ch 7 pic

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 ​Nucleophilic Substitution and Elimination Reactions 1: 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: Beginning Concepts in Designing a Multistep Synthesis

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 K 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        Nucleophilic Substitution and Elimination Reactions: Competition among SN2, SN1, E2, and E1 Reactions

9.1     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: Beginning Concepts in Designing a Multistep Synthesis

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     ZieglerNatta 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     AcidBase 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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