Organic Chemistry

by Wade, Leroy Skip G

• ISBN13: 9780131478718
• ISBN10: 0131478710
• Edition: 6th
• Format: Hardcover
• Copyright: 2006-01-01
• Publisher: Prentice Hall

Summary

In a highly accessible fashion, this top-selling book bridges the gap between conceptual understanding and actual applicationwhile strongly emphasizing the development of problem-solving skills. The book focuses on traditional organic chemistry topics and offers up-to-date aspects of spectroscopy, relevant photographs, and many applications to polymer chemistry integrated throughout the book.

Table of Contents

Preface	xxiii
About the Author	xli
1 Introduction and Review	1	(38)
1-1 The Origins of Organic Chemistry	1	(2)
1-2 Principles of Atomic Structure	3	(3)
1-3 Bond Formation: The Octet Rule	6	(1)
1-4 Lewis Structures	7	(1)
1-5 Multiple Bonding	8	(1)
Summary: Common Bonding Patterns (Uncharged)	9	(1)
1-6 Electronegativity and Bond Polarity	9	(2)
1-7 Formal Charges	11	(1)
1-8 Ionic Structures	12	(1)
Summary: Common Bonding Patterns in Organic Compounds and Ions	13	(1)
1-9 Resonance	13	(4)
1-10 Structural Formulas	17	(3)
1-11 Molecular Formulas and Empirical Formulas	20	(1)
1-12 Arrhenius Acids and Bases	21	(1)
1-13 Bransted-Lowry Acids and Bases	22	(7)
1-14 Lewis Acids and Bases	29	(3)
Chapter 1 Glossary	32	(2)
Study Problems	34	(5)
2 Structure and Properties of Organic Molecules	39	(42)
2-1 Wave Properties of Electrons in Orbitals	39	(2)
2-2 Molecular Orbitals	41	(3)
2-3 Pi Bonding	44	(1)
2-4 Hybridization and Molecular Shapes	45	(4)
2-5 Drawing Three-Dimensional Molecules	49	(1)
2-6 General Rules of Hybridization and Geometry	50	(4)
2-7 Bond Rotation	54	(2)
2-8 Isomerism	56	(2)
2-9 Polarity of Bonds and Molecules	58	(3)
2-10 Intermolecular Forces	61	(4)
2-11 Polarity Effects on Solubilities	65	(3)
2-12 Hydrocarbons	68	(3)
2-13 Organic Compounds Containing Oxygen	71	(2)
2-14 Organic Compounds Containing Nitrogen	73	(2)
Chapter 2 Glossary	75	(2)
Study Problems	77	(4)
3 Structure and Stereochemistry of Alkanes	81	(44)
3-1 Classification of Hydrocarbons (Review)	81	(1)
3-2 Molecular Formulas of Alkanes	82	(1)
3-3 Nomenclature of Alkanes	83	(6)
Summary: Rules for Naming Alkanes	88	(1)
3-4 Physical Properties of Alkanes	89	(2)
3-5 Uses and Sources of Alkanes	91	(2)
3-6 Reactions of Alkanes	93	(1)
3-7 Structure and Conformations of Alkanes	94	(4)
3-8 Conformations of Butane	98	(2)
3-9 Conformations of Higher Alkanes	100	(1)
3-10 Cycloalkanes	100	(3)
3-11 cis-trans Isomerism in Cycloalkanes	103	(1)
3-12 Stabilities of Cycloalkanes; Ring Strain	103	(4)
3-13 Cyclohexane Conformations	107	(4)
3-14 Conformations of Monosubstituted Cyclohexanes	111	(3)
3-15 Conformations of Disubstituted Cyclohexanes	114	(3)
3-16 Bicyclic Molecules	117	(2)
Chapter 3 Glossary	119	(3)
Study Problems	122	(3)
4 The Study of Chemical Reactions	125	(42)
4-1 Introduction	125	(1)
4-2 Chlorination of Methane	125	(1)
4-3 The Free-Radical Chain Reaction	126	(4)
Key Mechanism: Free-Radical Halogenation	128	(2)
4-4 Equilibrium Constants and Free Energy	130	(3)
4-5 Enthalpy and Entropy	133	(1)
4-6 Bond-Dissociation Enthalpies	134	(1)
4-7 Enthalpy Changes in Chlorination	135	(2)
4-8 Kinetics and the Rate Equation	137	(2)
4-9 Activation Energy and the Temperature Dependence of Rates	139	(1)
4-10 Transition States	140	(2)
4-11 Rates of Multistep Reactions	142	(1)
4-12 Temperature Dependence of Halogenation	143	(1)
4-13 Selectivity in Halogenation	144	(5)
4-14 The Hammond Postulate	149	(4)
4-15 Radical Inhibitors	153	(2)
4-16 Reactive Intermediates	155	(5)
Summary: Reactive Intermediates	160	(1)
Chapter 4 Glossary	160	(3)
Study Problems	163	(4)
5 Stereochemistry	167	(45)
5-1 Introduction	167	(1)
5-2 Chirality	168	(6)
5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms	174	(5)
5-4 Optical Activity	179	(5)
5-5 Biological Discrimination of Enantiomers	184	(1)
5-6 Racemic Mixtures	185	(1)
5-7 Enantiomeric Excess and Optical Purity	186	(1)
5-8 Chirality of Conformationally Mobile Systems	187	(2)
5-9 Chiral Compounds without Asymmetric Atoms	189	(2)
5-10 Fischer Projections	191	(5)
Summary: Fischer Projections and Their Use	196	(1)
5-11 Diastereomers	196	(2)
Summary: Types of Isomers	197	(1)
5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons	198	(1)
5-13 Meso Compounds	199	(2)
5-14 Absolute and Relative Configuration	201	(2)
5-15 Physical Properties of Diastereomers	203	(1)
5-16 Resolution of Enantiomers	204	(3)
Chapter 5 Glossary	207	(2)
Study Problems	209	(3)
6 Alkyl Halides: Nucleophilic Substitution and Elimination	212	(67)
6-1 Introduction	212	(1)
6-2 Nomenclature of Alkyl Halides	213	(2)
6-3 Common Uses of Alkyl Halides	215	(2)
6-4 Structure of Alkyl Halides	217	(1)
6-5 Physical Properties of Alkyl Halides	218	(2)
6-6 Preparation of Alkyl Halides	220	(5)
Summary: Methods for Preparing Alkyl Halides	223	(2)
6-7 Reactions of Alkyl Halides: Substitution and Elimination	225	(1)
6-8 Second-Order Nucleophilic Substitution: The SN2 Reaction	226	(2)
Key Mechanism: The SN2 Reaction	227	(1)
6-9 Generality of the SN2 Reaction	228	(2)
Summary: SN2 Reactions of Alkyl Halides	228	(2)
6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile	230	(4)
Summary: Trends in Nucleophilicity	231	(3)
6-11 Reactivity of the Substrate in SN2 Reactions	234	(4)
6-12 Stereochemistry of the SN2 Reaction	238	(2)
6-13 First-Order Nucleophilic Substitution: The SN1 Reaction	240	(4)
Key Mechanism: The 5N1 Reaction	241	(3)
6-14 Stereochemistry of the SN1 Reaction	244	(2)
6-15 Rearrangements in SN I Reactions	246	(3)
6-16 Comparison of SN1 and SN2 Reactions	249	(3)
Summary: Nucleophilic Substitutions	251	(1)
6-17 First-Order Elimination: The El Reaction	252	(5)
Key Mechanism: The El Reaction	252	(4)
Summary: Carbocation Reactions	256	(1)
6-18 Positional Orientation of Elimination: Zaitsev's Rule	257	(1)
6-19 Second-Order Elimination: The E2 Reaction	258	(3)
Key Mechanism: The E2 Reaction	259	(2)
6-20 Stereochemistry of the E2 Reaction	261	(1)
6-21 Comparison of El and E2 Elimination Mechanisms	262	(8)
Summary: Elimination Reactions	264	(3)
Summary: Reactions of Alkyl Halides	267	(3)
Chapter 6 Glossary	270	(3)
Study Problems	273	(6)
7 Structure and Synthesis of Alkenes	279	(42)
7-1 Introduction	279	(1)
7-2 The Orbital Description of the Alkene Double Bond	280	(1)
7-3 Elements of Unsaturation	281	(2)
7-4 Nomenclature of Alkenes	283	(2)
7-5 Nomenclature of Cis-Trans Isomers	285	(3)
Summary: Rules for Naming Alkenes	287	(1)
7-6 Commercial Importance of Alkenes	288	(2)
7-7 Stability of Alkenes	290	(6)
7-8 Physical Properties of Alkenes	296	(2)
7-9 Alkene Synthesis by Elimination of Alkyl Halides	298	(8)
7-10 Alkene Synthesis by Dehydration of Alcohols	306	(3)
Key Mechanism: Acid-Catalyzed Dehydration of an Alcohol	307	(2)
7-11 Alkene Synthesis by High-Temperature Industrial Methods	309	(7)
Summary: Methods for Synthesis of Alkenes	314	(2)
Chapter 7 Glossary	316	(2)
Study Problems	318	(3)
8 Reactions of Alkenes	321	(61)
8-1 Reactivity of the Carbon-Carbon Double Bond	321	(1)
8-2 Electrophilic Addition to Alkenes	322	(2)
Key Mechanism: Electrophilic Addition to Alkenes	322	(2)
8-3 Addition of Hydrogen Halides to Alkenes	324	(6)
8-4 Addition of Water: Hydration of Alkenes	330	(3)
8-5 Hydration by Oxymercuration-Demercuration	333	(2)
8-6 Alkoxymercuration-Demercuration	335	(1)
8-7 Hydroboration of Alkenes	336	(6)
8-8 Addition of Halogens to Alkenes	342	(3)
8-9 Formation of Halohydrins	345	(3)
8-10 Catalytic Hydrogenation of Alkenes	348	(2)
8-11 Addition of Carbenes to Alkenes	350	(3)
8-12 Epoxidation of Alkenes	353	(2)
8-13 Acid-Catalyzed Opening of Epoxides	355	(3)
8-14 Syn Hydroxylation of Alkenes	358	(2)
8-15 Oxidative Cleavage of Alkenes	360	(3)
8-16 Polymerization of Alkenes	363	(11)
Summary: Reactions of Alkenes	370	(4)
Chapter 8 Glossary	374	(2)
Study Problems	376	(6)
9 Alkynes	382	(35)
9-1 Introduction	382	(1)
9-2 Nomenclature of Alkynes	383	(1)
9-3 Physical Properties of Alkynes	384	(1)
9-4 Commercial Importance of Alkynes	384	(2)
9-5 Electronic Structure of Alkynes	386	(1)
9-6 Acidity of Alkynes; Formation of Acetylide Ions	387	(2)
9-7 Synthesis of Alkynes from Acetylides	389	(4)
9-8 Synthesis of Alkynes by Elimination Reactions	393	(3)
Summary: Syntheses of Alkynes	396	(1)
9-9 Addition Reactions of Alkynes	396	(10)
9-10 Oxidation of Alkynes	406	(6)
Summary: Reactions of Alkynes	409	(3)
Chapter 9 Glossary	412	(1)
Study Problems	413	(4)
10 Structure and Synthesis of Alcohols	417	(43)
10-1 Introduction	417	(1)
10-2 Structure and Classification of Alcohols	417	(2)
10-3 Nomenclature of Alcohols and Phenols	419	(4)
10-4 Physical Properties of Alcohols	423	(2)
10-5 Commercially Important Alcohols	425	(2)
10-6 Acidity of Alcohols and Phenols	427	(3)
10-7 Synthesis of Alcohols: Introduction and Review	430	(2)
Summary: Previous Alcohol Syntheses	430	(2)
10-8 Organometallic Reagents for Alcohol Synthesis	432	(3)
10-9 Addition of Organometallic Reagents to Carbonyl Compounds	435	(8)
Key Mechanism: Grignard Reactions	435	(7)
Summary: Grignard Reactions	442	(1)
10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides	443	(2)
10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols	445	(6)
Summary: Reactions of LiAlH4 and NaBH4	448	(1)
Summary: Alcohol Syntheses	449	(2)
10-12 Thiols (Mercaptans)	451	(3)
Chapter 10 Glossary	454	(1)
Study Problems	455	(5)
11 Reactions of Alcohols	460	(48)
11-1 Oxidation States of Alcohols and Related Functional Groups	460	(2)
11-2 Oxidation of Alcohols	462	(3)
11-3 Additional Methods for Oxidizing Alcohols	465	(2)
11-4 Biological Oxidation of Alcohols	467	(2)
11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates	469	(3)
Summary: SN2 Reactions of Tosylate Esters	471	(1)
11-6 Reduction of Alcohols	472	(1)
11-7 Reactions of Alcohols with Hydrohalic Acids	472	(5)
11-8 Reactions of Alcohols with Phosphorus Halides	477	(1)
11-9 Reactions of Alcohols with Thionyl Chloride	478	(2)
11-10 Dehydration Reactions of Alcohols	480	(8)
11-11 Unique Reactions of Diols	488	(2)
11-12 Esterification of Alcohols	490	(1)
11-13 Esters of Inorganic Acids	491	(3)
11-14 Reactions of Alkoxides	494	(8)
Key Mechanism: The Williamson Ether Synthesis	494	(5)
Summary: Reactions of Alcohols	499	(3)
Chapter 11 Glossary	502	(1)
Study Problems	503	(5)
12 Infrared Spectroscopy and Mass Spectrometry	508	(51)
12-1 Introduction	508	(1)
12-2 The Electromagnetic Spectrum	509	(1)
12-3 The Infrared Region	510
12-4 Molecular Vibrations 51	1	(512)
12-5 1R-Active and IR-Inactive Vibrations	513	(1)
12-6 Measurement of the IR Spectrum	514	(3)
12-7 Infrared Spectroscopy of Hydrocarbons	517	(5)
12-8 Characteristic Absorptions of Alcohols and Amines	522	(1)
12-9 Characteristic Absorptions of Carbonyl Compounds	523	(6)
12-10 Characteristic Absorptions of C-N Bonds	529	(1)
12-11 Simplified Summary of IR Stretching Frequencies	530	(2)
12-12 Reading and Interpreting IR Spectra (Solved Problems)	532	(5)
12-13 Introduction to Mass Spectrometry	537	(4)
12-14 Determination of the Molecular Formula by Mass Spectrometry	541	(3)
12-15 Fragmentation Patterns in Mass Spectrometry	544	(7)
Summary: Common Fragmentation Patterns	549	(2)
Chapter 12 Glossary	551	(1)
Study Problems	552	(7)
13 Nuclear Magnetic Resonance Spectroscopy	559	(64)
13-1 Introduction	559	(1)
13-2 Theory of Nuclear Magnetic Resonance	559	(3)
13-3 Magnetic Shielding by Electrons	562	(2)
13-4 The NMR Spectrometer	564	(1)
13-5 The Chemical Shift	565	(7)
13-6 The Number of Signals	572	(1)
13-7 Areas of the Peaks	573	(3)
13-8 Spin-Spin Splitting	576	(9)
13-9 Complex Splitting	585	(3)
13-10 Stereochemical Nonequivalence of Protons	588	(3)
13-11 Time Dependence of NMR Spectroscopy	591	(8)
Problem-Solving Strategy: Interpreting Proton NMR Spectra	594	(5)
13-12 Carbon-13 NMR Spectroscopy	599	(8)
13-13 Interpreting Carbon NMR Spectra	607	(2)
13-14 Nuclear Magnetic Resonance Imaging	609	(5)
Problem-Solving Strategy: Spectroscopy Problems	610	(4)
Chapter 13 Glossary	614	(2)
Study Problems	616	(7)
14 Ethers, Epoxides, and Sulfides	623	(40)
14-1 Introduction	623	(1)
14-2 Physical Properties of Ethers	623	(5)
14-3 Nomenclature of Ethers	628	(3)
14-4 Spectroscopy of Ethers	631	(2)
14-5 The Williamson Ether Synthesis	633	(1)
14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration	634	(1)
14-7 Industrial Synthesis: Bimolecular Dehydration of Alcohols	635	(1)
Summary: Syntheses of Ethers	636	(1)
14-8 Cleavage of Ethers by HBr and HI	636	(3)
14-9 Autoxidation of Ethers	639	(1)
Summary: Reactions of Ethers	639	(1)
14-10 Sulfides (Thioethers)	640	(2)
14-11 Synthesis of Epoxides	642	(3)
Summary: Epoxide Syntheses	645	(1)
14-12 Acid-Catalyzed Ring Opening of Epoxides	645	(4)
14-13 Base-Catalyzed Ring Opening of Epoxides	649	(1)
14-14 Orientation of Epoxide Ring Opening	650	(2)
14-15 Reactions of Epoxides with Grignard and Organolithium Reagents	652	(1)
14-16 Epoxy Resins: The Advent of Modern Glues	653	(3)
Summary: Reactions of Epoxides	655	(1)
Chapter 14 Glossary	656	(2)
Study Problems	658	(5)
15 Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy	663	(42)
15-1 Introduction	663	(1)
15-2 Stabilities of Dienes	663	(2)
15-3 Molecular Orbital Picture of a Conjugated System	665	(4)
15-4 Allylic Cations	669	(1)
15-5 1,2- and 1,4-Addition to Conjugated Dienes	670	(2)
15-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene	672	(2)
15-7 Allylic Radicals	674	(2)
15-8 Molecular Orbitals of the Allylic System	676	(2)
15-9 Electronic Configurations of the Ally! Radical, Cation, and Anion	678	(1)
15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates	679	(1)
15-11 The Diels-Alder Reaction	680	(9)
Key Mechanism: The Diels-Alder Reaction	680	(9)
15-12 The Diels-Alder as an Example of a Pericyclic Reaction	689	(3)
15-13 Ultraviolet Absorption Spectroscopy	692	(7)
Chapter 15 Glossary	699	(2)
Study Problems	701	(4)
16 Aromatic Compounds	705	(44)
16-1 Introduction: The Discovery of Benzene	705	(1)
16-2 The Structure and Properties of Benzene	705	(4)
16-3 The Molecular Orbitals of Benzene	709	(3)
16-4 The Molecular Orbital Picture of Cyclobutadiene	712	(2)
16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds	714	(1)
16-6 Hackers Rule	714	(2)
16-7 Molecular Orbital Derivation of Hiickel's Rule	716	(1)
16-8 Aromatic Ions	717	(6)
16-9 Heterocyclic Aromatic Compounds	723	(4)
16-10 Polynuclear Aromatic Hydrocarbons	727	(2)
16-11 Aromatic Allotropes of Carbon	729	(2)
16-12 Fused Heterocyclic Compounds	731	(1)
16-13 Nomenclature of Benzene Derivatives	732	(2)
16-14 Physical Properties of Benzene and Its Derivatives	734	(1)
16-15 Spectroscopy of Aromatic Compounds	735	(3)
Chapter 16 Glossary	738	(2)
Study Problems	740	(9)
17 Reactions of Aromatic Compounds	749	(56)
17-1 Electrophilic Aromatic Substitution	749	(2)
Key Mechanism: Electrophilic Aromatic Substitution	750	(1)
17-2 Halogenation of Benzene	751	(2)
17-3 Nitration of Benzene	753	(2)
17-4 Sulfonation of Benzene	755	(2)
17-5 Nitration of Toluene: The Effect of Alkyl Substitution	757	(2)
17-6 Activating, Ortho, Para-Directing Substituents	759	(4)
Summary: Activating, Ortho, Para-Directors	762	(1)
17-7 Deactivating, Meta-Directing Substituents	763	(3)
Summary: Deactivating, Meta-Directors	766	(1)
17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing	766	(2)
Summary: Directing Effects of Substituents	768	(1)
17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution	768	(3)
17-10 The Friedel-Crafts Alkylation	771	(4)
17-11 The Friedel-Crafts Acylation	775	(5)
Summary: Comparison of Friedel-Crafts Alkylation and Acylation	778	(2)
17-12 Nucleophilic Aromatic Substitution	780	(5)
17-13 Addition Reactions of Benzene Derivatives	785	(2)
17-14 Side-Chain Reactions of Benzene Derivatives	787	(4)
17-15 Reactions of Phenols	791	(6)
Summary: Reactions of Aromatic Compounds	794	(3)
Chapter 17 Glossary	797	(3)
Study Problems	800	(5)
18 Ketones and Aldehydes	805	(65)
18-1 Carbonyl Compounds	805	(1)
18-2 Structure of the Carbonyl Group	806	(1)
18-3 Nomenclature of Ketones and Aldehydes	806	(3)
18-4 Physical Properties of Ketones and Aldehydes	809	(2)
18-5 Spectroscopy of Ketones and Aldehydes	811	(7)
18-6 Industrial Importance of Ketones and Aldehydes	818	(1)
18-7 Review of Syntheses of Ketones and Aldehydes	818	(4)
18-8 Synthesis of Ketones and Aldehydes Using 1,3-Dithianes	822	(1)
18-9 Synthesis of Ketones from Carboxylic Acids	823	(1)
18-10 Synthesis of Ketones from Nitriles	824	(1)
18-11 Synthesis of Aldehydes and Ketones from Acid Chlorides	825	(4)
Summary: Syntheses of Ketones and Aldehydes	826	(3)
18-12 Reactions of Ketones and Aldehydes: Nucleophilic Addition	829	(3)
Key Mechanism: Nucleophilic Additions to Carbonyl Groups	831	(1)
18-13 The Wittig Reaction	832	(4)
18-14 Hydration of Ketones and Aldehydes	836	(2)
18-15 Formation of Cyanohydrins	838	(2)
18-16 Formation of Imines	840	(3)
Key Mechanism: Formation of Imines	840	(3)
18-17 Condensations with Hydroxylamine and Hydrazines	843	(2)
Summary: Condensations of Amines with Ketones and Aldehydes	844	(1)
18-18 Formation of Acetals	845	(5)
Key Mechanism: Formation of Acetals	846	(2)
Problem-Solving Strategy: Proposing Reaction Mechanisms	848	(2)
18-19 Use of Acetals as Protecting Groups	850	(2)
18-20 Oxidation of Aldehydes	852	(1)
18-21 Reductions of Ketones and Aldehydes	853	(5)
Summary: Reactions of Ketones and Aldehydes	855	(3)
Glossary	858	(3)
Study Problems	861	(9)
19 Amines	870	(65)
19-1 Introduction	870	(1)
19-2 Nomenclature of Amines	871	(2)
19-3 Structure of Amines	873	(2)
19-4 Physical Properties of Amines	875	(2)
19-5 Basicity of Amines	877	(1)
19-6 Effects on Amine Basicity	878	(2)
19-7 Salts of Amines	880	(2)
19-8 Amine Salts as Phase-Transfer Catalysts	882	(2)
19-9 Spectroscopy of Amines	884	(4)
19-10 Reactions of Amines with Ketones and Aldehydes (Review)	888	(1)
19-11 Aromatic Substitution of Arylamines and Pyridine (Review)	888	(4)
19-12 Alkylation of Amines by Alkyl Halides	892	(1)
19-13 Acylation of Amines by Acid Chlorides	893	(2)
19-14 Formation of Sulfonamides	895	(2)
19-15 Amines as Leaving Groups: The Hofmann Elimination	897	(3)
19-16 Oxidation of Amines: The Cope Elimination	900	(2)
19-17 Reactions of Amines with Nitrous Acid	902	(2)
19-18 Reactions of Arenediazonium Salts	904	(7)
Summary: Reactions of Amines	908	(3)
19-19 Synthesis of Amines by Reductive Amination	911	(2)
19-20 Synthesis of Amines by Acylation-Reduction	913	(2)
19-21 Syntheses Limited to Primary Amines	915	(8)
Summary: Synthesis of Amines	921	(2)
Chapter 19 Glossary	923	(3)
Study Problems	926	(9)
20 Carboxylic Acids	935	(43)
20-1 Introduction	935	(1)
20-2 Nomenclature of Carboxylic Acids	935	(4)
20-3 Structure and Physical Properties of Carboxylic Acids	939	(1)
20-4 Acidity of Carboxylic Acids	940	(4)
20-5 Salts of Carboxylic Acids	944	(3)
20-6 Commercial Sources of Carboxylic Acids	947	(1)
20-7 Spectroscopy of Carboxylic Acids	948	(4)
20-8 Synthesis of Carboxylic Acids	952	(5)
Summary: Syntheses of Carboxylic Acids	955	(2)
20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic Acyl Substitution	957	(1)
20-10 Condensation of Acids with Alcohols: The Fischer Esterification	958	(4)
Key Mechanism: Fischer Esterification	959	(3)
20-11 Esterification Using Diazomethane	962	(1)
20-12 Condensation of Acids with Amines: Direct Synthesis of Amides	963	(1)
20-13 Reduction of Carboxylic Acids	963	(2)
20-14 Alkylation of Carboxylic Acids to Form Ketones	965	(1)
20-15 Synthesis and Use of Acid Chlorides	966	(4)
Summary: Reactions of Carboxylic Acids	968	(2)
Chapter 20 Glossary	970	(1)
Study Problems	971	(7)
21 Carboxylic Acid Derivatives	978	(63)
21-1 Introduction	978	(1)
21-2 Structure and Nomenclature of Acid Derivatives	979	(6)
21-3 Physical Properties of Carboxylic Acid Derivatives	985	(3)
21-4 Spectroscopy of Carboxylic Acid Derivatives	988	(6)
21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution	994	(9)
Key Mechanism: Addition-Elimination Mechanism of Nucleophilic Acyl Substitution	995	(8)
21-6 Transesterification	1003	(3)
21-7 Hydrolysis of Carboxylic Acid Derivatives	1006	(5)
21-8 Reduction of Acid Derivatives	1011	(2)
21-9 Reactions of Acid Derivatives with Organometallic Reagents	1013	(1)
21-10 Summary of the Chemistry of Acid Chlorides	1014	(2)
21-11 Summary of the Chemistry of Anhydrides	1016	(3)
21-12 Summary of the Chemistry of Esters	1019	(3)
21-13 Summary of the Chemistry of Amides	1022	(3)
21-14 Summary of the Chemistry of Nitriles	1025	(1)
21-15 Thioesters	1026	(2)
21-16 Esters and Amides of Carbonic Acid	1028	(2)
Chapter 21 Glossary	1030	(2)
Study Problems	1032	(9)
22 Condensations and Alpha Substitutions of Carbonyl Compounds	1041	(56)
22-1 Introduction	1041	(1)
22-2 Enols and Enolate Ions	1042	(4)
22-3 Alpha Halogenation of Ketones	1046	(5)
22-4 a Bromination of Acids: The HVZ Reaction	1051	(1)
22-5 Alkylation of Enolate Ions	1052	(1)
22-6 Formation and Alkylation of Enamines	1053	(3)
22-7 The Aldol Condensation of Ketones and Aldehydes	1056	(4)
Key Mechanism: Base-Catalyzed Aldol Condensation	1056	(4)
22-8 Dehydration of Aldol Products	1060	(1)
Key Mechanism: Base-Catalyzed Dehydration of an Aldol	1060	(1)
22-9 Crossed Aldol Condensations	1061	(3)
Problem-Solving Strategy: Proposing Reaction Mechanisms	1062	(2)
22-10 Aldol Cyclizations	1064	(1)
22-11 Planning Syntheses Using Aldol Condensations	1065	(2)
22-12 The Claisen Ester Condensation	1067	(3)
Key Mechanism: The Claisen Ester Condensation	1067	(3)
22-13 The Dieckmann Condensation: A Claisen Cyclization	1070	(1)
22-14 Crossed Claisen Condensations	1071	(3)
22-15 Syntheses Using /3-Dicarbonyl Compounds	1074	(2)
22-16 The Malonic Ester Synthesis	1076	(3)
22-17 The Acetoacetic Ester Synthesis	1079	(2)
22-18 Conjugate Additions: The Michael Reaction	1081	(4)
22-19 The Robinson Annulation	1085	(3)
Problem-Solving Strategy: Proposing Reaction
Mechanisms	1086	(2)
Summary: Enolate Additions and Condensations	1088	(2)
Chapter 22 Glossary	1090	(2)
Study Problems	1092	(5)
23 Carbohydrates and Nucleic Acids	1097	(56)
23-1 Introduction	1097	(1)
23-2 Classification of Carbohydrates	1098	(1)
23-3 Monosaccharides	1099	(3)
23-4 Erythro and Threo Diastereomers	1102	(1)
23-5 Epimers	1103	(1)
23-6 Cyclic Structures of Monosaccharides	1104	(4)
23-7 Anomers of Monosaccharides; Mutarotation	1108	(2)
23-8 Reactions of Monosaccharides: Side Reactions in Base	1110	(2)
23-9 Reduction of Monosaccharides	1112	(1)
23-10 Oxidation of Monosaccharides; Reducing Sugars	1113	(2)
23-11 Nonreducing Sugars: Formation of Glycosides	1115	(2)
23-12 Ether and Ester Formation	1117	(2)
23-13 Reactions with Phenylhydrazine: Osazone Formation	1119	(1)
23-14 Chain Shortening: The Ruff Degradation	1120	(1)
23-15 Chain Lengthening: The Kiliani-Fischer Synthesis	1121	(3)
Summary: Reactions of Sugars	1122	(2)
23-16 Fischer's Proof of the Configuration of Glucose	1124	(3)
23-17 Determination of Ring Size; Periodic Acid Cleavage of Sugars	1127	(2)
23-18 Disaccharides	1129	(5)
23-19 Polysaccharides	1134	(3)
23-20 Nucleic Acids: Introduction	1137	(2)
23-21 Ribonucleosides and Ribonucleotides	1139	(2)
23-22 The Structure of Ribonucleic Acid	1141	(1)
23-23 Deoxyribose and the Structure of Deoxyribonucleic Acid	1141	(4)
23-24 Additional Functions of Nucleotides	1145	(2)
Chapter 23 Glossary	1147	(2)
Study Problems	1149	(4)
24 Amino Acids, Peptides, and Proteins	1153	(47)
24-1 Introduction	1153	(1)
24-2 Structure and Stereochemistry of the a-Amino Acids	1154	(4)
24-3 Acid-Base Properties of Amino Acids	1158	(2)
24-4 Isoelectric Points and Electrophoresis	1160	(1)
24-5 Synthesis of Amino Acids	1161	(6)
Summary: Syntheses of Amino Acids	1166	(1)
24-6 Resolution of Amino Acids	1167	(1)
24-7 Reactions of Amino Acids	1167	(3)
Summary: Reactions of Amino Acids	1170	(1)
24-8 Structure and Nomenclature of Peptides and Proteins	1170	(4)
24-9 Peptide Structure Determination	1174	(6)
24-10 Solution-Phase Peptide Synthesis	1180	(3)
24-11 Solid-Phase Peptide Synthesis	1183	(5)
24-12 Classification of Proteins	1188	(1)
24-13 Levels of Protein Structure	1189	(2)
24-14 Protein Denaturation	1191	(2)
Chapter 24 Glossary	1193	(3)
Study Problems	1196	(4)
25 Lipids	1200	(22)
25-1 Introduction	1200	(1)
25-2 Waxes	1200	(1)
25-3 Triglycerides	1201	(3)
25-4 Saponification of Fats and Oils; Soaps and Detergents	1204	(4)
25-5 Phospholipids	1208	(1)
25-6 Steroids	1209	(3)
25-7 Prostaglandins	1212	(1)
25-8 Terpenes	1213	(4)
Chapter 25 Glossary	1217	(1)
Study Problems	1218	(4)
26 Synthetic Polymers	1222	(21)
26-1 Introduction	1222	(1)
26-2 Addition Polymers	1223	(6)
26-3 Stereochemistry of Polymers	1229	(1)
26-4 Stereochemical Control of Polymerization; Ziegler-Natta Catalysts	1230	(1)
26-5 Natural and Synthetic Rubbers	1230	(2)
26-6 Copolymers of Two or More Monomers	1232	(1)
26-7 Condensation Polymers	1232	(4)
26-8 Polymer Structure and Properties	1236	(2)
Chapter 26 Glossary	1238	(2)
Study Problems	1240	(3)
Appendices	1243
1A NMR Absorption Positions of Protons in Various Structural Environments	1244	(2)
1B Spin-Spin Coupling Constants	1246	(1)
1C 13C Chemical Shifts in Organic Compounds	1247	(1)
2A Characteristic Infrared Group Frequencies	1248	(3)
2B IR: Characteristic Infrared Absorptions of Functional Groups	1251	(2)
3 UV: The Woodward-Fieser Rules for Predicting UV-Visible Spectra	1253	(4)
4A Methods and Suggestions for Proposing Mechanisms	1257	(3)
4B Suggestions for Developing Multistep Syntheses	1260	(1)
5 pKa Values for Representative Compounds	1261
Answers to Selected Problems	A1
Photo Credits	PC1
Index	l1