Chemistry and creativity Writing Reaction Mechanisms in Organic Chemistry
Description
Writing Reaction Mechanisms in Organic Chemistry
By
Audrey Miller
Philippa Solomon
Writing Reaction Mechanisms in Organic Chemistry, Second Edition, is an invaluable guide to charting the movements of atoms and electrons in the reactions of organic molecules. Miller and Solomon illustrate that understanding organic reactions is based on applying general principles rather than the rote memorization of unrelated processes, and, in turn, emphasize that writing mechanisms is a practical method of applying knowledge of previously encountered reactions and reaction conditions to new reactions. Students and research chemists alike will find this book useful in providing a method of organizing and synthesizing an oftentimes overwhelming quantity of information into a set of general principles and guidelines for determining and describing organic reaction mechanisms.
Content
Molecular Structure and Reactivity.General Principles for Writing Organic Mechanisms. Reactions of Nucleophiles and Bases.Reactions Involving Acids and Other Electrophiles. Radicals and Radical Anions.Pericyclic Reactions.Additional Problems.
1 Introduction: Molecular Structure and Reactivity
1. How to Write Lewis Structures and Calculate Formal Charges
A. Determining the Number of Bonds
B. Determining the Number of Rings and/or [pi] Bonds (Degree of Unsaturation
2C. Drawing the Lewis Structure
D. Formal Charge
2. Representations of Organic Compounds
3. Geometry and Hybridization
4. Electronegativities and Dipoles
5. Resonance Structures
A. Drawing Resonance Structures
B. Rules for Resonance Structures
6. Aromaticity and Antiaromaticity
A. Aromatic Carbocycles
B. Aromatic Heterocycles
C. Antiaromaticity
7. Tautomers and Equilibrium
8. Acidity and Basicity
9. Nucleophiles and Electrophiles
A. Nucleophilicity
B. Substrate
C. Solvent
2 General Principles for Writing Reaction Mechanisms
1. Balancing Equations
2. Using Arrows to Show Moving Electrons
3. Mechanisms in Acidic and Basic Media
4. Electron-Rich Species: Bases or Nucleophiles?
5. Trimolecular Steps
6. Stability of Intermediates
7. Driving Forces for Reactions
A. Leaving Groups
B. Formation of a Small Stable Molecule
8. Structural Relationships between Starting Materials and Products
9. Solvent Effects
10. A Last Word
3 Reactions of Nucleophiles and Bases
1. Nucleophilic Substitution
A. The S[subscript N]2 Reaction
B. Nucleophilic Substitution at Aliphatic sp[superscript 2] Carbon (Carbonyl Groups)
C. Nucleophilic Substitution at Aromatic Carbons
2. Eliminations at Saturated Carbon
A. E2 Elimination
B. Ei Elimination
3. Nucleophilic Addition to Carbonyl Compounds
A. Addition of Organometallic Reagents
B. Reaction of Nitrogen-Containing Nucleophiles with Aldehydes and Ketones
C. Reactions of Carbon Nucleophiles with Carbonyl Compounds
4. Base-Promoted Rearrangements
A. The Favorskii Rearrangement
B. The Benzilic Acid Rearrangement
5. Additional Mechanisms in Basic Media
4 Reactions Involving Acids and Other Electrophiles
1. Stability of Carbocations
2. Formation of Carbocations
A. Ionization
B. Addition of an Electrophile to a [pi] Bond
C. Reaction of an Alkyl Halide with a Lewis Acid
3. The Fate of Carbocations
4. Rearrangement of Carbocations
A. The Dienone-Phenol Rearrangement
B. The Pinacol Rearrangement
5. Electrophilic Addition
A. Regiospecificity
B. Stereochemistry
6. Acid-Catalyzed Reactions of Carbonyl Compounds
A. Hydrolysis of Carboxylic Acid Derivatives
B. Hydrolysis and Formation of Acetals and Orthoesters
C. 1,4-Addition
7. Electrophilic Aromatic Substitution
8. Carbenes
A. Singlet and Triplet Carbenes
B. Formation of Carbenes
C. Reactions of Carbenes
9. Electrophilic Heteroatoms
A. Electron-Deficient Nitrogen
B. Rearrangements Involving Electrophilic Nitrogen
C. Rearrangement Involving Electron-Deficient Oxygen
5 Radicals and Radical Anions
1. Introduction
2. Formation of Radicals
A. Homolytic Bond Cleavage
B. Hydrogen Abstraction from Organic Molecules
C. Organic Radicals Derived from Functional Groups
3. Radical Chain Processes
4. Radical Inhibitors
5. Determining the Thermodynamic Feasibility of Radical Reactions
6. Addition of Radicals
A. Intermolecular Radical Addition
B. Intramolecular Radical Addition: Radical Cyclization Reactions
7. Fragmentation Reactions
A. Loss of CO
B. Loss of a Ketone
C. Loss of N
D. Loss of CO
8. Rearrangement of Radicals
9. The S Reaction
10. The Birch Reduction
11. A Radical Mechanism for the Rearrangement of Some Anions
6 Pericyclic Reactions
1. Introduction
A. Types of Pericyclic Reactions
B. Theories of Pericyclic Reactions
2. Electrocyclic Reactions
A. Selection Rules for Electrocyclic Reactions
B. Stereochemistry of Electrocyclic Reactions (Conrotatory and Disrotatory Processes)
C. Electrocyclic Reactions of Charged Species (Cyclopropyl Cations)
3. Cycloadditions
A. Terminology of Cycloadditions
B. Selection Rules for Cycloadditions
C. Secondary Interactions
D. Cycloadditions of Charged Species
4. Sigmatropic Rearrangements
A. Terminology
5. The Ene Reaction
6. A Molecular Orbital View of Pericyclic Processes
A. Orbitals
B. Molecular Orbitals
C. Generating and Analyzing [pi] Molecular Orbitals
D. HOMOs and LUMOs
E. Correlation Diagrams
F. Frontier Orbitals
7 Additional Problems
Appendix A Lewis Structures of Common Functional Groups
Appendix B Symbols and Abbreviations Used in Chemical Notation
Appendix C
Relative Acidities of Common Organic and Inorganic
Substances
