March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure

3555 Pages·2013·42.69 MB·English

by  Michael B. Smith

Contents
Cover
Title Page
Copyright
Preface
Common Abbreviations
Biographical Statement
Part I: Introduction
Chapter 1: Localized Chemical Bonding
2
1.A. Covalent Bonding
1.B. Multiple Valence
1.C. Hybridization
1.D. Multiple Bonds
1.E. Photoelectron Spectroscopy
1.F. Electronic Structures of Molecules
1.G. Electronegativity
1.H. Dipole Moment
1.I. Inductive and Field Effects
55
1.J. Bond Distances
1.K. Bond Angles
95
1.L Bond Energies
Chapter 2: Delocalized Chemical Bonding
2.A. Molecular Orbitals
2.B. Bond Energies and Distances in Compounds Containing
Delocalized Bonds
2.C. Molecules that have Delocalized Bonds
51
2.D. Cross-Conjugation
2.E. The Rules of Resonance
2.F. The Resonance Effect
2.G. Steric Inhibition of Resonance and the Influences of Strain
2.H. Pπ–dπ Bonding. Ylids
98
2.I. Aromaticity
208
2.J. Alternant and Nonalternant Hydrocarbons
2.K. Aromatic Systems with Electron Numbers Other than Six
2.L. Other Aromatic Compounds
2.M. Hyperconjugation
431
2.N. Tautomerism
Chapter 3: Bonding Weaker Than Covalent
2
3.A. Hydrogen Bonding
3.B. π–π Interactions
3.C. Addition Compounds
190
3.D. Catenanes and Rotaxanes
3.E. Cucurbit[n]uril-Based Gyroscane
Chapter 4: Stereochemistry and Conformation
3
4.A. Optical Activity and Chirality
4.B. What Kinds of Molecules Display Optical Activity?
4.C. The Fischer Projection
4.D. Absolute Configuration
4.E. The Cause of Optical Activity
4.F. Molecules with more than One Stereogenic Center
4.G. Asymmetric Synthesis
160
4.H. Methods of Resolution
207
4.I. Optical Purity
4.J. cis–trans Isomerism
4.K. Out–In Isomerism
4.L. Enantiotopic and Diastereotopic Atoms, Groups, and
259
Faces
4.M. Stereospecific and Stereoselective Syntheses
4.N. Conformational Analysis
412
4.O. Molecular Mechanics
4.P. Strain
Chapter 5: Carbocations, Carbanions, Free Radicals,
Carbenes, and Nitrenes
2
5.A. Carbocations
5.B. Carbanions
5.C. Free Radicals
5.D. Carbenes
5.E. Nitrenes
Chapter 6: Mechanisms and Methods of Determining
Them
6.A. Types of Mechanism
6.B. Types of Reaction
6.C. Thermodynamic Requirements For Reaction
6.D. Kinetic Requirements For Reaction
17
6.E. The Baldwin Rules For Ring Closure
6.F. Kinetic and Thermodynamic Control
6.G. The Hammond Postulate
6.H. Microscopic Reversibility
6.I. Marcus Theory
33
6.J. Methods of Determining Mechanisms
Chapter 7: Irradiation Processes in Organic Chemistry
3
7.A. Photochemistry
7.B. Sonochemistry
7.C. Microwave Chemistry
Chapter 8: Acids and Bases
8.A. Brønsted Theory
8.B. The Mechanism of Proton-Transfer Reactions
124
8.C. Measurements of Solvent Acidity
148
8.D. Acid and Base Catalysis
8.E. Lewis Acids and Bases
8.F. The Effects of Structure on the Strengths of Acids and
175
Bases
8.G. The Effects of the Medium on Acid and Base Strength
Chapter 9: Effects of Structure and Medium on Reactivity
9.A. Resonance and Field Effects
9.B. Steric Effects
9.C. Quantitative Treatments of the Effect of Structure on
16
Reactivity
9.D. Effect of Medium on Reactivity and Rate
Part II: Introduction
Chapter 10: Aliphatic Substitution, Nucleophilic and
Organometallic
10.A. Mechanisms
10.B. SET Mechanisms
113
10.C. The Neighboring-Group Mechanism
10.D. The S I Mechanism
N
10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic
Rearrangements
10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon:
The Tetrahedral Mechanism
10.G. Reactivity
10.H. Reactions
Chapter 11: Aromatic Substitution, Electrophilic
11.A. Mechanisms
11.B. Orientation and Reactivity
11.C. Quantitative Treatments of Reactivity in the Substrate
11.D. A Quantitative Treatment of Reactivity of the Electrophile:
The Selectivity Relationship
11.E. The Effect of the Leaving Group
11.F. Reactions
Chapter 12: Aliphatic, Alkenyl, and Alkynyl Substitution,
Electrophilic and Organometallic
12.A. Mechanisms
12.B. Reactivity
12.C. Reactions
Chapter 13: Aromatic Substitution: Nucleophilic and
Organometallic
13.A. Mechanisms
13.B. Reactivity
13.C. Reactions
Chapter 14: Substitution Reactions: Radical
14.A. Mechanisms
14.B. Reactivity
14.C. Reactions
Chapter 15: Addition to Carbon–Carbon Multiple Bonds
15.A. Mechanisms
15.B. Orientation and Reactivity
15.C. Reactions
Chapter 16: Addition to Carbon–Hetero Multiple Bonds
16.A. Mechanism and Reactivity
16.B. Reactions
Chapter 17: Eliminations
17.A. Mechanisms And Orientation
17.B. Regiochemistry of the Double Bond
17.C. Stereochemistry of the Double Bond
17.D. Reactivity
17.E. Mechanisms and Orientation in Pyrolytic Eliminations
17.F. Reactions
Chapter 18: Rearrangements
18.A. Mechanisms
18.B. Longer Nucleophilic Rearrangements
54
18.C. Free Radical Rearrangements
86
18.D. Carbene Rearrangements
94
18.E. Electrophilic Rearrangements
18.F. Reactions
Chapter 19: Oxidations and Reductions
19.A. Mechanisms
19.B. Reactions
Appendix A: The Literature of Organic Chemistry
Appendix B: Classification of Reactions by Type of
Compounds Synthesized
Indexes
Author Index
Subject Index

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Library of Congress Cataloging-in-Publication Data:
Smith, Michael, 1946 Oct. 17-March's Advanced Organic Chemistry :
Reactions, Mechanisms, and Structure. – 7th Edition / Michael B. Smith,
Professor of Chemistry.