Organic Chemistry, 5/E
Paula Y. Bruice

ISBN-10: 0131963163
ISBN-13: 9780131963160

Publisher: Prentice Hall
Copyright: 2007
Format: Cloth; 1440 pp
Published: 03/21/2006

Suggested retail price: $185.80
Not available for purchase at this time.

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.

Content and Approach

  • Functional groups are organized around mechanistic similarities.
    • This organization allows a great deal of material to be understood in light of unifying principles of reactivity.
  • Synthesis and reactivity are tied together.
    • When discussing a functional group's reactivity, the text covers the synthesis of compounds that are formed as a result of that reactivity, often by having students design synthetic schemes.  This strategy helps prevent students from having to memorize lists of unrelated reactions.  It also economizes the presentation, allowing more material to be covered in less time.

Synthesis

  • Students are introduced to synthetic chemistry and retrosynthetic analysis early in the book (chapters 3 and 5).
    • Since students have a limited number of reactions to work with at this point, the early introduction provides a greater progression to learning this skill.
  • "Designing a Synthesis" sections appear throughout the text–Help students learn to efficiently design multi-step syntheses. Many multi-step problems include the synthesis of compounds that students recognize (Novocain, Valium, ketoprofen).
    • Provides a good way for students to review reactions they have learned. Also shows how synthetic organic chemists approach problems.

Bioorganic Chemistry

  • Rich biological applications, more than any other organic text.
    • Shows students how chemistry relates to bio and medical fields.
  • Bioorganic and applied topics–Covered in over 130 interest boxes integrated throughout the text meant to serve as intriguing asides.  For example:
    • Why are Dalmatians the only mammals that exrete uric acid?
    • Why is life based on carbon instead of silicon?
    • Trans fats
  • In the first 2/3 of the text, the bioorganic material often appears at the end of the chapters for easy identification and assignability/exclusion.
    • Ties the chemistry to the biology that students (most of whom are pre-meds) are learning simultaneously.
  • Chapters 21-27 focus heavily on bioorganic topics.
    • The chapters have the unique distinction of containing more chemistry than is typically found in the corresponding parts of a biochemistry text.

Pedagogical Devices

  • End-of-Chapter Summaries
    • Recapitulate the major concepts of the chapter in a concise narrative format.
  • "Voice box" annotations
    • Helps students focus on the points being discussed.
  • Biographical sketches Brief biographies of the chemists who defined Organic Chemistry.
    • Humanizes the science by reinforcing for students that these discoveries were the result of personal endeavor, sometimes after overcoming significant adversities.
  • Margin notes
    • Emphasize core ideas and remind students of important principles to help them grasp concepts in the text.
  • Reaction Summaries included in each chapter that covers reactions.
    • Ensures that students understand and can explain how each reaction occurs.
  • Chapter-end treatment of key terms–Offers a handy page reference to refresh skills.
    • Helps students assess their knowledge of the language of organic chemistry before proceeding.

Problem-Solving Support

  • Solved Problems throughout the chapter.
    • Help students learn how to approach and solve problems before testing themselves at the end of the chapter.
  • Problem-Solving Strategies–Each problem-solving strategy is followed by an exercise that gives students an opportunity to use the problem-solving skill just learned.
    • Teach students how to approach a variety of problems, organize their thoughts, and improve their problem-solving abilities.
  • Graded problem difficulty
    • The end-of-chapter problems vary in difficulty.  They begin with drill problems that integrate material from the entire chapter, requiring students to think in terms of all the material in the chapter rather than focusing on individual sections.  The problems become more challenging as the student proceeds, often reinforcing concepts from prior chapters.  The net result for the student is a progressive building of both problem solving ability and confidence.
  • More problems throughout–Over 1800 problems for assignment and student practice. 

THOROUGHLY ENHANCED content revision based on free-form content reviews.

  • The "free-form" response format allows for a broad range of feedback, unconstrained by preconceptions built into traditional review questionnaires.  
  • All radicals are now covered in a single chapter (Chapter 11).
  • Nucleophilic substitution and elimination now appear earlier, in Chapters 8-10.
  • Oxidation of alcohol added to Chapter 10.
  • Epoxide formation added to Chapter 4.
    • These changes allow for a wide variety of synthetic problems earlier.

NEW Chapter 25:  Chemistry of Metabolism

  • This new chapter "completes" the coenzyme coverage, so students can see how reactions fit into metabolism.

NEW "Building on Fundamentals" lists at the beginning of each chapter emphasize and repeat principles so they become a core part of a student’s knowledge.

  • Explicity illustrates for students that the same principles are repeated throughout their course.

NEW Concept heading statements frame the context of the discussion to follow rather than merely title the section. 

           

NEW Stepped-out mechanisms clearly delineate the mechanisms of the reactions in a way that is integral to the text, but significantly highlighted

 

ADDITIONAL/REVISED EXERCISES All problems throughout the text have been extensively reviewed and revised.  Usuccessful problems have been excised and replaced by new problems.  In addition, the total number of problems has increased.

  • This edition contains 230 more problems. 
  • All problems are field tested and verified by over 400 students in Paula Bruice's classes before they are included in the text.
  • New problems and revisions to existing problems originate from suggestions by reviewers and Paula Bruice's students. 

 THREE NEW SPECIAL TOPICS TUTORIALS in the Study Guide, making a total of seven.  The Tutorials can effectively replace the need for the additional books students are often asked to purchase.  Now available:

  • NEW Drawing Curved Arrows #2
    • One-electron processes
  • NEW Drawing Resonance Structures
  • NEW Molecular Orbital Theory
  • Kinetics
  • Using Molecular Models
  • Acids/Bases
  • Drawing Curved Arrows #1
    • Two-electron processes

 

TABLE OF CONTENTS

 

 

PART I:  AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART II:  ELECTROPHILIC ADDITION REACTIONS, STEREOCHEMISTRY, AND ELECTRON DEELOCALIZATION

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART III:  SUBSTITUTION AND ELIMINATION REACTIONS

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART IV:  IDENTIFICATION OF ORGANIC COMPOUNDS

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART V:  AROMATIC COMPOUNDS

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART VI:  CARBONYL COMPOUNDS 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

CHAPTER 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

 

 

 

PART VII:  OXIDATION-REDUCTION REACTIONS AND AMINES

 

CHAPTER 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

 

 

CHAPTER 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                                       

 

 

 

PART VIII:  BIOORGANIC COMPOUNDS

 

CHAPTER 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

 

           

           

CHAPTER 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

 

 

 

CHAPTER 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                                    

 

 

 

CHAPTER 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                                                                                              

 

 

 

CHAPTER 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

 

 

 

CHAPTER 26.  LIPIDS                                &nbs