Organic Chemistry
11th Edition

Organic Chemistry
T. W. Graham Solomons
Craig B. Fryhle, Scott A. Snyder

© 2014

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Topics covered

1 The Basics

BONDING AND MOLECULAR STRUCTURE

  1. Life and the Chemistry of Carbon Compounds—We are Stardust
  2. Atomic Structure
  3. Chemical Bonds: The Octet Rule
  4. HOW TO Write Lewis Structures
  5. Formal Charges and HOW TO Calculate Them
  6. Isomers: Different Compounds that Have the Same Molecular Formula
  7. HOW TO Write and Interpret Structural Formulas
  8. Resonance Theory
  9. Quantum Mechanics and Atomic Structure
  10. Atomic Orbitals and Electron Configuration
  11. Molecular Orbitals
  12. The Structure of Methane and Ethane: 3 Hybridization
  13. The Structure of Ethene (Ethylene): 2 Hybridization
  14. The Structure of Ethyne (Acetylene): Hybridization
  15. A Summary of Important Concepts That Come from Quantum Mechanics
  16. How toPredict Molecular Geometry: The Valence Shell Electron Pair Repulsion Model
  17. Applications of Basic Principles

2 Families of Carbon Compounds

FUNCTIONAL GROUPS, INTERMOLECULAR FORCES, AND INFRARED (IR) SPECTROSCOPY

  1. Hydrocarbons: Representative Alkanes, Alkenes, Alkynes, and Aromatic Compounds
  2. Polar Covalent Bonds
  3. Polar and Nonpolar Molecules
  4. Functional Groups
  5. Alkyl Halides or Haloalkanes
  6. Alcohols and Phenols
  7. Ethers
  8. Amines
  9. Aldehydes and Ketones
  10. Carboxylic Acids, Esters, and Amides
  11. Nitriles
  12. Summary of Important Families of Organic Compounds
  13. Physical Properties and Molecular Structure
  14. Summary of Attractive Electric Forces
  15. Infrared Spectroscopy: An Instrumental Method for Detecting Functional Groups
  16. Interpreting IR Spectra
  17. Applications of Basic Principles

3 Acids and Bases

AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

  1. Acid–Base Reactions
  2. How to Use Curved Arrows in Illustrating Reactions
  3. Lewis Acids and Bases
  4. Heterolysis of Bonds to Carbon: Carbocations and Carbanions
  5. The Strength of Brønsted–Lowry Acids and Bases: a and pa
  6. How to Predict the Outcome of Acid–Base Reactions
  7. Relationships Between Structure and Acidity
  8. Energy Changes
  9. The Relationship Between the Equilibrium Constant and the Standard Free-Energy Change, Δ°
  10. Acidity: Carboxylic Acids versus Alcohols
  11. The Effect of the Solvent on Acidity
  12. Organic Compounds as Bases
  13. A Mechanism for an Organic Reaction
  14. Acids and Bases in Nonaqueous Solutions
  15. Acid–Base Reactions and the Synthesis of Deuterium- and Tritium-Labeled Compounds
  16. Applications of Basic Principles

4 Nomenclature and Conformations of Alkanes and Cycloalkanes

  1. Introduction to Alkanes and Cycloalkanes
  2. Shapes of Alkanes
  3. How to Name Alkanes, Alkyl Halides, and Alcohols: The IUPAC System
  4. How to Name Cycloalkanes
  5. How to Name Alkenes and Cycloalkenes
  6. How to Name Alkynes
  7. Physical Properties of Alkanes and Cycloalkanes
  8. Sigma Bonds and Bond Rotation
  9. Conformational Analysis of Butane
  10. The Relative Stabilities of Cycloalkanes: Ring Strain
  11. Conformations of Cyclohexane: The Chair and the Boat
  12. Substituted Cyclohexanes: Axial and Equatorial Hydrogen Groups
  13. Disubstituted Cycloalkanes: Cis–Trans Isomerism
  14. Bicyclic and Polycyclic Alkanes
  15. Chemical Reactions of Alkanes
  16. Synthesis of Alkanes and Cycloalkanes
  17. How to Gain Structural Information from Molecular Formulas and the Index of Hydrogen Deficiency
  18. Applications of Basic Principles

5 Stereochemistry

CHIRAL MOLECULES

  1. Chirality and Stereochemistry
  2. Isomerism: Constitutional Isomers and Stereoisomers
  3. Enantiomers and Chiral Molecules
  4. Molecules Having One Chirality Center are Chiral
  5. More about the Biological Importance of Chirality
  6. How to Test for Chirality: Planes of Symmetry
  7. Naming Enantiomers: The ,-System
  8. Properties of Enantiomers: Optical Activity
  9. The Origin of Optical Activity
  10. The Synthesis of Chiral Molecules
  11. Chiral Drugs
  12. Molecules with More than One Chirality Center
  13. Fischer Projection Formulas
  14. Stereoisomerism of Cyclic Compounds
  15. Relating Configurations through Reactions in which No Bonds to the Chirality Center Are Broken
  16. Separation of Enantiomers: Resolution
  17. Compounds with Chirality Centers Other than Carbon
  18. Chiral Molecules That Do Not Possess a Chirality Center

6 Ionic Reactions

NUCLEOPHILIC SUBSTITUTION AND ELIMINATION REACTIONS OF ALKYL HALIDES

  1. Alkyl Halides
  2. Nucleophilic Substitution Reactions
  3. Nucleophiles
  4. Leaving Groups
  5. Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction
  6. A Mechanism for the SN2 Reaction
  7. Transition State Theory: Free-Energy Diagrams
  8. The Stereochemistry of SN2 Reactions
  9. The Reaction of -Butyl Chloride with Water: An SN1 Reaction
  10. A Mechanism for the SN1 Reaction
  11. Carbocations
  12. The Stereochemistry of SN1 Reactions
  13. Factors Affecting the Rates of SN1 and SN2 Reactions
  14. Organic Synthesis: Functional Group Transformations Using SN2 Reactions
  15. Elimination Reactions of Alkyl Halides
  16. The E2 Reaction
  17. The E1 Reaction
  18. How to Determine Whether Substitution or Elimination Is Favored
  19. Overall Summary

7 Alkenes and Alkynes I

PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES

  1. Introduction
  2. The ()–() System for Designating Alkene Diastereomers
  3. Relative Stabilities of Alkenes
  4. Cycloalkenes
  5. Synthesis of Alkenes via Elimination Reactions
  6. Dehydrohalogenation of Alkyl Halides
  7. Acid-Catalyzed Dehydration of Alcohols
  8. Carbocation Stability and the Occurrence of Molecular Rearrangements
  9. The Acidity of Terminal Alkynes
  10. Synthesis of Alkynes by Elimination Reactions
  11. Terminal Alkynes Can Be Converted to Nucleophiles for Carbon–Carbon Bond Formation
  12. Hydrogenation of Alkenes
  13. Hydrogenation: The Function of the Catalyst
  14. Hydrogenation of Alkynes
  15. An Introduction to Organic Synthesis

8 Alkenes and Alkynes II

ADDITION REACTIONS

  1. Addition Reactions of Alkenes
  2. Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikov’s Rule
  3. Stereochemistry of the Ionic Addition to an Alkene
  4. Addition of Water to Alkenes: Acid-Catalyzed Hydration
  5. Alcohols from Alkenes through Oxymercuration–Demercuration: Markovnikov Addition
  6. Alcohols from Alkenes through Hydroboration–Oxidation: Anti-Markovnikov Syn Hydration
  7. Hydroboration: Synthesis of Alkylboranes
  8. Oxidation and Hydrolysis of Alkylboranes
  9. Summary of Alkene Hydration Methods
  10. Protonolysis of Alkylboranes
  11. Electrophilic Addition of Bromine and Chlorine to Alkenes
  12. Stereospecific Reactions
  13. Halohydrin Formation
  14. Divalent Carbon Compounds: Carbenes
  15. Oxidation of Alkenes: Syn 1,2-Dihydroxylation
  16. Oxidative Cleavage of Alkenes
  17. Electrophilic Addition of Bromine and Chlorine to Alkynes
  18. Addition of Hydrogen Halides to Alkynes
  19. Oxidative Cleavage of Alkynes
  20. How to Plan a Synthesis: Some Approaches and Examples

9 Nuclear Magnetic Resonance and Mass Spectrometry

TOOLS FOR STRUCTURE DETERMINATION

  1. Introduction
  2. Nuclear Magnetic Resonance (NMR) Spectroscopy
  3. How to Interpret Proton NMR Spectra
  4. Nuclear Spin: The Origin of the Signal
  5. Detecting the Signal: Fourier Transform NMR Spectrometers
  6. The Chemical Shift
  7. Shielding and Deshielding of Protons
  8. Chemical Shift Equivalent and Nonequivalent Protons
  9. Signal Splitting: Spin–Spin Coupling
  10. Proton NMR Spectra and Rate Processes
  11. Carbon-13 NMR Spectroscopy
  12. Two-Dimensional (2D) NMR Techniques
  13. An Introduction to Mass Spectrometry
  14. Formation of Ions: Electron Impact Ionization
  15. Depicting the Molecular Ion
  16. Fragmentation
  17. Isotopes in Mass Spectra
  18. GC/MS Analysis
  19. Mass Spectrometry of Biomolecules

10 Radical Reactions

  1. Introduction: How Radicals Form and How They React
  2. Homolytic Bond Dissociation Energies
  3. Reactions of Alkanes with Halogens
  4. Chlorination of Methane: Mechanism of Reaction
  5. Halogenation of Higher Alkanes
  6. The Geometry of Alkyl Radicals
  7. Reactions That Generate Tetrahedral Chirality Centers
  8. Allylic Substitution and Allylic Radicals
  9. Benzylic Substitution and Benzylic Radicals
  10. Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide
  11. Radical Polymerization of Alkenes: Chain-Growth Polymers
  12. Other Important Radical Reactions

11 Alcohols and Ethers

SYNTHESIS AND REACTIONS

  1. Structure and Nomenclature
  2. Physical Properties of Alcohols and Ethers
  3. Important Alcohols and Ethers
  4. Synthesis of Alcohols from Alkenes
  5. Reactions of Alcohols
  6. Alcohols as Acids
  7. Conversion of Alcohols into Alkyl Halides
  8. Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides
  9. Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl2
  10. Tosylates, Mesylates, and Triflates: Leaving Group Derivatives of Alcohols
  11. Synthesis of Ethers
  12. Reactions of Ethers
  13. Epoxides
  14. Reactions of Epoxides
  15. Anti 1,2-Dihydroxylation of Alkenes via Epoxides
  16. Crown Ethers
  17. Summary of Reactions of Alkenes, Alcohols, and Ethers

12 Alcohols from Carbonyl Compounds

OXIDATION–REDUCTION AND ORGANOMETALLIC COMPOUNDS

  1. Structure of the Carbonyl Group
  2. Oxidation–Reduction Reactions in Organic Chemistry
  3. Alcohols by Reduction of Carbonyl Compounds
  4. Oxidation of Alcohols
  5. Organometallic Compounds
  6. Preparation of Organolithium and Organomagnesium Compounds
  7. Reactions of Organolithium and Organomagnesium Compounds
  8. Alcohols from Grignard Reagents
  9. Protecting Groups

13 Conjugated Unsaturated Systems

  1. Introduction
  2. The Stability of the Allyl Radical
  3. The Allyl Cation
  4. Resonance Theory Revisited
  5. Alkadienes and Polyunsaturated Hydrocarbons
  6. 1,3-Butadiene: Electron Delocalization
  7. The Stability of Conjugated Dienes
  8. Ultraviolet–Visible Spectroscopy
  9. Electrophilic Attack on Conjugated Dienes: 1,4-Addition
  10. The Diels–Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes

14 Aromatic Compounds

  1. The Discovery of Benzene
  2. Nomenclature of Benzene Derivatives
  3. Reactions of Benzene
  4. The Kekulé Structure for Benzene
  5. The Thermodynamic Stability of Benzene
  6. Modern Theories of the Structure of Benzene
  7. Hückel’s Rule: The 4n Plus 2 Electron Rule
  8. Other Aromatic Compounds
  9. Heterocyclic Aromatic Compounds
  10. Aromatic Compounds in Biochemistry
  11. Spectroscopy of Aromatic Compounds

15 Reactions of Aromatic Compounds

  1. Electrophilic Aromatic Substitution Reactions
  2. A General Mechanism for Electrophilic Aromatic Substitution
  3. Halogenation of Benzene
  4. Nitration of Benzene
  5. Sulfonation of Benzene
  6. Friedel–Crafts Alkylation
  7. Friedel–Crafts Acylation
  8. Limitations of Friedel–Crafts Reactions
  9. Synthetic Applications of Friedel–Crafts Acylations: The Clemmensen and Wolff–Kishner Reductions
  10. Substituents Can Affect Both the Reactivity of the Ring and the Orientation of the Incoming Group
  11. How Substituents Affect Electrophilic Aromatic Substitution: A Closer Look
  12. Reactions of the Side Chain of Alkylbenzenes
  13. Alkenylbenzenes
  14. Synthetic Applications
  15. Allylic and Benzylic Halides in Nucleophilic Substitution Reactions
  16. Reduction of Aromatic Compounds

16 Aldehydes and Ketones

NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP

  1. Introduction
  2. Nomenclature of Aldehydes and Ketones
  3. Physical Properties
  4. Synthesis of Aldehydes
  5. Synthesis of Ketones
  6. Nucleophilic Addition to the Carbon–Oxygen Double Bond
  7. The Addition of Alcohols: Hemiacetals and Acetals
  8. The Addition of Primary and Secondary Amines
  9. The Addition of Hydrogen Cyanide: Cyanohydrins
  10. The Addition of Ylides: The Wittig Reaction
  11. Oxidation of Aldehydes
  12. The Baeyer–Villiger Oxidation
  13. Chemical Analyses for Aldehydes and Ketones
  14. Spectroscopic Properties of Aldehydes and Ketones
  15. Summary of Aldehyde and Ketone Addition Reactions

17 Carboxylic Acids and Their Derivatives

NUCLEOPHILIC ADDITION–ELIMINATION AT THE ACYL CARBON

  1. Introduction
  2. Nomenclature and Physical Properties
  3. Preparation of Carboxylic Acids
  4. Acyl Substitution: Nucleophilic Addition–Elimination at the Acyl Carbon
  5. Acyl Chlorides
  6. Carboxylic Acid Anhydrides
  7. Esters
  8. Amides
  9. Derivatives of Carbonic Acid
  10. Decarboxylation of Carboxylic Acids
  11. Chemical Tests for Acyl Compounds
  12. Polyesters and Polyamides: Step-Growth Polymers
  13. Summary of the Reactions of Carboxylic Acids and Their Derivatives

18 Reactions at the A Carbon of Carbonyl Compounds

ENOLS AND ENOLATES

  1. The Acidity of the a Hydrogens of Carbonyl Compounds: Enolate Anions
  2. Keto and Enol Tautomers
  3. Reactions via Enols and Enolates
  4. Lithium Enolates
  5. Enolates of b-Dicarbonyl Compounds
  6. Synthesis of Methyl Ketones: The Acetoacetic Ester Synthesis
  7. Synthesis of Substituted Acetic Acids: The Malonic Ester Synthesis
  8. Further Reactions of Active Hydrogen Compounds
  9. Synthesis of Enamines: Stork Enamine Reactions
  10. Summary of Enolate Chemistry

19 Condensation and Conjugate Addition Reactions of Carbonyl Compounds

MORE CHEMISTRY OF ENOLATES

  1. Introduction
  2. The Claisen Condensation: A Synthesis of b-Keto Esters
  3. b-Dicarbonyl Compounds by Acylation of Ketone Enolates
  4. Aldol Reactions: Addition of Enolates and Enols to Aldehydes and Ketones
  5. Crossed Aldol Condensations
  6. Cyclizations via Aldol Condensations
  7. Additions to a,b-Unsaturated Aldehydes and Ketones
  8. The Mannich Reaction
  9. Summary of Important Reactions

20 Amines

  1. Nomenclature
  2. Physical Properties and Structure of Amines
  3. Basicity of Amines: Amine Salts
  4. Preparation of Amines
  5. Reactions of Amines
  6. Reactions of Amines with Nitrous Acid
  7. Replacement Reactions of Arenediazonium Salts
  8. Coupling Reactions of Arenediazonium Salts
  9. Reactions of Amines with Sulfonyl Chlorides
  10. Synthesis of Sulfa Drugs
  11. Analysis of Amines
  12. Eliminations Involving Ammonium Compounds
  13. Summary of Preparations and Reactions of Amines

21 Phenols and Aryl Halides

NUCLEOPHILIC AROMATIC SUBSTITUTION

  1. Structure and Nomenclature of Phenols
  2. Naturally Occurring Phenols
  3. Physical Properties of Phenols
  4. Synthesis of Phenols
  5. Reactions of Phenols as Acids
  6. Other Reactions of the OH Group of Phenols
  7. Cleavage of Alkyl Aryl Ethers
  8. Reactions of the Benzene Ring of Phenols
  9. The Claisen Rearrangement
  10. Quinones
  11. Aryl Halides and Nucleophilic Aromatic Substitution
  12. Spectroscopic Analysis of Phenols and Aryl Halides

22 Carbohydrates

  1. Introduction
  2. Monosaccharides
  3. Mutarotation
  4. Glycoside Formation
  5. Other Reactions of Monosaccharides
  6. Oxidation Reactions of Monosaccharides
  7. Reduction of Monosaccharides: Alditols
  8. Reactions of Monosaccharides with Phenylhydrazine: Osazones
  9. Synthesis and Degradation of Monosaccharides
  10. The D Family of Aldoses
  11. Fischer’s Proof of the Configuration of D-(+)-Glucose
  12. Disaccharides
  13. Polysaccharides
  14. Other Biologically Important Sugars
  15. Sugars That Contain Nitrogen
  16. Glycolipids and Glycoproteins of the Cell Surface: Cell Recognition and the Immune System
  17. Carbohydrate Antibiotics
  18. Summary of Reactions of Carbohydrates

23 Lipids

  1. Introduction
  2. Fatty Acids and Triacylglycerols
  3. Terpenes and Terpenoids
  4. Steroids
  5. Prostaglandins
  6. Phospholipids and Cell Membranes
  7. Waxes

24 Amino Acids and Proteins

  1. Introduction
  2. Amino Acids
  3. Synthesis of a-Amino Acids
  4. Polypeptides and Proteins
  5. Primary Structure of Polypeptides and Proteins
  6. Examples of Polypeptide and Protein Primary Structure
  7. Polypeptide and Protein Synthesis
  8. Secondary, Tertiary, and Quaternary Structures of Proteins
  9. Introduction to Enzymes
  10. Lysozyme: Mode of Action of an Enzyme
  11. Serine Proteases
  12. Hemoglobin: A Conjugated Protein
  13. Purification and Analysis of Polypeptides and Proteins

25 Nucleic Acids and Protein Synthesis

  1. Introduction
  2. Nucleotides and Nucleosides
  3. Laboratory Synthesis of Nucleosides and Nucleotides
  4. Deoxyribonucleic Acid: DNA
  5. RNA and Protein Synthesis
  6. Determining the Base Sequence of DNA: The Chain-Terminating (Dideoxynucleotide) Method
  7. Laboratory Synthesis of Oligonucleotides
  8. The Polymerase Chain Reaction
  9. Sequencing of the Human Genome: An Instruction Book for the Molecules of Life

ANSWERS TO SELECTED PROBLEMS A-1
GLOSSARY GL-1
INDEX I-1