Description
Helps to develop new perspectives and a deeper understanding of organic chemistry
Instructors and students alike have praised Perspectives on Structure and Mechanism in Organic Chemistry because it motivates readers to think about organic chemistry in new and exciting ways. Based on the author's first hand classroom experience, the text uses complementary conceptual models to give new perspectives on the structures and reactions of organic compounds.
The first five chapters of the text discuss the structure and bonding of stable molecules and reactive intermediates. These are followed by a chapter exploring the methods that organic chemists use to study reaction mechanisms. The remaining chapters examine different types of acid-base, substitution, addition, elimination, pericyclic, and photochemical reactions.
This Second Edition has been thoroughly updated and revised to reflect the latest findings in physical organic chemistry. Moreover, this edition features:
- New references to the latest primary and review literature
- More study questions to help readers better understand and apply new concepts in organic chemistry
- Coverage of new topics, including density functional theory, quantum theory of atoms in molecules, Marcus theory, molecular simulations, effect of solvent on organic reactions, asymmetric induction in nucleophilic additions to carbonyl compounds, and dynamic effects on reaction pathways
The nearly 400 problems in the text do more than allow students to test their understanding of the concepts presented in each chapter. They also encourage readers to actively review and evaluate the chemical literature and to develop and defend their own ideas.
With its emphasis on complementary models and independent problem-solving, this text is ideal for upper-level undergraduate and graduate courses in organic chemistry.
Chapter
Group Increment Calculation of Heats of Formation
Homolytic and Heterolytic Bond Dissociation Energies
Electronegativity and Bond Polarity
Complementary Theoretical Models of Bonding
Pictorial Representations of Bonding Concepts
The Sp3 Hybridization Model for Methane
Are There Sp3 Hybrid Orbitals in Methane?
Valence Shell Electron Pair Repulsion Theory
Variable Hybridization and Molecular Geometry
1.4 Complementary Descriptions of the Double Bond
The (α,π Description of Ethene
The Bent Bond Description of Ethene
Predictions of Physical Properties with the Two Models
1.5 Choosing Models in Organic Chemistry
Chapter 2 Stereochemistry
Symmetric, Asymmetric, Dissymmetric, and Nondissymmetric Molecules
Designation of Molecular Configuration
Additional Stereochemical Nomenclature
2.3 Manifestations of Stereoisomerism
Configuration and Optical Activity
Other Physical Properties of Stereoisomers
Stereochemical Relationships of Substituents
Chirotopicity and Stereogenicity
Chapter 3 Conformational Analysis and Molecular Mechanics
3.1 Molecular Conformation
3.2 Conformational Analysis
Angle Strain and Baeyer Strain Theory
Application of Conformational Analysis to Cycloalkanes
Conformational Analysis of Substituted Cyclohexanes
3.4 Molecular Strain and limits to Molecular Stability
Chapter 4 Applications of Molecular Orbital Theory and Valence Bond Theory
4.1 Introduction to Molecular Orbital Theory
Huckel Molecular Orbital Theory
Correlation of Physical Properties with Results of HMO Calculations
Other Parameters Generated Through HMO Theory
Properties of Odd Alternant Hydrocarbons
Aromaticity in Small Ring Systems
Dewar Resonance Energy and Absolute Hardness
4.3 Contemporary Computational Methods
Perturbational Molecular Orbital Theory
Density Functional Theory
Resonance Structures and Resonance Energies
Choosing a Computational Model
Chapter 5 Reactive Intermediates
5.1 Reaction Coordinate Diagrams
Early Evidence for the Existence of Radicals
Detection and Characterization of Radicals
Structure and Bonding of Radicals
Thermochemical Data for Radicals
Structure and Geometry of Carbenes
Carbonium Ions and Carbenium Ions
Structure and Geometry of Carbocations
Rearrangements of Carbocations
Structure and Geometry of Carbanions
5.6 Choosing Models of Reactive Intermediates
Chapter 6 Methods of Studying Organic Reactions
6.1 Molecular Change and Reaction Mechanisms
6.2 Methods to Determine Reaction Mechanisms
Identification of Reaction Products
Determination of Intermediates
6.3 Applications of Kinetics in Studying Reaction Mechanisms
6.4 Arrhenius Theory and Transition-State Theory
6.5 Reaction Barriers and Potential Energy Surfaces
6.6 Kinetic Isotope Effects
Primary Kinetic Isotope Effects
Secondary Kinetic Isotope Effects
6.8 Linear Free Energy Relationships
Chapter 7 Acid and Base Catalysis of Organic Reactions
7.1 Acidity and Basicity of Organic Compounds
Acid-Base Measurements in Solution
Acid-Base Reactions in the Gas Phase
Comparison of Gas Phase and Solution Acidities
7.2 Acid and Base Catalysis of Chemical Reactions
7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds and Carboxylic Acid Derivatives
Addition to the Carbonyl Group
Enolization of Carbonyl Compounds
Acid-Catalyzed Hydrolysis of Esters
Alkaline Hydrolysis of Esters
Chapter 8 Substitution Reactions
8.2 Nucleophilic Aliphatic Substitution
Hard-Soft Acid-Base Theory and Nucleophilicity
Leaving Group Effects in SN2 Reactions
Aliphatic Substitution and Single Electron Transfer
8.3 Electrophilic Aromatic Substitution
Quantitative Measurement of SEAr Rate Constants: Partial Rate Factors
Lewis Structures as Models of Reactivity in SEAr Reactions
8.4 Nucleophilic Aromatic and Vinylic Substitution
Nucleophilic Aromatic Substitution
Nucleophilic Vinylic Substitution
Nucleophilic Substitution Involving Benzyne Intermediates
Radical-Nucleophilic Substitution
Chapter 9 Addition Reactions
9.2 Addition of Halogens to Alkenes
Electrophilic Addition of Bromine to Alkenes
Addition of Other Halogens to Alkenes
9.3 Other Addition Reactions
Addition of Hydrogen Halides to Alkenes
Electrophilic Addition to Alkynes and Cumulenes
Nucleophilic Addition to Alkenes and Alkynes
Nucleophilic Addition to Carbonyl Compounds
Chapter 10 Elimination Reactions
10.2 Dehydrohalogenation and Related 1,2-Elimination Reactions
Potential Energy Surfaces for 1/2-Elimination
Competition Between Substitution and Elimination
Stereochemistry of 1/2-Elimination Reactions
Regiochemistry of 1/2-Elimination Reactions
10.3 Other 1,2-Elimination Reactions
Dehalogenation of Vicinal Dihalides
Chapter 11 Pericyclic Reactions
11.2 Electrocyclic Transformations
Definitions and Selection Rules
State Correlation Diagrams
11.3 Sigmatropic Reactions
Selection Rules for Sigmatropic Reactions
Further Examples of Sigmatropic Reactions
11.4 Cycloaddition Reactions
Selection Rules for Cycloaddition Reactions
11.5 Other Concerted Reactions
11.6 A General Selection Rule for Pericyclic Reactions
11.7 Alternative Conceptual Models for Concerted Reactions
Frontier Molecular Orbital Theory
Huckel and Mobius Aromaticity of Transition Structures
Synchronous and Nonsynchronous Concerted Reactions
The Role of Reaction Dynamics in Rearrangements
Chapter 12 Photochemistry
12.1 Photophysical Processes
Energy and Electronic States
Designation of Spectroscopic Transitions
Selection Rules for Radiative Transitions
Fluorescence and Phosphorescence
Energy Transfer and Electron Transfer
12.2 Fundamentals of Photochemical Kinetics
Actinometry and Quantum Yield Determinations
Rate Constants for Unimolecular Processes
Transient Detection and Monitoring
Bimolecular Decay of Excited States: Stern–Volmer Kinetics
12.3 Physical Properties of Excited States
Acidity and Basicity in Excited States
Bond Angles and Dipole Moments of Excited State Molecules
12.4 Representative Photochemical Reactions
Photochemical Reactions of Alkenes and Dienes
Photochemical Reactions of Carbonyl Compounds
Photochemical Reactions of α,ß-Unsaturated Carbonyl Compounds
Photochemical Reactions of Aromatic Compounds
Photosubstitution Reactions
o Bond Photodissociation Reactions
Singlet Oxygen and Organic Photochemistry
12.5 Some Applications of Organic Photochemistry
References for Selected Problems
Perspectives on Structure and Mechanism in Organic Chemistry
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