Organic Chemistry & eBook

by Vollhardt, K. Peter C.; Schore, Neil E.

• ISBN13: 9780716778738
• ISBN10: 0716778734
• Edition: 5th
• Format: Display
• Copyright: 2006-03-31
• Publisher: W. H. Freeman

Table of Contents

Preface: A User's Guide to Organic Chemistry: Structure and Function	xx
Structure and Bonding in Organic Molecules	1	(50)
The Scope of Organic Chemistry: An Overview	2	(3)
Chemical Highlight 1-1 Saccharin: One of the Oldest Synthetic Organic Compounds in Commercial Use	4	(1)
Coulomb Forces: A Simplified View of Bonding	5	(2)
Ionic and Covalent Bonds: The Octet Rule	7	(7)
Electron-Dot Model of Bonding: Lewis Structures	14	(5)
Resonance Forms	19	(4)
Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus	23	(6)
Molecular Orbitals and Covalent Bonding	29	(3)
Hybrid Orbitals: Bonding in Complex Molecules	32	(6)
Structures and Formulas of Organic Molecules	38	(13)
Chapter Integration Problems	41	(4)
Important Concepts	45	(1)
Problems	46	(5)
Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules	51	(45)
Kinetics and Thermodynamics of Simple Chemical Processes	52	(6)
Acids and Bases; Electrophiles and Nucleophiles	58	(8)
Chemical Highlight 2-1 Stomach Acid and Food Digestion	59	(7)
Functional Groups: Centers of Reactivity	66	(3)
Straight-Chain and Branched Alkanes	69	(2)
Naming the Alkanes	71	(5)
Structural and Physical Properties of Alkanes	76	(3)
Rotation about Single Bonds: Conformations	79	(4)
Chemical Highlight 2-2 ``Sexual Swindle'' by Means of Chemical Mimicry	79	(4)
Rotation in Substituted Ethanes	83	(13)
Chapter Integration Problems	87	(2)
Important Concepts	89	(1)
Problems	90	(6)
Reactions of Alkanes: Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity	96	(35)
Strength of Alkane Bonds: Radicals	97	(3)
Structure of Alkyl Radicals: Hyperconjugation	100	(1)
Conversion of Petroleum: Pyrolysis	101	(4)
Chemical Highlight 3-1 Petroleum and Gasoline: Our Main Energy Sources	104	(1)
Chlorination of Methane: The Radical Chain Mechanism	105	(5)
Other Radical Halogenations of Methane	110	(2)
Chlorination of Higher Alkanes: Relative Reactivity and Selectivity	112	(4)
Selectivity in Radical Halogenation with Fluorine and Bromine	116	(2)
Synthetic Radical Halogenation	118	(1)
Synthetic Chlorine Compounds and the Stratospheric Ozone Layer	119	(3)
Chemical Highlight 3-2 Chlorination, Chloral, and DDT	119	(3)
Combustion and the Relative Stabilities of Alkanes	122	(9)
Chapter Integration Problems	124	(2)
Important Concepts	126	(1)
Problems	127	(4)
Cycloalkanes	131	(37)
Names and Physical Properties of Cycloalkanes	132	(2)
Ring Strain and the Structure of Cycloalkanes	134	(5)
Cyclohexane: A Strain-Free Cycloalkane	139	(5)
Substituted Cyclohexanes	144	(4)
Larger Cycloalkanes	148	(1)
Polycyclic Alkanes	149	(2)
Carbocyclic Products in Nature	151	(17)
Chemical Highlight 4-1 Cubane Derivatives with Potential as Explosives: Octanitrocubane	151	(4)
Chemical Highlight 4-2 Cholesterol: How Is It Bad and How Bad Is It?	155	(1)
Chemical Highlight 4-3 Controlling Fertility: From ``the Pill'' to RU-486	156	(2)
Chapter Integration Problems	158	(3)
Important Concepts	161	(1)
Problems	162	(6)
Stereoisomers	168	(47)
Chiral Molecules	170	(4)
Chemical Highlight 5-1 Chiral Substances in Nature	173	(1)
Optical Activity	174	(3)
Absolute Configuration: R--S Sequence Rules	177	(5)
Chemical Highlight 5-2 Absolute Configuration: A Historical Note	181	(1)
Fischer Projections	182	(4)
Molecules Incorporating Several Stereocenters: Diastereomers	186	(4)
Chemical Highlight 5-3 Stereoisomers of Tartaric Acid	189	(1)
Meso Compounds	190	(2)
Stereochemistry in Chemical Reactions	192	(9)
Chemical Highlight 5-4 Chiral Drugs: Racemic or Enantiomerically Pure?	194	(4)
Chemical Highlight 5-5 Why Is Nature ``Handed''?	198	(3)
Resolution: Separation of Enantiomers	201	(14)
Chapter Integration Problems	204	(2)
Important Concepts	206	(1)
Problems	207	(8)
Properties and Reactions of Haloalkanes: Bimolecular Nucleophilic Substitution	215	(35)
Physical Properties of Haloalkanes	215	(3)
Chemical Highlight 6-1 Halogenated Steroids as Anti-Inflammatory and Anti-Asthmatic Agents	217	(1)
Nucleophilic Substitution	218	(3)
Reaction Mechanisms Involving Polar Functional Groups: Using ``Electron-Pushing'' Arrows	221	(2)
A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics	223	(3)
Frontside or Backside Attack? Stereochemistry of the SN2 Reaction	226	(2)
Consequences of Inversion in SN2 Reactions	228	(3)
Structure and SN2 Reactivity: The Leaving Group	231	(1)
Structure and SN2 Reactivity: The Nucleophile	232	(7)
Structure and SN2 Reactivity: The Substrate	239	(11)
Chemical Highlight 6-2 The Dilemma of Bromomethane: Highly Useful but Also Highly Toxic	240	(3)
Chapter Integration Problems	243	(2)
Important Concepts	245	(1)
Problems	245	(5)
Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination	250	(35)
Solvolysis of Tertiary and Secondary Haloalkanes	250	(2)
Unimolecular Nucleophilic Substitution	252	(3)
Stereochemical Consequences of SN1 Reactions	255	(1)
Effects of Solvent, Leaving Group, and Nucleophile on Unimolecular Substitution	256	(2)
Effect of the Alkyl Group on the SN1 Reaction: Carbocation Stability	258	(4)
Chemical Highlight 7-1 Unusually Stereoselective SN1 Displacement in Anticancer Drug Synthesis	261	(1)
Unimolecular Elimination: E1	262	(3)
Bimolecular Elimination: E2	265	(3)
Competition Between Substitution and Elimination: Structure Determines Function	268	(3)
Summary of Reactivity of Haloalkanes	271	(14)
Chapter Integration Problems	273	(2)
New Reactions	275	(1)
Important Concepts	276	(1)
Problems	276	(9)
Hydroxy Functional Group: Alcohols: Properties, Preparation, and Strategy of Synthesis	285	(47)
Naming the Alcohols	286	(1)
Structural and Physical Properties of Alcohols	287	(3)
Alcohols as Acids and Bases	290	(3)
Industrial Sources of Alcohols: Carbon Monoxide and Ethene	293	(1)
Synthesis of Alcohols by Nucleophilic Substitution	294	(1)
Synthesis of Alcohols: Oxidation--Reduction Relation Between Alcohols and Carbonyl Compounds	295	(8)
Chemical Highlight 8-1 Biological Oxidation and Reduction	298	(3)
Chemical Highlight 8-2 The Breath Analyzer Test	301	(2)
Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis	303	(3)
Organometallic Reagents in the Synthesis of Alcohols	306	(3)
Chemical Highlight 8-3 Transition Metal-Catalyzed Cross-Coupling Reactions	308	(1)
Complex Alcohols: An Introduction to Synthetic Strategy	309	(23)
Chapter Integration Problems	318	(3)
New Reactions	321	(4)
Important Concepts	325	(1)
Problems	325	(7)
Further Reactions of Alcohols and the Chemistry of Ethers	332	(55)
Reactions of Alcohols with Base: Preparation of Alkoxides	333	(1)
Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols	334	(3)
Carbocation Rearrangements	337	(5)
Organic and Inorganic Esters from Alcohols	342	(4)
Names and Physical Properties of Ethers	346	(3)
Williamson Ether Synthesis	349	(5)
Chemical Highlight 9-1 Chemiluminescence of 1,2-Dioxacyclobutanes	350	(4)
Synthesis of Ethers: Alcohols and Mineral Acids	354	(1)
Reactions of Ethers	355	(3)
Chemical Highlight 9-2 Protecting Groups in Synthesis	357	(1)
Reactions of Oxacyclopropanes	358	(6)
Chemical Highlight 9-3 Hydrolytic Kinetic Resolution of Oxacyclopropanes	360	(4)
Sulfur Analogs of Alcohols and Ethers	364	(3)
Physiological Properties and Uses of Alcohols and Ethers	367	(20)
Chemical Highlight 9-4 Garlic and Sulfur	370	(1)
Chapter Integration Problems	371	(3)
New Reactions	374	(2)
Important Concepts	376	(1)
Problems	377	(10)
Using Nuclear Magnetic Resonance Spectroscopy to Deduce Structure	387	(59)
Physical and Chemical Tests	388	(1)
Defining Spectroscopy	388	(3)
Hydrogen Nuclear Magnetic Resonance	391	(5)
Chemical Highlight 10-1 Recording an NMR Spectrum	394	(2)
Using NMR Spectra to Analyze Molecular Structure: The Proton Chemical Shift	396	(5)
Tests for Chemical Equivalence	401	(4)
Chemical Highlight 10-2 Magnetic Resonance Imaging in Medicine	404	(1)
Integration	405	(2)
Spin--Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens	407	(8)
Spin--Spin Splitting: Some Complications	415	(7)
Chemical Highlight 10-3 The Nonequivalence of Diastereotopic Hydrogens	418	(4)
Carbon-13 Nuclear Magnetic Resonance	422	(24)
Chemical Highlight 10-4 Correlated NMR Spectra: COSY and HETCOR	428	(2)
Chemical Highlight 10-5 Structural Characterization of Natural Products: Antioxidants from Grape Seeds	430	(2)
Chapter Integration Problems	432	(3)
Important Concepts	435	(1)
Problems	436	(10)
Alkenes; Infrared Spectroscopy and Mass Spectrometry	446	(54)
Naming the Alkenes	447	(3)
Structure and Bonding in Ethene: The Pi Bond	450	(3)
Physical Properties of Alkenes	453	(1)
Nuclear Magnetic Resonance of Alkenes	454	(6)
Chemical Highlight 11-1 Prostaglandins	459	(1)
Infrared Spectroscopy	460	(4)
Measuring the Molecular Mass of Organic Compounds: Mass Spectrometry	464	(4)
Fragmentation Patterns of Organic Molecules	468	(5)
Degree of Unsaturation: Another Aid to Identifying Molecular Structure	473	(2)
Catalytic Hydrogenation of Alkenes: Relative Stability of Double Bonds	475	(2)
Preparation of Alkenes from Haloalkanes and Alkyl Sulfonates: Bimolecular Elimination Revisited	477	(4)
Preparation of Alkenes by Dehydration of Alcohols	481	(19)
Chemical Highlight 11-2 Acid-Catalyzed Dehydration of α-Terpineol	483	(1)
Chapter Integration Problems	484	(2)
New Reactions	486	(1)
Important Concepts	487	(1)
Problems	488	(12)
Reactions of Alkenes	500	(61)
Why Addition Reactions Proceed: Thermodynamic Feasibility	501	(1)
Catalytic Hydrogenation	501	(3)
Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides	504	(4)
Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control	508	(2)
Electrophilic Addition of Halogens to Alkenes	510	(3)
The Generality of Electrophilic Addition	513	(3)
Oxymercuration--Demercuration: A Special Electrophilic Addition	516	(4)
Chemical Highlight 12-1 Juvenile Hormone Analogs in the Battle against Insect-Borne Diseases	517	(3)
Hydroboration--Oxidation: A Stereospecific Anti-Markovnikov Hydration	520	(2)
Diazomethane, Carbenes, and Cyclopropane Synthesis	522	(2)
Oxacyclopropane (Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids	524	(2)
Vicinal Syn Dihydroxylation with Osmium Tetroxide	526	(3)
Chemical Highlight 12-2 Enantioselective Dihydroxylation in the Synthesis of Antitumor Drugs	528	(1)
Oxidative Cleavage: Ozonolysis	529	(2)
Radical Additions: Anti-Markovnikov Product Formation	531	(2)
Dimerization, Oligomerization, and Polymerization of Alkenes	533	(2)
Synthesis of Polymers	535	(5)
Chemical Highlight 12-3 Polymers in the Clean-Up of Oil Spills	536	(2)
Chemical Highlight 12-4 Polymer-Supported Synthesis of Chemical Libraries	538	(2)
Ethene: An Important Industrial Feedstock	540	(1)
Alkenes in Nature: Insect Pheromones	541	(20)
Chemical Highlight 12-5 Metal-Catalyzed Alkene Metathesis for Constructing Medium and Large Rings	542	(2)
Chapter Integration Problems	544	(2)
New Reactions	546	(3)
Important Concepts	549	(1)
Problems	550	(11)
Alkynes: The Carbon--Carbon Triple Bond	561	(41)
Naming the Alkynes	562	(1)
Properties and Bonding in the Alkynes	563	(2)
Spectroscopy of the Alkynes	565	(5)
Preparation of Alkynes by Double Elimination	570	(1)
Preparation of Alkynes from Alkynyl Anions	571	(1)
Reduction of Alkynes: The Relative Reactivity of the Two Pi Bonds	572	(4)
Electrophilic Addition Reactions of Alkynes	576	(3)
Anti-Markovnikov Additions to Triple Bonds	579	(1)
Chemistry of Alkenyl Halides	580	(2)
Ethyne as an Industrial Starting Material	582	(3)
Chemical Highlight 13-1 Metal-Catalyzed Stille, Suzuki, and Sonogashira Coupling Reactions	582	(3)
Naturally Occurring and Physiologically Active Alkynes	585	(17)
Chapter Integration Problems	588	(1)
New Reactions	589	(4)
Important Concepts	593	(1)
Problems	593	(9)
Delocalized Pi Systems: Investigation by Ultraviolet and Visible Spectroscopy	602	(63)
Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System	603	(3)
Radical Allylic Halogenation	606	(1)
Nucleophilic Substitution of Allylic Halides: SN1 and SN2	607	(2)
Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles	609	(1)
Two Neighboring Double Bonds: Conjugated Dienes	610	(4)
Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control	614	(4)
Chemical Highlight 14-1 Use of a Fungicidal Diene in Making Wine: Sorbic Acid	615	(3)
Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene	618	(2)
A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition	620	(12)
Chemical Highlight 14-2 Conducting Organic Polymers: Materials for the Future?	622	(6)
Chemical Highlight 14-3 The Diels-Alder Reaction is ``Green''	628	(4)
Electrocyclic Reactions	632	(6)
Chemical Highlight 14-4 An Extraordinary Electrocyclic Reaction of Anticancer Agents	636	(2)
Polymerization of Conjugated Dienes: Rubber	638	(4)
Electronic Spectra: Ultraviolet and Visible Spectroscopy	642	(23)
Chemical Highlight 14-5 The Contributions of IR, MS, and UV to the Characterization of Viniferone	647	(1)
Chapter Integration Problems	648	(3)
New Reactions	651	(2)
Important Concepts	653	(1)
Problems	653	(7)
Interlude: A Summary of Organic Reaction Mechanisms	660	(5)
Benzene and Aromaticity: Electrophilic Aromatic Substitution	665	(56)
Naming the Benzenes	667	(2)
Structure and Resonance Energy of Benzene: A First Look at Aromaticity	669	(3)
Pi Molecular Orbitals of Benzene	672	(2)
Spectral Characteristics of the Benzene Ring	674	(5)
Polycyclic Aromatic Hydrocarbons	679	(6)
Chemical Highlight 15-1 The Allotropes of Carbon: Graphite, Diamond, and Fullerenes	680	(5)
Other Cyclic Polyenes: Huckel's Rule	685	(5)
Chemical Highlight 15-2 Juxtaposing Aromatic and Antiaromatic Rings in Fused Hydrocarbons	686	(4)
Huckel's Rule and Charged Molecules	690	(2)
Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution	692	(3)
Halogenation of Benzene: The Need for a Catalyst	695	(1)
Nitration and Sulfonation of Benzene	696	(3)
Friedel-Crafts Alkylation	699	(3)
Limitations of Friedel-Crafts Alkylations	702	(2)
Friedel-Crafts Alkanoylation (Acylation)	704	(17)
Chapter Integration Problems	708	(3)
New Reactions	711	(2)
Important Concepts	713	(1)
Problems	713	(8)
Electrophilic Attack on Derivatives of Benzene: Substituents Control Regioselectivity	721	(42)
Activation or Deactivation by Substituents on a Benzene Ring	722	(2)
Directing Inductive Effects of Alkyl Groups	724	(4)
Directing Effects of Substituents in Conjugation with the Benzene Ring	728	(7)
Chemical Highlight 16-1 Explosive Nitroarenes: TNT and Picric Acid	731	(4)
Electrophilic Attack on Disubstituted Benzenes	735	(3)
Synthetic Strategies Toward Substituted Benzenes	738	(6)
Reactivity of Polycyclic Benzenoid Hydrocarbons	744	(4)
Polycyclic Aromatic Hydrocarbons and Cancer	748	(15)
Chapter Integration Problems	750	(3)
New Reactions	753	(1)
Important Concepts	754	(1)
Problems	755	(8)
Aldehydes and Ketones: The Carbonyl Group	763	(51)
Naming the Aldehydes and Ketones	764	(2)
Structure of the Carbonyl Group	766	(2)
Spectroscopic Properties of Aldehydes and Ketones	768	(5)
Preparation of Aldehydes and Ketones	773	(2)
Reactivity of the Carbonyl Group: Mechanisms of Addition	775	(3)
Addition of Water to Form Hydrates	778	(1)
Addition of Alcohols to Form Hemiacetals and Acetals	779	(3)
Acetals as Protecting Groups	782	(2)
Nucleophilic Addition of Ammonia and Its Derivatives	784	(5)
Chemical Highlight 17-1 Imines in Biological Transformations	786	(3)
Deoxygenation of the Carbonyl Group	789	(2)
Addition of Hydrogen Cyanide to Give Cyanohydrins	791	(1)
Addition of Phosphorus Ylides: The Wittig Reaction	792	(3)
Chemical Highlight 17-2 The Wittig Reaction in Synthesis	794	(1)
Oxidation by Peroxycarboxylic Acids: The Baeyer-Villiger Oxidation	795	(1)
Oxidative Chemical Tests for Aldehydes	796	(18)
Chapter Integration Problems	798	(2)
New Reactions	800	(3)
Important Concepts	803	(1)
Problems	803	(11)
Enols, Enolates, and the Aldol Condensation: α,β-Unsaturated Aldehydes and Ketones	814	(42)
Acidity of Aldehydes and Ketones: Enolate Ions	815	(1)
Keto-Enol Equilibria	816	(3)
Halogenation of Aldehydes and Ketones	819	(2)
Alkylation of Aldehydes and Ketones	821	(3)
Attack by Enolates on the Carbonyl Function: Aldol Condensation	824	(4)
Crossed Aldol Condensation	828	(2)
Chemical Highlight 18-1 Enzyme-Catalyzed Stereoselective Aldol Condensations in Nature	829	(1)
Intramolecular Aldol Condensation	830	(2)
Chemical Highlight 18-2 Enzymes in Synthesis: Stereoselective Crossed Aldol Condensations	830	(2)
Properties of α,β-Unsaturated Aldehydes and Ketones	832	(2)
Chemical Highlight 18-3 Reactions of Unsaturated Aldehydes in Nature: The Chemistry of Vision	832	(2)
Conjugate Additions to α,β-Unsaturated Aldehydes and Ketones	834	(2)
1,2- and 1,4-Additions of Organometallic Reagents	836	(3)
Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation	839	(17)
Chemical Highlight 18-4 Prostaglandins: α,β-Dialkylation in Synthesis	840	(1)
Chapter Integration Problems	841	(3)
New Reactions	844	(3)
Important Concepts	847	(1)
Problems	847	(9)
Carboxylic Acids	856	(53)
Naming the Carboxylic Acids	857	(2)
Structural and Physical Properties of Carboxylic Acids	859	(2)
Chemical Highlight 19-1 Toxicity of Oxalic Acid	859	(2)
Spectroscopy and Mass Spectrometry of Carboxylic Acids	861	(3)
Acidic and Basic Character of Carboxylic Acids	864	(3)
Carboxylic Acid Synthesis in Industry	867	(1)
Methods for Introducing the Carboxy Functional Group	867	(3)
Substitution at the Carboxy Carbon: The Addition--Elimination Mechanism	870	(3)
Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides and Anhydrides	873	(3)
Carboxylic Acid Derivatives: Esters	876	(4)
Carboxylic Acid Derivatives: Amides	880	(2)
Reduction of Carboxylic Acids by Lithium Aluminum Hydride	882	(1)
Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction	882	(2)
Biological Activity of Carboxylic Acids	884	(25)
Chemical Highlight 19-2 Soaps from Long-Chain Carboxylates	885	(2)
Chemical Highlight 19-3 Trans Fatty Acids and Your Health	887	(2)
Chemical Highlight 19-4 Biodegradable Polyester Plastics	889	(2)
Chapter Integration Problems	891	(3)
New Reactions	894	(3)
Important Concepts	897	(1)
Problems	897	(12)
Carboxylic Acid Derivatives	909	(47)
Relative Reactivities, Structures, and Spectra of Carboxylic Acid Derivatives	910	(4)
Chemistry of Alkanoyl Halides	914	(4)
Chemistry of Carboxylic Anhydrides	918	(1)
Chemistry of Esters	919	(5)
Esters in Nature: Waxes, Fats, Oils, and Lipids	924	(4)
Chemical Highlight 20-1 Alternatives to Petroleum: Fuels from Vegetable Oil	926	(2)
Amides: The Least Reactive Carboxylic Acid Derivatives	928	(5)
Chemical Highlight 20-2 Battling the Bugs: Antibiotic Wars	930	(3)
Amidates and Their Halogenation: The Hofmann Rearrangement	933	(4)
Chemical Highlight 20-3 Methyl Isocyanate, Carbamate-based Insecticides, and Safety in the Chemical Industry	936	(1)
Alkanenitriles: A Special Class of Carboxylic Acid Derivatives	937	(19)
Chapter Integration Problems	941	(3)
New Reactions	944	(4)
Important Concepts	948	(1)
Problems	948	(8)
Amines and Their Derivatives: Functional Groups Containing Nitrogen	956	(45)
Naming the Amines	957	(1)
Structural and Physical Properties of Amines	958	(4)
Chemical Highlight 21-1 Physiologically Active Amines and Weight Control	960	(2)
Spectroscopy of the Amine Group	962	(3)
Acidity and Basicity of Amines	965	(4)
Chemical Highlight 21-2 Separation of Amines from Other Organic Compounds by Aqueous Extraction Techniques	968	(1)
Synthesis of Amines by Alkylation	969	(3)
Synthesis of Amines by Reductive Amination	972	(3)
Synthesis of Amines from Carboxylic Amides	975	(1)
Quaternary Ammonium Salts: Hofmann Elimination	975	(2)
Mannich Reaction: Alkylation of Enols by Iminium Ions	977	(2)
Nitrosation of Amines	979	(22)
Chemical Highlight 21-3 N-Nitrosodialkanamines and Cancer	980	(2)
Chemical Highlight 21-4 Amines in Industry: Nylon	982	(3)
Chapter Integration Problems	985	(3)
New Reactions	988	(5)
Important Concepts	993	(1)
Problems	993	(8)
Chemistry of Benzene Substituents: Alkylbenzenes, Phenols, and Benzenamines	1001	(60)
Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization	1002	(4)
Benzylic Oxidations and Reductions	1006	(3)
Names and Properties of Phenols	1009	(4)
Chemical Highlight 22-1 Two Phenols in the News: Bisphenol A and Resveratrol	1012	(1)
Preparation of Phenols: Nucleophilic Aromatic Substitution	1013	(9)
Alcohol Chemistry of Phenols	1022	(2)
Chemical Highlight 22-2 Aspirin: A Phenyl Alkanoate Drug	1023	(1)
Electrophilic Substitution of Phenols	1024	(4)
An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement	1028	(2)
Oxidation of Phenols: Benzoquinones	1030	(3)
Chemical Highlight 22-3 Chemical Warfare in Nature: The Bombardier Beetle	1032	(1)
Oxidation-Reduction Processes in Nature	1033	(5)
Arenediazonium Salts	1038	(3)
Electrophilic Substitution with Arenediazonium Salts: Diazo Coupling	1041	(20)
Chemical Highlight 22-4 William Perkin and the Origins of Industrial and Medicinal Chemistry	1042	(2)
Chapter Integration Problems	1044	(2)
New Reactions	1046	(6)
Important Concepts	1052	(1)
Problems	1052	(9)
Ester Enolates and the Claisen Condensation: Synthesis of β-Dicarbonyl Compounds; Acyl Anion Equivalents	1061	(35)
β-Dicarbonyl Compounds: Claisen Condensations	1062	(7)
Chemical Highlight 23-1 Claisen Condensations in Biochemistry	1066	(3)
β-Dicarbonyl Compounds as Synthetic Intermediates	1069	(5)
β-Dicarbonyl Anion Chemistry: Michael Additions	1074	(2)
Alkanoyl (Acyl) Anion Equivalents: Preparation of α-Hydroxyketones	1076	(20)
Chemical Highlight 23-2 Thiamine: A Natural, Metabolically Active Thiazolium Salt	1080	(3)
Chapter Integration Problems	1083	(4)
New Reactions	1087	(1)
Important Concepts	1088	(1)
Problems	1089	(7)
Carbohydrates: Polyfunctional Compounds in Nature	1096	(49)
Names and Structures of Carbohydrates	1097	(4)
Conformations and Cyclic Forms of Sugars	1101	(4)
Anomers of Simple Sugars: Mutarotation of Glucose	1105	(2)
Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids	1107	(2)
Oxidative Cleavage of Sugars	1109	(1)
Reduction of Monosaccharides to Alditols	1110	(1)
Carbonyl Condensations with Amine Derivatives	1111	(1)
Ester and Ether Formation: Glycosides	1112	(4)
Chemical Highlight 24-1 18F-Labeled Glucose as a Radiotracer: Imaging the Human Brain	1113	(2)
Chemical Highlight 24-2 Protecting Groups in Vitamin C Synthesis	1115	(1)
Step-by-Step Buildup and Degradation of Sugars	1116	(4)
Chemical Highlight 24-3 Sugar Biochemistry	1118	(2)
Relative Configurations of the Aldoses: An Exercise in Structure Determination	1120	(2)
Complex Sugars in Nature: Disaccharides	1122	(5)
Chemical Highlight 24-4 Carbohydrate-Derived Sugar Substitutes	1124	(3)
Polysaccharides and Other Sugars in Nature	1127	(18)
Chapter Integration Problem	1133	(2)
New Reactions	1135	(3)
Important Concepts	1138	(1)
Problems	1139	(6)
Heterocycles: Heteroatoms in Cyclic Organic Compounds	1145	(46)
Naming the Heterocycles	1148	(1)
Nonaromatic Heterocycles	1149	(4)
Chemical Highlight 25-1 Azacyclopropene Antibiotics	1150	(2)
Chemical Highlight 25-2 Smoking, Nicotine, and Cancer	1152	(1)
Structure and Properties of Aromatic Heterocyclopentadienes	1153	(3)
Reactions of the Aromatic Heterocyclopentadienes	1156	(4)
Structure and Preparation of Pyridine: An Azabenzene	1160	(4)
Reactions of Pyridine	1164	(3)
Chemical Highlight 25-3 Pyridinium Salts in Nature: Nicotinamide Adenine Dinucleotide	1166	(1)
Quinoline and Isoquinoline: The Benzopyridines	1167	(3)
Chemical Highlight 25-4 Azanaphthalenes in Nature	1168	(2)
Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature	1170	(21)
Chemical Highlight 25-5 Nature Is Not Always Green: Natural Pesticides	1172	(2)
Chapter Integration Problems	1174	(4)
New Reactions	1178	(2)
Important Concepts	1180	(1)
Problems	1180	(11)
Amino Acids, Peptides, Proteins, and Nucleic Acids: Nitrogen-Containing Polymers in Nature	1191
Structure and Properties of Amino Acids	1192	(6)
Chemical Highlight 26-1 Arginine and Nitric Oxide in Biochemistry and Medicine	1197	(1)
Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry	1198	(3)
Synthesis of Enantiomerically Pure Amino Acids	1201	(2)
Chemical Highlight 26-2 Synthesis of Optically Pure Amino Acids: Phase-Transfer Catalysis	1202	(1)
Peptides and Proteins: Amino Acid Oligomers and Polymers	1203	(8)
Determination of Primary Structure: Amino Acid Sequencing	1211	(5)
Synthesis of Polypeptides: A Challenge in the Application of Protecting Groups	1216	(3)
Merrifield Solid-Phase Peptide Synthesis	1219	(2)
Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin	1221	(2)
Biosynthesis of Proteins: Nucleic Acids	1223	(5)
Chemical Highlight 26-3 Synthetic Nucleic Acid Bases and Nucleosides in Medicine	1225	(3)
Protein Synthesis Through RNA	1228	(3)
DNA Sequencing and Synthesis: Cornerstones of Gene Technology	1231
Chemical Highlight 26-4 DNA Fingerprinting	1238	(5)
Chapter Integration Problems	1243	(3)
New Reactions	1246	(1)
Important Concepts	1247	(1)
Problems	1248
MCAT® Questions	1	(1)
Answers to Exercises	1	(1)
Photograph Credits	1	(1)
Index	1