1: Structure and Bonding in Organic Compounds
- 1.1 Brief Review of Atomic Structure
- 1.2 Atomic Properties
- 1.3 Ionic and Covalent Bonds
- 1.4 Strategies for Writing Lewis Structures
- 1.5 Formal Charge
- 1.6 Molecular Geometry
- 1.7 Resonance Structures
- 1.8 Valence Shell Electron Pair Repulsion Theory
- 1.9 Dipole Moments
- 1.10 Molecular Orbital Theory
- 1.11 The Hydrogen Molecule
- 1.12 Bonding in Carbon Compounds
- 1.13 sp3 Hybridization of Carbon in Methane
- 1.14 sp3 Hybridization of Carbon in Ethane
- 1.15 sp2 Hybridization of Carbon in Ethene
- 1.16 sp Hybridization of Carbon in Ethyne
- 1.17 Effect of Hybridization on Bond Length and Bond Strength
- 1.18 Hybridization of Nitrogen
- 1.19 Hybridization of Oxygen
- Exercises
2: Part I: Functional Groups and Their Properties
- 2.1 Introduction to Functional Groups: Hydrocarbons and Haloalkanes
- 2.2 Functional Groups that Contain Oxygen
- 2.3 Functional Groups that Contain Nitrogen
- 2.4 Functional Groups that Contain Sulfur
- 2.5 Structural Formulas
- 2.6 Bond-Line Structures
- 2.7 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
3: Introduction to Organic Reaction Mechanisms
- 3.1 Acid–Base reaction
- 3.2 Chemical Equilibrium and Equilibrium Constants
- 3.3 pH and pK Values
- 3.4 Effect of Structure on Acidity
- 3.5 Standard Free Energy Changes in Chemical Reactions
- 3.6 Enthalpy Changes in Chemical Reactions
- 3.7 Bond Dissociation Energies
- 3.8 Introduction to Reaction Mechanisms
- 3.9 Structures and Stabilities Of Carbon Radicals, Carbocations, and Carbanions
- 3.10 Factors that influence reaction rates
- 3.11 Reaction Rate Theory
- 3.12 Stability and reactivity
- End-of-Chapter Exercises
4: Alkanes and Cycloalkanes: Structures and Reactions
- 4.1 Classes of Hydrocarbons
- 4.2 Alkanes
- 4.3 Nomenclature of Alkanes
- 4.4 Conformation of Alkanes
- 4.5 Cycloalkanes
- 4.6 Conformations of cycloalkanes
- 4.7 Conformational Mobility of cyclohexane
- 4.8 Monosubstituted Cyclohexanes
- 4.9 Disubstituted Cyclohexanes
- 4.10 Polycyclic Molecules
- 4.11 Physical Properties of Alkanes
- 4.12 Stabilities of Alkyl Radicals
- 4.13 Chlorination of an Alkane–A Radical Reaction
- Exercises
5: Alkenes Structures and Properties
- 5.1 Alkenes
- 5.2 Structure and Bonding of Alkenes
- 5.3 Unsaturation Number
- 5.4 Geometric Isomerism
- 5.5 E,Z Nomenclature of Geometrical Isomers
- 5.6 Nomenclature of Alkenes
- 5.7 Physical Properties of Alkenes
- 5.8 Stability of Alkenes
- 5.9 Reduction of Alkenes
- 5.10 Mechanism of Catalytic Hydrogenation
- 5.11 Heats of hydrogenation of alkenes
- Exercise
6: Alkenes: Addition Reactions
- 6.1 Characteristics of Addition Reactions
- 6.2 Addition of Hydrogen Halides to Alkenes
- 6.3 The Mechanistic Basis of Markovnikov's Rule
- 6.4 Carbocation Rearrangement Reactions
- 6.5 Hydration of Alkenes
- 6.6 Addition of Halogens
- 6.7 Addition of Carbenes
- 6.8 Epoxidation of Alkenes
- 6.9 Dihydroxylatin of Alkenes
- 6.10 Ozonolysis of Alkenes
- Exercises
7: Alkynes
- 7.1 Occurrence and Uses of Alkynes
- 7.2 Structure and Properties of Alkynes
- 7.3 IUPAC Names of Alkynes
- 7.4 Acidity of Terminal Alkynes
- 7.5 Hydrogenation of Alkynes
- 7.6 Electrophilic Addition Reactions
- 7.7 Synthesis of Alkynes
- Exercises
8: Stereochemistry
- 8.1 Stereoisomers
- 8.2 Mirror Image Objects, Mirror Image Molecules, and Chirality
- 8.3 Optical Activity
- 8.4 Fischer Projection Formulas
- 8.5 Absolute Configuration
- 8.6 Molecules with Two (or More) Stereogenic Centers
- 8.7 Cyclic Molecules with Stereogenic Centers
- 8.8 Separation of Enantiomers
- 8.9 Chemical Reactions at Stereogenic Centers
- 8.10 Reactions that Produce Stereogenic Centers
- 8.11 Reactions that Form Diastereomers
- 8.12 Prochiral Centers
- Exercises
9: Haloalkanes and Alcohols: Introduction to Nucleophilic Substitution and Elimination Reactions
- 9.1 Functionalized Hydrocarbons
- 9.2 Nomenclature of Haloalkanes
- 9.3 Nomenclature of Alcohols
- 9.4 Structure and Properties of Haloalkanes
- 9.5 Structure and Properties of Alcohols
- 9.6 Organometallic Compounds
- 9.7 Reactions of Haloalkanes
- 9.8 Nucleophilic Substitution Reactions of Haloalkanes
- 9.9 Mechanisms of Nucleophilic Substitution Reactions of Haloalkanes
- 9.10 Reactions of Alcohols
- 9.11 Acid–Base Reactions of Alcohols
- 9.12 Substitution Reactions of Alcohols
- 9.13 Alternate Methods for the Synthesis of Alkyl Halides
- 9.14 Elimination Reactions
- 9.15 Regioselectivity in Dehydrohalogenation
- 9.16 Mechanisms of Dehydrohalogenation Reactions
- 9.17 Regioselectivity in Dehydration Reactions
- Exercises
10: Nucleophilic Substitution and Elimination Reactions
- 10.1 Properties of Nucleophiles
- 10.2 Biological SN2 Reactions Bysulfur-Containing Nucleophiles
- 10.3 Stereochemistry of Nucleophilic Substitution Reactions
- 10.4 SN1 Versus SN2 Reactions
- 10.5 Mechanisms of Elimination Reactions
- 10.6 Effects of Structure on Competing Substitution and Elimination Reactions
- Exercises
11: Conjugated Alkenes and Allylic Systems
- 11.1 Classes of Dienes
- 11.2 Stability of Conjugated Dienes
- 11.3 Molecular Orbitals of Ethene and 1,3-Butadiene
- 11.4 Structural Effects of Conjugation in 1,3-Butadiene
- 11.5 Allylic Systems
- 11.6 Hückel Molecular Orbitals of Allyl Systems
- 11.7 Electrophilic Addition to Conjugated Dienes
- 11.8 The Diels-Alder Reaction
- 11.9 The Electromagnetic Spectrum
- 11.10 Ultraviolet-Visible Spectroscopy of Alkenes and Conjugated Systems
- Exercises
12: Arenes and Aromaticity
- 12.1 Aromatic Compounds
- 12.2 The Covalent Structure of Benzene
- 12.3 The Hückel Rule
- 12.4 Molecular Orbitals of Aromatic and Antiaromatic Compounds
- 12.5 Heterocyclic Aromatic Compounds
- 12.6 Polycyclic Aromatic Compounds
- Exercises
13: Electrophilic Aromatic Substitution
- 13.1 Nomenclature of Benzene Derivatives
- 13.2 Mechanism of Electrophilic Aromatic Substitution
- 13.3 Common Electrophilic Aromatic Substitution Reactions
- 13.4 Substituent Effects on the Reactivity of Benzene Rings
- 13.5 Interpretation of the Effect of Substituents on Reaction Rates
- 13.6 Interpretation of Directing Effects
- 13.7 Functional Group Modification
- 13.8 Synthesis of Substituted Aromatic Compounds
- Exercises
14: Methods for Structure Determination Nuclear Magnetic Resonance and Mass Spectrometry
- 14.1 structure determination
- 14.2 Nuclear Magnetic Resonance Spectroscopy
- 14.3 The Chemical Shift
- 14.4 Detecting Sets of Nonequivalent Hydrogen Atoms
- 14.5 Effects of Structure on Chemical Shift
- 14.6 Relative Peak Areas and Proton Counting
- 14.7 Spin–Spin Splitting
- 14.8 Effect of Structure on Coupling Constants
- 14.9 Effect of Dynamic Processes
- 14.10 Carbon-13 NMR Spectroscopy
- 14.11 Introduction to Mass Spectrometry
- Exercises
15: Alcohols: Reactions and Synthesis
- 15.1 Overview of Alcohol Reactions
- 15.2 Converting Alcohols into Esters
- 15.3 Conversion of Alcohols to Haloalkanes
- 15.4 Oxidation of Alcohols
- 15.5 Reactions of Vicinal Diols
- 15.6 Synthesis of Alcohols
- 15.7 Synthesis of Alcohols from Haloalkanes
- 15.8 Indirect Hydration Methods
- 15.9 Reduction of Carbonyl Compounds
- 15.10 Alcohol Synthesis Using Grignard Reagents
- 15.11 Thiols and Thioethers
- Exercises
16: Ethers and Epoxides
- 16.1 Structure of Ethers
- 16.2 Nomenclature of Ethers
- 16.3 Physical Properties of Ethers
- 16.4 Polyether Antibiotics
- 16.5 Synthesis of Ethers: Alkoxymercuration-Demercuration of Alkenes
- 16.6 The Williamson Ether Synthesis
- 16.7 Reactions of Ethers
- 16.8 Ethers as Protecting Groups
- 16.9 Synthesis of Epoxides
- 16.10 Reactions of Epoxides
- 16.11 Sulfides
- 16.12 Spectroscopy of Ethers, Thiols, and Sulfides
- Exercises
17: Organometallic Chemistry of Transition Metal Elements and Introduction to Retrosynthesis
- 17.1 Brief Overview of Transition Metal Complexes
- 17.2 The Gilman Reagent
- 17.3 Overview of Palladiumcatalyzed Cross-Coupling Reactions
- 17.4 The Suzuki Coupling Reaction
- 17.5 The Heck Reaction
- 17.6 The Sonogashira Reaction
- 17.7 The Wilkinson Catalyst: Homogeneous Catalytic Hydrogenation
- 17.8 Asymmetric Hydrogenation with Chiral Ruthenium Catalysts
- 17.9 The Grubbs Reaction: A Metathesis Reaction for Alkene Synthesis
- 17.9 Introduction to Retrosynthesis: Thinking Backwards
- Exercises
18: Aldehydes and Ketones
- 18.1 The Carbonyl Group
- 18.2 Nomenclature of Aldehydes and Ketones
- 18.3 Physical Properties of Aldehydes and Ketones
- 18.4 Oxidation–Reduction Reactions of Carbonyl Compounds
- 18.5 Synthesis of Carbonyl Compounds: A Review
- 18.6 Carbonyl Compounds: A Preview
- 18.7 Spectroscopy of Aldehydes and Ketones
- Exercises
19: Aldehydes and Ketones: Nucleophilic Addition Reactions
- 19.1 Relative Stabilities of Aldehydes and Ketones
- 19.2 Formation of Cyanohydrins
- 19.3 Hydration of Carbonyl Compounds
- 19.4 Mechanisms of Acid- and Base-Catalyzed Carbonyl Addition Reactions
- 19.5 Formation of Acetals and Ketals
- 19.6 Acetals as Protecting Groups
- 19.7 Thioacetals and Thioketals
- 19.8 Addition of Nitrogen Compounds to Aldehydes and Ketones
- 19.9 The Wittig Reaction
- Exercises
20: Carboxylic Acids
- 20.1 Carboxylic Acids and Acyl Groups
- 20.2 Nomenclature of Carboxylic Acids
- 20.3 Physical Properties of Carboxylic Acids
- 20.4 Acidity of Carboxylic Acids
- 20.5 Carboxylate Anions
- 20.6 Synthesis of Carboxylic Acids
- 20.7 Reduction of Carboxylic Acids
- 20.8 Decarboxylation Reactions
- 20.9 Reactions of Carboxylic Acids and Their Derivatives: A Preview
- 20.10 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
21: Carboxylic Acid Derivatives
- 21.1 Nomenclature of Carboxylic Acid Derivatives
- 21.2 Physical Properties of Acyl Derivatives
- 21.3 Basicity of Carboxylic Acid Derivatives
- 21.4 Mechanism of Nucleophilic Acyl Substitution
- 21.5 Hydrolysis of Acyl Derivatives
- 21.6 Reaction of Acyl Derivatives with Alcohols
- 21.7 Reaction of Acyl Derivatives with Amines
- 21.8 Reduction of Acyl Derivatives
- 21.9 Reaction of Acyl Derivatives with Organometallic Reagents
- 21.10 Infrared Spectroscopy of Acyl derivatives
- 21.11 NMR Spectroscopy of Acyl Derivatives
- Exercises
22: Condensation Reactions of Carbonyl Compounds
- 22.1 The α-Carbon Atom of Aldehydes and Ketones
- 22.2 Keto–Enol Equilibria of Aldehydes and Ketones
- 22.3 Consequences of Enolization
- 22.4 α-Halogenation Reactions of Aldehydes and Ketones
- 22.5 Alkylation of Enolate Ions
- 22.6 The Aldol Condensation of Aldehydes
- 22.7 Mixed Aldol Condensation Reactions
- 22.8 Intramolecular Aldol Condensation Reactions
- 22.9 Conjugation in α-β-Unsaturated Aldehydes and Ketones
- 22.10 Conjugate Addition Reactions
- 22.11 The Michael Reaction and Robinson Annulation
- 22.12 The α-Hydrogen Atoms of Acid Derivatives
- 22.13 Reaction at the α-Carbon of Acid Derivatives
- 22.14 The Claisen Condensation
- 22.15 Aldol-Type Condensations of Acid Derivations
- 22.16 β -Dicarbonyl Compounds in Synthesis
- 22.17 Michael Condensations of Acid Derivatives
- Exercises
23: Amines and Amides
- 23.1 Organic Nitrogen Compounds
- 23.2 Bonding and Structure of Amines
- 23.3 Classification and Nomenclature of Amines
- 23.4 Physical Properties of Amines
- 23.5 Basicity of Amines
- 23.6 Solubility of Ammonium Salts
- 23.7 Synthesis of Amines by Substitution Reactions
- 23.8 Synthesis of Amines by Reduction
- 23.9 The Hofmann Rearrangement
- 23.10 Overview of Amine Reactions
- 23.11 Enamines
- 23.12 Sulfonamides
- 23.13 Quaternary Ammonium Salts
- 23.14 spectroscopy of amines
- Exercises
24: Aryl Halides, Phenols, and Anilines
- 24.1 Properties of Aromatic Compounds
- 24.2 Acid-Base Properties of Phenols and Anilines
- 24.3 Converting Aryl Halides to Grignard Reagents and Organolithium Reagents
- 24.4 Nucleophilic Aromatic Substitution
- 24.5 An Overview of Phenol Reactions
- 24.6 Reactions of Phenoxide Ions
- 24.7 Quinones
- 24.8 Substitution Reactions of Aryldiazonium Salts
- 24.9 Azo Compounds
- Exercises
25: Pericyclic Reactions
- 25.1 Concerted Reactions
- 25.2 Classification of Pericyclic Reactions
- 25.3 Molecular Orbitals in Pericyclic Reactions
- 25.4 Eiectrocyclic Reactions
- 25.5 Cycloaddition Reactions
- 25.6 Sigmatropic Rearrangements
- Exercises
26: Carbohydrates
- 26.1 Carbohydrates in the Biosphere
- 26.2 Classification of Carbohydrates
- 26.3 Chirality of Monosaccharides
- 26.4 Isomerizations of Monosaccharides
- 26.5 Cyclic Monosaccharides: Hemiacetals and Hemiketals
- 26.6 Reduction and Oxidation of Monosaccharides
- 26.7 Glocosides
- 26.8 Disaccharides
- 26.9 Polysaccharides
- 26.10 Chemical Determination of Monsoaccharide Structures
- 26.11 Determination of Ring Size
- 26.12 Structure of Disaccharides
- 26.13 Human Blood Group Antigens
- Exercises
27: Amino Acids, Peptides, and Proteins
- 27.1 The Structures of α-Amino Acids
- 27.2 Acid-Base Equilibria of α-Amino Acids
- 27.3 Isoionic Point and Titration of α-Amino Acids
- 27.4 Synthesis of α-Amino Acids
- 27.5 Chiral Synthesis of α-Amino Acids
- 27.6 Reactions of α-Amino Acids
- 27.7 Peptides
- 27.8 Overview of Peptide Synthesis
- 27.9 Solid-Phase Peptide Synthesis
- 27.10 Determination of the Amino Acid Composition of Proteins
- 27.11 Determination of the Amino Acid Sequence of Proteins
- 27.12 Bonding in Proteins
- 27.13 Protein Structure
- 27.14 Oxygen Storage and Transport: Myoglobin and Hemoglobin
- Exercises
28: Synthetic Polymers
- 28.1 Natural and Synthetic Polymers
- 28.2 Physical Properties of Polymers
- 28.3 Classes of Polymers
- 28.4 Polymerization Methods
- 28.5 Addition Polymerization
- 28.6 Copolymerization of Alkenes
- 28.7 Cross-Linked Polymers
- 28.8 Stereochemistry of Addition Polymerization
- 28.9 Condensation Polymers
- 28.10 Polyesters
- 28.11 Polycarbonates
- 28.12 Polyamides
- 28.13 Phenol-Formaldehyde Polymers
- 28.14 Polyurethanes
- Exercises
Appendix pKa Values
Appendix A: Heats of Formation (kJ mole− 1)
Appendix IR Absorptions (cm− 1)
Appendix 1H NMR and 13C NMR Chemical Shifts (ppm)
Glossary
A Brief Overview of Thermodynamics
- 1 First Law of Thermodynamics
- 2 Estimating ∆H°rxn from Bond Energies
- 3 Second Law of Thermodynamics
- 3 Entropy changes in chemical reactions
- 3 Free Energy
- 4 Contributions of ΔH°rxn and ΔS°rxn to ΔG°rxn
Chemical Kinetics
- 1 Practical Kinetics
- 2 Transition State Theory
- 3 The Hammond Postulate
Summary of Synthetic Methods
Solutions to In-Chapter Problems
- Chapter 1
- Chapter 2
- Chapter 3
- Chapter 4
- Chapter 5
- Chapter 6
- Chapter 7
- Chapter 8
- Chapter 9
- Chapter 10
- Chapter 11
- Chapter 12
- Chapter 13
- Chapter 14
- Chapter 15
- Chapter 16
- Chapter 17
- Chapter 18
- Chapter 19
- Chapter 20
- Chapter 21
- Chapter 22
- Chapter 22
- Chapter 24
- Chapter 25
- Chapter 26
- Chapter 27
- Chapter 28