Ouellette R.J., Rawn J.D. Organic Chemistry: Structure, Mechanism, and Synthesis

Elsevier Inc., 2014. 1188 p. ISBN: 978-0-12-800780-8
Organic Chemistry provides a comprehensive discussion of the basic principles of organic chemistry in their relation to a host of other fields in both physical and biological sciences. This book is written based on the premise that there are no shortcuts in organic chemistry, and that understanding and mastery cannot be achieved without devoting adequate time and attention to the theories and concepts of the discipline. It lays emphasis on connecting the basic principles of organic chemistry to real world challenges that require analysis, not just recall.
This text covers topics ranging from structure and bonding in organic compounds to functional groups and their properties; identification of functional groups by infrared spectroscopy; organic reaction mechanisms; structures and reactions of alkanes and cycloalkanes; nucleophilic substitution and elimination reactions; conjugated alkenes and allylic systems; electrophilic aromatic substitution; carboxylic acids; and synthetic polymers. Throughout the book, principles logically evolve from one to the next, from the simplest to the most complex examples, with abundant connections between the text and real world applications. There are extensive examples of biological relevance, along with a chapter on organometallic chemistry not found in other standard references.
This book will be of interest to chemists, life scientists, food scientists, pharmacists, and students in the physical and life sciences.Structure and Bonding in Organic Compounds
Brief Review of Atomic Structure
Atomic Properties
Ionic and Covalent Bonds
Strategies for Writing Lewis Structures
Formal Charge
Molecular Geometry
Resonance Structures
Valence Shell Electron Pair Repulsion Theory
Dipole Moments
Molecular Orbital Theory
The Hydrogen Molecule
Bonding in Carbon Compounds
sp3 Hybridization of Carbon in Methane
sp3 Hybridization of Carbon in Ethane
sp2 Hybridization of Carbon in Ethene
sp Hybridization of Carbon in Ethyne
Effect of Hybridization on Bond Length and Bond Strength
Hybridization of Nitrogen
Hybridization of Oxygen
Exercises
Part I: Functional Groups and Their Properties
Introduction to Functional Groups: Hydrocarbons and Haloalkanes
Functional Groups that Contain Oxygen
Functional Groups that Contain Nitrogen
Functional Groups that Contain Sulfur
Structural Formulas
Bond-Line Structures
Isomers
Part II: Identification of Functional Groups by Infrared Spectroscopy
2.8 Spectroscopy
2.9 Infrared Spectroscopy
2.10 Identifying Hydrocarbons
2.11 Identifying Oxygen-Containing Compounds
2.12 Identifying Nitrogen-Containing Compounds
2.13 Bending Deformations
End-of-Chapter Exercises
Introduction to Organic Reaction Mechanisms
Acid–Base reaction
Chemical Equilibrium and Equilibrium Constants
pH and pK Values
Effect of Structure on Acidity
Standard Free Energy Changes in Chemical Reactions
Enthalpy Changes in Chemical Reactions
Bond Dissociation Energies
Introduction to Reaction Mechanisms
Structures and Stabilities Of Carbon Radicals, Carbocations, and Carbanions
Factors that influence reaction rates
Reaction Rate Theory
Stability and reactivity
End-of-Chapter Exercises
Alkanes and Cycloalkanes: Structures and Reactions
Classes of Hydrocarbons
Alkanes
Nomenclature of Alkanes
Conformation of Alkanes
Cycloalkanes
Conformations of cycloalkanes
Conformational Mobility of cyclohexane
Monosubstituted Cyclohexanes
Disubstituted Cyclohexanes
Polycyclic Molecules
Physical Properties of Alkanes
Stabilities of Alkyl Radicals
Chlorination of an Alkane–A Radical Reaction
Exercises
Alkenes Structures and Properties
Alkenes
Structure and Bonding of Alkenes
Unsaturation Number
Geometric Isomerism
E,Z Nomenclature of Geometrical Isomers
Nomenclature of Alkenes
Physical Properties of Alkenes
Stability of Alkenes
Reduction of Alkenes
Mechanism of Catalytic Hydrogenation
Heats of hydrogenation of alkenes
Exercise
Alkenes: Addition Reactions
Characteristics of Addition Reactions
Addition of Hydrogen Halides to Alkenes
The Mechanistic Basis of Markovnikov's Rule
Carbocation Rearrangement Reactions
Hydration of Alkenes
Addition of Halogens
Addition of Carbenes
Epoxidation of Alkenes
Dihydroxylatin of Alkenes
Ozonolysis of Alkenes
Exercises
Alkynes
Occurrence and Uses of Alkynes
Structure and Properties of Alkynes
IUPAC Names of Alkynes
Acidity of Terminal Alkynes
Hydrogenation of Alkynes
Electrophilic Addition Reactions
Synthesis of Alkynes
Exercises
Stereochemistry
Stereoisomers
Mirror Image Objects, Mirror Image Molecules, and Chirality
Optical Activity
Fischer Projection Formulas
Absolute Configuration
Molecules with Two (or More) Stereogenic Centers
Cyclic Molecules with Stereogenic Centers
Separation of Enantiomers
Chemical Reactions at Stereogenic Centers
Reactions that Produce Stereogenic Centers
Reactions that Form Diastereomers
Prochiral Centers
Exercises
Haloalkanes and Alcohols: Introduction to Nucleophilic Substitution and Elimination Reactions
Functionalized Hydrocarbons
Nomenclature of Haloalkanes
Nomenclature of Alcohols
Structure and Properties of Haloalkanes
Structure and Properties of Alcohols
Organometallic Compounds
Reactions of Haloalkanes
Nucleophilic Substitution Reactions of Haloalkanes
Mechanisms of Nucleophilic Substitution Reactions of Haloalkanes
Reactions of Alcohols
Acid–Base Reactions of Alcohols
Substitution Reactions of Alcohols
Alternate Methods for the Synthesis of Alkyl Halides
Elimination Reactions
Regioselectivity in Dehydrohalogenation
Mechanisms of Dehydrohalogenation Reactions
Regioselectivity in Dehydration Reactions
Exercises
Nucleophilic Substitution and Elimination Reactions
Properties of Nucleophiles
Biological SN2 Reactions Bysulfur-Containing Nucleophiles
Stereochemistry of Nucleophilic Substitution Reactions
SN1 Versus SN2 Reactions
Mechanisms of Elimination Reactions
Effects of Structure on Competing Substitution and Elimination Reactions
Exercises
Conjugated Alkenes and Allylic Systems
Classes of Dienes
Stability of Conjugated Dienes
Molecular Orbitals of Ethene and 1,3-Butadiene
Structural Effects of Conjugation in 1,3-Butadiene
Allylic Systems
Hückel Molecular Orbitals of Allyl Systems
Electrophilic Addition to Conjugated Dienes
The Diels-Alder Reaction
The Electromagnetic Spectrum
Ultraviolet-Visible Spectroscopy of Alkenes and Conjugated Systems
Exercises
Arenes and Aromaticity
Aromatic Compounds
The Covalent Structure of Benzene
The Hückel Rule
Molecular Orbitals of Aromatic and Antiaromatic Compounds
Heterocyclic Aromatic Compounds
Polycyclic Aromatic Compounds
Exercises
Electrophilic Aromatic Substitution
Nomenclature of Benzene Derivatives
Mechanism of Electrophilic Aromatic Substitution
Common Electrophilic Aromatic Substitution Reactions
Substituent Effects on the Reactivity of Benzene Rings
Interpretation of the Effect of Substituents on Reaction Rates
Interpretation of Directing Effects
Functional Group Modification
Synthesis of Substituted Aromatic Compounds
Exercises
Methods for Structure Determination Nuclear Magnetic Resonance and Mass Spectrometry
Structure determination
Nuclear Magnetic Resonance Spectroscopy
The Chemical Shift
Detecting Sets of Nonequivalent Hydrogen Atoms
Effects of Structure on Chemical Shift
Relative Peak Areas and Proton Counting
Spin–Spin Splitting
Effect of Structure on Coupling Constants
Effect of Dynamic Processes
Carbon-13 NMR Spectroscopy
Introduction to Mass Spectrometry
Exercises
Alcohols: Reactions and Synthesis
Overview of Alcohol Reactions
Converting Alcohols into Esters
Conversion of Alcohols to Haloalkanes
Oxidation of Alcohols
Reactions of Vicinal Diols
Synthesis of Alcohols
Synthesis of Alcohols from Haloalkanes
Indirect Hydration Methods
Reduction of Carbonyl Compounds
Alcohol Synthesis Using Grignard Reagents
Thiols and Thioethers
Exercises
Ethers and Epoxides
Structure of Ethers
Nomenclature of Ethers
Physical Properties of Ethers
Polyether Antibiotics
Synthesis of Ethers: Alkoxymercuration-Demercuration of Alkenes
The Williamson Ether Synthesis
Reactions of Ethers
Ethers as Protecting Groups
Synthesis of Epoxides
Reactions of Epoxides
Sulfides
Spectroscopy of Ethers, Thiols, and Sulfides
Exercises
Organometallic Chemistry of Transition Metal Elements and Introduction to Retrosynthesis
Brief Overview of Transition Metal Complexes
The Gilman Reagent
Overview of Palladiumcatalyzed Cross-Coupling Reactions
The Suzuki Coupling Reaction
The Heck Reaction
The Sonogashira Reaction
The Wilkinson Catalyst: Homogeneous Catalytic Hydrogenation
Asymmetric Hydrogenation with Chiral Ruthenium Catalysts
The Grubbs Reaction: A Metathesis Reaction for Alkene Synthesis
Introduction to Retrosynthesis: Thinking Backwards
Exercises
Aldehydes and Ketones
The Carbonyl Group
Nomenclature of Aldehydes and Ketones
Physical Properties of Aldehydes and Ketones
Oxidation–Reduction Reactions of Carbonyl Compounds
Synthesis of Carbonyl Compounds: A Review
Carbonyl Compounds: A Preview
Spectroscopy of Aldehydes and Ketones
Exercises
Aldehydes and Ketones: Nucleophilic Addition Reactions
Relative Stabilities of Aldehydes and Ketones
Formation of Cyanohydrins
Hydration of Carbonyl Compounds
Mechanisms of Acid- and Base-Catalyzed Carbonyl Addition Reactions
Formation of Acetals and Ketals
Acetals as Protecting Groups
Thioacetals and Thioketals
Addition of Nitrogen Compounds to Aldehydes and Ketones
The Wittig Reaction
Exercises
Carboxylic Acids
Carboxylic Acids and Acyl Groups
Nomenclature of Carboxylic Acids
Physical Properties of Carboxylic Acids
Acidity of Carboxylic Acids
Carboxylate Anions
Synthesis of Carboxylic Acids
Reduction of Carboxylic Acids
Decarboxylation Reactions
Reactions of Carboxylic Acids and Their Derivatives: A Preview
Conversion of Carboxylic Acids into Acyl Halides
20.11 Conversion of Carboxylic Acids into Esters
20.12 Mechanism of Esterification
20.13 Brief Synthetic Review
20.14 Spectroscopy of Carboxylic Acids
Exercises
Carboxylic Acid Derivatives
Nomenclature of Carboxylic Acid Derivatives
Physical Properties of Acyl Derivatives
Basicity of Carboxylic Acid Derivatives
Mechanism of Nucleophilic Acyl Substitution
Hydrolysis of Acyl Derivatives
Reaction of Acyl Derivatives with Alcohols
Reaction of Acyl Derivatives with Amines
Reduction of Acyl Derivatives
Reaction of Acyl Derivatives with Organometallic Reagents
Infrared Spectroscopy of Acyl derivatives
NMR Spectroscopy of Acyl Derivatives
Exercises
Condensation Reactions of Carbonyl Compounds
The α-Carbon Atom of Aldehydes and Ketones
Keto–Enol Equilibria of Aldehydes and Ketones
Consequences of Enolization
α-Halogenation Reactions of Aldehydes and Ketones
Alkylation of Enolate Ions
The Aldol Condensation of Aldehydes
Mixed Aldol Condensation Reactions
Intramolecular Aldol Condensation Reactions
Conjugation in α-β-Unsaturated Aldehydes and Ketones
Conjugate Addition Reactions
The Michael Reaction and Robinson Annulation
The α-Hydrogen Atoms of Acid Derivatives
Reaction at the α-Carbon of Acid Derivatives
The Claisen Condensation
Aldol-Type Condensations of Acid Derivations
β -Dicarbonyl Compounds in Synthesis
Michael Condensations of Acid Derivatives
Exercises
Amines and Amides
Organic Nitrogen Compounds
Bonding and Structure of Amines
Classification and Nomenclature of Amines
Physical Properties of Amines
Basicity of Amines
Solubility of Ammonium Salts
Synthesis of Amines by Substitution Reactions
Synthesis of Amines by Reduction
The Hofmann Rearrangement
Overview of Amine Reactions
Enamines
Sulfonamides
Quaternary Ammonium Salts
Spectroscopy of amines
Exercises
Aryl Halides, Phenols, and Anilines
Properties of Aromatic Compounds
Acid-Base Properties of Phenols and Anilines
Converting Aryl Halides to Grignard Reagents and Organolithium Reagents
Nucleophilic Aromatic Substitution
An Overview of Phenol Reactions
Reactions of Phenoxide Ions
Quinones
Substitution Reactions of Aryldiazonium Salts
Azo Compounds
Exercises
Pericyclic Reactions
Concerted Reactions
Classification of Pericyclic Reactions
Molecular Orbitals in Pericyclic Reactions
Eiectrocyclic Reactions
Cycloaddition Reactions
Sigmatropic Rearrangements
Exercises
Carbohydrates
Carbohydrates in the Biosphere
Classification of Carbohydrates
Chirality of Monosaccharides
Isomerizations of Monosaccharides
Monosaccharides: Hemiacetals and Hemiketals
Reduction and Oxidation of Monosaccharides
Glocosides
Disaccharides
Polysaccharides
Chemical Determination of Monsoaccharide Structures
Determination of Ring Size
Structure of Disaccharides
Human Blood Group Antigens
Exercises
Amino Acids, Peptides, and Proteins
The Structures of α-Amino Acids
Acid-Base Equilibria of α-Amino Acids
Isoionic Point and Titration of α-Amino Acids
Synthesis of α-Amino Acids
Chiral Synthesis of α-Amino Acids
Reactions of α-Amino Acids
Peptides
Overview of Peptide Synthesis
Solid-Phase Peptide Synthesis
Determination of the Amino Acid Composition of Proteins
Determination of the Amino Acid Sequence of Proteins
Bonding in Proteins
Protein Structure
Oxygen Storage and Transport: Myoglobin and Hemoglobin
Exercises
Synthetic Polymers
Natural and Synthetic Polymers
Physical Properties of Polymers
Classes of Polymers
Polymerization Methods
Addition Polymerization
Copolymerization of Alkenes
Cross-Linked Polymers
Stereochemistry of Addition Polymerization
Condensation Polymers
Polyesters
Polycarbonates
Polyamides
Phenol-Formaldehyde Polymers
Polyurethanes
Exercises