March’s Advanced Organic Chemistry – Reactions, Mechanisms, and Structure

March’s Advanced Organic Chemistry – Reactions, Mechanisms, and Structure
اسم المؤلف
Michael B. Smith
24 أغسطس 2020
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March’s Advanced Organic Chemistry – Reactions, Mechanisms, and Structure
Eighth Edition
Michael B. Smith
Professor Emeritus
University of Connecticut
Department of Chemistry
69 Eldredge Road
Willington, Ct Usa
New Reaction Sections Correlation: 7th Edition ? 8th
Edition Xv
Preface 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. P?–d? Bonding: Ylids 52
Vvi Contents
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 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. ?–? 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 180contents Vii
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 292viii Contents
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 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 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. Br?nsted Theory 339
8.a.i. Br?nsted Acids 340
8.a.ii. Br?nsted 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 391contents Ix
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 S
N2 Mechanism 404
10.a.ii. The S
N1 Mechanism 410
10.a.iii. Ion Pairs in the S
N1 Mechanism 414
10.a.iv. Mixed S
N1 and Sn2 Mechanisms 418
10.b. Set Mechanisms 420
10.c. The Neighboring-group Mechanism 422
10.c.i. Neighboring-group Participation by ? And ? Bonds:
Nonclassical Carbocations 425
10.d. The S
Ni 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 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 S
E1 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 620x Contents
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. S
E2 and Sei 688
12.a.ii. The S
E1 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 S
Nar Mechanism 768
13.a.ii. The S
N1 Mechanism 771
13.a.iii. The Benzyne Mechanism 772
13.a.iv. The S
Rn1 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 823contents Xi
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 1089xii Contents
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 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 1350contents Xiii
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
Author Index 1669
Subject Index
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