Organic Chemistry

Structure, Mechanism, and Synthesis

1st Edition - June 6, 2014
Imprint: Elsevier
Authors: Robert J. Ouellette, J. David Rawn
Language: English
eBook ISBN:
9 7 8 - 0 - 1 2 - 8 0 1 0 8 2 - 2

Organic Chemistry provides a comprehensive discussion of the basic principles of organic chemistry in their relation to a host of other fields in both physical and biologica… Read more

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Organic Chemistry provides a comprehensive discussion of the basic principles of organic chemistry in their relation to a host of other fields in both physical and biological sciences. This book is written based on the premise that there are no shortcuts in organic chemistry, and that understanding and mastery cannot be achieved without devoting adequate time and attention to the theories and concepts of the discipline. It lays emphasis on connecting the basic principles of organic chemistry to real world challenges that require analysis, not just recall.

This text covers topics ranging from structure and bonding in organic compounds to functional groups and their properties; identification of functional groups by infrared spectroscopy; organic reaction mechanisms; structures and reactions of alkanes and cycloalkanes; nucleophilic substitution and elimination reactions; conjugated alkenes and allylic systems; electrophilic aromatic substitution; carboxylic acids; and synthetic polymers. Throughout the book, principles logically evolve from one to the next, from the simplest to the most complex examples, with abundant connections between the text and real world applications. There are extensive examples of biological relevance, along with a chapter on organometallic chemistry not found in other standard references.

This book will be of interest to chemists, life scientists, food scientists, pharmacists, and students in the physical and life sciences.

1: Structure and Bonding in Organic Compounds

1.1 Brief Review of Atomic Structure
1.2 Atomic Properties
1.3 Ionic and Covalent Bonds
1.4 Strategies for Writing Lewis Structures
1.5 Formal Charge
1.6 Molecular Geometry
1.7 Resonance Structures
1.8 Valence Shell Electron Pair Repulsion Theory
1.9 Dipole Moments
1.10 Molecular Orbital Theory
1.11 The Hydrogen Molecule
1.12 Bonding in Carbon Compounds
1.13 sp³ Hybridization of Carbon in Methane
1.14 sp³ Hybridization of Carbon in Ethane
1.15 sp² Hybridization of Carbon in Ethene
1.16 sp Hybridization of Carbon in Ethyne
1.17 Effect of Hybridization on Bond Length and Bond Strength
1.18 Hybridization of Nitrogen
1.19 Hybridization of Oxygen
Exercises

2: Part I: Functional Groups and Their Properties

2.1 Introduction to Functional Groups: Hydrocarbons and Haloalkanes
2.2 Functional Groups that Contain Oxygen
2.3 Functional Groups that Contain Nitrogen
2.4 Functional Groups that Contain Sulfur
2.5 Structural Formulas
2.6 Bond-Line Structures
2.7 Isomers
Part II: Identification of Functional Groups by Infrared Spectroscopy
2.8 Spectroscopy
2.9 Infrared Spectroscopy
2.10 Identifying Hydrocarbons
2.11 Identifying Oxygen-Containing Compounds
2.12 Identifying Nitrogen-Containing Compounds
2.13 Bending Deformations
End-of-Chapter Exercises

3: Introduction to Organic Reaction Mechanisms

3.1 Acid–Base reaction
3.2 Chemical Equilibrium and Equilibrium Constants
3.3 pH and pK Values
3.4 Effect of Structure on Acidity
3.5 Standard Free Energy Changes in Chemical Reactions
3.6 Enthalpy Changes in Chemical Reactions
3.7 Bond Dissociation Energies
3.8 Introduction to Reaction Mechanisms
3.9 Structures and Stabilities Of Carbon Radicals, Carbocations, and Carbanions
3.10 Factors that influence reaction rates
3.11 Reaction Rate Theory
3.12 Stability and reactivity
End-of-Chapter Exercises

4: Alkanes and Cycloalkanes: Structures and Reactions

4.1 Classes of Hydrocarbons
4.2 Alkanes
4.3 Nomenclature of Alkanes
4.4 Conformation of Alkanes
4.5 Cycloalkanes
4.6 Conformations of cycloalkanes
4.7 Conformational Mobility of cyclohexane
4.8 Monosubstituted Cyclohexanes
4.9 Disubstituted Cyclohexanes
4.10 Polycyclic Molecules
4.11 Physical Properties of Alkanes
4.12 Stabilities of Alkyl Radicals
4.13 Chlorination of an Alkane–A Radical Reaction
Exercises

5: Alkenes Structures and Properties

5.1 Alkenes
5.2 Structure and Bonding of Alkenes
5.3 Unsaturation Number
5.4 Geometric Isomerism
5.5 E,Z Nomenclature of Geometrical Isomers
5.6 Nomenclature of Alkenes
5.7 Physical Properties of Alkenes
5.8 Stability of Alkenes
5.9 Reduction of Alkenes
5.10 Mechanism of Catalytic Hydrogenation
5.11 Heats of hydrogenation of alkenes
Exercise

6: Alkenes: Addition Reactions

6.1 Characteristics of Addition Reactions
6.2 Addition of Hydrogen Halides to Alkenes
6.3 The Mechanistic Basis of Markovnikov's Rule
6.4 Carbocation Rearrangement Reactions
6.5 Hydration of Alkenes
6.6 Addition of Halogens
6.7 Addition of Carbenes
6.8 Epoxidation of Alkenes
6.9 Dihydroxylatin of Alkenes
6.10 Ozonolysis of Alkenes
Exercises

7: Alkynes

7.1 Occurrence and Uses of Alkynes
7.2 Structure and Properties of Alkynes
7.3 IUPAC Names of Alkynes
7.4 Acidity of Terminal Alkynes
7.5 Hydrogenation of Alkynes
7.6 Electrophilic Addition Reactions
7.7 Synthesis of Alkynes
Exercises

8: Stereochemistry

8.1 Stereoisomers
8.2 Mirror Image Objects, Mirror Image Molecules, and Chirality
8.3 Optical Activity
8.4 Fischer Projection Formulas
8.5 Absolute Configuration
8.6 Molecules with Two (or More) Stereogenic Centers
8.7 Cyclic Molecules with Stereogenic Centers
8.8 Separation of Enantiomers
8.9 Chemical Reactions at Stereogenic Centers
8.10 Reactions that Produce Stereogenic Centers
8.11 Reactions that Form Diastereomers
8.12 Prochiral Centers
Exercises

9: Haloalkanes and Alcohols: Introduction to Nucleophilic Substitution and Elimination Reactions

9.1 Functionalized Hydrocarbons
9.2 Nomenclature of Haloalkanes
9.3 Nomenclature of Alcohols
9.4 Structure and Properties of Haloalkanes
9.5 Structure and Properties of Alcohols
9.6 Organometallic Compounds
9.7 Reactions of Haloalkanes
9.8 Nucleophilic Substitution Reactions of Haloalkanes
9.9 Mechanisms of Nucleophilic Substitution Reactions of Haloalkanes
9.10 Reactions of Alcohols
9.11 Acid–Base Reactions of Alcohols
9.12 Substitution Reactions of Alcohols
9.13 Alternate Methods for the Synthesis of Alkyl Halides
9.14 Elimination Reactions
9.15 Regioselectivity in Dehydrohalogenation
9.16 Mechanisms of Dehydrohalogenation Reactions
9.17 Regioselectivity in Dehydration Reactions
Exercises

10: Nucleophilic Substitution and Elimination Reactions

10.1 Properties of Nucleophiles
10.2 Biological S_N2 Reactions Bysulfur-Containing Nucleophiles
10.3 Stereochemistry of Nucleophilic Substitution Reactions
10.4 S_N1 Versus S_N2 Reactions
10.5 Mechanisms of Elimination Reactions
10.6 Effects of Structure on Competing Substitution and Elimination Reactions
Exercises

11: Conjugated Alkenes and Allylic Systems

11.1 Classes of Dienes
11.2 Stability of Conjugated Dienes
11.3 Molecular Orbitals of Ethene and 1,3-Butadiene
11.4 Structural Effects of Conjugation in 1,3-Butadiene
11.5 Allylic Systems
11.6 Hückel Molecular Orbitals of Allyl Systems
11.7 Electrophilic Addition to Conjugated Dienes
11.8 The Diels-Alder Reaction
11.9 The Electromagnetic Spectrum
11.10 Ultraviolet-Visible Spectroscopy of Alkenes and Conjugated Systems
Exercises

12: Arenes and Aromaticity

12.1 Aromatic Compounds
12.2 The Covalent Structure of Benzene
12.3 The Hückel Rule
12.4 Molecular Orbitals of Aromatic and Antiaromatic Compounds
12.5 Heterocyclic Aromatic Compounds
12.6 Polycyclic Aromatic Compounds
Exercises

13: Electrophilic Aromatic Substitution

13.1 Nomenclature of Benzene Derivatives
13.2 Mechanism of Electrophilic Aromatic Substitution
13.3 Common Electrophilic Aromatic Substitution Reactions
13.4 Substituent Effects on the Reactivity of Benzene Rings
13.5 Interpretation of the Effect of Substituents on Reaction Rates
13.6 Interpretation of Directing Effects
13.7 Functional Group Modification
13.8 Synthesis of Substituted Aromatic Compounds
Exercises

14: Methods for Structure Determination Nuclear Magnetic Resonance and Mass Spectrometry

14.1 structure determination
14.2 Nuclear Magnetic Resonance Spectroscopy
14.3 The Chemical Shift
14.4 Detecting Sets of Nonequivalent Hydrogen Atoms
14.5 Effects of Structure on Chemical Shift
14.6 Relative Peak Areas and Proton Counting
14.7 Spin–Spin Splitting
14.8 Effect of Structure on Coupling Constants
14.9 Effect of Dynamic Processes
14.10 Carbon-13 NMR Spectroscopy
14.11 Introduction to Mass Spectrometry
Exercises

15: Alcohols: Reactions and Synthesis

15.1 Overview of Alcohol Reactions
15.2 Converting Alcohols into Esters
15.3 Conversion of Alcohols to Haloalkanes
15.4 Oxidation of Alcohols
15.5 Reactions of Vicinal Diols
15.6 Synthesis of Alcohols
15.7 Synthesis of Alcohols from Haloalkanes
15.8 Indirect Hydration Methods
15.9 Reduction of Carbonyl Compounds
15.10 Alcohol Synthesis Using Grignard Reagents
15.11 Thiols and Thioethers
Exercises

16: Ethers and Epoxides

16.1 Structure of Ethers
16.2 Nomenclature of Ethers
16.3 Physical Properties of Ethers
16.4 Polyether Antibiotics
16.5 Synthesis of Ethers: Alkoxymercuration-Demercuration of Alkenes
16.6 The Williamson Ether Synthesis
16.7 Reactions of Ethers
16.8 Ethers as Protecting Groups
16.9 Synthesis of Epoxides
16.10 Reactions of Epoxides
16.11 Sulfides
16.12 Spectroscopy of Ethers, Thiols, and Sulfides
Exercises

17: Organometallic Chemistry of Transition Metal Elements and Introduction to Retrosynthesis

17.1 Brief Overview of Transition Metal Complexes
17.2 The Gilman Reagent
17.3 Overview of Palladiumcatalyzed Cross-Coupling Reactions
17.4 The Suzuki Coupling Reaction
17.5 The Heck Reaction
17.6 The Sonogashira Reaction
17.7 The Wilkinson Catalyst: Homogeneous Catalytic Hydrogenation
17.8 Asymmetric Hydrogenation with Chiral Ruthenium Catalysts
17.9 The Grubbs Reaction: A Metathesis Reaction for Alkene Synthesis
17.9 Introduction to Retrosynthesis: Thinking Backwards
Exercises

18: Aldehydes and Ketones

18.1 The Carbonyl Group
18.2 Nomenclature of Aldehydes and Ketones
18.3 Physical Properties of Aldehydes and Ketones
18.4 Oxidation–Reduction Reactions of Carbonyl Compounds
18.5 Synthesis of Carbonyl Compounds: A Review
18.6 Carbonyl Compounds: A Preview
18.7 Spectroscopy of Aldehydes and Ketones
Exercises

19: Aldehydes and Ketones: Nucleophilic Addition Reactions

19.1 Relative Stabilities of Aldehydes and Ketones
19.2 Formation of Cyanohydrins
19.3 Hydration of Carbonyl Compounds
19.4 Mechanisms of Acid- and Base-Catalyzed Carbonyl Addition Reactions
19.5 Formation of Acetals and Ketals
19.6 Acetals as Protecting Groups
19.7 Thioacetals and Thioketals
19.8 Addition of Nitrogen Compounds to Aldehydes and Ketones
19.9 The Wittig Reaction
Exercises

20: Carboxylic Acids

20.1 Carboxylic Acids and Acyl Groups
20.2 Nomenclature of Carboxylic Acids
20.3 Physical Properties of Carboxylic Acids
20.4 Acidity of Carboxylic Acids
20.5 Carboxylate Anions
20.6 Synthesis of Carboxylic Acids
20.7 Reduction of Carboxylic Acids
20.8 Decarboxylation Reactions
20.9 Reactions of Carboxylic Acids and Their Derivatives: A Preview
20.10 Conversion of Carboxylic Acids into Acyl Halides
20.11 Conversion of Carboxylic Acids into Esters
20.12 Mechanism of Esterification
20.13 Brief Synthetic Review
20.14 Spectroscopy of Carboxylic Acids
Exercises

21: Carboxylic Acid Derivatives

21.1 Nomenclature of Carboxylic Acid Derivatives
21.2 Physical Properties of Acyl Derivatives
21.3 Basicity of Carboxylic Acid Derivatives
21.4 Mechanism of Nucleophilic Acyl Substitution
21.5 Hydrolysis of Acyl Derivatives
21.6 Reaction of Acyl Derivatives with Alcohols
21.7 Reaction of Acyl Derivatives with Amines
21.8 Reduction of Acyl Derivatives
21.9 Reaction of Acyl Derivatives with Organometallic Reagents
21.10 Infrared Spectroscopy of Acyl derivatives
21.11 NMR Spectroscopy of Acyl Derivatives
Exercises

22: Condensation Reactions of Carbonyl Compounds

22.1 The α-Carbon Atom of Aldehydes and Ketones
22.2 Keto–Enol Equilibria of Aldehydes and Ketones
22.3 Consequences of Enolization
22.4 α-Halogenation Reactions of Aldehydes and Ketones
22.5 Alkylation of Enolate Ions
22.6 The Aldol Condensation of Aldehydes
22.7 Mixed Aldol Condensation Reactions
22.8 Intramolecular Aldol Condensation Reactions
22.9 Conjugation in α-β-Unsaturated Aldehydes and Ketones
22.10 Conjugate Addition Reactions
22.11 The Michael Reaction and Robinson Annulation
22.12 The α-Hydrogen Atoms of Acid Derivatives
22.13 Reaction at the α-Carbon of Acid Derivatives
22.14 The Claisen Condensation
22.15 Aldol-Type Condensations of Acid Derivations
22.16 β -Dicarbonyl Compounds in Synthesis
22.17 Michael Condensations of Acid Derivatives
Exercises

23: Amines and Amides

23.1 Organic Nitrogen Compounds
23.2 Bonding and Structure of Amines
23.3 Classification and Nomenclature of Amines
23.4 Physical Properties of Amines
23.5 Basicity of Amines
23.6 Solubility of Ammonium Salts
23.7 Synthesis of Amines by Substitution Reactions
23.8 Synthesis of Amines by Reduction
23.9 The Hofmann Rearrangement
23.10 Overview of Amine Reactions
23.11 Enamines
23.12 Sulfonamides
23.13 Quaternary Ammonium Salts
23.14 spectroscopy of amines
Exercises

24: Aryl Halides, Phenols, and Anilines

24.1 Properties of Aromatic Compounds
24.2 Acid-Base Properties of Phenols and Anilines
24.3 Converting Aryl Halides to Grignard Reagents and Organolithium Reagents
24.4 Nucleophilic Aromatic Substitution
24.5 An Overview of Phenol Reactions
24.6 Reactions of Phenoxide Ions
24.7 Quinones
24.8 Substitution Reactions of Aryldiazonium Salts
24.9 Azo Compounds
Exercises

25: Pericyclic Reactions

25.1 Concerted Reactions
25.2 Classification of Pericyclic Reactions
25.3 Molecular Orbitals in Pericyclic Reactions
25.4 Eiectrocyclic Reactions
25.5 Cycloaddition Reactions
25.6 Sigmatropic Rearrangements
Exercises

26: Carbohydrates

26.1 Carbohydrates in the Biosphere
26.2 Classification of Carbohydrates
26.3 Chirality of Monosaccharides
26.4 Isomerizations of Monosaccharides
26.5 Cyclic Monosaccharides: Hemiacetals and Hemiketals
26.6 Reduction and Oxidation of Monosaccharides
26.7 Glocosides
26.8 Disaccharides
26.9 Polysaccharides
26.10 Chemical Determination of Monsoaccharide Structures
26.11 Determination of Ring Size
26.12 Structure of Disaccharides
26.13 Human Blood Group Antigens
Exercises

27: Amino Acids, Peptides, and Proteins

27.1 The Structures of α-Amino Acids
27.2 Acid-Base Equilibria of α-Amino Acids
27.3 Isoionic Point and Titration of α-Amino Acids
27.4 Synthesis of α-Amino Acids
27.5 Chiral Synthesis of α-Amino Acids
27.6 Reactions of α-Amino Acids
27.7 Peptides
27.8 Overview of Peptide Synthesis
27.9 Solid-Phase Peptide Synthesis
27.10 Determination of the Amino Acid Composition of Proteins
27.11 Determination of the Amino Acid Sequence of Proteins
27.12 Bonding in Proteins
27.13 Protein Structure
27.14 Oxygen Storage and Transport: Myoglobin and Hemoglobin
Exercises

28: Synthetic Polymers

28.1 Natural and Synthetic Polymers
28.2 Physical Properties of Polymers
28.3 Classes of Polymers
28.4 Polymerization Methods
28.5 Addition Polymerization
28.6 Copolymerization of Alkenes
28.7 Cross-Linked Polymers
28.8 Stereochemistry of Addition Polymerization
28.9 Condensation Polymers
28.10 Polyesters
28.11 Polycarbonates
28.12 Polyamides
28.13 Phenol-Formaldehyde Polymers
28.14 Polyurethanes
Exercises

Appendix pK_a Values

Appendix A: Heats of Formation (kJ mole^{− 1})

Appendix IR Absorptions (cm^{− 1})

Appendix ¹H NMR and ¹³C NMR Chemical Shifts (ppm)

Glossary

A Brief Overview of Thermodynamics

1 First Law of Thermodynamics
2 Estimating ∆H°_rxn from Bond Energies
3 Second Law of Thermodynamics
3 Entropy changes in chemical reactions
3 Free Energy
4 Contributions of ΔH°_rxn and ΔS°_rxn to ΔG°_rxn

Chemical Kinetics

1 Practical Kinetics
2 Transition State Theory
3 The Hammond Postulate

Summary of Synthetic Methods

Solutions to In-Chapter Problems

Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
Chapter 13
Chapter 14
Chapter 15
Chapter 16
Chapter 17
Chapter 18
Chapter 19
Chapter 20
Chapter 21
Chapter 22
Chapter 22
Chapter 24
Chapter 25
Chapter 26
Chapter 27
Chapter 28

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Structure, Mechanism, and Synthesis

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Robert J. Ouellette

J. David Rawn

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