Organic Chemistry - Rilegato

Francis A. Carey is a native of Pennsylvania, educated in the public schools of Philadelphia, at Drexel University (B.S. in chemistry, 1959), and at Penn State (Ph.D. 1963). Following postdoctoral work at Harvard and military service, he was appointed to the chemistry faculty of the University of Virginia in 1966. Prior to retiring in 2000, he regularly taught the two-semester lecture courses in general chemistry and organic chemistry.  With his students, Professor Carey has published over forty research papers in synthetic and mechanistic organic chemistry. In addition to this text, he is coauthor (with Robert C. Atkins) of Organic Chemistry: A Brief Course and (with Richard J. Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates. He was a member of the Committee of Examiners of The Graduate Record Examination in Chemistry from 1993-2000.  Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava.

Chapter 1 - Structure Determines Properties

1.1 Atoms, Electrons, and Orbitals

1.2 Ionic Bonds

1.3 Covalent Bonds, Lewis Structures, and the Ocelet Rule

1.4 Double Bonds and Triple Bonds

1.5 Polar Covalent Bonds and Electronegativity

Electrostatic Potential Maps

1.6 Structural Formuala of Organic Molecules

1.7 Formal Charge

1.8 Resonance

1.9 The Shape of Some Simple Molecules

Molecular Modeling

1.10 Molecular Dipole Moments

1.11 Curved Arrows and Chemical Reactions

1.12 Acids and Bases: The Arrhenius View

1.13 Acids and Bases: The Brønsted-Lowry View

1.14 What Happened to pKb?

1.15 How Structure Affects Acid Strength

1.16 Acid-Base Equilibria

1.17 Lewis Acids and Lewis Bases

1.18 Summary

Problems

Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures.

Chapter 2 - Alkanes and Cycloakanes: Introduction to Hydrocarbons

2.1 Classes of Hydrocarbons

2.2 Electron Waves and Chemical Bonds

2.3 Bonding in H2: The Valence Bond Model

2.4 Bonding in H2: The Molecular Orbital Model

2.5 Introduction to Alkanes: Methane, Ethane, and Propane

Methane and the Biosphere

2.6 sp3 Hybridization and Bonding in Methane

2.7 Bonding in Ethane

2.8 Isomeric Alkanes: The Butanes

2.9 Higher n -Alkanes

2.10 The C5H12 Isomers

2.11 IUPAC Nomenclature of Unbranched Alkanes

What's in a Name? Organic Nonmenclature

2.12 Applying the IUPAC Rules: The Names of the C6H14 Isomers

2.13 Alkyl Groups

2.14 IUPAC Names of Highly Branched Alkanes

2.15 Cycloalkane Nomenclature

2.16 Sources of Alkanes and Cycloalkanes

2.17 Physical Properties of Alkanes and Cycloalkanes

2.18 Chemical Properties. Combustion of Alkanes

2.19 Oxidation-Reduction in Organic Chemistry

Thermochemistry

2.20 sp2 Hybridization and Bonding in Ethylene

2.21 sp Hybridization and Bonding in Acetylene

2.22 Which Theory of Chemical Bonding is Best?

2.23 Summary

Problems

Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes

Chapter 3 - Alkanes andCycloalkanes: Conformations and cis-trans Stereoisomers

3.1 Conformational Analysis of Ethane

3.2 Conformational Analysis of Butane

Molecular Mechanics Applied to Alkanes and Cycloalkanes

3.3 Conformations of Higher Alkanes

3.4 The Shapes of Cycloalkanes: Planar or Nonplanar

3.5 Small Rings: Cyclopropane and Cyclobutane

3.6 Cyclopentane

3.7 Conformations of Cyclohexane

3.8 Axial and Equatorial Bonds in Cyclohexane

3.9 Conformational Inversion (Ring Flipping) in Cyclohexane

3.10 Conformational Analysis of Monosubstituted Cyclohexanes

3.11 Disubstituted Cycloalkanes. Stereoisomers

Enthalpy, Free Energy, and Equilibrium Constant

3.12 Conformational Analysis of Disubstituted Cyclohexanes

3.13 Medium and Large Rings

3.14 Polycyclic Ring Systems

3.15 Heterocyclic Compounds

3.16 Summary

Problems

Descriptive Passage and Interpretive Problems 3: Cylic Forms of Carbohydrates

Chapter 4 - Alcohols and Alkyl Halides

4.1 Functional Groups

4.2 IUPAC Nomenclature of Alkyl Halides

4.3 IUPAC Nomenclature of Alcohols

4.4 Classes of Alcohols and Alkyl Halides

4.5 Bonding in Alcohols and Alkyl Halides

4.6 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces

4.7 Preparation of Alkyl Halides From Alcohols and Hydrogen Halides

4.8 Mechanism of the Reaction of Alcohols with Hydrogen Halides

4.9 Potential Energy Diagrams for Multistep Reactions. The SN1 Mechanism

4.10 Structure, Bonding, and Stability of Carbocations

4.11 Effect of Alcohol Structure on Reaction Rate

4.12 Reaction of Primary Alcohols with Hydrogen Halides. The SN2 Mechanism

4.13 Other Methods for Converting Alcohols to Alkyl Halides

4.14 Halogenation of Alkanes

4.15 Chlorination of Methane

4.16 Structure and Stability of Free Radicals

4.17 Mechanism of Methane Chlorination

4.18 Halogenation of Higher Alkanes

From Bond Enthalpies to Heats of Reaction

4.19 Summary

Problems

Descriptive Passage and Interpretive Problems 4: More About Potential Energy Diagrams

Chapter 5 - Structure and Preparation of Alkenes: Elimination Reactions

5.1 Alkene Nomenclature

5.2 Structure and Bonding in Alkenes

Ethylene

5.3 Isomerism in Alkenes

5.4 Naming Stereoisomeric Alkenes by the E-Z Notational System

5.5 Physical Properties on Alkenes

5.6 Relative Stabilities of Alkenes

5.7 Cycloalkenes

5.8 Preparations of Alkenes: Elimination Reactions

5.9 Dehydration of Alcohols

5.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule

5.11 Stereoselectivity in Alcohol Dehydration

5.12 The E1 and E2 Mechanisms of Alcohol Dehydration

5.13 Rearrangements in Alcohol Dehydration

5.14 Dehydrohalogenation of Alkyl Halides

5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides

5.16 Anti Elimination in E2 Reactions: Stereoelectronic Effects

5.17 Isotope Effects and the E2 Mechanism

5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides

5.19 Summary

Problems

Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions

Chapter 6 - Reactions of Alkenes

6.1 Hydrogenation of Alkenes

6.2 Heats of Hydrogenation

6.3 Stereochemistry of Alkene Hydrogenation

6.4 Electrophilic Addition of Hydrogen Halides to Alkenes

6.5 Regioselectivity of Hydrogen Halide Addition: Markovnikov's Rule

6.6 Mechanistic Basis for Markovnikov's Rule

Rules, Laws, Theories, and the Scientific Method

6.7 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes

6.8 Free-Radical Addition of Hydrogen Bromide to Alkenes

6.9 Addition of Sulfuric Acid to Alkenes

6.10 Acid-Catalyzed Hydration of Alkenes

6.11 Thermodynamics of Addition - Elimination Equilibria

6.12 Hydroboration-Oxidation of Alkenes

6.13 Stereochemistry of Hydroboration-Oxidation

6.14 Mechanism of Hydroboration-Oxidation

6.15 Addition of Halogens to Alkenes

6.16 Stereochemistry of Halogen Addition

6.17 Mechanism of Halogen Addition to Alkenes: Halonium Ions

6.18 Conversion of Alkenes to Vicinal Halohydrins

6.19 Epoxidation of Alkenes

6.20 Ozonolysis of Alkenes

6.21 Introduction to Organic Chemical Synthesis

6.22 Reactions of Alkenes with Alkenes: Polymerization

Ethylene and Propane: The Most Important Industrial Organic Chemicals

6.23 Summary

Problems

Descriptive Passage and Interpretive Problems 6: Some Unusual Electrophilic Additions

Chapter 7 - Stereochemistry

7.1 Molecular Chirality: Enantiomers

7.2 The Chirality Center

7.3 Symmetry in Achiral Structures

7.4 Optical Activity

7.5 Absolute and Relative Configuration

7.6 The Cahn-Ingold-Prelog R-S Notation System

7.7 Fischer Projections

7.8 Properties of Enantiomers

Chiral Drugs

7.9 Reactions That Create a Chirality Center

7.10 Chiral Molecules With Two Chirality Centers

7.11 Achiral Molecules With Two Chirality Centers

7.12 Molecules With Multiple Chirality Centers

Chirality of Disubstituted Cyclohexanes

7.13 Reactions That Produce Diastereomers

7.14 Resolution of Enantiomers

7.15 Stereoregular Polymers

7.16 Chirality Centers Other Than Carbon

7.17 Summary

Problems

Descriptive Passage and Interpretive Problems 7: Prochirality

Chapter 8 - Nucleophilic Substitution

8.1 Functional Group Transformation by Nucleophilic Substitution

8.2 Relative Reactivity of Halide Leaving Groups

8.3 The SN2 Mechanism of Nucleophilic Substitution

8.4 Steric Effects and SN2 Reaction Rates

8.5 Nucleophiles and Nucleophilicity

8.6 The SN1 Mechanism of Nucleophilic Substitution

Enzyme-Catalyzed Nucleophilic Substitution of Alkyl Halides

8.7 Carbocation Stability and SN1 Reaction Rates

8.8 Stereochemistry of SN1 Reactions

8.9 Carbocation Rearrangements in SN1 Reactions

8.10 Effect of Solvent on the Rate of Nucleophilic Substitution

8.11 Substitution and Elimination as Competing Reactions

8.12 Nucleophilic Substitution of Alkyl Sulfonates

8.13 Looking Back: Reactions of Alcohols with Hydrogen Halides

8.14 Summary

Problems

Descriptive Passage and Interpretive Problems 8: Nucleophilic Substitution

Chapter 9 - Alkynes

9.1 Sources of Alkynes

9.2 Nomenclature

9.3 Physical Properties of Alkynes

9.4 Structure and Bonding in Alkynes: sp Hybridization

9.5 Acidity of Acetylene and Terminal Alkynes

9.6 Preparation of Alkynes by Alkylation of Acetylene and Terminal Alkynes

9.7 Preparation of Alkynes by Elimination Reactions

9.8 Reactions of Alkynes

9.9 Hydrogenation of Alkynes

9.10 Metal-Ammonia Reduction of Alkynes

9.11 Addition of Hydrogen Halides to Alkynes

9.12 Hydration of Alkynes

9.13 Addition of Halogens to Alkynes

Some Things That Can Be Made From Acetylene...But Aren't

9.14 Ozonolysis of Alkynes

9.15 Summary

Problems

Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes

Chapter 10 - Conjugation in alkadienes and Allylic Systems