March's Advanced Organic Chemistry

Diese überarbeitete und aktualisierte Ausgabe von March's Advanced Organic Chemistry erklärt die Theorien der organischen Chemie anhand von Beispielen und Reaktionen. Planung und Ausführung von mehrstufigen synthetischen Reaktionen werden ausführlich erläutert. Auch die 8. Auflage ist ein Muss für Studenten und Praktiker der organischen Chemie und verwandter Disziplinen.

Auteur

MICHAEL B. SMITH, PHD, is Professor Emeritus in the Department of Chemistry at the University of Connecticut. He is a coauthor of the fifth through seventh editions of March's Advanced Organic Chemistry and the author of Volumes 6 - 13 of the Compendium of Organic Synthetic Methods, as well as several other monographs and textbooks.

Texte du rabat

THE COMPLETELY REVISED AND UPDATED, DEFINITIVE RESOURCE FOR STUDENTS AND PROFESSIONALS IN ORGANIC CHEMISTRY The revised and updated eighth 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, Eighth 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 eighth 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.

Résumé
Diese überarbeitete und aktualisierte Ausgabe von March's Advanced Organic Chemistry erklärt die Theorien der organischen Chemie anhand von Beispielen und Reaktionen. Planung und Ausführung von mehrstufigen synthetischen Reaktionen werden ausführlich erläutert. Auch die 8. Auflage ist ein Muss für Studenten und Praktiker der organischen Chemie und verwandter Disziplinen.

Contenu

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

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. - 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 …