Introduction A Brief History of Organic Chemistry The Variety and Beauty of Organic Molecules Why Is an Acid-BaseTheme Important? Acids and Bases in General Chemistry Acids and Bases in Organic Chemistry How Are the Two Acid-Base Definitions Related? Acid and Base Strength Lewis Acids and Lewis Bases Why Is Acid-Base Chemistry a Theme for Organic Chemistry? Biological Relevance Bonding The Elements What Is a Chemical Bond? Ionic versus Covalent The Covalent Carbon-Carbon Bond Molecular Orbitals Tetrahedral Carbons and sp3 Hybridization How Strong Is a Covalent Bond? Bond Dissociation Energy Polarized Covalent sigma-Bonds Biological Relevance Alkanes, Isomers, and an Introduction to Nomenclature The Fundamental Structure of Alkanes Based on the sp3 Hybrid Model Millions of Hydrocarbons: Alkanes Combustion Analysis and Empirical Formulas The Acid or Base Properties of Alkanes Isomers Naming Millions of Isomers: Rules of Nomenclature. The IUPAC Rules of Nomenclature Rings Made of Carbon. Cyclic Compounds Biological Relevance Functional Groups Introducing a Functional Group: Alkenes Another Hydrocarbon Functional Group: Alkynes Hydrocarbons with Several Multiple Bonds Reactivity of Polarized Covalent sigma-Bonds Formal Charge Heteroatom Functional Groups Acid-Base Properties of Functional Groups Polarity and Intermolecular Forces Functional Groups with Polarized pi-Bonds Benzene: A Special Cyclic Hydrocarbon Biological Relevance Acids, Bases, Nucleophiles, and Electrophiles Acid-Base Equilibria Polarized Hydrogen-Heteroatom Bonds: Acidic Units Factors That Influence the Strength of a Bronsted-Lowry Acid Organic Bases Lewis Acids and Lewis Bases A Positive Carbon Atom Can Accept Electrons Nucleophiles Biological Relevance Chemical Reactions, Bond Energy, and Kinetics A Chemical Reaction Bond Dissociation Enthalpy and Reactions Transition States Reactive Intermediates Free Energy. Influence of Enthalpy and Entropy Energetics. Starting Materials, Transition States, Intermediates, and Products on a Reaction Curve Competing Reactions Mechanisms Why Does a Chemical Reaction Occur? Defining a "Reactive" Center Reversible Chemical Reactions Kinetics No Reaction Biological Relevance Rotamers and Conformation Rotamers Longer Chain Alkanes: Increased Torsional Strain Conformations of Alkenes and Alkynes: Introducing pi-Bonds Influence of Heteroatoms on the Rotamer Population Cyclic Alkanes Substituted Cyclohexanes Larger Rings Cyclic Alkenes Introducing Heteroatoms into a Ring Biological Relevance Stereoisomers: Chirality, Enantiomers, and Diastereomers Stereogenic Carbons and Stereoisomers Specific Rotation: A Physical Property Absolute Configuration (R and S Nomenclature) Alkenes Diastereomers Stereogenic Centers in Cyclic Molecules Stereogenic Centers in Complex Molecules Optical Resolution Biological Relevance Acid-Base Reactions of pi-Bonds Alkenes and Acid-Base Chemistry Carbocation Intermediates Alkenes React with Weak Acids in the Presence of an Acid Catalyst Alkenes React as Lewis Bases Alkenes React as Lewis Bases with Electrophilic Oxygen. Oxidation of Alkenes to Oxiranes Alkynes React as Bronsted-Lowry Bases or Lewis Bases Reactions That Are Not Formally Acid-Base Reactions Non-ionic Reactions: Radical Intermediates and Alkene Polymerization Synthetic Transformations Biological Relevance Nucleophiles: Lewis Base-Like Reactions at sp3 Carbon Alkyl Halides, Sulfonate Esters, and the Electrophilic C-X Bond Nucleophiles and Bimolecular Substitution (the SN2 Reaction) Functional Group Transformations via the SN2 Reaction A Tertiary Halide Reacts with a Nucleophile When the Solvent Is Water Carbocation Rearrangements Solvolysis Reactions of Alkyl Halides Preparation of Halides and Sulfonate Esters by Substitution Reactions Reactions of Ethers Free Radical Halogenation of Alkanes Applications to Synthesis Biological Relevance Base-Induced Elimination Reactions Bimolecular Elimination Stereochemical Consequences of the E2 Reaction The E2 Reaction in Cyclic Molecules Unimolecular Elimination Intramolecular Elimination 1,3 Elimination: Decarboxylation Elimination Reactions of Vinyl Halides: Formation of Alkynes Elimination Functional Group Exchanges Biological Relevance Substitution and Elimination Reactions Can Compete A Few Simplifying Assumptions Protic versus Aprotic and Water Nucleophilic Strength versus Base Strength The Nature of the Halide What about Secondary Halides? Strength and Limitations of the Simplifying Assumptions When Do the Assumptions Fail? Spectroscopic Methods of Identification Light and Energy Mass Spectrometry Infrared Spectroscopy Nuclear Magnetic Resonance Spectroscopy The Structure of an Unknown Molecule May Be Determined Carbon-13 NMR Spectroscopy: Counting the Carbons Biological Relevance Organometallic Reagents Introducing Magnesium into a Molecule Reaction of Aryl and Vinyl Halides with Magnesium Grignard Reagents Are Bases Grignard Reagents Are Poor Nucleophiles with Alkyl Halides Organolithium Reagents Organocuprates Organometallic Disconnections Biological Relevance Carbonyl Compounds: Structure, Nomenclature, Reactivity The Carbonyl Group Aldehydes and Ketones. Nomenclature Chemical Reactivity of Ketones and Aldehydes Carboxylic Acids. Nomenclature and Properties Dicarboxylic Acids Dicarboxylic Acids Have Two pKa Values Carboxylic Acid Derivatives. Nomenclature and Properties Acyl Substitution with Carboxylic Acid Derivatives Sulfonic Acids Biological Relevance Oxidation Defining an Oxidation Oxidation of Alcohols with Chromium(VI) Oxidation of Alkenes Oxidative Cleavage Summary of Functional Group Exchanges Biological Relevance Reactions of Aldehydes and Ketones Chemical Reactivity of the Carbonyl Group Reversible versus Irreversible Acyl Addition Reaction of Aldehydes or Ketones with Strong Nucleophiles Organometallic Reagents Are Nucleophiles Water: A Weak Nucleophile That Gives Reversible Acyl Addition Alcohols: Neutral Nucleophiles That Give Reactive Products Amines Are Nucleophiles That React to Give Imines or Enamines Carbon-Carbon Bond-Forming Reactions and Functional Group Modification Biological Relevance Reduction Defining a Reduction Hydrides as Reducing Agents Catalytic Hydrogenation Dissolving Metal Reductions Summary of Functional Group Exchanges Biological Relevance Carboxylic Acid Derivatives and Acyl Substitution Chemical Reactivity of Carboxylic Acid Derivatives Acyl Substitution. Acid Derivatives React with Water: Hydrolysis Preparation of Acid Chlorides Preparation of Acid Anhydrides Preparation of Esters Amides The Reaction of Carboxylic Acid Derivatives with Carbon Nucleophiles Reaction of Organometallics with Other Electrophilic "Carbonyl" Molecules Dicarboxylic Acid Derivatives Baeyer-Villiger Oxidation Sulfonic Acid Derivatives Sulfate Esters and Phosphate Esters Nitriles Are Carboxylic Acid Derivatives Carbon-Carbon Bond-Forming Reactions and Functional Group Exchanges of Acid Derivatives Biological Relevance Aromatic Compounds and Benzene Derivatives Benzene and Aromaticity Functionalized Benzene Derivatives and a New Nomenclature System Electrophilic Aromatic Substitution Disubstituted Benzene Derivatives Polysubstituted Benzene Derivatives Reduction of Aromatic Compounds Aromaticity in Monocyclic Molecules Other Than Benzene Polynuclear Aromatic Hydrocarbons Aromatic Amines and Diazonium Salts Nucleophilic Aromatic Substitution Aromatic Disconnections and Functional Group Exchange Reactions Synthesis of Aromatic Compounds Biological Relevance Enolate Anions: Acyl Addition and Acyl Substitution Aldehydes and Ketones Are Weak Acids Enolate Anions Are Nucleophiles. The Aldol Condensation Non-nucleophilic Bases Enolate Anions from Unsymmetrical Ketones Dehydration of Aldol Products The Intramolecular Aldol Condensation Ester Enolates Decarboxylation Enolate Alkylation Phosphorus Ylids and the Wittig Reaction Many New Synthetic Possibilities Biological Relevance Difunctional Molecules: Dienes and Conjugated Carbonyl Compounds Conjugated Dienes Conjugated Carbonyl Compounds Detecting Conjugation: Ultraviolet Spectroscopy Reactions of Conjugated pi-Bonds Polymers from Conjugated Molecules Synthetic Possibilities Biological Relevance Difunctional Molecules: Pericyclic Reactions Frontier Molecular Orbitals: HOMOs and LUMOs Reactivity of Dienes and Alkenes Selectivity Sigmatropic Rearrangements Review of Synthetic Transformations Biological Relevance Disconnections and Synthesis What Is Synthesis? Specifying a Starting Material for a Given Target The Starting Material Is Unknown Disconnection of Molecules with Problematic Structural Features Heteroaromatic Compounds Nitrogen in an Aromatic Ring Oxygen and Sulfur in an Aromatic Ring Substitution Reactions in Heterocyclic Aromatic Compounds Reduced Forms of Heterocycles Heteroaromatic Compounds with More Than One Ring Aromatic Substitution Reactions of Polycyclic Heterocycles Synthesis of Heterocycles Biological Relevance Multifunctional Compounds: Amino Acids and Peptides A Review of Reactions That Form Amines Reactions of Amines Difunctional Molecules: Amino Acids Biological Relevance. Peptides Are Polyamides of Amino Acid Residues Biological Relevance. Proteins and Enzymes Are Polypeptides New Synthetic Methodology Multifunctional Compounds: Carbohydrates Polyhydroxy Carbonyl Compounds Biological Relevance. Oligosaccharides and Polysaccharides Reactions of Carbohydrates Synthesis of Carbohydrates Biological Relevance. Nucleosides and Nucleotides (Heterocycles Combined with Sugars) Biological Relevance. Polynucleotides Synthesis of Polynucleotides Index
Acid-base chemistry can be used to tie together the range of reaction types needed to establish an understanding of organic chemistry. With this in mind, the author offers an alternative pedagogic approach built around a unifying theme rather than rely on the functional group approach taken with most organic chemistry instruction. This makes the material more practical and consequently, more memorable. The book delves into structure, nomenclature, and properties, and covers bonding, organometallic reagents, isomers, nucleophiles and electrophiles, chirality, simple aromatic compounds, acyl addition and substitution, difunctional molecules, and pericyclic reactions.