds to One Side 883
15.C.iii. Reactions in which Hydrogen Adds to Neither Side 981
15.C.iv. Cycloaddition Reactions 1014
16. Addition to Carbon–Hetero Multiple Bonds 1067
16.A. Mechanism and Reactivity 1067
16.A.i. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The
Tetrahedral Mechanism 1069
16.B. Reactions 1075
16.B.i. Reactions in which Hydrogen or a Metallic Ion Adds to the
Heteroatom 1075
16.B.ii. Acyl Substitution Reactions 1189
16.B.iii. Reactions in which Carbon Adds to the Heteroatom 1239
16.B.iv. Addition to Isocyanides 1246
16.B.v. Nucleophilic Substitution at a Sulfonyl Sulfur Atom 1248
17. Eliminations 1253
17.A. Mechanisms and Orientation 1253
17.A.i. The E2 Mechanism 1254
17.A.ii. The E1 Mechanism 1261
17.A.iii. The E1cB Mechanism 1262
17.A.iv. The E1–E2–E1cB Spectrum 1267
17.A.v. The E2C Mechanism 1268
17.B. The regiochemistry of the Double Bond 1269
17.C. Stereochemistry of the Double Bond 1273
17.D. Reactivity 1274
17.D.i. Effect of Substrate Structure 1274
17.D.ii. Effect of the Attacking Base 1276
17.D.iii. Effect of the Leaving Group 1276
17.D.iv. Effect of the Medium 1277
17.E. Mechanisms and Orientation in Pyrolytic Eliminations 1278
17.E.i. Mechanisms 1278
17.E.ii. Orientation in Pyrolytic Eliminations 1281
17.E.iii. 1,4-Conjugate Eliminations 1282
17.F. Reactions 1282
17.F.i. Reactions in which CC and CC Bonds are Formed 1282
17.F.ii. Fragmentations 1307
17.F.iii. Reactions in which CN or CN Bonds are Formed 1310
17.F.iv. Reactions in which CO Bonds are Formed 1314
17.F.v. Reactions in which NN Bonds are Formed 1315
17.F.vi. Extrusion Reactions 1316
18. Rearrangements 1321
18.A. Mechanisms 1322
18.A.i. Nucleophilic Rearrangements 1322
18.A.ii. The Actual Nature of the Migration 1324
18.A.iii. Migratory Aptitudes 1328
18.A.iv. Memory Effects 1330
18.B. Longer Nucleophilic Rearrangements 1331
18.C. Free Radical Rearrangements 1333
18.D. Carbene Rearrangements 1337
18.E. Electrophilic Rearrangements 1337
18.F. Reactions 1337
18.F.i. 1,2-Rearrangements 1338
18.F.ii. Non-1,2 Rearrangements 1380
19. Oxidations and Reductions 1433
19.A. Mechanisms 1434
19.B. Reactions 1436
19.B.i. Oxidations 1437
19.B.ii. Reductions 1497

APPENDIX A: THE LITERATURE OF ORGANIC CHEMISTRY 1569

APPENDIX B: CLASSIFICATION OF REACTIONS BY TYPE OF

COMPOUNDS SYNTHESIZED 1605

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