Chapter 7 builds upon the foundations of curved arrow notation and charge stability that students learn in Chapter 6. Students see that ionic reactions are driven largely by the flow of electrons from an electron-rich site to an electron-poor site and that total bond energy is also an important driving force. Students also learn how to simplify ionic and organometallic species to work more comfortably with mechanisms. These concepts are applied toward the ten most common elementary steps, making up the bulk of multistep mechanisms that students will encounter throughout the year. Karty aims at expanding students’ understanding of organic chemistry through introducing biomolecules, special interest and connections boxes, and green chemistry.
Click here to view Chapter 7.
The new Third Edition includes a new video series that models the critical thinking skills that students need to master. Redesigned, two-column Solved Problems then coach students in applying those critical thinking skills to solving chemical equations, which helps them avoid overreliance on memorization. Interactive features in the book and Smartwork consistently give students opportunities to practice what they’ve learned as well.
Click here for a general overview of the new Third Edition.
Brief Table of Contents
1 Atomic and Molecular Structure
Interchapter A Nomenclature: The Basic System for Naming Organic Compounds: Alkanes, Haloalkanes, Nitroalkanes, Cycloalkanes, and Ethers
2 Three-Dimensional Geometry, Intermolecular Interactions, and Physical Properties
3 Valence Bond Theory and Molecular Orbital Theory
Interchapter B Naming Alkenes, Alkynes, and Benzene Derivatives
4 Isomerism 1: Conformers and Constitutional Isomers
5 Isomerism 2: Chirality, Enantiomers, and Diastereomers
6 The Proton Transfer Reaction: An Introduction to Mechanisms, Equilibria, Free Energy Diagrams, and Charge Stability
7 An Overview of the Most Common Elementary Steps
Interchapter C Molecular Orbital Theory and Chemical Reactions
Interchapter D Naming Compounds with a Functional Group That Calls for a Suffix: Alcohols, Amines, Ketones, Aldehydes, Carboxylic Acids, and Carboxylic Acid Derivatives
8 An Introduction to Multistep Mechanisms: SN1 and E1 Reactions and Their Comparisons to SN2 and E2 Reactions
9 Competition among SN2, SN1, E2, and E1 Reactions
10 Organic Synthesis 1: Nucleophilic Substitution and Elimination Reactions and Functional Group Transformations
11 Organic Synthesis 2: Reactions That Alter the Carbon Skeleton, and Designing Multistep Syntheses
12 Electrophilic Addition to Nonpolar π Bonds 1: Addition of a Brønsted Acid
13 Electrophilic Addition to Nonpolar π Bonds 2: Reactions Involving Cyclic Transition States
14 Conjugation, and Aromaticity
15 Structure Determination 1: Mass Spectrometry
16 Structure Determination 2: Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy
17 Structure Determination 3: Nuclear Magnetic Resonance Spectroscopy
18 Nucleophilic Addition to Polar π Bonds 1: Reagents That Are Strongly Nucleophilic
19 Nucleophilic Addition to Polar π Bonds 2: Reagents That Are Weakly Nucleophilic or Non-nucleophilic, and Acid and Base Catalysis
20 Redox Reactions; Organometallic Reagents and Their Reactions
21 Organic Synthesis 3: Intermediate Topics in Synthesis Design
22 Nucleophilic Addition–Elimination Reactions 1: Reagents That Are Strongly Nucleophilic
23 Nucleophilic Addition–Elimination Reactions 2: Reagents That Are Weakly Nucleophilic or Non-nucleophilic
24 Aromatic Substitution 1: Electrophilic Aromatic Substitution on Benzene, and Useful Accompanying Reactions
25 Aromatic Substitution 2: Reactions of Substituted Benzenes and Other Rings
26 The Diels–Alder Reaction, Syn Dihydroxylation, and Oxidative Cleavage
27 Reactions Involving Radicals
28 Polymers
29 Biomolecules 1: An Overview of the Four Major Classes of Biomolecules
30 Biomolecules 2: Representative Biochemical Processes Involving Biomolecules
Full Table of Contents
1 Atomic and Molecular Structure
1.1 What Is Organic Chemistry?
1.2 Why Carbon?
1.3 Atomic Structure and Ground State Electron Configurations
1.4 The Covalent Bond: Bond Energy and Bond Length
1.5 Lewis Dot Structures and the Octet Rule
1.6 Strategies for Success: Drawing Lewis Dot Structures Quickly
1.7 Electronegativity, Polar Covalent Bonds, and Bond Dipoles
1.8 Ionic Bonds
1.9 Assigning Electrons to Atoms in Molecules: Formal Charge
1.10 Resonance Theory
1.11 Strategies for Success: Drawing All Resonance Structures
1.12 Shorthand Notations
1.13 An Overview of Organic Compounds: Functional Groups
THE ORGANIC CHEMISTRY OF BIOMOLECULES
1.14 An Introduction to Proteins, Carbohydrates, and Nucleic Acids: Fundamental Building Blocks and Functional Groups
INTERCHAPTER
A Nomenclature: The Basic System for Naming Organic Compounds: Alkanes, Haloalkanes, Nitroalkanes, Cycloalkanes, and Ethers
A.1 The Need for Systematic Nomenclature: An Introduction to the IUPAC System
A.2 Alkanes and Substituted Alkanes
A.3 Haloalkanes and Nitroalkanes: Roots, Prefixes, and Locator Numbers
A.4 Alkyl Substituents: Branched Alkanes and Substituted Branched Alkanes
A.5 Cyclic Alkanes and Cyclic Alkyl Groups
A.6 Ethers and Alkoxy Groups
A.7 Trivial Names or Common Names
2 Three-Dimensional Geometry, Intermolecular Interactions, and Physical Properties
2.1 Valence Shell Electron Pair Repulsion (VSEPR) Theory: Three-Dimensional Geometry
2.2 Dash–Wedge Notation
2.3 Strategies for Success: The Molecular Modeling Kit
2.4 Net Molecular Dipoles
2.5 Physical Properties, Functional Groups, and Intermolecular Interactions
2.6 Melting Points, Boiling Points, and Intermolecular Interactions
2.7 Solubility
2.8 Strategies for Success: Ranking Boiling Points and Solubilities of Structurally Similar Compounds
2.9 Protic and Aprotic Solvents
THE ORGANIC CHEMISTRY OF BIOMOLECULES
2.10 An Introduction to Lipids
3 Valence Bond Theory and Molecular Orbital Theory
3.1 An Introduction to Valence Bond Theory and 𝜎 Bonds: An Example with H2
3.2 Valence Bond Theory and Tetrahedral Electron Geometry: Alkanes and sp3 Hybridization
3.3 Valence Bond Theory and Lone Pairs of Electrons
3.4 Valence Bond Theory and Trigonal Planar Electron Geometry: Double Bonds, sp2 Hybridization, π Bonds, and Carbocations
3.5 Valence Bond Theory and Linear Electron Geometry: Triple Bonds and sp Hybridization
3.6 Strategies for Success: Quickly Identifying Hybridization and the Number of 𝜎 and π Bonds from a Lewis Structure
3.7 Bond Rotations about Single and Double Bonds: Cis and Trans Configurations
3.8 Strategies for Success: Molecular Modeling Kits, Bond Rotations, and Extended Geometries
3.9 Hybridization, Bond Characteristics, and Effective Electronegativity
3.10 A Deeper Look: Molecular Orbital Theory and the Wave Nature of Electrons
3.11 A Deeper Look: Hybrid Atomic Orbitals and a Combined Molecular Orbital–Valence Bond Model
INTERCHAPTER
B Naming Alkenes, Alkynes, and Benzene Derivatives
B.1 Alkenes, Alkynes, Cycloalkenes, and Cycloalkynes: Molecules with One Carbon-Carbon Double Bond or Carbon-Carbon Triple Bond
B.2 Molecules with Multiple Carbon-Carbon Double Bonds or Carbon-Carbon Triple Bonds
B.3 Benzene and Benzene Derivatives
4 Isomerism 1: Conformers and Constitutional Isomers
4.1 Conformers: Rotational Conformations, Newman Projections, and Dihedral Angles
4.2 Conformers: Energy Changes and Conformational Analysis
4.3 Conformers: Ring Strain and the Most Stable Conformations of Cyclic Alkanes
4.4 A Deeper Look: Calculating Ring Strain from Heats of Combustion
4.5 Conformers: Cyclohexane and Chair Flips
4.6 Strategies for Success: Drawing Chair Conformations of Cyclohexane
4.7 Conformers: Monosubstituted Cyclohexanes
4.8 Conformers: Disubstituted Cyclohexanes, Cis and Trans Isomers, and Haworth Projections
4.9 Strategies for Success: Molecular Modeling Kits and Chair Flips
4.10 Constitutional Isomerism: Identifying Constitutional Isomers
4.11 Constitutional Isomers: Index of Hydrogen Deficiency (Degree of Unsaturation)
4.12 Strategies for Success: Drawing All Constitutional Isomers of a Given Formula
THE ORGANIC CHEMISTRY OF BIOMOLECULES
4.13 Constitutional Isomers and Biomolecules: Amino Acids and Monosaccharides
4.14 Saturation and Unsaturation in Fats and Oils
5 Isomerism 2: Chirality, Enantiomers, and Diastereomers
5.1 Defining Configurational Isomers, Enantiomers, and Diastereomers
5.2 Enantiomers, Mirror Images, and Superimposability
5.3 Strategies for Success: Drawing Mirror Images
5.4 Chirality and the Plane of Symmetry Test
5.5 Chiral Centers
5.6 Absolute Stereochemical Configurations: R/S Designations of Chiral Centers
5.7 Mirror Images That Rapidly Interconvert: Single-Bond Rotation and Nitrogen Inversion
5.8 Diastereomers: Double-Bond Configurations and Chiral Centers
5.9 Strategies for Success: Drawing All Stereoisomers of a Molecule with Chiral Centers
5.10 Fischer Projections and Stereochemistry
5.11 Strategies for Success: Converting between Fischer Projections and Zigzag Conformations
5.12 Physical and Chemical Properties of Isomers
5.13 Separating Configurational Isomers
5.14 Optical Activity
THE ORGANIC CHEMISTRY OF BIOMOLECULES
5.15 The Chirality of Biomolecules
5.16 The d/l System for Classifying Monosaccharides and Amino Acids
5.17 The d Family of Aldoses
6 The Proton Transfer Reaction: An Introduction to Mechanisms, Equilibria, Free Energy Diagrams, and Charge Stability
6.1 An Introduction to Reaction Mechanisms: The Proton Transfer Reaction and Curved Arrow Notation
6.2 Proton Transfer Reaction Outcomes: pKa Values and Acid and Base Strengths
6.3 A Deeper Look: Chemical Equilibrium, Equilibrium Constants, and Ka Values
6.4 Gibbs Free Energy and the Reaction Free Energy Diagram
6.5 A Deeper Look: Gibbs Free Energy, Equilibrium Constants, Enthalpy, and Entropy
6.6 Functional Groups and Acidity
6.7 Relative Strengths of Charged and Uncharged Acids: The Reactivity of Charged Species
6.8 Relative Acidities of Protons on Atoms with Like Charges
6.9 Strategies for Success: Ranking Acid and Base Strengths by Using the CARDIN-al Rule
THE ORGANIC CHEMISTRY OF BIOMOLECULES
6.10 The Structure of Amino Acids in Solution as a Function of pH
7 An Overview of the Most Common Elementary Steps
7.1 Mechanisms as Predictive Tools: The Proton Transfer Step Revisited
7.2 Bimolecular Nucleophilic Substitution (SN2) Steps
7.3 Bond-Forming (Coordination) and Bond-Breaking (Heterolysis) Steps
7.4 Nucleophilic Addition and Nucleophile Elimination Steps
7.5 Bimolecular Elimination (E2) Steps
7.6 Electrophilic Addition and Electrophile Elimination Steps
7.7 Carbocation Rearrangements: 1,2-Hydride Shifts and 1,2-Alkyl Shifts
7.8 The Driving Force for Chemical Reactions
7.9 Carbocations and Charge Stability
7.10 Keto–Enol Tautomerization: An Example of Bond Energies as the Major Driving Force
INTERCHAPTER
C Molecular Orbital Theory and Chemical Reactions
C.1 An Overview of Frontier Molecular Orbital Theory
C.2 Frontier Molecular Orbital Theory and Elementary Steps
INTERCHAPTER
D Naming Compounds with a Functional Group That Calls for a Suffix: Alcohols, Amines, Ketones, Aldehydes, Carboxylic Acids, and Carboxylic Acid Derivatives
D.1 The Basic System for Naming Compounds with a Functional Group That Calls for a Suffix
D.2 Naming Alcohols and Amines
D.3 Naming Ketones and Aldehydes
D.4 Naming Carboxylic Acids, Acid Chlorides, Amides, and Nitriles
D.5 Naming Esters and Acid Anhydrides
8 An Introduction to Multistep Mechanisms: SN1 and E1 Reactions and Their Comparisons to SN2 and E2 Reactions
8.1 The Unimolecular Nucleophilic Substitution (SN1) Reaction: Intermediates, Overall Reactants, and Overall Products
8.2 The Unimolecular Elimination (E1) Reaction
8.3 The Kinetics of SN2, SN1, E2, and E1 Reactions: Evidence for Reaction Mechanisms
8.4 A Deeper Look: Theoretical Rate Laws and Transition State Theory
8.5 Stereochemistry of Nucleophilic Substitution and Elimination Reactions
8.6 The Reasonableness of a Mechanism: Proton Transfers and Carbocation Rearrangements
8.7 Resonance-Delocalized Intermediates in Mechanisms
9 Competition among SN2, SN1, E2, and E1 Reactions
9.1 Identifying the Competition among SN2, SN1, E2, and E1 Reactions
9.2 Rate-Determining Steps Revisited: Simplified Pictures of SN2, SN1, E2, and E1 Reactions
9.3 Factor 1: Strength of the Attacking Species
9.4 Factor 2: Concentration of the Attacking Species
9.5 Factor 3: Leaving Group Ability
9.6 Factor 4: Type of Carbon Bonded to the Leaving Group
9.7 Factor 5: Solvent Effects
9.8 Factor 6: Heat
9.9 Strategies for Success: Predicting the Outcome of an SN2/SN1/E2/E1 Competition
9.10 Regioselectivity in Elimination Reactions: Alkene Stability and Zaitsev’s Rule
9.11 A Deeper Look: Hyperconjugation and Alkene Stability
9.12 Intermolecular Reactions versus Intramolecular Cyclizations
THE ORGANIC CHEMISTRY OF BIOMOLECULES
9.13 Nucleophilic Substitution Reactions and Monosaccharides: The Formation and Hydrolysis of Glycosides
10 Organic Synthesis: Nucleophilic Substitution and Elimination Reactions and Functional Group Transformations
10.1 The Language of Organic Synthesis
10.2 Writing the Reactions of an Organic Synthesis
10.3 Cataloging Reactions: Functional Group Transformations and Carbon–Carbon Bonding-Forming and Bond-Breaking Reactions
10.4 Options and Limitations in Synthesis: Ether Formation by the Williamson Synthesis and Condensation
10.5 Converting Alcohols into Alkyl Halides: PBr3 and PCl3
10.6 Halogenation of α Carbons
10.7 Epoxides as Substrates
10.8 Formation of Epoxides by Nucleophilic Substitution
10.9 Diazomethane Formation of Methyl Esters
10.10 Amines and Quaternary Ammonium Salts from Alkyl Halides
10.11 Hofmann Elimination
10.12 Generating Alkynes by Elimination Reactions
11 Organic Synthesis 2: Reactions That Alter the Carbon Skeleton, and Designing Multistep Syntheses
11.1 Reactions That Alter the Carbon Skeleton and Retrosynthetic Analysis
11.2 Carbon Nucleophiles and the Opening of Epoxides
11.3 Alkylation of α Carbons: Regioselectivity and Kinetic versus Thermodynamic Control
11.4 Synthetic Traps
11.5 Strategies for Success: Improving Your Proficiency with Solving Multistep Syntheses
11.6 Green Chemistry
11.7 A Deeper Look: Considerations of Percent Yield
12 Electrophilic Addition to Nonpolar π Bonds 1: Addition of a Brønsted Acid
12.1 The General Electrophilic Addition Mechanism: Addition of a Strong Brønsted Acid to an Alkene
12.2 Benzene Rings Do Not Readily Undergo Electrophilic Addition of Brønsted Acids
12.3 Regiochemistry: Production of the More Stable Carbocation and Markovnikov’s Rule
12.4 Carbocation Rearrangements
12.5 Stereochemistry in the Addition of a Brønsted Acid to an Alkene
12.6 Addition of a Weak Acid: Acid Catalysis
12.7 Electrophilic Addition of a Strong Brønsted Acid to an Alkyne
12.8 Acid-Catalyzed Hydration of an Alkyne: Synthesis of a Ketone
12.9 Electrophilic Addition of a Brønsted Acid to a Conjugated Diene: 1,2-Addition and 1,4-Addition
12.10 Kinetic versus Thermodynamic Control in Electrophilic Addition to a Conjugated Diene
12.11 Organic Synthesis: Additions of Brønsted Acids to Alkenes and Alkynes
THE ORGANIC CHEMISTRY OF BIOMOLECULES
12.12 Terpenes and Their Biosynthesis: Carbocation Chemistry in Nature
13 Electrophilic Addition to Nonpolar π Bonds 2: Reactions Involving Cyclic Transition States
13.1 Electrophilic Addition via a Three-Membered Ring: The General Mechanism
13.2 Electrophilic Addition of Carbenes: Formation of Cyclopropane Rings
13.3 Epoxide Formation with Peroxy Acids
13.4 Electrophilic Addition Involving Molecular Halogens: Synthesis of 1,2-Dihalides and Halohydrins
13.5 Oxymercuration–Reduction: Addition of Water
13.6 Hydroboration–Oxidation: Anti-Markovnikov Syn Addition of Water to an Alkene
13.7 Hydroboration–Oxidation of Alkynes
13.8 Organic Synthesis: Using Electrophilic Addition Reactions That Proceed through a Cyclic Transition State
13.9 Organic Synthesis: Catalytic Hydrogenation of Alkenes and Alkynes
14 Conjugation and Aromaticity
14.1 The Allyl Cation and Buta-1,3-diene: Resonance and the Conjugation of p Orbitals in Acyclic π Systems
14.2 Isolated π Systems
14.3 A Deeper Look: Heats of Hydrogenation and the Stability of Conjugated π Bonds
14.4 The Allyl Anion: Conjugation and Lone Pairs of Electrons
14.5 Cyclic π Systems: Benzene as an Aromatic Compound, and Cyclobutadiene as an Antiaromatic Compound
14.6 A Deeper Look: Using Heats of Hydrogenation to Determine Aromaticity
14.7 Hückel’s Rules: Assessing Aromaticity Using Lewis Structures
14.8 A Deeper Look: Molecular Orbital Theory, Conjugation, and Aromaticity
THE ORGANIC CHEMISTRY OF BIOMOLECULES
14.9 Aromaticity and DNA
15 Structure Determination 1: Mass Spectrometry
15.1 An Overview of Mass Spectrometry
15.2 Features of a Mass Spectrum, the Nitrogen Rule, and Fragmentation
15.3 Isotopes and Mass Spectra: M + 1 and M + 2 Peaks
15.4 A Deeper Look: Estimating the Number of Carbon Atoms from the M + 1 Peak
15.5 Strategies for Success: Determining a Molecular Formula from the Mass Spectrum of an Organic Compound
15.6 A Deeper Look: Fragmentation Pathways in Mass Spectrometry
16 Structure Determination 2: Infrared Spectroscopy and Ultraviolet–Visible Spectroscopy
16.1 Overview of Infrared Spectroscopy
16.2 General Theory of Infrared Spectroscopy
16.3 Location of Peaks in an Infrared Spectrum
16.4 The Ball-and-Spring Model for Explaining Infrared Peak Locations
16.5 Intensities of Peaks in an Infrared Spectrum
16.6 Some Important Infrared Stretches
16.7 Strategies for Success: Structure Elucidation Using Infrared Spectroscopy
16.8 A Deeper Look: Infrared Bending Vibrations
16.9 An Overview of Ultraviolet–Visible Spectroscopy
16.10 Ultraviolet–Visible Spectra and Molecular Structure: Conjugation and Lone Pairs
16.11 A Deeper Look: Molecular Orbital Theory and Ultraviolet–Visible Spectroscopy
17 Structure Determination 3: Nuclear Magnetic Resonance Spectroscopy
17.1 Nuclear Magnetic Resonance Spectroscopy: An Overview
17.2 Nuclear Spin and the Nuclear Magnetic Resonance Signal
17.3 Shielding, Chemical Distinction, and the Number of NMR Signals
17.4 The Time Scale of Nuclear Magnetic Resonance Spectroscopy
17.5 Characteristic Chemical Shifts, Inductive Effects, and Magnetic Anisotropy
17.6 Strategies for Success: Predicting Approximate Chemical Shift Values
17.7 A Deeper Look: A Quantitative Examination of the NMR Signal and Chemical Shift and a Look at Deuterated Solvents
17.8 Integration of Signals
17.9 Splitting of the Signal by Spin–Spin Coupling: The N + 1 Rule
17.10 Coupling Constants and Complex Signal Splitting
17.11 A Deeper Look: Signal Resolution and the Strength of Bext
17.12 Carbon Signals: 13C Nuclear Magnetic Resonance Spectroscopy
17.13 A Deeper Look: DEPT 13C NMR Spectroscopy and 2-D NMR Spectra
17.14 Strategies for Success: Elucidating Molecular Structure Using Nuclear Magnetic Resonance Spectroscopy
18 Nucleophilic Addition to Polar π Bonds 1: Reagents That Are Strongly Nucleophilic
18.1 An Overview of the General Mechanism: Addition of Strong Nucleophiles
18.2 Substituent Effects: Relative Reactivity of Ketones and Aldehydes in Nucleophilic Addition
18.3 Reactions of Hydride Reagents: LiAlH4, NaBH4, and NaH
18.4 Reactions of Organometallic Compounds: Alkyllithium Reagents and Grignard Reagents
18.5 Compatibility of Functional Groups in Reactions Involving Alkyllithium and Grignard Reagents
18.6 Wittig Reagents and the Wittig Reaction: Synthesis of Alkenes
18.7 Generating Wittig Reagents
18.8 Direct Addition versus Conjugate Addition
18.9 Lithium Dialkylcuprates and the Selectivity of Organometallic Reagents
18.10 Organic Synthesis: Grignard and Alkyllithium Reactions in Synthesis
18.11 Organic Synthesis: Considerations of Direct Addition versus Conjugate Addition
18.12 Organic Synthesis: Considerations of Regiochemistry in the Formation of Alkenes
19 Nucleophilic Addition to Polar π Bonds 2: Reagents That Are Weakly Nucleophilic or Non-nucleophilic, and Acid and Base Catalysis
19.1 Weak Nucleophiles as Reagents: Acid and Base Catalysis
19.2 Addition of HCN: The Formation of Cyanohydrins
19.3 Direct Addition versus Conjugate Addition of Weak Nucleophiles and HCN
19.4 Formation and Hydrolysis of Acetals, Imines, and Enamines
19.5 Organic Synthesis: Synthesizing Amines via Reductive Amination
19.6 The Wolff–Kishner Reduction
19.7 Hydrolysis of Nitriles
19.8 Enolate Nucleophiles: Aldol Additions
19.9 Aldol Condensations
19.10 Aldol Reactions Involving Ketones
19.11 Crossed Aldol Reactions
19.12 Intramolecular Aldol Reactions
19.13 The Robinson Annulation
19.14 Organic Synthesis: Aldol and Robinson Annulation Reactions in Synthesis
THE ORGANIC CHEMISTRY OF BIOMOLECULES
19.15 Ring Opening and Ring Closing of Monosaccharides
20 Redox Reactions; Organometallic Reagents and Their Reactions
20.1 Identifying Reactions as Redox Reactions
20.2 A Deeper Look: Calculating Oxidation States
20.3 Catalytic Hydrogenation: A Review of Alkene and Alkyne Reductions, Reductions of Other Functional Groups, and Selectivity
20.4 Reactions That Reduce Carbon-Oxygen Double Bond to CH2: Wolff–Kishner, Clemmensen, and Raney–Nickel Reductions
20.5 Oxidations of Alcohols and Aldehydes
20.6 Generating Organometallic Reagents: Grignard Reagents, Alkyllithium Reagents, and Lithium Dialkylcuprates
20.7 Useful Reactions That Form Carbon–Carbon Bonds: Coupling and Alkene Metathesis Reactions
21 Organic Synthesis 3: Intermediate Topics in Synthesis Design
21.1 Considerations When a Synthesis Calls for a New Carbon–Carbon Bond
21.2 Avoiding Synthetic Traps: Selective Reagents and Protecting Groups
22 Nucleophilic Addition–Elimination Reactions 1: Reagents That Are Strongly Nucleophilic
22.1 An Introduction to Nucleophilic Addition–Elimination Reactions: Transesterification
22.2 Acyl Substitution Involving Other Carboxylic Acid Derivatives: The Thermodynamics of Acyl Substitution
22.3 Reaction of an Ester with Hydroxide (Saponification) and the Reverse Reaction
22.4 Carboxylic Acids from Amides; the Gabriel Synthesis of Primary Amines
22.5 Haloform Reactions
22.6 Hydride Reducing Agents: Sodium Borohydride (NaBH4) and Lithium Aluminum Hydride (LiAlH4)
22.7 A Deeper Look: Diisobutylaluminum Hydride (DIBAH) and Lithium Tri-tert-butoxyaluminum Hydride (LTBA) as Specialized Reducing Agents
22.8 Organometallic Reagents
23 Nucleophilic Addition–Elimination Reactions 2: Reagents That Are Weakly Nucleophilic or Non-nucleophilic
23.1 The General Nucleophilic Addition–Elimination Mechanism Involving Weak Nucleophiles: Alcoholysis and Hydrolysis of Acid Chlorides
23.2 Relative Reactivities of Acid Derivatives: Rates of Hydrolysis
23.3 Aminolysis of Acid Derivatives
23.4 Synthesis of Acid Halides: Getting to the Top of the Stability Ladder
23.5 The Hell–Volhard–Zelinsky Reaction: Synthesizing α-Bromo Carboxylic Acids
23.6 Sulfonyl Chlorides: Synthesis of Mesylates, Tosylates, and Triflates
23.7 Base and Acid Catalysis in Nucleophilic Addition–Elimination Reactions
23.8 Baeyer–Villiger Oxidations
23.9 Claisen Condensations
23.10 Organic Synthesis: Decarboxylation, the Malonic Ester Synthesis, and the Acetoacetic Ester Synthesis
THE ORGANIC CHEMISTRY OF BIOMOLECULES
23.11 Determining the Amino Acid Sequence of a Protein
24 Aromatic Substitution 1: Electrophilic Aromatic Substitution on Benzene, and Useful Accompanying Reactions
24.1 The General Mechanism of Electrophilic Aromatic Substitution
24.2 Halogenation
24.3 Friedel–Crafts Alkylation
24.4 Limitations of Friedel–Crafts Alkylation
24.5 Friedel–Crafts Acylation
24.6 Nitration
24.7 Sulfonation
24.8 Organic Synthesis: Considerations of Carbocation Rearrangements and the Synthesis of Primary Alkylbenzenes
24.9 Organic Synthesis: Common Reactions Used Along with Electrophilic Aromatic Substitution Reactions
25 Aromatic Substitution 2: Reactions of Substituted Benzenes and Other Rings
25.1 Regiochemistry of Electrophilic Aromatic Substitution: Defining Ortho/Para and Meta Directors
25.2 What Characterizes Ortho/Para and Meta Directors, and Why?
25.3 Activation and Deactivation of Benzene toward Electrophilic Aromatic Substitution
25.4 Impact of Substituent Effects on the Outcome of Electrophilic Aromatic Substitution Reactions
25.5 Impact of Reaction Conditions on Substituent Effects
25.6 Electrophilic Aromatic Substitution on Disubstituted Benzenes
25.7 Electrophilic Aromatic Substitution Involving Aromatic Rings other than Benzene
25.8 Azo Coupling and Azo Dyes
25.9 Nucleophilic Aromatic Substitution Mechanisms
25.10 Organic Synthesis: Considerations of Regiochemistry, and Attaching Groups in the Correct Order
25.11 Organic Synthesis: Interconverting Ortho/Para and Meta Directors
25.12 Organic Synthesis: Considerations of Protecting Groups
26 The Diels–Alder Reaction, Syn Dihydroxylation, and Oxidative Cleavage
26.1 Curved Arrow Notation and Examples
26.2 Conformation of the Diene
26.3 Substituent Effects on the Reaction Rate
26.4 Stereochemistry of Diels–Alder Reactions
26.5 Regiochemistry of Diels–Alder Reactions
26.6 A Deeper Look: The Reversibility of Diels–Alder Reactions; the Retro Diels–Alder Reaction
26.7 A Deeper Look: A Molecular Orbital Picture of the Diels–Alder Reaction:
26.8 Syn Dihydroxylation of Alkenes and Alkynes with OsO4 or KMnO4
26.9 Oxidative Cleavage of Alkenes and Alkynes
26.10 Organic Synthesis: The Diels–Alder Reaction in Synthesis
27 Reactions Involving Radicals
27.1 Homolysis: Curved Arrow Notation and Radical Initiators
27.2 Structure and Stability of Alkyl Radicals
27.3 Common Elementary Steps That Radicals Undergo
27.4 Radical Halogenation of Alkanes: Synthesis of Alkyl Halides
27.5 Radical Addition of HBr: Anti-Markovnikov Addition
27.6 Stereochemistry of Radical Halogenation and HBr Addition
27.7 Dissolving Metal Reductions: Hydrogenation of Alkenes and Alkynes
27.8 Organic Synthesis: Radical Reactions in Synthesis
28 Polymers
28.1 Radical Polymerization: Polystyrene as a Model
28.2 Anionic and Cationic Polymerization Reactions
28.3 Ziegler–Natta Catalysts and Coordination Polymerization
28.4 Ring-Opening Polymerization Reactions
28.5 Step-Growth Polymerization
28.6 Linear, Branched, and Network Polymers
28.7 Modification of Pendant Groups
28.8 Cross-linking
28.9 General Aspects of Polymer Structure
28.10 Properties of Polymers
28.11 Uses of Polymers: The Relationship between Structure and Function in Materials for Food Storage
28.12 Going Green with Polymers: Recycling, Biodegradable Polymers, and Renewable Sources
THE ORGANIC CHEMISTRY OF BIOMOLECULES
28.13 Biological Polymers
29 Biomolecules 1: An Overview of the Four Major Classes of Biomolecules
29.1 Amino Acids as Building Blocks of Proteins
29.2 Acid–Base Properties of Amino Acids: Ionization State as a Function of pH
29.3 Electrophoresis and Isoelectric Focusing of Amino Acids
29.4 Levels of Protein Structure: Primary, Secondary, Tertiary, and Quaternary Structures
29.5 Sequencing Peptides
29.6 Synthesizing Peptides in the Laboratory
29.7 Monosaccharides as Building Blocks of Carbohydrates
29.8 Classification of Monosaccharides, and the D Family of Aldohexoses
29.9 The Fischer Proof of the Structure of Glucose
29.10 Ring Closing and Ring Opening of Sugars
29.11 Glycosides, Glycosidic Linkages, and Reducing Sugars
29.12 Polysaccharide Structure and Function
29.13 Nucleotides as Building Blocks of Nucleic Acids
29.14 Complementarity among Nitrogenous Bases, and the DNA Double Helix
29.15 Fats, Oils, and Fatty Acids
29.16 Phospholipids and Cell Membranes
29.17 Steroids, Terpenes, and Terpenoids
29.18 Prostaglandins
29.19 Waxes
30 Biomolecules 2: Representative Biochemical Processes Involving Biomolecules
30.1 Proteins as Enzymes
30.2 Metabolism of Carbohydrates: Glycolysis and Gluconeogenesis
30.3 Degradation and Synthesis of Fats, Oils, and Fatty Acids
30.4 Biosynthesis of Cholesterol and Terpenes
30.5 Storing and Accessing Genetic Information in DNA
30.6 Cell Signaling: An Example Involving G Proteins
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