Organic chemistry

Contents
Dedication and Preface
Chapter 1 Structure and Bonding
Why This Chapter?
1.1 Atomic Structure: The Nucleus
1.2 Atomic Structure: Orbitals
1.3 Atomic Structure: Electron Configurations
1.4 Development of Chemical Bonding Theory
1.5 Describing Chemical Bonds: Valence Bond Theory
1.6 sp3 Hybrid Orbitals and the Structure of Methane
1.7 sp3 Hybrid Orbitals and the Structure of Ethane
1.8 sp2 Hybrid Orbitals and the Structure of Ethylene
1.9 sp Hybrid Orbitals and the Structure of Acetylene
1.10 Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur
1.11 Describing Chemical Bonds: Molecular Orbital Theory
1.12 Drawing Chemical Structures
Chemistry Matters — Organic Foods: Risk versus Benefit
Key Terms
Summary
Additional Problems
Chapter 2 Polar Covalent Bonds; Acids and Bases
Why This Chapter?
2.1 Polar Covalent Bonds and Electronegativity
2.2 Polar Covalent Bonds and Dipole Moments
2.3 Formal Charges
2.4 Resonance
2.5 Rules for Resonance Forms
2.6 Drawing Resonance Forms
2.7 Acids and Bases: The Brønsted–Lowry Definition
2.8 Acid and Base Strength
2.9 Predicting Acid–Base Reactions from pKa Values
2.10 Organic Acids and Organic Bases
2.11 Acids and Bases: The Lewis Definition
2.12 Noncovalent Interactions between Molecules
Chemistry Matters — Alkaloids: From Cocaine to Dental Anesthetics
Key Terms
Summary
Additional Problems
Chapter 3 Organic Compounds: Alkanes and Their Stereochemistry
Why This Chapter?
3.1 Functional Groups
3.2 Alkanes and Alkane Isomers
3.3 Alkyl Groups
3.4 Naming Alkanes
3.5 Properties of Alkanes
3.6 Conformations of Ethane
3.7 Conformations of Other Alkanes
Chemistry Matters — Gasoline
Key Terms
Summary
Additional Problems
Chapter 4 Organic Compounds: Cycloalkanes and Their Stereochemistry
Why This Chapter?
4.1 Naming Cycloalkanes
4.2 Cis–Trans Isomerism in Cycloalkanes
4.3 Stability of Cycloalkanes: Ring Strain
4.4 Conformations of Cycloalkanes
4.5 Conformations of Cyclohexane
4.6 Axial and Equatorial Bonds in Cyclohexane
4.7 Conformations of Monosubstituted Cyclohexanes
4.8 Conformations of Disubstituted Cyclohexanes
4.9 Conformations of Polycyclic Molecules
Chemistry Matters — Molecular Mechanics
Key Terms
Summary
Additional Problems
Chapter 5 Stereochemistry at Tetrahedral Centers
Why This Chapter?
5.1 Enantiomers and the Tetrahedral Carbon
5.2 The Reason for Handedness in Molecules: Chirality
5.3 Optical Activity
5.4 Pasteur’s Discovery of Enantiomers
5.5 Sequence Rules for Specifying Configuration
5.6 Diastereomers
5.7 Meso Compounds
5.8 Racemic Mixtures and the Resolution of Enantiomers
5.9 A Review of Isomerism
5.10 Chirality at Nitrogen, Phosphorus, and Sulfur
5.11 Prochirality
5.12 Chirality in Nature and Chiral Environments
Chemistry Matters — Chiral Drugs
Key Terms
Summary
Additional Problems
Chapter 6 An Overview of Organic Reactions
Why This Chapter?
6.1 Kinds of Organic Reactions
6.2 How Organic Reactions Occur: Mechanisms
6.3 Polar Reactions
6.4 An Example of a Polar Reaction: Addition of HBr to Ethylene
6.5 Using Curved Arrows in Polar Reaction Mechanisms
6.6 Radical Reactions
6.7 Describing a Reaction: Equilibria, Rates, and Energy Changes
6.8 Describing a Reaction: Bond Dissociation Energies
6.9 Describing a Reaction: Energy Diagrams and Transition States
6.10 Describing a Reaction: Intermediates
6.11 A Comparison Between Biological Reactions and Laboratory Reactions
Chemistry Matters — Where Do Drugs Come From?
Key Terms
Summary
Additional Problems
Chapter 7 Alkenes: Structure and Reactivity
Why This Chapter?
7.1 Industrial Preparation and Use of Alkenes
7.2 Calculating the Degree of Unsaturation
7.3 Naming Alkenes
7.4 Cis–Trans Isomerism in Alkenes
7.5 Alkene Stereochemistry and the E,Z Designation
7.6 Stability of Alkenes
7.7 Electrophilic Addition Reactions of Alkenes
7.8 Orientation of Electrophilic Additions: Markovnikov’s Rule
7.9 Carbocation Structure and Stability
7.10 The Hammond Postulate
7.11 Evidence for the Mechanism of Electrophilic Additions: Carbocation Rearrangements
Chemistry Matters — Bioprospecting: Hunting for Natural Products
Key Terms
Summary
Additional Problems
Chapter 8 Alkenes: Reactions and Synthesis
Why This Chapter?
8.1 Preparing Alkenes: A Preview of Elimination Reactions
8.2 Halogenation of Alkenes: Addition of X2
8.3 Halohydrins from Alkenes: Addition of HO-X
8.4 Hydration of Alkenes: Addition of H2O by Oxymercuration
8.5 Hydration of Alkenes: Addition of H2O by Hydroboration
8.6 Reduction of Alkenes: Hydrogenation
8.7 Oxidation of Alkenes: Epoxidation and Hydroxylation
8.8 Oxidation of Alkenes: Cleavage to Carbonyl Compounds
8.9 Addition of Carbenes to Alkenes: Cyclopropane Synthesis
8.10 Radical Additions to Alkenes: Chain-Growth Polymers
8.11 Biological Additions of Radicals to Alkenes
8.12 Reaction Stereochemistry: Addition of H2O to an Achiral Alkene
8.13 Reaction Stereochemistry: Addition of H2O to a Chiral Alkene
Chemistry Matters — Terpenes: Naturally Occurring Alkenes
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 9 Alkynes: An Introduction to Organic Synthesis
Why This Chapter?
9.1 Naming Alkynes
9.2 Preparation of Alkynes: Elimination Reactions of Dihalides
9.3 Reactions of Alkynes: Addition of HX and X2
9.4 Hydration of Alkynes
9.5 Reduction of Alkynes
9.6 Oxidative Cleavage of Alkynes
9.7 Alkyne Acidity: Formation of Acetylide Anions
9.8 Alkylation of Acetylide Anions
9.9 An Introduction to Organic Synthesis
Chemistry Matters — The Art of Organic Synthesis
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 10 Organohalides
Why This Chapter?
10.1 Names and Structures of Alkyl Halides
10.2 Preparing Alkyl Halides from Alkanes: Radical Halogenation
10.3 Preparing Alkyl Halides from Alkenes: Allylic Bromination
10.4 Stability of the Allyl Radical: Resonance Revisited
10.5 Preparing Alkyl Halides from Alcohols
10.6 Reactions of Alkyl Halides: Grignard Reagents
10.7 Organometallic Coupling Reactions
10.8 Oxidation and Reduction in Organic Chemistry
Chemistry Matters — Naturally Occurring Organohalides
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 11 Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
Why This Chapter?
11.1 The Discovery of Nucleophilic Substitution Reactions
11.2 The SN2 Reaction
11.3 Characteristics of the SN2 Reaction
11.4 The SN1 Reaction
11.5 Characteristics of the SN1 Reaction
11.6 Biological Substitution Reactions
11.7 Elimination Reactions: Zaitsev’s Rule
11.8 The E2 Reaction and the Deuterium Isotope Effect
11.9 The E2 Reaction and Cyclohexane Conformation
11.10 The E1 and E1cB Reactions
11.11 Biological Elimination Reactions
11.12 A Summary of Reactivity: SN1, SN2, E1, E1cB, and E2
Chemistry Matters — Green Chemistry
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 12 Structure Determination: Mass Spectrometry and Infrared Spectroscopy
Why This Chapter?
12.1 Mass Spectrometry of Small Molecules: Magnetic-Sector Instruments
12.2 Interpreting Mass Spectra
12.3 Mass Spectrometry of Some Common Functional Groups
12.4 Mass Spectrometry in Biological Chemistry: Time-of-Flight (TOF) Instruments
12.5 Spectroscopy and the Electromagnetic Spectrum
12.6 Infrared Spectroscopy
12.7 Interpreting Infrared Spectra
12.8 Infrared Spectra of Some Common Functional Groups
Chemistry Matters — X-Ray Crystallography
Key Terms
Summary
Additional Problems
Chapter 13 Structure Determination: Nuclear Magnetic Resonance Spectroscopy
Why This Chapter?
13.1 Nuclear Magnetic Resonance Spectroscopy
13.2 The Nature of NMR Absorptions
13.3 Chemical Shifts
13.4 Chemical Shifts in 1H NMR Spectroscopy
13.5 Integration of 1H NMR Absorptions: Proton Counting
13.6 Spin–Spin Splitting in 1H NMR Spectra
13.7 1H NMR Spectroscopy and Proton Equivalence
13.8 More Complex Spin–Spin Splitting Patterns
13.9 Uses of 1H NMR Spectroscopy
13.10 13C NMR Spectroscopy: Signal Averaging and FT–NMR
13.11 Characteristics of 13C NMR Spectroscopy
13.12 DEPT 13C NMR Spectroscopy
13.13 Uses of 13C NMR Spectroscopy
Chemistry Matters — Magnetic Resonance Imaging (MRI)
Key Terms
Summary
Additional Problems
Chapter 14 Conjugated Compounds and Ultraviolet Spectroscopy
Why This Chapter?
14.1 Stability of Conjugated Dienes: Molecular Orbital Theory
14.2 Electrophilic Additions to Conjugated Dienes: Allylic Carbocations
14.3 Kinetic versus Thermodynamic Control of Reactions
14.4 The Diels–Alder Cycloaddition Reaction
14.5 Characteristics of the Diels–Alder Reaction
14.6 Diene Polymers: Natural and Synthetic Rubbers
14.7 Ultraviolet Spectroscopy
14.8 Interpreting Ultraviolet Spectra: The Effect of Conjugation
14.9 Conjugation, Color, and the Chemistry of Vision
Chemistry Matters — Photolithography
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 15 Benzene and Aromaticity
Why This Chapter?
15.1 Naming Aromatic Compounds
15.2 Structure and Stability of Benzene
15.3 Aromaticity and the Hückel 4n + 2 Rule
15.4 Aromatic Ions
15.5 Aromatic Heterocycles: Pyridine and Pyrrole
15.6 Polycyclic Aromatic Compounds
15.7 Spectroscopy of Aromatic Compounds
Chemistry Matters — Aspirin, NSAIDs, and COX-2 Inhibitors
Key Terms
Summary
Additional Problems
Chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution
Why This Chapter?
16.1 Electrophilic Aromatic Substitution Reactions: Bromination
16.2 Other Aromatic Substitutions
16.3 Alkylation and Acylation of Aromatic Rings: The Friedel–Crafts Reaction
16.4 Substituent Effects in Electrophilic Substitutions
16.5 Trisubstituted Benzenes: Additivity of Effects
16.6 Nucleophilic Aromatic Substitution
16.7 Benzyne
16.8 Oxidation of Aromatic Compounds
16.9 Reduction of Aromatic Compounds
16.10 Synthesis of Polysubstituted Benzenes
Chemistry Matters — Combinatorial Chemistry
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 17 Alcohols and Phenols
Why This Chapter?
17.1 Naming Alcohols and Phenols
17.2 Properties of Alcohols and Phenols
17.3 Preparation of Alcohols: A Review
17.4 Alcohols from Carbonyl Compounds: Reduction
17.5 Alcohols from Carbonyl Compounds: Grignard Reaction
17.6 Reactions of Alcohols
17.7 Oxidation of Alcohols
17.8 Protection of Alcohols
17.9 Phenols and Their Uses
17.10 Reactions of Phenols
17.11 Spectroscopy of Alcohols and Phenols
Chemistry Matters — Ethanol: Chemical, Drug, and Poison
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 18 Ethers and Epoxides; Thiols and Sulfides
Why This Chapter?
18.1 Names and Properties of Ethers
18.2 Preparing Ethers
18.3 Reactions of Ethers: Acidic Cleavage
18.4 Cyclic Ethers: Epoxides
18.5 Reactions of Epoxides: Ring-Opening
18.6 Crown Ethers
18.7 Thiols and Sulfides
18.8 Spectroscopy of Ethers
Chemistry Matters — Epoxy Resins and Adhesives
Key Terms
Summary
Summary of Reactions
Additional Problems
Preview of Carbonyl Chemistry
Chapter 19 Aldehydes and Ketones: Nucleophilic Addition Reactions
Why This Chapter?
19.1 Naming Aldehydes and Ketones
19.2 Preparing Aldehydes and Ketones
19.3 Oxidation of Aldehydes and Ketones
19.4 Nucleophilic Addition Reactions of Aldehydes and Ketones
19.5 Nucleophilic Addition of H2O: Hydration
19.6 Nucleophilic Addition of HCN: Cyanohydrin Formation
19.7 Nucleophilic Addition of Hydride and Grignard Reagents: Alcohol Formation
19.8 Nucleophilic Addition of Amines: Imine and Enamine Formation
19.9 Nucleophilic Addition of Hydrazine: The Wolff–Kishner Reaction
19.10 Nucleophilic Addition of Alcohols: Acetal Formation
19.11 Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction
19.12 Biological Reductions
19.13 Conjugate Nucleophilic Addition to α,β‑Unsaturated Aldehydes and Ketones
19.14 Spectroscopy of Aldehydes and Ketones
Chemistry Matters — Enantioselective Synthesis
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 20 Carboxylic Acids and Nitriles
Why This Chapter?
20.1 Naming Carboxylic Acids and Nitriles
20.2 Structure and Properties of Carboxylic Acids
20.3 Biological Acids and the Henderson–Hasselbalch Equation
20.4 Substituent Effects on Acidity
20.5 Preparing Carboxylic Acids
20.6 Reactions of Carboxylic Acids: An Overview
20.7 Chemistry of Nitriles
20.8 Spectroscopy of Carboxylic Acids and Nitriles
Chemistry Matters — Vitamin C
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
Why This Chapter?
21.1 Naming Carboxylic Acid Derivatives
21.2 Nucleophilic Acyl Substitution Reactions
21.3 Reactions of Carboxylic Acids
21.4 Chemistry of Acid Halides
21.5 Chemistry of Acid Anhydrides
21.6 Chemistry of Esters
21.7 Chemistry of Amides
21.8 Chemistry of Thioesters and Acyl Phosphates: Biological Carboxylic Acid Derivatives
21.9 Polyamides and Polyesters: Step-Growth Polymers
21.10 Spectroscopy of Carboxylic Acid Derivatives
Chemistry Matters — β-Lactam Antibiotics
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 22 Carbonyl Alpha-Substitution Reactions
Why This Chapter?
22.1 Keto–Enol Tautomerism
22.2 Reactivity of Enols: α-Substitution Reactions
22.3 Alpha Halogenation of Aldehydes and Ketones
22.4 Alpha Bromination of Carboxylic Acids
22.5 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation
22.6 Reactivity of Enolate Ions
22.7 Alkylation of Enolate Ions
Chemistry Matters — Barbiturates
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 23 Carbonyl Condensation Reactions
Why This Chapter?
23.1 Carbonyl Condensations: The Aldol Reaction
23.2 Carbonyl Condensations versus Alpha Substitutions
23.3 Dehydration of Aldol Products: Synthesis of Enones
23.4 Using Aldol Reactions in Synthesis
23.5 Mixed Aldol Reactions
23.6 Intramolecular Aldol Reactions
23.7 The Claisen Condensation Reaction
23.8 Mixed Claisen Condensations
23.9 Intramolecular Claisen Condensations: The Dieckmann Cyclization
23.10 Conjugate Carbonyl Additions: The Michael Reaction
23.11 Carbonyl Condensations with Enamines: The Stork Enamine Reaction
23.12 The Robinson Annulation Reaction
23.13 Some Biological Carbonyl Condensation Reactions
Chemistry Matters — A Prologue to Metabolism
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 24 Amines and Heterocycles
Why This Chapter?
24.1 Naming Amines
24.2 Structure and Properties of Amines
24.3 Basicity of Amines
24.4 Basicity of Arylamines
24.5 Biological Amines and the Henderson–Hasselbalch Equation
24.6 Synthesis of Amines
24.7 Reactions of Amines
24.8 Reactions of Arylamines
24.9 Heterocyclic Amines
24.10 Spectroscopy of Amines
Chemistry Matters — Green Chemistry II: Ionic Liquids
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 25 Biomolecules: Carbohydrates
Why This Chapter?
25.1 Classification of Carbohydrates
25.2 Representing Carbohydrate Stereochemistry: Fischer Projections
25.3 D,L Sugars
25.4 Configurations of the Aldoses
25.5 Cyclic Structures of Monosaccharides: Anomers
25.6 Reactions of Monosaccharides
25.7 The Eight Essential Monosaccharides
25.8 Disaccharides
25.9 Polysaccharides and Their Synthesis
25.10 Some Other Important Carbohydrates
Chemistry Matters — Sweetness
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 26 Biomolecules: Amino Acids, Peptides, and Proteins
Why This Chapter?
26.1 Structures of Amino Acids
26.2 Amino Acids and the Henderson–Hasselbalch Equation: Isoelectric Points
26.3 Synthesis of Amino Acids
26.4 Peptides and Proteins
26.5 Amino Acid Analysis of Peptides
26.6 Peptide Sequencing: The Edman Degradation
26.7 Peptide Synthesis
26.8 Automated Peptide Synthesis: The Merrifield Solid-Phase Method
26.9 Protein Structure
26.10 Enzymes and Coenzymes
26.11 How Do Enzymes Work? Citrate Synthase
Chemistry Matters — The Protein Data Bank
Key Terms
Summary
Summary of Reactions
Additional Problems
Chapter 27 Biomolecules: Lipids
Why This Chapter?
27.1 Waxes, Fats, and Oils
27.2 Soap
27.3 Phospholipids
27.4 Prostaglandins and Other Eicosanoids
27.5 Terpenoids
27.6 Steroids
27.7 Biosynthesis of Steroids
Chemistry Matters — Saturated Fats, Cholesterol, and Heart Disease
Key Terms
Summary
Additional Problems
Chapter 28 Biomolecules: Nucleic Acids
Why This Chapter?
28.1 Nucleotides and Nucleic Acids
28.2 Base Pairing in DNA
28.3 Replication of DNA
28.4 Transcription of DNA
28.5 Translation of RNA: Protein Biosynthesis
28.6 DNA Sequencing
28.7 DNA Synthesis
28.8 The Polymerase Chain Reaction
Chemistry Matters — DNA Fingerprinting
Key Terms
Summary
Additional Problems
Chapter 29 The Organic Chemistry of Metabolic Pathways
Why This Chapter?
29.1 An Overview of Metabolism and Biochemical Energy
29.2 Catabolism of Triacylglycerols: The Fate of Glycerol
29.3 Catabolism of Triacylglycerols: β-Oxidation
29.4 Biosynthesis of Fatty Acids
29.5 Catabolism of Carbohydrates: Glycolysis
29.6 Conversion of Pyruvate to Acetyl CoA
29.7 The Citric Acid Cycle
29.8 Carbohydrate Biosynthesis: Gluconeogenesis
29.9 Catabolism of Proteins: Deamination
29.10 Some Conclusions about Biological Chemistry
Chemistry Matters — Statin Drugs
Key Terms
Summary
Additional Problems
Chapter 30 Orbitals and Organic Chemistry: Pericyclic Reactions
Why This Chapter?
30.1 Molecular Orbitals of Conjugated Pi Systems
30.2 Electrocyclic Reactions
30.3 Stereochemistry of Thermal Electrocyclic Reactions
30.4 Photochemical Electrocyclic Reactions
30.5 Cycloaddition Reactions
30.6 Stereochemistry of Cycloadditions
30.7 Sigmatropic Rearrangements
30.8 Some Examples of Sigmatropic Rearrangements
30.9 A Summary of Rules for Pericyclic Reactions
Chemistry Matters — Vitamin D, the Sunshine Vitamin
Key Terms
Summary
Additional Problems
Chapter 31 Synthetic Polymers
Why This Chapter?
31.1 Chain-Growth Polymers
31.2 Stereochemistry of Polymerization: Ziegler–Natta Catalysts
31.3 Copolymers
31.4 Step-Growth Polymers
31.5 Olefin Metathesis Polymerization
31.6 Intramolecular Olefin Metathesis
31.7 Polymer Structure and Physical Properties
Chemistry Matters — Degradable Polymers
Key Terms
Summary
Additional Problems
Appendix A Nomenclature of Polyfunctional Organic Compounds
Name Part 1. The Suffix: Functional-Group Precedence
Name Part 2. The Parent: Selecting the Main Chain or Ring
Name Parts 3 and 4. The Prefixes and Locants
Writing the Name
Additional Reading
Appendix B Acidity Constants for Some Organic Compounds
Appendix C Glossary
Appendix D Periodic Table
Answer Key
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 23
Chapter 24
Chapter 25
Chapter 26
Chapter 27
Chapter 28
Chapter 29
Chapter 30
Chapter 31
Index