Organic Chemistry with Companion Website + GradeTracker + Access Code Card
International Edition
5th Edition
Published on 31. December 2007
Book
Mixed media product
978-0-13-225662-9 (ISBN)
Description
For full-year courses in organic chemistry taken by science and pre-health professions majors.
This innovative text is organized in a way that discourages rote memorization, by emphasizing what functional groups do rather than how they are made, highlighting mechanistic similarities and tying synthesis and reactivity together. Bruice's writing has been praised for anticipating students' questions, appealing to their visual and problem solving needs. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.
This innovative text is organized in a way that discourages rote memorization, by emphasizing what functional groups do rather than how they are made, highlighting mechanistic similarities and tying synthesis and reactivity together. Bruice's writing has been praised for anticipating students' questions, appealing to their visual and problem solving needs. The text balances coverage of traditional topics with bioorganic chemistry, recognizing the importance of bioorganic topics to today's students.
More details
Edition
5th edition
Language
English
Place of publication
United States
Publishing group
Pearson Education (US)
Target group
Professional and scholarly
Dimensions
Height: 265 mm
Width: 217 mm
Thickness: 44 mm
Weight
2840 gr
ISBN-13
978-0-13-225662-9 (9780132256629)
Copyright in bibliographic data and cover images is held by Nielsen Book Services Limited or by the publishers or by their respective licensors: all rights reserved.
Schweitzer Classification
Other editions
New editions
Book
01/2010
6th Edition
Pearson
€205.49
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Person
Paula Yurkanis Bruice was raised primarily in Massachusetts, Germany, and Switzerland and was graduated from the Girls' Latin School in Boston. She received an A.B. from Mount Holyoke College and a Ph.D. in chemistry from the University of Virginia. She received an NIH postdoctoral fellowship for study in biochemistry at the University of Virginia Medical School, and she held a postdoctoral appointment in the Department of Pharmacology at Yale Medical School.
She is a member of the faculty at the University of California, Santa Barbara, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, and two Mortar Board Professor of the Year Awards. Her research interests concern the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading mystery/suspense novels and her pets (three dogs, two cats, and a parrot).
She is a member of the faculty at the University of California, Santa Barbara, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, and two Mortar Board Professor of the Year Awards. Her research interests concern the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading mystery/suspense novels and her pets (three dogs, two cats, and a parrot).
Content
I: AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY
1. ELECTRONIC STRUCTURE AND BONDING ? ACIDS AND BASES
1.1 The Structure of an Atom
1.2 How the Electrons in an Atom are Distributed
1.3 Ionic and Covalent Bonds
Ionic Bonds are Formed by the Transfer of Electrons
Covalent Bonds are Formed by Sharing Electrons
Polar Covalent Bonds
1.4 How the Structure of a Compound is Represented
Lewis Structures
Kekule Structures
Condensed Structures
1.5 Atomic Orbitals
1.6 An Introduction to Molecular Orbital Theory
1.7 How Single Bonds are Formed in Organic Compounds
The Bonds in Methane
The Bonds in Ethane
1.8 How a Double Bond is Formed: The Bonds in Ethene
1.9 How a Triple Bonds is Formed: The Bonds in Ethyne
1.10 The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion
The Methyl Cation
The Methyl Radical
The Methyl Anion
1.11 The Bonds in Water
1.12 The Bonds in Ammonia and in the Ammonium Ion
1.13 The Bonds in the Hydrogen Halides
1.14 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles
1.15 The Dipole Moments of Molecules
1.16 An Introduction to Acids and Bases
1.17 pKa and pH
1.18 Organic Acids and Bases
1.19 How to Predict the Outcome of an Acid-Base Reaction
1.20 How the Structure of an Acid Affects Its Acidity
1.21 How Substituents Affect the Strength of an Acid
1.22 An Introduction to Delocalized Electrons
1.23 A Summary of the Factors that Determine Acid Strength
1.24 How the pH Affects the Structure of an Organic Compound
1.25 Buffer Solutions
1.26 The Second Definition of Acid and Base: Lewis Acids and Bases
2. AN INTRODUCTION TO ORGANIC COMPOUNDS NOMENCLATURE, PHYSICAL PROPERTIES, AND REPRESENTATION OF STRUCTURE
2.1 How Alkyl Substituents are Named
2.2 Nomenclature of Alkanes
2.3 Nomenclature of Cycloalkanes
2.4 Nomenclature of Alkyl Halides
2.5 Nomenclature of Ethers
2.6 Nomenclature of Alcohols
2.7 Nomenclature of Amines
2.8 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines
2.9 The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines
Boiling Points
Melting Points
Solubility
2.10 Rotation Occurs About Carbon-Carbon Bonds
2.11 Some Cycloalkanes Have Ring Strain
2.12 Conformations of Cyclohexane
2.13 Conformers of Monosubstituted Cyclohexanes
2.14 Conformers of Disubstituted Cyclohexanes
II: ELECTROPHILIC ADDITION REACTIONS, STEREOCHEMISTRY, AND ELECTRON DEELOCALIZATION
3. ALKENES: STRUCTURE, NOMENCLATURE AND AN INTRODUCTION TO REACTIVITY ? THERMODYNAMICS AND KINETICS
3.1 Molecular Formulas and the Degree of Unsaturation
3.2 Nomenclature of Alkenes
3.3 The Structures of Alkenes
3.4 Alkenes Can Have Cis and Trans Isomers
3.5 Naming Alkenes Using the E,Z System
3.6 How Alkenes React ? Curved Arrows Show the Flow of Electrons
3.7 Thermodynamics and Kinetics
A Reaction Coordinate Diagram Describes the Reaction Pathway
Thermodynamics: How Much Product Is Formed?
Kinetics: How Fast Is the Product Formed?
3.8 Using a Reaction Coordinate Diagram to Describe a Reaction
4. THE REACTIONS OF ALKENES
4.1 Addition of a Hydrogen Halide to an Alkene
4.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon
4.3 The Structure of the Transition State Lies Partway Between the Structures of the Reactants and Products
4.4 Electrophilic Addition Reactions Are Regioselective
4.5 Acid-Catalyzed Addition Reactions
Addition of Water to an Alkene
Addition of an Alcohol to an Alkene
4.6 A Carbocation will Rearrange if It Can Form a More Stable Carbocation
4.7 Addition of a Halogen to an Alkene
4.8 Oxymercuration-Demercuration: Are Other Ways to Add Water or Alcohol to an Alkene
4.9 Addition of a Peroxyacid to an Alkene
4.10 Addition of Borane to an Alkene: Hydroboration-Oxidation
4.11 Addition of Hydrogen to an Alkene ? The Relative Stabilities of Alkenes
4.12 Reactions and Synthesis
5. STEREOCHEMISTRY: THE ARRANGEMENT OF ATOMS IN SPACE; THE STEREOCHEMISTRY OF ADDITION REACTIONS
5.1 Cis-Trans Isomers Result From Restricted Rotation
5.2 A Chiral Object has a Nonsuperimposable Mirror Image
5.3 An Asymmetric Center Is a Cause of Chirality In a Molecule
5.4 Isomers with One Asymmetric Center
5.5 Asymmetric Centers and Stereocenters
5.6 How to Draw Enantiomers
5.7 Naming Enantiomers by the R,S System
5.8 Chiral Compounds are Optically Active
5.9 How Specific Rotation is Measured
5.10 Enantiomeric Excess
5.11 Isomers with More than One Asymmetric Center
5.12 Meso Compounds Have Asymmetric Centers but are Optically Inactive
5.13 How to Name Isomers with More than One Asymmetric Center
5.14 Reactions of Compounds that Contain a Asymmetric Center
5.15 The Absolute Configuration of (+)-Glyceraldehyde
5.16 How Enantiomers Can be Separated
5.17 Nitrogen and Phosphorous Atoms Can be Asymmetric Centers
5.18 The Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions
5.19 The Stereochemistry of Electrophilic Addition Reactions of Alkenes
Addition Reactions that Form a Product with One Asymmetric Center
Addition Reactions that Form Products with Two Asymmetric Centers
Addition Reactions that Form a Carbocation Intermediate
The Stereochemistry of Hydrogen Addition
The Stereochemistry of Peroxyacid Addition
The Stereochemistry of Hydroboration-Oxidation
Addition Reactions that Form a Cyclic Bromonium Ion Intermediate
5.20 The Stereochemistry of Enzyme-Catalyzed Reactions
5.21 Enantiomers can be Distinguished by Biological Molecules
Enymes
Receptors
6. THE REACTIONS OF ALKYNES ? AN INTRODUCTION TO MULTISTEP SYNTHESIS
6.1 The Nomenclature of Alkynes
6.2 How to Name a Compound That Has More than One Functional Group
6.3 The Physical Properties of Unsaturated Hydrocarbons
6.4 The Structure of Alkynes
6.5 How Alkynes React
6.6 Addition of Hydrogen Halides and Addition of Halogens to an Alkyne
6.7 Addition of Water to an Alkyne
6.8 Addition of Borane to an Alkyne: Hydroboration-Oxidation
6.9 Addition of Hydrogen to an Alkyne
6.10 A Hydrogen Bonded to an sp Carbon is "Acidic"
6.11 Synthesis Using Acetylide Ions
6.12 Designing a Synthesis I: An Introduction to Multistep Synthesis
7. DELOCALIZED ELECTRONS AND THEIR EFFECT ON STABILITY, REACTIVITY, AND pKa ? MORE ABOUT MOLECULAR ORBITAL THEORY
7.1 Benzene Has Delocalized Electrons
7.2 The Bonding in Benzene
7.3 Resonance Contributors and the Resonance Hybrid
7.4 How to Draw Resonance Contributors
7.5 The Predicted Stabilites of Resonance Contributors
7.6 Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound
7.7 Examples That Illustrate the Effect of Delocalized Electrons on Stability
Stability of Dienes
Stability of Allylic and Benzylic Cations
7.8 A Molecular Orbital Description of Stability
1,3-Butadiene and 1,4-Pentadiene
1,3,5-Hexatriene and Benzene
7.9 How Delocalized Electrons Affect pKa
7.10 Delocalized Electrons Can Affect the Product of a Reaction
Reactions of Isolated Dienes
Reactions of Conjugated Dienes
7.11 Thermodynamic versus Kinetic Control of Reactions
7.12 The Diels-Alder Reaction Is a 1,4-Addition Reaction
A Molecular Orbital Description of the Diels-Alder Reaction
Predicting the Product When Both Reagents Are Unsymmetrically Substituted
Conformations of the Diene
The Stereochemistry of the Diels-Alder Reaction
III: SUBSTITUTION AND ELIMINATION REACTIONS
8. SUBSTITUTION REACTIONS OF OF ALKYL HALIDES
8.1 How Alkyl Halides React
8.2 The Mechanism of an SN2 Reaction
8.3 Factors that Affect SN2 Reactions
The Leaving Group
The Nucleophile
Nucleophilicity is Affected by the Solvent
Nucleophilicity is Affected by Steric Effects
8.4 The Reversibility of an SN2 Reaction Depends on the Basicities of the Leaving Groups in the Forward and Reverse Directions
8.5 The Mechanism of an SN1 Reaction
8.6 Factors that Affect an SN1 Reaction
The Leaving Group
The Nucleophile
Carbocation Rearrangements
8.7 More About the Stereochemistry of SN2 and SN1 Reactions
Stereochemistry of SN2 Reactions
Stereochemistry of SN1 Reactions
8.8 Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides
8.9 Competition Between SN2 and SN1 Reactions
8.10 The Role of the Solvent in SN2 and SN1 Reactions
How a Solvent Affects Reaction Rates in General
How a Solvent Affects the Rate of an SN1 Reaction
How a Solvent Affects the Rate of an SN2 Reaction
8.11 Biological Methylating Reagents Have Good Leaving Groups
9. ELIMINATION REACTIONS OF ALKYL HALIDES ? COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION
9.1 The E2 Reaction
9.2 An E2 Reaction is Regioselective
9.3 The E1 Reaction
9.4 Competition Between E2 and E1 Reactions
9.5 E2 and E1 Reactions are Stereoselective
The Stereoisomers Formed in an E2 Reaction
The Stereoisomers Formed in an E1 Reaction
9.6 Elimination from Substituted Cyclohexanes
E2 Reactions of Substituted Cyclohexanes
E1 Reactions of Substituted Cyclohexanes
9.7 A Kinetic Isotope Effect Can Help Determine a Mechanism
9.8 Competition Between Substitution and Elimination
SN2/E2 Conditions
SN1/E1 Conditions
9.9 Substitution and Elimination Reactions in Synthesis
Using Substitution Reactions to Synthesize Compounds
Using Elimination Reactions to Synthesize Compounds
9.10 Consecutive E2 Elimination Reactions
9.11 Intermolecular Versus Intramolecular Reactions
9.12 Designing a Synthesis II: Approaching the Problem
10. REACTIONS OF ALCOHOLS, AMINES, ETHERS, EXPOXIDES, AND SULFUR-CONTAINING COMPOUNDS ? ORGANOMETALLIC COMPOUNDS
10.1 Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides
10.2 Other Methods for Converting Alcohols into Alkyl Halides
10.3 Converting Alcohols into Sulfonate Esters
10.4 Elimination Reactions of Alcohols: Dehydration
10.5 Oxidation of Alcohols
10.6 Amines do not Undergo Substitution or Elimination Reactions but Are the Most Common Organic Bases
10.7 Nucleophilic Substitution Reactions of Ethers
10.8 Nucleophilic Substitution Reactions of Epoxides
10.9 Arene Oxides
10.10 Crown Ethers
10.11 Thiols, Sulfides, and Sulfonium Salts
10.12 Organometallic Compounds
10.13 Coupling Reactions
11. RADICALS ? REACTIONS OF ALKANES
11.1 Alkanes are Unreactive Compounds
11.2 Chlorination and Bromination of Alkanes
11.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron
11.4 The Distribution of Products Depends on Probability and Reactivity
11.5 The Reactivity-Selectivity Principle
11.6 Addition of Radicals to an Alkene
11.7 Stereochemistry of Radical Substitution and Addition Reactions
11.8 Radical Substitution of Benzylic and Allylic Hydrogens
11.9 Designing a Synthesis III: More Practice with Multistep Synthesis
11.10 Radical Reactions Occur in Biological Systems
11.11 Radicals and Stratospheric Ozone
IV: IDENTIFICATION OF ORGANIC COMPOUNDS
12. MASS SPECTROMETRY, INFRARED SPECTROSCOPY, AND ULTRAVIOLET/VISIBLE SPECTROSCOPY
12.1 Mass Spectrometry
12.2 The Mass Spectrum. Fragmentation
12.3 Isotopes in Mass Spectrometry
12.4 High-Resolution Mass Spectrometry Can Determine Molecular Formulas
12.5 Fragmentation Patterns of Functional Groups
Alkyl Halides
Ethers
Alcohols
Ketones
12.6 Spectroscopy and the Electromagnetic Spectrum
12.7 Infrared Spectroscopy
Obtaining an Infrared Spectrum
The Functional Group and Fingerprint Regions
12.8 Characteristic Infrared Absorption Bands
12.9 The Intensity of Absorption Bands
12.10 The Position of Absorption Bands
Hooke's Law
The Effect of Bond Order
12.11 The Position of an Absorption Band is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding
O-GH Absorption Bands
C-H Absortion Bands
12.12 The Shape of Absorption Bands
12.13 The Absence of Absorption Bands
12.14 Some Vibrations are Infrared Inactive
12.15 A Lesson in Interpreting Infrared Spectra
12.16 Ultraviolet and Visible Spectroscopy
12.17 The Beer-Lambert Law
12.18 The Effect of Conjugation on lmax
12.19 The Visible Spectrum and Color
12.20 Uses of UV/Vis Spectroscopy
13. NMR SPECTROSCOPY
13.1 An Introduction to NMR Spectroscopy
13.2 Fourier Transform NMR
13.3 Shielding Causes Different Hydrogens to Show Signals at Different Frequencies
13.4 The Number of Signals in an 1H NMR Spectrum
13.5 The Chemical Shift Tells How Far the Signal Is from the Reference Signal
13.6 The Relative Positions of 1H NMR Signals
13.7 Characteristic Values of Chemical Shifts
13.8 Diamagnetic Anisotropy
13.9 The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal
13.10 Splitting of the Signals is Desribed by the N+1 Rule
13.11 More Examples of 1H NMR Spectra
13.12 Coupling Constants Identify Coupled Protons
13.13 Splitting Diagrams Explain the Multiplicity of a Signal
13.14 The Time Dependence of NMR Spectroscopy
13.15 Protons Bonded to Oxygen and Nitrogen
13.16 The Use of Deuterium in 1H NMR Spectroscopy
13.17 The Resolution of 1H NMR Spectra
13.18 13C NMR Spectroscopy
13.19 DEPT 13C NMR Spectra
13.20 Two-Dimensional NMR Spectroscopy
13.21 NMR Used in Medicine is Called Magnetic Resonance Imaging
V: AROMATIC COMPOUNDS
14. AROMATICITY ? REACTIONS OF BENZENE
14.1 Aromatic Compounds are Unusually Stable
14.2 The Two Criteria for Aromaticity
14.3 Applying the Criteria for Aromaticity
14.4 Aromatic Heterocyclic Compounds
14.5 Some Chemical Consequences of Aromaticity
14.6 Antiaromaticity
14.7 A Molecular Orbital Description of Aromaticity and Antiaromaticity
14.8 Nomenclature of Monosubstituted Benzenes
14.9 How Benzene Reacts
14.10 General Mechanism for Electrophilic Aromatic Substitution Reactions
14.11 Halogenation of Benzene
14.12 Nitration of Benzene
14.13 Sulfonation of Benzene
14.14 Friedel-Crafts Acylation of Benzene
14.15 Friedel-Crafts Alkylation of Benzene
14.16 Alkylation of Benzene by Acylation-Reduction
14.17 Using Coupling Reactions to Alkylate Benzene
14.18 It is important to Have More than One Way to Carry Out a Reaction
14.19 How Some Substituents on a Benzene Ring Can Be Chemically Changed
15. REACTIONS OF SUBSTITUTED BENZENES
15.1 Nomenclature of Disubstituted and Polysubstituted Benzenes
15.2 Some Substituents Increase the Reactivity of a Benzene Ring and Some Decrease Its Reactivity
Inductive Electron Withdrawal
Electron Donation by Hyperconjugation
Resonance Electron Donation and Withdrawal
Relative Reactivity of Substituted Benzenes
15.3 The Effect of Substituents on Orientation
15.4 The Effect of Substituents on pKa
15.5 The Ortho/Para Ratio
15.6 Additional Considerations Regarding Substituent Effects
15.7 Designing a Synthesis III: Synthesis of Monosubstituted and Disubstituted Benzenes
15.8 Synthesis of Trisubstituted Benzenes
15.9 Synthesis of Substituted Benzenes Using Arenediazonium Salts
15.10 The Arenediazonium Ion as an Electrophile
15.11 Mechanism for the Reaction of Amines with Nitrous Acid
15.12 Nucleophilic Aromatic Substitution: An Addition-Elimination Mechanism
15.13 Nucleophilic Aromatic Substitution: An Elimination-Addition Mechanism that Forms a Benzyne Intermediate
15.14 Polycyclic Benzenoid Hydrocarbons
VI: CARBONYL COMPOUNDS
16. CARBONYL COMPOUNDS I: NUCLEOPHILIC ACYL SUBSTITUTION
16.1 Nomenclature of Carboxylic Acids and Caboxylic Acid Derivatives
16.2 Structures of Carboxylic Acids and Carboxylic Acid Derivatives
16.3 Physical Properties of Carbonyl Compounds
16.4 Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives
16.5 How Class I Carbonyl Compounds React
16.6 Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives
16.7 General Mechanism for Nucleophilic Acyl Substitution Reactions
16.8 Reactions of Acyl Halides
16.9 Reactions of Acid Anhydrides
16.10 Reactions of Esters
16.11 Acid-Catalyzed Ester Hydrolysis
16.12 Hydroxide-Ion Promoted Ester Hydrolysis
16.13 How the Mechanism for Nucleophilic Acyl Substitution Reactions Was Confirmed
16.14 Soaps, Detergents, and Micelles
16.15 Reactions of Carboxylic Acids
16.16 Reactions of Amides
16.17 The Hydrolysis of Amides Is Catalyzed by Acids
16.18 Hydrolysis of an Imide: A Way to Synthesize Primary Amines
16.19 Hydrolysis of Nitriles
16.20 Designing a Synthesis V: The Synthesis of Cyclic Compounds
16.21 How Chemists Activate Carboxylic Acids
16.22 How Cells Activate Carboxylic Acids
16.23 Dicarboxylic Acids and Their Derivatives
17. CARBONYL COMPOUNDS II:
17.1 Nomenclature of Aldehydes and Ketones
17.2 Relative Reactivities of Carbonyl Compounds
17.3 How Aldehydes and Ketones React
17.4 Reactions of Carbonyl Compounds with Grignard Reagents
17.5 Reactions of Carbonyl Compounds with Acetylide Ions
17.6 Reactions of Carbonyl Compounds with Hydride Ion
17.7 Reactions of Aldehydes and Ketones with Hydrogen Cyanide
17.8 Reactions of Aldehydes and Ketones with Amines and Derivatives of Amines
17.9 Reactions of Aldehydes and Ketones with Water
17.10 Reactions of Aldehydes and Ketones with Alcohols
17.11 Protecting Groups
17.12 Addition of Sulfur Nucleophiles
17.13 The Wittig Reaction Forms an Alkene
17.14 Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces
17.15 Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents
17.16 Nucleophilic Addition to a,b-Unsaturated Aldehydes and Ketones
17.17 Nucleophilic Addition to a,b-Unsaturated Carboxylic Acid Derivatives
17.18 Enzyme-Catalyzed Additions to a,b-Unsaturated Carbonyl Compounds
18. CARBONYL COMPOUNDS III: REACTIONS AT THE a-CARBON
18.1 Acidity of an a-Hydrogens
18.2 Keto-Enol Tautomers
18.3 Enolization
18.4 How Enols and Enolate Ions React
18.5 Halogenation of the a-Carbon of Aldehydes and Ketones.
Acid-Catalyzed Halogenation
Base-Promoted Halogenation
The Haloform Reaction
18.6 Halogenation of the a-Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction
18.7 a-Halogenated Carbonyl Compounds Are Useful in Synthesis
18.8 Using Lithium Diisopropylamide (LDA) to Form an Enolate
18.9 Alkylation of the a-Carbon of Carbonyl Compounds
18.10 Alkylation and Acylation of the a-Carbon Using an Enamine Intermediate
18.11 Alkylation of the b-Carbon: The Michael Reaction
18.12 An Aldol Addition Forms b-Hydroxyaldehydes or b -Hydroxyketones
18.13 Dehydration of Aldol Addition Products Forms a,b-Unsaturated Aldehydes and Ketones
18.14 The Mixed Aldol Addition
18.15 A Claisen Condensation Forms a b-Keto Ester
18.16 The Mixed Claisen Condensation
18.17 Intramolecular Condensation and Addition Reactions
Intramolecular Claisen Condensations
Intramolecular Aldol Additions
The Robinson Annulation
18.18 3-Oxocarboxylic Acids Can Be Dehydrated
18.19 The Malonic Ester Synthesis: A Way to Snthesize a Carboxylic Acid
18.20 The Acetoacetic Ester Synthesis: A Way Synthesize a Methyl Ketone
18.21 Designing a Synthesis VII: Making New Carbon-Carbon Bonds
18.22 Reactions at the a-Carbon in Biological Systems
A Biological Aldol Condensation
A Biological Claisen Condensation
A Biological Decarboxylation
VII: OXIDATION-REDUCTION REACTIONS AND AMINES
19. MORE ABOUT OXIDATION-REDUCTION REACTIONS
19.1 Reduction Reactions
Reduction by Addition of Two Hydrogen Atoms
Reduction by Addition of an Electron, a Proton, an Electron, and a Proton
Reduction by Addition of a Hydride Ion and a Proton
19.2 Oxidation of Alcohols
19.3 Oxidation of Aldehydes and Ketones
19.4 Designing a Synthesis VIII: Controlling Stereochemistry
19.5 Hydroxylation of Alkenes
19.6 Oxidative Cleavage of 1,2-Diols
19.7 Oxidative Cleavage of Alkenes
19.8 Oxidative Cleavage of Alkynes
19.9 Designing a Synthesis IX: Functional Group Interconversion
20. MORE ABOUT AMINES. HETEROCYCLIC COMPOUNDS
20.1 More About Amine Nomenclature
20.2 Amines Invert Rapidly
20.3 More About the Acid-Base Properties of Amines
20.4 Amines React as Bases and as Nucleophiles
20.5 Quaternary Ammonium Hydroxides Undergo Elimination Reactions
20.6 Phase-Transfer Catalysis
20.7 Oxidation of Amines: The Cope Elimination Reaction
20.8 Synthesis of Amines
20.9 Aromatic Five-Membered Ring Heterocycles
20.10 Aromatic Six-Membered-Ring Heterocycles
20.11 Amine Heterocycles Have Important Roles in Nature
VIII: BIOORGANIC COMPOUNDS
21. CARBOHYDRATES
21.1 Classification of Carbohydrtes
21.2 The D and L Notation
21.3 Configurations of the Aldoses
21.4 Configurations of the Ketoses
21.5 Reactions of Monosaccharides in Basic Solutions
21.6 Redox Reactions of Monosaccharides
21.7 Monosaccharides Form Crystalline Osazones
21.8 Lengthening the Chain: The Kiliani-Fischer Synthesis
21.9 Shortening the Chain: The Wohl Degradation
21.10 Stereochemistry of Glucose: the Fischer Proof
21.11 Monosaccharides Form Cyclic Hemiacetals
21.12 Glucose Is the Most Stable Aldohexose
21.13 Acylation and Alkylation of Monosaccharides
21.14 Formation of Glycosides
21.15 The Anomeric Effect
21.16 Reducing and Nonreducing Sugars
21.17 Determination of Ring Size
21.18 Disaccharides
21.19 Polysaccharides
21.20 Some Naturally Occurring Products Derived from Carbohydrates
21.21 Carbohydrates on Cell Surfaces
21.22 Synthetic Sweeteners
22. AMINO ACIDS, PEPTIDES, AND PROTEINS
22.1 Classification and Nomenclature of Amino Acids
22.2 Configuration of the Amino Acids
22.3 Acid-Base Properties of Amino Acids
22.4 The Isoelectric Point
22.5 Separation of Amino Acids
22.6 Resolution of Racemic Mixtures of Amino Acids
22.7 Peptide Bonds and Disulfide Bonds
22.8 Some Interesting Peptides
22.9 The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation
22.10 Automated Peptide Synthesis
22.11 An Introduction to Protein Structure
22.12 How to Determine the Primary Structure of a Peptide or a Protein
22.13 Secondary Structure of Proteins
22.14 Tertiary Structure of Proteins
22.15 Quaternary Structure of Proteins
22.16 Protein Denaturation
23. CATALYSIS
23.1 Catalysis in Organic Reactions
23.2 Acid Catalysis
23.3 Base Catalysis
23.4 Nucleophilic Catalysis
23.5 Metal-Ion Catalysis
23.6 Intramolecular Reactions
23.7 Intramolecular Catalysis
23.8 Catalysis in Biological Reactions
23.9 Enzyme-Catalyzed Reactions
Mechanism for Carboxypeptidase A
Mechanism for Serine Proteases
Mechanism for Lysozyme
Mechanism for Glucose-6-phosphate Isomerase
Mechanism of Aldolase
24. THE ORGANIC MECHANISMS OF THE COENZYMES
24.1 An Introduction to Metabolism
24.2 The Vitamin Needed for Many Redox Reactions: Vitamin B3
24.3 Flavin Adenine Dinucleotide and Flavin Mononucleotide: Vitamin B2
23.4 Thiamine Pyrophosphate: Vitamin B1
23.5 Biotin: Vitamin H
24.6 Pyridoxal Phosphate: Vitamin B6
24.7 Coenzyme B12: Vitamin B12
24.8 Tetrahydrofolate: Folic Acid
24.9 Vitamin KH2: Vitamin K
25: THE CHEMISTRY OF METABOLISM
25.1 The Four Stages of Catabolism
25.2 ATP Is the Carrier of Chemical Energy
25.3 There Are Three Mechanisms for Phosphoryl Transfer Reactions
25.4 The "High-Energy" Character of Phosphoanhydride Bonds
25.5 Why ATP Is Kinetically Stable in a Cell
25.6 The Catabolism of Fats
25.7 The Catabolism of Carbohydrates
25.8 The Fates of Pyruvate
25.9 The Catabolism of Proteins
25.10 The Citric Acid Cycle
25.11 Oxidative Phosphorylation
25.12 Anabolism
26. LIPIDS
26.1 Fatty Acids Are Long-Chain Carboxylic Acids
26.2 Waxes Are High-Molecular Weight Esters
26.3 Fats and Oils
26.4 Phospholipids and Sphingolipids are the Components of Membranes
26.5 Prostaglandins Regulate Physiological Responses
26.6 Terpenes Contain Carbon Atoms in Multiples of Five
26.7 Vitamin A Is a Terpene
26.8 How Terpenes Are Biosynthesized
26.9 Steroids Are Chemical Messengers
26.10 How Nature Synthesizes Cholesterol
26.11 Synthetic Steroids
27. NUCLEOSIDES, NUCLEOTIDES, AND NUCLEIC ACIDS
27.1 Nucleosides and Nucleotides
27.2 Other Important Nucleotides
27.3 Nucleic Acids Are Composed of Nucleotide Subunits
27.4 DNA Is Stable but RNA Is Easily Cleaved
27.5 Biosynthesis of DNA Is Called Replication
27.6 Biosynthesis of RNA Is Called Transcription
27.7 There Are Three Kinds of RNA
27.8 Biosynthesis of Proteins Is Called Translation
27.9 Why DNA Contains Thymine Instead of Uracil
27.10 How the Base Sequence of DNA Is Determined
27.11 Polymerase Chain Reaction (PCR)
27.12 Genetic Engineering
27.13 Laboratory Synthesis of DNA Strands
IX: SPECIAL TOPICS IN ORGANIC CHEMISTRY
28. SYNTHETIC POLYMERS
28.1 There Are Two Major Classes of Synthetic Polymers
28.2 Chain-Growth Polymers
Radical Polymerization
Branching of the Polymer Chain
Cationic Polymerization
Anionic Polymerization
28.3 Stereochemistry of Polymerization. Ziegler-Natta Catalysts
28.4 Polymerization of Dienes. The Manufacture of Rubber
28.5 Copolymers
28.6 Step-Growth Polymers
28.7 Physical Properties of Polymers
29. PERICYCLIC REACTIONS
29.1 There Are Three Kinds of Pericyclic Reations
29.2 Molecular Orbitals and Orbital Symmetry
29.3 Electrocyclic Reactions
29.4 Cycloaddition Reactions
29.5 Sigmatropic Rearrangements
Migration of Hydrogen
Migration of Carbon
29.6 Pericyclic Rections in Biological Systems
Biological Cycloaddition Reactions
A Biological Reaction Involving an Electrocyclic Reaction and a Sigmatropic
Rearrangement
29.7 Summary of the Selection Rules for Pericyclic Reactions
30. THE ORGANIC CHEMISTRY OF DRUGS: DISCOVERY AND DESIGN
30.1 Naming Drugs
30.2 Lead Compounds
30.3 Molecular Modification
30.4 Random Screening
30.5 Serendipity in Drug Development
30.6 Receptors
30.7 Drugs as Enzyme Inhibitors
30.8 Designing a Suicide Substrate
30.9 Quantitative Structure-Activity Relationships (QSARs)
30.10 Molecular Modeling
30.11 Combinatorial Organic Synthesis
30.12 Antiviral Drugs
30.13 Economics of Drugs: Governmental Regulations
1. ELECTRONIC STRUCTURE AND BONDING ? ACIDS AND BASES
1.1 The Structure of an Atom
1.2 How the Electrons in an Atom are Distributed
1.3 Ionic and Covalent Bonds
Ionic Bonds are Formed by the Transfer of Electrons
Covalent Bonds are Formed by Sharing Electrons
Polar Covalent Bonds
1.4 How the Structure of a Compound is Represented
Lewis Structures
Kekule Structures
Condensed Structures
1.5 Atomic Orbitals
1.6 An Introduction to Molecular Orbital Theory
1.7 How Single Bonds are Formed in Organic Compounds
The Bonds in Methane
The Bonds in Ethane
1.8 How a Double Bond is Formed: The Bonds in Ethene
1.9 How a Triple Bonds is Formed: The Bonds in Ethyne
1.10 The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion
The Methyl Cation
The Methyl Radical
The Methyl Anion
1.11 The Bonds in Water
1.12 The Bonds in Ammonia and in the Ammonium Ion
1.13 The Bonds in the Hydrogen Halides
1.14 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles
1.15 The Dipole Moments of Molecules
1.16 An Introduction to Acids and Bases
1.17 pKa and pH
1.18 Organic Acids and Bases
1.19 How to Predict the Outcome of an Acid-Base Reaction
1.20 How the Structure of an Acid Affects Its Acidity
1.21 How Substituents Affect the Strength of an Acid
1.22 An Introduction to Delocalized Electrons
1.23 A Summary of the Factors that Determine Acid Strength
1.24 How the pH Affects the Structure of an Organic Compound
1.25 Buffer Solutions
1.26 The Second Definition of Acid and Base: Lewis Acids and Bases
2. AN INTRODUCTION TO ORGANIC COMPOUNDS NOMENCLATURE, PHYSICAL PROPERTIES, AND REPRESENTATION OF STRUCTURE
2.1 How Alkyl Substituents are Named
2.2 Nomenclature of Alkanes
2.3 Nomenclature of Cycloalkanes
2.4 Nomenclature of Alkyl Halides
2.5 Nomenclature of Ethers
2.6 Nomenclature of Alcohols
2.7 Nomenclature of Amines
2.8 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines
2.9 The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines
Boiling Points
Melting Points
Solubility
2.10 Rotation Occurs About Carbon-Carbon Bonds
2.11 Some Cycloalkanes Have Ring Strain
2.12 Conformations of Cyclohexane
2.13 Conformers of Monosubstituted Cyclohexanes
2.14 Conformers of Disubstituted Cyclohexanes
II: ELECTROPHILIC ADDITION REACTIONS, STEREOCHEMISTRY, AND ELECTRON DEELOCALIZATION
3. ALKENES: STRUCTURE, NOMENCLATURE AND AN INTRODUCTION TO REACTIVITY ? THERMODYNAMICS AND KINETICS
3.1 Molecular Formulas and the Degree of Unsaturation
3.2 Nomenclature of Alkenes
3.3 The Structures of Alkenes
3.4 Alkenes Can Have Cis and Trans Isomers
3.5 Naming Alkenes Using the E,Z System
3.6 How Alkenes React ? Curved Arrows Show the Flow of Electrons
3.7 Thermodynamics and Kinetics
A Reaction Coordinate Diagram Describes the Reaction Pathway
Thermodynamics: How Much Product Is Formed?
Kinetics: How Fast Is the Product Formed?
3.8 Using a Reaction Coordinate Diagram to Describe a Reaction
4. THE REACTIONS OF ALKENES
4.1 Addition of a Hydrogen Halide to an Alkene
4.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon
4.3 The Structure of the Transition State Lies Partway Between the Structures of the Reactants and Products
4.4 Electrophilic Addition Reactions Are Regioselective
4.5 Acid-Catalyzed Addition Reactions
Addition of Water to an Alkene
Addition of an Alcohol to an Alkene
4.6 A Carbocation will Rearrange if It Can Form a More Stable Carbocation
4.7 Addition of a Halogen to an Alkene
4.8 Oxymercuration-Demercuration: Are Other Ways to Add Water or Alcohol to an Alkene
4.9 Addition of a Peroxyacid to an Alkene
4.10 Addition of Borane to an Alkene: Hydroboration-Oxidation
4.11 Addition of Hydrogen to an Alkene ? The Relative Stabilities of Alkenes
4.12 Reactions and Synthesis
5. STEREOCHEMISTRY: THE ARRANGEMENT OF ATOMS IN SPACE; THE STEREOCHEMISTRY OF ADDITION REACTIONS
5.1 Cis-Trans Isomers Result From Restricted Rotation
5.2 A Chiral Object has a Nonsuperimposable Mirror Image
5.3 An Asymmetric Center Is a Cause of Chirality In a Molecule
5.4 Isomers with One Asymmetric Center
5.5 Asymmetric Centers and Stereocenters
5.6 How to Draw Enantiomers
5.7 Naming Enantiomers by the R,S System
5.8 Chiral Compounds are Optically Active
5.9 How Specific Rotation is Measured
5.10 Enantiomeric Excess
5.11 Isomers with More than One Asymmetric Center
5.12 Meso Compounds Have Asymmetric Centers but are Optically Inactive
5.13 How to Name Isomers with More than One Asymmetric Center
5.14 Reactions of Compounds that Contain a Asymmetric Center
5.15 The Absolute Configuration of (+)-Glyceraldehyde
5.16 How Enantiomers Can be Separated
5.17 Nitrogen and Phosphorous Atoms Can be Asymmetric Centers
5.18 The Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions
5.19 The Stereochemistry of Electrophilic Addition Reactions of Alkenes
Addition Reactions that Form a Product with One Asymmetric Center
Addition Reactions that Form Products with Two Asymmetric Centers
Addition Reactions that Form a Carbocation Intermediate
The Stereochemistry of Hydrogen Addition
The Stereochemistry of Peroxyacid Addition
The Stereochemistry of Hydroboration-Oxidation
Addition Reactions that Form a Cyclic Bromonium Ion Intermediate
5.20 The Stereochemistry of Enzyme-Catalyzed Reactions
5.21 Enantiomers can be Distinguished by Biological Molecules
Enymes
Receptors
6. THE REACTIONS OF ALKYNES ? AN INTRODUCTION TO MULTISTEP SYNTHESIS
6.1 The Nomenclature of Alkynes
6.2 How to Name a Compound That Has More than One Functional Group
6.3 The Physical Properties of Unsaturated Hydrocarbons
6.4 The Structure of Alkynes
6.5 How Alkynes React
6.6 Addition of Hydrogen Halides and Addition of Halogens to an Alkyne
6.7 Addition of Water to an Alkyne
6.8 Addition of Borane to an Alkyne: Hydroboration-Oxidation
6.9 Addition of Hydrogen to an Alkyne
6.10 A Hydrogen Bonded to an sp Carbon is "Acidic"
6.11 Synthesis Using Acetylide Ions
6.12 Designing a Synthesis I: An Introduction to Multistep Synthesis
7. DELOCALIZED ELECTRONS AND THEIR EFFECT ON STABILITY, REACTIVITY, AND pKa ? MORE ABOUT MOLECULAR ORBITAL THEORY
7.1 Benzene Has Delocalized Electrons
7.2 The Bonding in Benzene
7.3 Resonance Contributors and the Resonance Hybrid
7.4 How to Draw Resonance Contributors
7.5 The Predicted Stabilites of Resonance Contributors
7.6 Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound
7.7 Examples That Illustrate the Effect of Delocalized Electrons on Stability
Stability of Dienes
Stability of Allylic and Benzylic Cations
7.8 A Molecular Orbital Description of Stability
1,3-Butadiene and 1,4-Pentadiene
1,3,5-Hexatriene and Benzene
7.9 How Delocalized Electrons Affect pKa
7.10 Delocalized Electrons Can Affect the Product of a Reaction
Reactions of Isolated Dienes
Reactions of Conjugated Dienes
7.11 Thermodynamic versus Kinetic Control of Reactions
7.12 The Diels-Alder Reaction Is a 1,4-Addition Reaction
A Molecular Orbital Description of the Diels-Alder Reaction
Predicting the Product When Both Reagents Are Unsymmetrically Substituted
Conformations of the Diene
The Stereochemistry of the Diels-Alder Reaction
III: SUBSTITUTION AND ELIMINATION REACTIONS
8. SUBSTITUTION REACTIONS OF OF ALKYL HALIDES
8.1 How Alkyl Halides React
8.2 The Mechanism of an SN2 Reaction
8.3 Factors that Affect SN2 Reactions
The Leaving Group
The Nucleophile
Nucleophilicity is Affected by the Solvent
Nucleophilicity is Affected by Steric Effects
8.4 The Reversibility of an SN2 Reaction Depends on the Basicities of the Leaving Groups in the Forward and Reverse Directions
8.5 The Mechanism of an SN1 Reaction
8.6 Factors that Affect an SN1 Reaction
The Leaving Group
The Nucleophile
Carbocation Rearrangements
8.7 More About the Stereochemistry of SN2 and SN1 Reactions
Stereochemistry of SN2 Reactions
Stereochemistry of SN1 Reactions
8.8 Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides
8.9 Competition Between SN2 and SN1 Reactions
8.10 The Role of the Solvent in SN2 and SN1 Reactions
How a Solvent Affects Reaction Rates in General
How a Solvent Affects the Rate of an SN1 Reaction
How a Solvent Affects the Rate of an SN2 Reaction
8.11 Biological Methylating Reagents Have Good Leaving Groups
9. ELIMINATION REACTIONS OF ALKYL HALIDES ? COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION
9.1 The E2 Reaction
9.2 An E2 Reaction is Regioselective
9.3 The E1 Reaction
9.4 Competition Between E2 and E1 Reactions
9.5 E2 and E1 Reactions are Stereoselective
The Stereoisomers Formed in an E2 Reaction
The Stereoisomers Formed in an E1 Reaction
9.6 Elimination from Substituted Cyclohexanes
E2 Reactions of Substituted Cyclohexanes
E1 Reactions of Substituted Cyclohexanes
9.7 A Kinetic Isotope Effect Can Help Determine a Mechanism
9.8 Competition Between Substitution and Elimination
SN2/E2 Conditions
SN1/E1 Conditions
9.9 Substitution and Elimination Reactions in Synthesis
Using Substitution Reactions to Synthesize Compounds
Using Elimination Reactions to Synthesize Compounds
9.10 Consecutive E2 Elimination Reactions
9.11 Intermolecular Versus Intramolecular Reactions
9.12 Designing a Synthesis II: Approaching the Problem
10. REACTIONS OF ALCOHOLS, AMINES, ETHERS, EXPOXIDES, AND SULFUR-CONTAINING COMPOUNDS ? ORGANOMETALLIC COMPOUNDS
10.1 Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides
10.2 Other Methods for Converting Alcohols into Alkyl Halides
10.3 Converting Alcohols into Sulfonate Esters
10.4 Elimination Reactions of Alcohols: Dehydration
10.5 Oxidation of Alcohols
10.6 Amines do not Undergo Substitution or Elimination Reactions but Are the Most Common Organic Bases
10.7 Nucleophilic Substitution Reactions of Ethers
10.8 Nucleophilic Substitution Reactions of Epoxides
10.9 Arene Oxides
10.10 Crown Ethers
10.11 Thiols, Sulfides, and Sulfonium Salts
10.12 Organometallic Compounds
10.13 Coupling Reactions
11. RADICALS ? REACTIONS OF ALKANES
11.1 Alkanes are Unreactive Compounds
11.2 Chlorination and Bromination of Alkanes
11.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron
11.4 The Distribution of Products Depends on Probability and Reactivity
11.5 The Reactivity-Selectivity Principle
11.6 Addition of Radicals to an Alkene
11.7 Stereochemistry of Radical Substitution and Addition Reactions
11.8 Radical Substitution of Benzylic and Allylic Hydrogens
11.9 Designing a Synthesis III: More Practice with Multistep Synthesis
11.10 Radical Reactions Occur in Biological Systems
11.11 Radicals and Stratospheric Ozone
IV: IDENTIFICATION OF ORGANIC COMPOUNDS
12. MASS SPECTROMETRY, INFRARED SPECTROSCOPY, AND ULTRAVIOLET/VISIBLE SPECTROSCOPY
12.1 Mass Spectrometry
12.2 The Mass Spectrum. Fragmentation
12.3 Isotopes in Mass Spectrometry
12.4 High-Resolution Mass Spectrometry Can Determine Molecular Formulas
12.5 Fragmentation Patterns of Functional Groups
Alkyl Halides
Ethers
Alcohols
Ketones
12.6 Spectroscopy and the Electromagnetic Spectrum
12.7 Infrared Spectroscopy
Obtaining an Infrared Spectrum
The Functional Group and Fingerprint Regions
12.8 Characteristic Infrared Absorption Bands
12.9 The Intensity of Absorption Bands
12.10 The Position of Absorption Bands
Hooke's Law
The Effect of Bond Order
12.11 The Position of an Absorption Band is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding
O-GH Absorption Bands
C-H Absortion Bands
12.12 The Shape of Absorption Bands
12.13 The Absence of Absorption Bands
12.14 Some Vibrations are Infrared Inactive
12.15 A Lesson in Interpreting Infrared Spectra
12.16 Ultraviolet and Visible Spectroscopy
12.17 The Beer-Lambert Law
12.18 The Effect of Conjugation on lmax
12.19 The Visible Spectrum and Color
12.20 Uses of UV/Vis Spectroscopy
13. NMR SPECTROSCOPY
13.1 An Introduction to NMR Spectroscopy
13.2 Fourier Transform NMR
13.3 Shielding Causes Different Hydrogens to Show Signals at Different Frequencies
13.4 The Number of Signals in an 1H NMR Spectrum
13.5 The Chemical Shift Tells How Far the Signal Is from the Reference Signal
13.6 The Relative Positions of 1H NMR Signals
13.7 Characteristic Values of Chemical Shifts
13.8 Diamagnetic Anisotropy
13.9 The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal
13.10 Splitting of the Signals is Desribed by the N+1 Rule
13.11 More Examples of 1H NMR Spectra
13.12 Coupling Constants Identify Coupled Protons
13.13 Splitting Diagrams Explain the Multiplicity of a Signal
13.14 The Time Dependence of NMR Spectroscopy
13.15 Protons Bonded to Oxygen and Nitrogen
13.16 The Use of Deuterium in 1H NMR Spectroscopy
13.17 The Resolution of 1H NMR Spectra
13.18 13C NMR Spectroscopy
13.19 DEPT 13C NMR Spectra
13.20 Two-Dimensional NMR Spectroscopy
13.21 NMR Used in Medicine is Called Magnetic Resonance Imaging
V: AROMATIC COMPOUNDS
14. AROMATICITY ? REACTIONS OF BENZENE
14.1 Aromatic Compounds are Unusually Stable
14.2 The Two Criteria for Aromaticity
14.3 Applying the Criteria for Aromaticity
14.4 Aromatic Heterocyclic Compounds
14.5 Some Chemical Consequences of Aromaticity
14.6 Antiaromaticity
14.7 A Molecular Orbital Description of Aromaticity and Antiaromaticity
14.8 Nomenclature of Monosubstituted Benzenes
14.9 How Benzene Reacts
14.10 General Mechanism for Electrophilic Aromatic Substitution Reactions
14.11 Halogenation of Benzene
14.12 Nitration of Benzene
14.13 Sulfonation of Benzene
14.14 Friedel-Crafts Acylation of Benzene
14.15 Friedel-Crafts Alkylation of Benzene
14.16 Alkylation of Benzene by Acylation-Reduction
14.17 Using Coupling Reactions to Alkylate Benzene
14.18 It is important to Have More than One Way to Carry Out a Reaction
14.19 How Some Substituents on a Benzene Ring Can Be Chemically Changed
15. REACTIONS OF SUBSTITUTED BENZENES
15.1 Nomenclature of Disubstituted and Polysubstituted Benzenes
15.2 Some Substituents Increase the Reactivity of a Benzene Ring and Some Decrease Its Reactivity
Inductive Electron Withdrawal
Electron Donation by Hyperconjugation
Resonance Electron Donation and Withdrawal
Relative Reactivity of Substituted Benzenes
15.3 The Effect of Substituents on Orientation
15.4 The Effect of Substituents on pKa
15.5 The Ortho/Para Ratio
15.6 Additional Considerations Regarding Substituent Effects
15.7 Designing a Synthesis III: Synthesis of Monosubstituted and Disubstituted Benzenes
15.8 Synthesis of Trisubstituted Benzenes
15.9 Synthesis of Substituted Benzenes Using Arenediazonium Salts
15.10 The Arenediazonium Ion as an Electrophile
15.11 Mechanism for the Reaction of Amines with Nitrous Acid
15.12 Nucleophilic Aromatic Substitution: An Addition-Elimination Mechanism
15.13 Nucleophilic Aromatic Substitution: An Elimination-Addition Mechanism that Forms a Benzyne Intermediate
15.14 Polycyclic Benzenoid Hydrocarbons
VI: CARBONYL COMPOUNDS
16. CARBONYL COMPOUNDS I: NUCLEOPHILIC ACYL SUBSTITUTION
16.1 Nomenclature of Carboxylic Acids and Caboxylic Acid Derivatives
16.2 Structures of Carboxylic Acids and Carboxylic Acid Derivatives
16.3 Physical Properties of Carbonyl Compounds
16.4 Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives
16.5 How Class I Carbonyl Compounds React
16.6 Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives
16.7 General Mechanism for Nucleophilic Acyl Substitution Reactions
16.8 Reactions of Acyl Halides
16.9 Reactions of Acid Anhydrides
16.10 Reactions of Esters
16.11 Acid-Catalyzed Ester Hydrolysis
16.12 Hydroxide-Ion Promoted Ester Hydrolysis
16.13 How the Mechanism for Nucleophilic Acyl Substitution Reactions Was Confirmed
16.14 Soaps, Detergents, and Micelles
16.15 Reactions of Carboxylic Acids
16.16 Reactions of Amides
16.17 The Hydrolysis of Amides Is Catalyzed by Acids
16.18 Hydrolysis of an Imide: A Way to Synthesize Primary Amines
16.19 Hydrolysis of Nitriles
16.20 Designing a Synthesis V: The Synthesis of Cyclic Compounds
16.21 How Chemists Activate Carboxylic Acids
16.22 How Cells Activate Carboxylic Acids
16.23 Dicarboxylic Acids and Their Derivatives
17. CARBONYL COMPOUNDS II:
17.1 Nomenclature of Aldehydes and Ketones
17.2 Relative Reactivities of Carbonyl Compounds
17.3 How Aldehydes and Ketones React
17.4 Reactions of Carbonyl Compounds with Grignard Reagents
17.5 Reactions of Carbonyl Compounds with Acetylide Ions
17.6 Reactions of Carbonyl Compounds with Hydride Ion
17.7 Reactions of Aldehydes and Ketones with Hydrogen Cyanide
17.8 Reactions of Aldehydes and Ketones with Amines and Derivatives of Amines
17.9 Reactions of Aldehydes and Ketones with Water
17.10 Reactions of Aldehydes and Ketones with Alcohols
17.11 Protecting Groups
17.12 Addition of Sulfur Nucleophiles
17.13 The Wittig Reaction Forms an Alkene
17.14 Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces
17.15 Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents
17.16 Nucleophilic Addition to a,b-Unsaturated Aldehydes and Ketones
17.17 Nucleophilic Addition to a,b-Unsaturated Carboxylic Acid Derivatives
17.18 Enzyme-Catalyzed Additions to a,b-Unsaturated Carbonyl Compounds
18. CARBONYL COMPOUNDS III: REACTIONS AT THE a-CARBON
18.1 Acidity of an a-Hydrogens
18.2 Keto-Enol Tautomers
18.3 Enolization
18.4 How Enols and Enolate Ions React
18.5 Halogenation of the a-Carbon of Aldehydes and Ketones.
Acid-Catalyzed Halogenation
Base-Promoted Halogenation
The Haloform Reaction
18.6 Halogenation of the a-Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction
18.7 a-Halogenated Carbonyl Compounds Are Useful in Synthesis
18.8 Using Lithium Diisopropylamide (LDA) to Form an Enolate
18.9 Alkylation of the a-Carbon of Carbonyl Compounds
18.10 Alkylation and Acylation of the a-Carbon Using an Enamine Intermediate
18.11 Alkylation of the b-Carbon: The Michael Reaction
18.12 An Aldol Addition Forms b-Hydroxyaldehydes or b -Hydroxyketones
18.13 Dehydration of Aldol Addition Products Forms a,b-Unsaturated Aldehydes and Ketones
18.14 The Mixed Aldol Addition
18.15 A Claisen Condensation Forms a b-Keto Ester
18.16 The Mixed Claisen Condensation
18.17 Intramolecular Condensation and Addition Reactions
Intramolecular Claisen Condensations
Intramolecular Aldol Additions
The Robinson Annulation
18.18 3-Oxocarboxylic Acids Can Be Dehydrated
18.19 The Malonic Ester Synthesis: A Way to Snthesize a Carboxylic Acid
18.20 The Acetoacetic Ester Synthesis: A Way Synthesize a Methyl Ketone
18.21 Designing a Synthesis VII: Making New Carbon-Carbon Bonds
18.22 Reactions at the a-Carbon in Biological Systems
A Biological Aldol Condensation
A Biological Claisen Condensation
A Biological Decarboxylation
VII: OXIDATION-REDUCTION REACTIONS AND AMINES
19. MORE ABOUT OXIDATION-REDUCTION REACTIONS
19.1 Reduction Reactions
Reduction by Addition of Two Hydrogen Atoms
Reduction by Addition of an Electron, a Proton, an Electron, and a Proton
Reduction by Addition of a Hydride Ion and a Proton
19.2 Oxidation of Alcohols
19.3 Oxidation of Aldehydes and Ketones
19.4 Designing a Synthesis VIII: Controlling Stereochemistry
19.5 Hydroxylation of Alkenes
19.6 Oxidative Cleavage of 1,2-Diols
19.7 Oxidative Cleavage of Alkenes
19.8 Oxidative Cleavage of Alkynes
19.9 Designing a Synthesis IX: Functional Group Interconversion
20. MORE ABOUT AMINES. HETEROCYCLIC COMPOUNDS
20.1 More About Amine Nomenclature
20.2 Amines Invert Rapidly
20.3 More About the Acid-Base Properties of Amines
20.4 Amines React as Bases and as Nucleophiles
20.5 Quaternary Ammonium Hydroxides Undergo Elimination Reactions
20.6 Phase-Transfer Catalysis
20.7 Oxidation of Amines: The Cope Elimination Reaction
20.8 Synthesis of Amines
20.9 Aromatic Five-Membered Ring Heterocycles
20.10 Aromatic Six-Membered-Ring Heterocycles
20.11 Amine Heterocycles Have Important Roles in Nature
VIII: BIOORGANIC COMPOUNDS
21. CARBOHYDRATES
21.1 Classification of Carbohydrtes
21.2 The D and L Notation
21.3 Configurations of the Aldoses
21.4 Configurations of the Ketoses
21.5 Reactions of Monosaccharides in Basic Solutions
21.6 Redox Reactions of Monosaccharides
21.7 Monosaccharides Form Crystalline Osazones
21.8 Lengthening the Chain: The Kiliani-Fischer Synthesis
21.9 Shortening the Chain: The Wohl Degradation
21.10 Stereochemistry of Glucose: the Fischer Proof
21.11 Monosaccharides Form Cyclic Hemiacetals
21.12 Glucose Is the Most Stable Aldohexose
21.13 Acylation and Alkylation of Monosaccharides
21.14 Formation of Glycosides
21.15 The Anomeric Effect
21.16 Reducing and Nonreducing Sugars
21.17 Determination of Ring Size
21.18 Disaccharides
21.19 Polysaccharides
21.20 Some Naturally Occurring Products Derived from Carbohydrates
21.21 Carbohydrates on Cell Surfaces
21.22 Synthetic Sweeteners
22. AMINO ACIDS, PEPTIDES, AND PROTEINS
22.1 Classification and Nomenclature of Amino Acids
22.2 Configuration of the Amino Acids
22.3 Acid-Base Properties of Amino Acids
22.4 The Isoelectric Point
22.5 Separation of Amino Acids
22.6 Resolution of Racemic Mixtures of Amino Acids
22.7 Peptide Bonds and Disulfide Bonds
22.8 Some Interesting Peptides
22.9 The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation
22.10 Automated Peptide Synthesis
22.11 An Introduction to Protein Structure
22.12 How to Determine the Primary Structure of a Peptide or a Protein
22.13 Secondary Structure of Proteins
22.14 Tertiary Structure of Proteins
22.15 Quaternary Structure of Proteins
22.16 Protein Denaturation
23. CATALYSIS
23.1 Catalysis in Organic Reactions
23.2 Acid Catalysis
23.3 Base Catalysis
23.4 Nucleophilic Catalysis
23.5 Metal-Ion Catalysis
23.6 Intramolecular Reactions
23.7 Intramolecular Catalysis
23.8 Catalysis in Biological Reactions
23.9 Enzyme-Catalyzed Reactions
Mechanism for Carboxypeptidase A
Mechanism for Serine Proteases
Mechanism for Lysozyme
Mechanism for Glucose-6-phosphate Isomerase
Mechanism of Aldolase
24. THE ORGANIC MECHANISMS OF THE COENZYMES
24.1 An Introduction to Metabolism
24.2 The Vitamin Needed for Many Redox Reactions: Vitamin B3
24.3 Flavin Adenine Dinucleotide and Flavin Mononucleotide: Vitamin B2
23.4 Thiamine Pyrophosphate: Vitamin B1
23.5 Biotin: Vitamin H
24.6 Pyridoxal Phosphate: Vitamin B6
24.7 Coenzyme B12: Vitamin B12
24.8 Tetrahydrofolate: Folic Acid
24.9 Vitamin KH2: Vitamin K
25: THE CHEMISTRY OF METABOLISM
25.1 The Four Stages of Catabolism
25.2 ATP Is the Carrier of Chemical Energy
25.3 There Are Three Mechanisms for Phosphoryl Transfer Reactions
25.4 The "High-Energy" Character of Phosphoanhydride Bonds
25.5 Why ATP Is Kinetically Stable in a Cell
25.6 The Catabolism of Fats
25.7 The Catabolism of Carbohydrates
25.8 The Fates of Pyruvate
25.9 The Catabolism of Proteins
25.10 The Citric Acid Cycle
25.11 Oxidative Phosphorylation
25.12 Anabolism
26. LIPIDS
26.1 Fatty Acids Are Long-Chain Carboxylic Acids
26.2 Waxes Are High-Molecular Weight Esters
26.3 Fats and Oils
26.4 Phospholipids and Sphingolipids are the Components of Membranes
26.5 Prostaglandins Regulate Physiological Responses
26.6 Terpenes Contain Carbon Atoms in Multiples of Five
26.7 Vitamin A Is a Terpene
26.8 How Terpenes Are Biosynthesized
26.9 Steroids Are Chemical Messengers
26.10 How Nature Synthesizes Cholesterol
26.11 Synthetic Steroids
27. NUCLEOSIDES, NUCLEOTIDES, AND NUCLEIC ACIDS
27.1 Nucleosides and Nucleotides
27.2 Other Important Nucleotides
27.3 Nucleic Acids Are Composed of Nucleotide Subunits
27.4 DNA Is Stable but RNA Is Easily Cleaved
27.5 Biosynthesis of DNA Is Called Replication
27.6 Biosynthesis of RNA Is Called Transcription
27.7 There Are Three Kinds of RNA
27.8 Biosynthesis of Proteins Is Called Translation
27.9 Why DNA Contains Thymine Instead of Uracil
27.10 How the Base Sequence of DNA Is Determined
27.11 Polymerase Chain Reaction (PCR)
27.12 Genetic Engineering
27.13 Laboratory Synthesis of DNA Strands
IX: SPECIAL TOPICS IN ORGANIC CHEMISTRY
28. SYNTHETIC POLYMERS
28.1 There Are Two Major Classes of Synthetic Polymers
28.2 Chain-Growth Polymers
Radical Polymerization
Branching of the Polymer Chain
Cationic Polymerization
Anionic Polymerization
28.3 Stereochemistry of Polymerization. Ziegler-Natta Catalysts
28.4 Polymerization of Dienes. The Manufacture of Rubber
28.5 Copolymers
28.6 Step-Growth Polymers
28.7 Physical Properties of Polymers
29. PERICYCLIC REACTIONS
29.1 There Are Three Kinds of Pericyclic Reations
29.2 Molecular Orbitals and Orbital Symmetry
29.3 Electrocyclic Reactions
29.4 Cycloaddition Reactions
29.5 Sigmatropic Rearrangements
Migration of Hydrogen
Migration of Carbon
29.6 Pericyclic Rections in Biological Systems
Biological Cycloaddition Reactions
A Biological Reaction Involving an Electrocyclic Reaction and a Sigmatropic
Rearrangement
29.7 Summary of the Selection Rules for Pericyclic Reactions
30. THE ORGANIC CHEMISTRY OF DRUGS: DISCOVERY AND DESIGN
30.1 Naming Drugs
30.2 Lead Compounds
30.3 Molecular Modification
30.4 Random Screening
30.5 Serendipity in Drug Development
30.6 Receptors
30.7 Drugs as Enzyme Inhibitors
30.8 Designing a Suicide Substrate
30.9 Quantitative Structure-Activity Relationships (QSARs)
30.10 Molecular Modeling
30.11 Combinatorial Organic Synthesis
30.12 Antiviral Drugs
30.13 Economics of Drugs: Governmental Regulations