Organic Chemistry I & II
Organic Chemistry I & II

Organic Chemistry I & II

Lead Author(s): Steven Forsey

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Organic Chemistry I & II is designed for instructors who want an active, dynamic, and understandable approach to support their own efforts in the classroom. This ever-evolving textbook includes auto-graded questions, videos and approachable language in order to make difficult concepts easier to understand and implement.

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Steven Forsey, “Organic Chemistry”, Only one edition needed

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Solomons et al., “Organic Chemistry”, 12th Edition

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David R. Klein, “Organic Chemistry”, 3rd Edition

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Pricing

Average price of textbook across most common format

Top Hat

Steven Forsey, “Organic Chemistry”, Only one edition needed

Up to 40-60% more affordable

Lifetime access on any device

McGraw-Hill

Carey & Giuliano, “Organic Chemistry”, 10th Edition

$219

Hardcover print text only

Wiley

Solomons et al., “Organic Chemistry”, 12th Edition

$301

Hardcover print text only

Wiley

David R. Klein, “Organic Chemistry”, 3rd Edition

$301

Hardcover print text only

Always up-to-date content, constantly revised by community of professors

Constantly revised and updated by a community of professors with the latest content

Top Hat

Steven Forsey, “Organic Chemistry”, Only one edition needed

McGraw-Hill

Carey & Giuliano, “Organic Chemistry”, 10th Edition

Wiley

Solomons et al., “Organic Chemistry”, 12th Edition

Wiley

David R. Klein, “Organic Chemistry”, 3rd Edition

In-book Interactivity

Includes embedded multi-media files and integrated software to enhance visual presentation of concepts directly in textbook

Top Hat

Steven Forsey, “Organic Chemistry”, Only one edition needed

McGraw-Hill

Carey & Giuliano, “Organic Chemistry”, 10th Edition

Wiley

Solomons et al., “Organic Chemistry”, 12th Edition

Wiley

David R. Klein, “Organic Chemistry”, 3rd Edition

Customizable

Ability to revise, adjust and adapt content to meet needs of course and instructor

Top Hat

Steven Forsey, “Organic Chemistry”, Only one edition needed

McGraw-Hill

Carey & Giuliano, “Organic Chemistry”, 10th Edition

Wiley

Solomons et al., “Organic Chemistry”, 12th Edition

Wiley

David R. Klein, “Organic Chemistry”, 3rd Edition

All-in-one Platform

Access to additional questions, test banks, and slides available within one platform

Top Hat

Steven Forsey, “Organic Chemistry”, Only one edition needed

McGraw-Hill

Carey & Giuliano, “Organic Chemistry”, 10th Edition

Wiley

Solomons et al., “Organic Chemistry”, 12th Edition

Wiley

David R. Klein, “Organic Chemistry”, 3rd Edition

About this textbook

Lead Authors

Dr. Steven Forsey, Ph.D.University of Waterloo

Steven Forsey is currently a Professor at University of Waterloo, teaching a variety of organic chemistry courses to Chemistry, Science, Chemical Engineering, Nanotechnology and distance education students. He received his Ph.D. (2004) for Synthetic Organic Chemistry from University of Waterloo, Ontario. He is a recipient of the Excellence of Science Teaching Award and has acted as the Teaching Fellow for the Department of Chemistry since 2016.

Contributing Authors

Felix NgassaGrand Valley State University

Neil GargUCLA

Jennifer ChaytorSaginaw Valley State University

Greg DomskiAugustana College

Christian E. MaduCollin Community College

Christopher NicholsonUniversity of West Florida

Franklin OwEast Los Angeles College, UCLA

Robert S. PhillipsUniversity of Georgia

Grigoriy SeredaUniversity of South Dakota

Simon E. LopezUniversity of Florida

Brannon McCulloughNorthern Arizona University

Jason JonesKennesaw State University

José BoquinAugustana College

Stephanie BrouetSaginaw Valley State University

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Version 5.1.3

Master Table of Contents

1.0 Introduction
1.1 Atomic Orbitals
1.2 Chemical Bonding
     
1.2.1 Ionic Bonding
     1.2.2 Covalent Bonding
          1.2.2A Valence Bond Theory
          1.2.2B Lewis Structures
          1.2.2C Bond-Line Drawings
          1.2.2D Valence Shell Electron Pair Repulsion (VSEPR) Theory
          1.2.2E Hybrid Orbital Theory
          1.2.2F Molecular Orbital Theory
          1.2.2G Resonance Structures
          1.2.2H Drawing Resonance Structures
          1.2.2I Evaluating the Relative Importance of Resonance Structures
          1.2.2J Drawing Resonance Structures via Pattern Recognition
          1.2.2K Localized vs. Delocalized Electrons
1.3 Intermolecular Forces
     1.3.1 Polarity
     1.3.2 Specific Intermolecular Forces
          1.3.2A Ion-Ion Forces
          1.3.2B Ion-Dipole Forces
          1.3.2C Hydrogen Bonding
          1.3.2D Dipole-Dipole Forces
          1.3.2E Induced Dipole-Induced Dipole (London Dispersion) Forces
     1.3.3 Physical Properties Affected by Intermolecular Forces
          1.3.3A Melting Point
          1.3.3B Boiling Point
          1.3.3C Miscibility and Solubility
          1.3.3D Hydrophilicity and Hydrophobicity
1.4 Chapter Summary


2.0 Introduction
2.1 Hydrocarbons
2.2 Alkanes
2.3 Branched Alkanes
2.4 Cyclic Alkanes
2.5 Bicyclic Compounds
2.6 Alkenes
     2.6.1 Classification of Alkenes
     2.6.2 Stereoisomers of Alkenes
2.7 Alkynes
2.8 Naming Hydrocarbons with Several Double or Triple Bonds
2.9 Functional Groups
2.10 Naming Complex Organic Compounds
2.11 Naming Alkyl Halides, Ethers and Alcohols
     2.11.1 Naming Alkyl Halides
     2.11.2 Naming Ethers
     2.11.3 Naming Alcohols
2.12 Naming Carbonyl Compounds
     2.12.1 Naming Aldehydes
     2.12.2 Naming Ketones
2.13 Naming Acyl Compounds
     2.13.1 Naming Carboxylic Acids
     2.13.2 Naming Esters
     2.13.3 Naming Amides
     2.13.4 Naming Acid Anhydrides
     2.13.5 Naming Acyl Halides
2.14 Naming Amines
2.15 Naming Nitriles
2.16 Acetyl Functional Group
2.17 Naming Organic Compounds with Multiple Functional Groups
2.18 Index of Hydrogen Deficiency (Degrees of Unsaturation)
   
2.18.1 Saturated and Unsaturated organic compounds and the Index of Hydrogen Deficiency (IHD)
   2.18.2 Heteroatoms and determining the index of hydrogen deficiency

3.1 Kinds of Organic Reactions
     3.1.1 Substitution Reactions
     3.1.2 Elimination Reactions
     3.1.3 Addition Reactions
3.2 Bond Breaking and Bond Making
     3.2.1 Bond Cleavage
     3.2.2 Bond Formation
3.3 Bond Dissociation Energy (BDE)
3.4 Thermodynamics
3.5 Enthalpy and Entropy
3.6 Energy Diagrams
     3.6.1 One-Step Reaction Mechanism
     3.6.2 Two-Step Reaction Mechanism
3.7 Kinetics
     3.7.1 Activation Energy
     3.7.2 Rate Equation
     3.7.3 Catalysts
3.8 Hammond Postulate
3.9 Kinetics vs. Thermodynamics
3.10 Nucleophiles and Electrophiles (Nucleophilic Sites and Electrophilic Sites)
3.11 Mechanisms and Arrow Pushing
Keeping it Real
3.12 Carbocation Rearrangements
3.13 Chapter Summary


4.0 Introduction
4.1 Acid-Base Equilibrium Reactions
     4.1.1 What Makes one Acid Stronger than the Other?
4.2 Factors that Affect Acid-Base Equilibrium
     4.2.1 Electronegativity
     4.2.2 Size of the Atom
     4.2.3 What is More Important: Electronegativity or Size?
     4.2.4 Inductive Effects
          4.2.4A Inductive Effects: The Nitro Group
     4.2.5 Solvation Effects
     4.2.6 Delocalization of Charge (Resonance)
     4.2.7 Delocalization of Charge onto the Nitro Group
4.3 Hybridization
4.4 Amines are Less Acidic than Alkynes
4.5 Bases
4.6 Amines
4.7 Hybridization
4.8 Electronegativity
4.9 Electron Donating and Solvent Effects
4.10 Resonance and Amides
4.11 Chapter Summary 


5.0 Introduction
5.1 Acyclic Alkanes
5.2 Conformational Analysis of Ethane
5.3 Conformational Analysis of Butane
5.4 Conformation Stability of Acyclic Alkanes
5.5 Conformations of Cyclohexanes
5.6 Visualizing the 3D Structure of Cyclohexane
5.7 Drawing Cyclohexane in a Chair Conformation
5.8 Conformations of Substituted Cyclohexanes and Potential Energy
5.9 More than one Substituent on Cyclohexane
5.10 Chapter Summary 


6.1 Overview of Isomers
     6.1.1 Structural or Constitutional Isomers
     6.1.2 Stereoisomers
6.2 Alkene E and Z System of Nomenclature
     6.2.1 What Happens if the Atoms at the Vinylic Positions are the Same?
     6.2.2 Double bonds and triple bonds and E, Z determination
6.3 Achiral Compounds and Planes of Symmetry
6.4 Chiral Molecules and Enantiomers
6.5 Nomenclature: The
R and S System Using the Cahn-Ingold-Prelog Convention
6.6 Shortcut for Determining
R or S if Lowest Priority is in the Front
6.7 Optical Activity
6.8 Racemic Mixture
6.9 Enantiomeric Excess and Racemic Mixture
6.10 Fischer Projections
6.11 Short Cut for Determining
R and S Configurations of Chiral Carbons in a Fisher Projection
6.12 Enantiomers and Diastereomers
6.13 How to Recognize Stereocenters
6.14 Meso Compounds
6.15 Chiral Molecules that do not have Chiral Molecules
6.16 Review
6.17 Chapter Summary


7.0 Introduction
7.1 Stereochemistry of the bimolecular nucleophilic substitution S
N2 reaction
7.2 Nucleophiles, electrophiles and the mechanisms
7.3 Factors that affect the rate of substitution reactions
 7.3.1 Introduction
 7.3.2 Nucleophilicity
 7.3.3 Leaving group
 7.3.4 Solvent Effects
7.4 Effects of electrophile structure
7.5 Review Questions
7.6 Chapter Summary 


8.0 Introduction to SN1 Reactions
8.1 Substitution Nucleophilic Unimolecular (S
N1)
 8.1.1 Stereochemistry of an SN1 reaction
8.2 Factors that Affect the Rate of the SN1 Reaction
 8.2.1 Introduction
 8.2.2 Leaving Group
 8.2.3 Solvent Effects
 8.2.4 How do you Relate Thermodynamic Stability with a Kinetic Rate?
 8.2.5 Solvolysis Reactions: The Solvent as the Nucleophile
 8.2.6 Mixed Solvent Reactions
 8.2.7 The Influence of Solvents on the Stereochemistry of the Products
8.3 Effect of Structure on the Rate of Reaction
 8.3.1 Electronic Effects
 8.3.2 Reactivity of Allylic, Benzylic, Vinyl, and Aryl Alkyl Halides
 8.3.3 Carbocation Rearrangement
8.4 How to Determine if a Reaction will Undergo an SN1 or an SN2 Mechanism (Hammond-Leffler Postulate)
 8.4.1 Step-by-Step Procedure for solving SN1and SN2 reactions
8.5 Chapter Summary


9.1 Definitions
9.2 Stability of Alkenes
9.3 E1 Reaction with Alkyl Halides

 9.3.1 Which Reaction Dominates with Alkyl Halides: the SN1 or the E1 reaction?
 9.3.2 Effect of Temperature
9.4 SN1/E1 Reactions, Regiochemistry, and Selectivity of E1 Products (Zaitsev’s
Rule)
9.5 Dehydration of Alcohols: the E1 Reaction Becomes Dominant
 9.5.1 Dehydration of Alcohols and Carbocation Rearrangements
 9.5.2 E1 Reactions and Stereochemistry
 9.5.3 SN1/E1 with Carbocation Rearrangement
9.6 Chapter Summary 


10.1 Definitions
10.2 Stability of Alkenes
10.3 E2 Reaction with Alkyl Halides
 10.3.1 E2: Zaitsev’s Rule and Regiochemistry
  10.3.1.1 Kinetics and the Rate of Product Formation
 10.3.2 E2: Anti-Coplanar Elimination and Stereospecific Reactions
  10.3.2.1 E2: Anti-Coplanar Elimination Orbital Explanation
 10.3.3 Cyclohexanes and E2, Diaxial Elimination
 10.3.4 Zaitsev’s Rule: Regiochemistry and Stereochemistry
 10.3.5 Hofmann Elimination: Bulky Bases and Regioselectivity
  10.3.5.1 Hofmann Elimination: Bulky and Poor Leaving groups and Regioselectivity
10.4 Kinetics vs Thermodynamics
10.5 Chapter Summary 


11.1 Definitions
11.2 Stability of Alkenes
11.3 Substitution/Elimination: Review of Reactions
 11.3.1 Review of SN2 Reactions
 11.3.2 Review: SN1 and SN1 vs SN2
 11.3.3 Review: SN1/E1
 11.3.4 Review: E2
11.4 Nucleophilicity vs Basicity
11.5 Two Halves to the Puzzle: You Need to Comprehend Both Before You Can Put the Puzzle Together
 11.5.1 First Half: Nucleophile or Base?
 11.5.2 Second Half: Electrophile, Hindered or Unhindered?
 11.5.3 A Guide to Solving Substitution/Elimination Questions
11.6 Substitution Reactions with Methyl Substrates
11.7 Substitution/Elimination with Primary Carbons
11.8 Substitution/Elimination with Secondary Carbons
11.9 Substitution/Elimination with Tertiary Carbons
11.10 Review Questions
11.11 Alcohols: S
N1 and SN2 Reactions
11.12 Chapter Summary 


12.1 Definitions
12.2 Carbocation Stability
 12.2.1 Hyperconjugation
 12.2.2 Adjacent Lone Pairs
 12.2.3 Adjacent π Bonds
 12.2.4 Inductive Effects
12.3 Hydrohalogenation: Addition of Hydrogen Halides
 12.3.1 General Reaction and Mechanism
 12.3.2 Hydrohalogenation: Regiochemistry and Markovnikov’s Rule
 12.3.3 Hydrohalogenation: Regiochemistry, Stereochemistry and Markovnikov’s Rule
 12.3.4 Hydrohalogenation: Carbocation Rearrangement
12.4 Hydration: Acid-catalyzed
12.5 Hydroboration-Oxidation of Alkenes to Produce Alcohols: Anti-Markovnikov’s Addition
 12.5.1 Reaction Overview: Regio- and Stereospecific Anti-Markovnikov’s Addition
 12.5.2 Hydroboration Mechanism
 12.5.3 Oxidation and Hydrolysis of Alkylboranes: Mechanism
12.6 Oxymercuration-Demercuration of Alkenes to Produce Alcohols: Markovnikov Addition
 12.6.1 Overview of Reaction: Regioselective and Stereospecific
 12.6.2 Oxymercuration-Demurcuration Mechanism
12.7 Halogenation. Electrophilic Addition of Bromine and Chlorine to Alkenes
 12.7.1 Overview of Reaction: Stereospecific
 12.7.2 Mechanism
12.8 Halohydrin Formation (Halogen + Alcohol) Regioselective and Stereospecific
 12.8.1 General Reaction
 12.8.2 Regioselective
12.9 Oxacyclopropane (Epoxide) Formation from Alkenes
 12.9.1 General Reaction
 12.9.2 Mechanism
 12.9.3 Stereospecific
12.10 Oxidation States of Carbon
 12.10.1 Overview
 12.10.2 Calculation of the Oxidation States
12.11 Hydrogenation of Alkenes: Stereospecific
 12.11.1 General Reaction
 12.11.2 Mechanism: Stereospecific
12.12 Syn Dihydroxylation: Oxidation with Osmium Tetroxide (OsO4) or Permanganate (KMnO4)
 12.12.1 General Reaction
 12.12.2 Mechanism: Stereospecific
12.13 Oxidative Cleavage: Ozonolysis
 12.13.1 General Reaction
 12.13.2 Mechanism
 12.13.3 Straight Forward Method to Answer Ozonolysis Questions
12.14 Anti-Markovnikov Addition of HBr with Peroxides: Regioselective
 12.14.1 General Reaction
 12.14.2 Free Radical Stability
 12.14.3 Mechanism: Regioselective
12.15 Chapter Summary 


13.1 Introduction
13.2 Structure and Bonding
13.3 Occurrence and Uses of Alkynes
13.4 Synthesis of Alkynes
 13.4.1 Using Acetylide Ions
 13.4.2 Elimination Reactions
13.5 Reactions of Alkynes
 13.5.1 Addition of Hydrogen Halides
 13.5.2 Addition of Halogens
 13.5.3 Reduction of Alkynes
 13.5.4 Hydration to Ketones and Aldehydes
 13.5.5 Oxidative Cleavage of Alkynes
13.6 Multistep Synthesis Using Alkynes
13.7 Chapter Summary 


14.1 Definitions
14.2 Carbocation Stability 

 14.2.1 Hyperconjugation
 14.2.2 Adjacent Lone Pairs
 14.2.3 Adjacent π Bonds
 14.2.4 Inductive Effects
14.3 Oxidation States of Carbon - Review from Chapter 12.10: Alkenes
 14.3.1 Calculation of the Oxidation States
14.4 Introduction to Alcohols
14.5 Synthesis of Alcohols

 14.5.1 Review: SN1, SN2, Acid-Catalyzed Hydration, Hydroboronation-Oxidation, Oxymercuration-Demercuration and Halohydrin Reactions
 14.5.2 Synthesis of Alcohols with the Grignard and Organolithium Reagents: Nucleophilic   Additions to Carbonyl Compounds
  14.5.2A Reaction with Carbonyl Groups to Form Alcohols
  14.5.2B Grignard and Organolithium Reagents as Strong Bases
  14.5.2C Limitations of Grignard and Organolithium Reagents
 14.5.3 Synthesis of Acetylenic Alcohols
 14.5.4 Alcohols by Reduction of Carbonyl Compounds with LiAlH4 and NaBH4
  14.5.4A Mechanism: Reduction of Aldehydes and Ketones with Sodium Borohydride
  14.5.4B Mechanism: Reduction of Aldehydes and Ketones with Lithium Aluminum Hydride
  14.5.4C Mechanism: Reduction of Esters and Carboxylic Acids with Lithium Aluminum Hydride
 14.5.5 Nucleophilic Ring-Opening of Oxiranes to Produce Alcohols
  14.5.5A Ring-Opening of an Asymmetrical Oxirane: Regioselective and Stereospecific
  14.5.5B Acid-Catalyzed Ring-Opening of Oxiranes to Produce Alcohols
  14.5.5C Acid-Catalyzed Ring-Opening of Asymmetrical Oxiranes: Regioselective and Stereospecific
  14.5.5D Ring-Opening of Oxiranes: Strong nucleophile Versus Acid-Catalyzed
14.6 Oxidation of Alcohols to Ketones and Carboxylic Acids
 14.6.1 Oxidation Mechanism
 14.6.2 Oxidation of Primary Alcohols to Aldehydes
14.7 Conversion of Alcohols into Better Leaving Groups
 14.7.1 SN2 and SN1 Reactions
 14.7.2 Phosphorus Halides (PBr3, P/I2, PCl3, PCl5)
 14.7.3 Thionyl Chloride (SOCl2)
 14.7.4 Sulfonates: Retention of Configuration
14.8 Dehydration of Alcohols
14.9 Chapter Summary 


15.1 Definitions
15.2 Carbocation Stability
15.3 Synthesis of Ethers
 15.3.1 Williamson Synthesis of Ethers
 15.3.2 Synthesis of Cyclic Ethers - Williamson Synthesis
15.4 Synthesis of Oxiranes (Epoxides)
 15.4.1 Williamson Synthesis with Halohydrins (Stereospecific)
 15.4.2 Synthesis of Oxiranes with Peroxycarboxylic Acids
15.5 Synthesis of Ethers by Oxymercuration-Demercuration
15.6 Protecting Groups for Alcohols
 15.6.1 Synthesis of tert-butyl Ethers by Alkylation of Alcohols
 15.6.2 Silyl Ether Protecting Groups
15.7 Reaction of Ethers
 15.7.1 Acidic Cleavage of Ethers
15.8 Nucleophilic Ring-Opening of Oxiranes
15.9 Chapter Summary 


16.1 Spectroscopy
16.2 Measurement of IR Spectra
16.3 Molecular Vibrations
 16.3.1 Characteristic Alcohols and Amines C-H Stretching Vibrations
 16.3.2 Characteristic C-H Stretching Vibrations
 16.3.3 Characteristic C=O Carbonyl Stretching Vibration
 16.3.4 Characteristic C-C Bonds and Nitriles C≡C
16.4 Analyzing the IR Spectrum
16.5 Mass Spectrometry
 16.5.1 High Resolution Mass Spectrometry
 16.5.2 Isotopic peaks
    16.5.3 Fragmentation in Mass Spectrometry
 16.5.3 Analyzing the Mass Spectrum
16.6 Chapter Summary


17.1 Introduction
 17.1.1 Theory of Nuclear Magnetic Resonance
17.2 Determining the Number of Signals: Sets of Equivalent Protons
 17.2.1 Aliphatic Hydrocarbons
 17.2.2 Cycloalkanes
 17.2.3 Alkenes
17.3 A Typical 1H-NMR Spectrum
 17.3.1 The Chemical Shift
  17.3.1.1 Diamagnetic Anisotropy
 17.3.2 Signal Intensity
 17.3.3 Splitting of Signals by Neighboring Sets of Protons
  17.3.3.1 Complex Splitting by Nonequivalent Sets of Protons
  17.3.3.2 Splitting by –OH, -NH, and Aryl Protons
17.4 13C-NMR Spectroscopy
 17.4.1 Determining the Number of Signals: Sets of Equivalent Carbons
 17.4.2 Chemical Shifts in 13C-NMR
 17.4.3 DEPT 13C-NMR Spectroscopy
17.5 Combined Spectroscopy Problems
17.6 Chapter Summary


18.1 Introduction
18.2 Homolysis and Bond Dissociation Energies
 18.2.1 Calculation of Heats of Reaction
 18.2.2 Bond Strength and Radical Stability
 18.2.3 Radicals Stabilized by Functional Groups
 18.2.4 Very Stable Radicals
 18.2.5 Radical Initiators
18.3 Radical Halogenation of Alkanes
 18.3.1 Chlorination of Methane and the Chain Reaction
 18.3.2 Selectivity of Halogenation Reactions
 18.3.3 Stereochemistry of Halogenation Reactions
 18.3.4 Benzylic Bromination
 18.3.5 Allylic Bromination
18.4 Addition of HBr to Alkenes with Peroxides
18.5 Chapter Summary


19.1 Introduction
 19.1.1 Classification of Dienes
 19.1.2 Preparation of Conjugated Dienes
 19.1.3 Bond Lengths
19.2 Stabilities of Conjugated Dienes
 19.2.1 Heats of Hydrogenation of Isolated vs Conjugated Dienes
 19.2.2 Conformation of Dienes
19.3 Molecular Orbital Picture of a Conjugated System
 19.3.1 MO Diagram of 1,3-butadiene
 19.3.2 MO Diagram of 1,3,5-hexatriene
19.4 Allylic Cations
 19.4.1 Definition
 19.4.2 Stability Relative to Other Carbocations
19.5 1,2- and 1,4-Addition to Conjugated Dienes
 19.5.1 The General Reaction
 19.5.2 The Mechanism
 19.5.3 Kinetic vs Thermodynamic Control in the Addition of HBr
19.6 Pericylic Reactions
19.7 The Diels-Alder Reaction

    19.7.1 The General Reaction and Mechanism
    19.7.2 Effect of the Dienes Conformation on the Rate of Reaction
    19.7.3 Effect of Substituents on the Rate of Reaction
    19.7.4 Stereochemistry of Diels-Alder Reactions
    19.7.5 The Endo and Exo Product
    19.7.6 Regiochemistry of Diels-Alder Reactions
    19.7.7 MO description of the Diels-Alder Reaction
         19.7.7.1 Overview
         19.7.7.2 Diels-Alder: Frontier Orbital Description
         19.7.7.3 FMO Explanation of the Substituent Effect
         19.7.7.4 FMO Explanation of the Endo Rule
     19.7.8 Photochemical [2+2] Cycloadditions
     19.7.9 Electrocyclic Reactions
         19.7.9.1 Stereochemistry of Thermal Electrocyclic Reactions
         19.7.9.2 Stereochemistry of Photochemical Electrocyclic Reactions
19.8 Ultraviolet-Visible (UV-Vis) Absorption Spectroscopy
 19.8.1 Absorption Spectroscopy and MO Theory
 19.8.2 Applications of Conjugated Systems
  19.8.2A Sunscreens
  19.8.2B Dyes
19.9 Chapter Summary


20.1 A Brief History of Benzene
20.2 Benzenes
 20.2.1 Nomenclature
 20.2.2 Physical Properties
20.3 Aromaticity
 20.3.1 Structure
 20.3.2 Stability
 20.3.3 Molecular Orbitals
 20.3.4 Huckel’s Rules
20.3.5 Annulenes
 20.3.5 Summary of Aromaticity
20.4 Other Aromatic Compounds
 20.4.1 Ions
 20.4.2 Heterocycles
 20.4.3 Benzenoids
20.5 Chapter Summary


21.1 Electrophilic Aromatic Substitution
 21.1.1 Halogenation of Benzene
 21.1.2 Nitration of Benzene
 21.1.3 Sulfonation of Benzene
 21.1.4 Friedel-Crafts Alkylation
 21.1.5 Friedel-Crafts Acylation
 21.1.6 Reactions Involving the Generation of Carbocation Intermediates
21.2 Disubstitution and Polysubstitution
 21.2.1 Effect Activating Groups: Ortho-Para Directors
 21.2.2 The Unusual Effect of Halogens: Ortho-Para Directors
 21.2.3 Effect of Deactivating Groups: Meta Directors
21.3 Electrophilic Aromatic Substitution on Disubstituted Benzenes
 21.3.1 Directing Effects Reinforce
 21.3.2 Directing Effects Oppose
 21.3.3 Effect of Crowding on Substitution
21.4 Nucleophilic Aromatic Substitution
 21.4.1 Elimination-Addition Mechanism (Benzyne Formation)
 21.4.2 Addition-Elimination Mechanism (SNAr Mechanism)
21.5 Reactions of Side Chains (Benzylic Position)
 21.5.1 Benzylic Halogenation
 21.5.2 Oxidation of Alkyl Benzenes
 21.5.3 Reduction of Ketones to Alkyl Benzenes
 21.5.4 Reduction of Nitro Groups to Amino Groups
 21.5.5 Hydrogenolysis of Benzyl Ethers
21.6 Aryl and vinyl cross-coupling reactions: Organocuprate reagents (Gilman), Heck reaction and Suzuki-Miyaura cross-coupling
21.7 Multistep Synthesis
21.8 Supplemental Material: Reactions with Aniline/Acetanilide and Phenol/Phenyl Acetate
21.9 Chapter Summary

22.1 Aldehydes and Ketones in Nature
22.2 Structure and Properties of Aldehydes and Ketones

 22.2.1 Bonding and Resonance in Carbonyls
 22.2.2 Physical Properties of Aldehydes and Ketones
22.3 Synthesis of Aldehydes and Ketones
 22.3.1 Synthesis from Alkenes (Review Section 12.13)
 22.3.2 Synthesis from Terminal Alkynes (Review Section 13.5.5)
 22.3.3 Synthesis from Aromatic Compounds (Review Section 21.1.5)
 22.3.4 Synthesis from Alcohols, Dess-Martin Periodinane (DMP) and Swern Oxidation (Review Section 14.6)
 22.3.5 Synthesis from Esters
 22.3.6 Synthesis from Nitriles
22.4 Nucleophilic Addition to Carbonyls
 22.4.1 General Mechanism of Nucleophilic Addition
 22.4.2 Reactivity of Aldehydes vs. Ketones Towards Nucleophilic Addition
 22.4.3 Nucleophilic Addition in Acidic Medium
 22.4.4 Nucleophilic Addition in Basic or Neutral Medium
22.5 Reactions of Aldehydes and Ketones
 22.5.1 Reduction to Alcohols (Review Section 14.4.5)
 22.5.2 Addition of Grignard Reagents (Review Chapter 14)
 22.5.3 Hydration of Ketones and Aldehydes
  22.5.3A Mechanism of Hydration of Ketones & Aldehydes under Acidic and Basic Conditions
 22.5.4 Cyanohydrin Formation
  22.5.4A Mechanism of Cyanohydrin Formation
 22.5.5 Acetal and Hemiacetal Formation
  22.5.5A Mechanism of Acetal Formation
  22.5.5B Cyclic Acetals
  22.5.5C Mechanism of Cyclic Acetal
  22.5.5D Anomeric effect
  22.5.5E Acetals as Protecting Groups
 22.5.6 Aldehyde Oxidations
  22.5.6A Tollen's Test
 22.5.7 Reactions with 1o amines
 22.5.8 Reactions with 2o amines
 22.5.9 Reduction to Alkanes
 22.5.10 Wittig Reaction
  22.5.10A Mechanism of Wittig
 22.5.11 Conjugate Addition
22.6 Summary of Key Reactions

23.1 Introduction
23.2 Biologically Important Amines
23.3 Basicity of Amines
23.4 Synthesis of Amines

 23.4.1 Reductive Amination
 23.4.2 Alkylation of Ammonia
 23.4.3 Gabriel Synthesis of 1° Amines
 23.4.4 Formation and Reduction of Azides and Nitriles
23.5 Reactions of Amines
 23.5.1 Reactions of Heterocyclic Amines
 23.5.2 Hofmann Elimination
 23.5.3 Cope Elimination
 23.5.4 Reactions with Acid Chlorides
 23.5.5 Reactions with Sulfonyl Chlorides
 23.5.6 Reactions with Nitrous Acid
 23.5.7 Reactions with Arene Diazonium Salts
23.6 Chapter Summary


24.1 Introduction
 24.1.1 Nomenclature of Carboxylic Acids
24.2 Commercial Sources of Carboxylic Acids
24.3 Synthesis of Carboxylic Acids

 24.3.1 Oxidation of Aldehydes and Primary Alcohols (Chapter 14.6)
 24.3.2 Oxidation of Alkynes to Give Carboxylic Acids (Chapter 13.5.6)
 24.3.3 Oxidation of Alkylbenzenes (Detailed mechanism in Chapter 21.5.2)
 24.3.4 Hydrolysis of Nitriles (Detailed mechanism in Chapter 25.2.7)
 24.3.5 Carboxylation of Grignard Reagents or Alkyllithium (Review of Grignard reaction,  Chapter 14.5.2)
24.4 Reaction of Carboxylic Acids: Nucleophilic Acyl Substitution (Chapter 25.1)
 24.4.1 Reactions of Carboxylic Acids
24.5 Condensation of Carboxylic Acids with Alcohols: The Fischer Esterification (Chapter 25.1.3)
24.6 Esterification Using Diazomethane
24.7 Condensation of Carboxylic Acid with Amines
24.8 Reduction of Carboxylic Acids (Detailed mechanism in Chapter 25.3.2)

 24.8.1 Lithium Aluminum Hydride Reduction of Carboxylic Acids (Detailed mechanism in Chapter 25.3.2)
 24.8.2 Borane Reduction of Carboxylic Acid
24.9 Alkylation of Carboxylic Acids to Form Ketones (Chapter 25.3.1)
24.10 Synthesis and Use of Acid Chloride (Chapter 25.2.2)

 24.10.1 Synthesis of Acid Chlorides
 24.10.2 Uses of Acid Chlorides
24.11 Summary of Reactions


25.1 Nucleophilic Acyl Substitution
 25.1.1 Leaving Group at the Carbonyl: Consequesnces for the Reaction with Nucleophiles
 25.1.2 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution
 25.1.3 Transesterification
 25.1.4 Hydrolysis of Carboxylic Acid Derivatives
25.2 Reactivity of Carboxylic Acid Derivatives
 25.2.1 Structure-Reactivity Relationship of Carboxylic Acid Derivatives
 25.2.2 Acid Chlorides: Preparation and Nucleophilic Acyl Substitution
 25.2.3 Nucleophilic Acid Substitution in Anhydrides
 25.2.4 Nucleophilic Acid Substitution in Esters
 25.2.5 Nucleophilic Acid Substitution in Thioesters and Derivatives of Similar Reactivity
 25.2.6 Preparation of Nitriles
 25.2.7 Hydrolysis of Amides
 25.2.8 Nucleophilic Acid Substitution in Nitriles and Carboxylates
 25.2.9 Reduction of Carboxylic Acid Derivatives by Electrophiic Reagents
25.3 Reactions of Carboxylic Acid Derivatives with Two Equivalents of a Nucleophile
 25.3.1 Reactions of Carboxylic Acid Derivatives with Organometallic Reagents
 25.3.2 Reduction of Carboxylic Acid Derivatives
25.4 Structure-Reactivity Relationship of Carboxylic Acid Derivatives: An Advanced Treatment
25.5 Reaction Review
25.6 Derivatives of Carbonic Acid


26.1 Reactions of Enols and Enolate Ions
 26.1.1 Keto-Enol Tautomerism
 26.1.2 Alkylation of Enolate Ions
 26.1.3 Formation and Alkylation of Enamines
 26.1.4 Alpha Halogenation of Ketones
 26.1.5 Bromination of Acids: HVZ Reaction
26.2 The Aldol Reactions of Ketones and Aldehydes
 26.2.1 Mechanism of Aldol Reaction and Variations of Aldol Products
 26.2.2 Crossed Aldol Condensation and Aldol Cyclizations
 26.2.3 Planning Synthesis Using Aldol Condensations
26.3 The Claisen Ester Condensation
 26.3.1 Mechanism of Claisen Condensation
 26.3.2 Crossed Claisen Condensation
 26.3.3 The Dieckmann Condensation: A Claisen Cyclization
26.4 Syntheses Using β-Dicarbonyl Compounds
 26.4.1 The Malonic Ester Synthesis
 26.4.2 The Acetoacetic Ester Synthesis
26.5 The Michael Reaction
 26.5.1 Nucleophilic Versus Electrophilic Conjugate Addition
 26.5.2 The Robinson Annulation
26.6 Chapter Summary


27.1 Introduction to Synthetic Polymers
27.2 Polymer Nomenclature

 27.2.1 Naming Vinyl Polymers
 27.2.2 Naming Non-Vinyl Polymers
27.3 Classification of Polymers
 27.3.1 Classifications Based on Molecular Structure 
  27.3.1.1 Homopolymers and Copolymers
  27.3.1.2 Classification According to Functional Groups
   27.3.1.2.1 Vinyl Polymers
   27.3.1.2.2 Non-Vinyl Polymers 
    27.3.1.2.2.1 Polyethers
    27.3.1.2.2.2 Polyesters
    27.3.1.2.2.3 Polycarbonates
    27.3.1.2.2.4 Polyamides
    27.3.1.2.2.5 Polyurethanes 
  27.3.1.3 Classification According toPolymer Formation Mechanism
   27.3.1.3.1 Chain Growth (Addition) Polymerization   
    27.3.1.3.1.1 Radical Polymerization
Keeping it Real
    27.3.1.3.1.2 Cationic Polymerization   
    27.3.1.3.1.3 Anionic Polymerization
Keeping it Real
    27.3.1.3.1.4 Coordination-Insertion Polymerization
   27.3.1.3.2 Step-Growth (Condensation) Polymerization
    27.3.1.3.2.1 Polyethers
    27.3.1.3.2.2 Polyesters
    27.3.1.3.2.3 Polycarbonates
    27.3.1.3.2.4 Polyamides
    27.3.1.3.2.5 Polyurethanes
 27.3.4 Industrial Classifications
  27.3.4.1 Plastics
  27.3.4.2 Fibers
  27.3.4.3 Elastomers
  27.3.4.4 Coatings and Adhesives
27.4 Physical Properties of Polymers
 27.4.1 Thermal Properties of Polymers
 27.4.2 Mechanical Properties
 27.4.3 Factors Affecting the Physical Properties of Polymers
  27.4.3.1 Molecular Weight/Chain Length
  27.4.3.2 Intermolecular Forces
  27.4.3.3 Stereochemical Configuration
  27.4.3.4 Polymer Branching
27.5 Polymer Recycling
 27.5.1 Polymer Recycling Codes
 27.5.2 Methods of Polymer Recycling
  27.5.2.1 Reuse
  27.5.2.2 Depolymerization
  27.5.2.3 Biodegradable Polymers


28.0 Introduction
 28.0.1 Water
 28.0.2 Polymerization
28.1 Carbohydrates
 28.1.1 Classification
 28.1.2 Stereochemistry (Review Chapter 6: Stereochemistry)
 28.1.3 Anomers and Glycosides
28.2 Lipids
 28.2.1 Triacylglycerols, fatty acids, and phospholipids
 28.2.2 Eicosanoids, Terpenoids, and Steroids
28.3 Amino Acids, Peptides, and Proteins
 28.3.1 Amino Acid Structure
 28.3.2 Isoelectric Points
28.4 Nucleic Acids
 28.4.1 Nucleotide Structure
     28.4.1 Base Pairing