Organic Chemistry

by Loudon, G. Marc

• ISBN13: 9780195119992
• ISBN10: 0195119991
• Edition: 4th
• Format: Hardcover
• Copyright: 2001-12-27
• Publisher: Oxford University Press

Summary

With a reputation for outstanding scientific quality, Organic Chemistry by G. Marc Loudon is a textbook that students will actually want to read. This much-anticipated fourth edition continues its predecessors' popular and unique mechanistic approach within a functional group framework.Enhanced biological and biochemical material makes it ideal for chemistry majors as well as pre-medical and pre-pharmacy students taking a full-year, sophomore- level course. Loudon's excellent use of language and reader-friendly style transform organic chemistry into a logical, understandable, andexciting subject for students. In use at undergraduate and graduate schools of all levels, this authoritative yet accessible volume is packed with effective analogies that enliven and clarify rigorous discussions of important concepts. For example, Loudon uses a flute player jumping between musical octaves to explain transitionsbetween quantum levels. An engaging detective with combined characteristics from Sherlock Holmes and James Bond depicts resonance structures. Thanks to humorous characters like Flick Flaskflinger and Professor Havno Scentz, problem-solving becomes simultaneously challenging and entertaining. Varyingfrom the routine to the complex, Loudon's problems are renowned for their originality, their range of difficulty levels, and their ability to teach students to understand and predict organic reactivity rather than just memorize facts. In addition, Loudon blends biological, environmental, andindustrial applications of organic chemistry into the body of the text-rather than separating them as "special topics"-giving students an integrated sense of the subject in its real-life context. Other Features DT Uses a high-resolution 300 MHz spectra run specifically for this text in an easy-to-read format that makes splitting patterns very clear. DT Includes new sections on transition-metal organometallic chemistry, reactions of pyridoxal phosphate, combinatorial synthesis, and drug design. DT Emphasizes both Bronsted and Lewis acid-base chemistry and their associated curved-arrow notations. DT Provides more than 1,500 excellent in-text problems that challenge students to think and analyze rather than just memorize. DT Presents "boxed asides" with interesting historical vignettes and analogies that enrich the text. DT Utilizes extensive cross-references between important concepts, thus saving students trips to the index. DT Supplemented by a CD-ROM--"Dynamic Organic Chemistry"--containing original animations (Mac and Windows compatible). DT Accompanied by a comprehensive Study Guide and Solutions Manual, acclaimed as one of the best in the field. This combination guide/manual supplies not only answers but also detailed solutions to all text problems. Its "Study Guide Links" show students how to solve problems, provide shortcuts tomastering particular topics, and offer detailed discussions of concepts that students often find difficult. Full chapter outlines, a glossary of terms, and reaction reviews are provided.

Author Biography

G. Marc Loudon is Cwalina Distinguished Professor of Medicinal Chemistry at Purdue University

Table of Contents

Preface	xxv
About the Author	xxxiii
Chemical Bonding and Chemical Structure	1	(42)
Introduction	1	(2)
What Is Organic Chemistry?	1	(1)
Emergence of Organic Chemistry	1	(1)
Why Study Organic Chemistry?	2	(1)
Classical Theories of Chemical Bonding	3	(8)
Electrons in Atoms	3	(1)
The Ionic Bond	4	(1)
The Covalent Bond	5	(4)
The Polar Covalent Bond	9	(2)
Structures of Covalent Compounds	11	(7)
Methods for Determining Molecular Geometry	12	(1)
Prediction of Molecular Geometry	12	(6)
Resonance Structures	18	(2)
Wave Nature of the Electron	20	(1)
Electronic Structure of the Hydrogen Atom	21	(6)
Orbitals, Quantum Numbers, and Energy	21	(2)
Spatial Characteristics of Orbitals	23	(4)
Summary: Atomic Orbitals of Hydrogen	27	(1)
Electronic Structures of More Complex Atoms	27	(3)
Another Look at the Covalent Bond: Molecular Orbitals	30	(5)
Molecular Orbital Theory	30	(4)
Molecular Orbital Theory and Lewis Structures	34	(1)
Hybrid Orbitals	35	(8)
Bonding in Methane	35	(2)
Bonding in Ammonia	37	(1)
Key Ideas in Chapter 1	38	(1)
Additional Problems	39	(4)
Alkanes	43	(39)
Hydrocarbons	43	(2)
Unbranched Alkanes	45	(2)
Conformations of Alkanes	47	(6)
Conformation of Ethane	47	(3)
Conformations of Butane	50	(3)
Constitutional Isomers and Nomenclature	53	(9)
Isomers	53	(1)
Organic Nomenclature	54	(1)
Substitutive Nomenclature of Alkanes	54	(5)
Highly Condensed Structures	59	(2)
Classification of Carbon Substitution	61	(1)
Cycloalkanes and Skeletal Structures	62	(3)
Physical Properties of Alkanes	65	(5)
Boiling Points	65	(3)
Melting Points	68	(1)
Other Physical Properties	69	(1)
Combustion and Elemental Analysis	70	(3)
Reactivity of Alkanes: Combustion	70	(1)
Elemental Analysis by Combustion	70	(3)
Occurrence and Use of Alkanes	73	(3)
Functional Groups, Compound Classes, and the ``R'' Notation	76	(6)
Functional Groups and Compound Classes	76	(1)
``R'' Notation	77	(1)
Key Ideas in Chapter 2	78	(1)
Additional Problems	78	(4)
Acids and Bases: The Curved-Arrow Notation	82	(29)
Lewis Acid-Base Association Reactions	82	(3)
Electron-Deficient Compounds	82	(1)
Reactions of Electron-Deficient Compounds with Lewis Bases	83	(1)
The Curved-Arrow Notation for Lewis Acid-Base Association and Dissociation Reactions	84	(1)
Electron-Pair Displacement Reactions	85	(4)
Electron-Pair Displacement Reactions as Lewis Acid-Base Reactions	85	(1)
The Curved-Arrow Notation for Electron-Pair Displacement Reactions	86	(3)
Review of the Curved-Arrow Notation	89	(2)
Use of the Curved-Arrow Notation to Represent Lewis Acid-Base Reactions	89	(1)
Use of the Curved-Arrow Notation to Derive Resonance Structures	89	(2)
Brnsted-Lowry Acids and Bases	91	(5)
Definition of Brnsted Acids and Bases	91	(1)
Strengths of Brnsted Acids	92	(1)
Strengths of Brnsted Bases	93	(1)
Equilibria in Acid-Base Reactions	94	(2)
Free Energy and Chemical Equilibrium	96	(3)
Relationship of Structure to Acidity	99	(12)
The Element Effect	99	(2)
The Polar Effect	101	(4)
Key Ideas in Chapter 3	105	(1)
Additional Problems	106	(5)
Introduction to Alkenes: Structure and Reactivity	111	(49)
Structure and Bonding in Alkenes	111	(8)
Carbon Hybridization in Alkenes	112	(4)
Cis-Trans Isomerism	116	(3)
Nomenclature of Alkenes	119	(7)
IUPAC Substitutive Nomenclature	119	(3)
Nomenclature of Stereoisomers: The E,Z System	122	(4)
Unsaturation Number	126	(1)
Physical Properties of Alkenes	127	(1)
Relative Stabilities of Alkene Isomers	128	(5)
Heats of Formation	128	(2)
Relative Stabilities of Alkene Isomers	130	(3)
Addition Reactions of Alkenes	133	(1)
Addition of Hydrogen Halides to Alkenes	134	(8)
Regioselectivity of Hydrogen Halide Addition	134	(2)
Carbocation Intermediates in Hydrogen Halide Addition	136	(2)
Structure and Stability of Carbocations	138	(2)
Carbocation Rearrangement in Hydrogen Halide Addition	140	(2)
Reaction Rates	142	(8)
The Transition State	143	(2)
Multistep Reactions and the Rate-Limiting Step	145	(2)
Hammond's Postulate	147	(3)
Catalysis	150	(10)
Catalytic Hydrogenation of Alkenes	150	(2)
Hydration of Alkenes	152	(2)
Enzyme Catalysis	154	(1)
Key Ideas in Chapter 4	155	(1)
Additional Problems	156	(4)
Addition Reactions of Alkenes	160	(41)
Reactions of Alkenes with Halogens	160	(4)
Addition of Chlorine and Bromine	160	(2)
Halohydrins	162	(2)
Writing Organic Reactions	164	(1)
Conversion of Alkenes Into Alcohols	165	(8)
Oxymercuration-Reduction of Alkenes	165	(3)
Hydroboration-Oxidation of Alkenes	168	(4)
Comparison of Methods for the Synthesis of Alcohols from Alkenes	172	(1)
Ozonolysis of Alkenes	173	(4)
Free-Radical Addition of Hydrogen Bromide to Alkenes	177	(13)
The Peroxide Effect	177	(1)
Free Radicals and the ``Fishhook'' Notation	178	(1)
Free-Radical Chain Reactions	179	(4)
Explanation of the Peroxide Effect	183	(4)
Bond Dissociation Energies	187	(3)
Polymers: Free-Radical Polymerization of Alkenes	190	(2)
Alkenes in the Chemical Industry	192	(9)
Key Ideas in Chapter 5	195	(1)
Additional Problems	195	(6)
Principles of Stereochemistry	201	(43)
Enantiomers, Chirality, and Symmetry	201	(5)
Enantiomers and Chirality	201	(3)
Asymmetric Carbon and Stereocenters	204	(1)
Chirality and Symmetry	205	(1)
Nomenclature of Enantiomers: The R,S System	206	(3)
Physical Properties of Enantiomers: Optical Activity	209	(4)
Polarized Light	209	(1)
Optical Activity	210	(3)
Optical Activities of Enantiomers	213	(1)
Racemates	213	(2)
Stereochemical Correlation	215	(2)
Diastereomers	217	(4)
Meso Compounds	221	(3)
Enantiomeric Resolution	224	(2)
Chiral Molecules Without Asymmetric Atoms	226	(2)
Conformational Stereoisomers	228	(3)
Stereoisomers Interconverted by Internal Rotations	228	(1)
Asymmetric Nitrogen: Amine Inversion	229	(2)
Fischer Projections	231	(4)
The Postulation of Tetrahedral Carbon	235	(9)
Key Ideas in Chapter 6	239	(1)
Additional Problems	239	(5)
Cyclic Compounds: Stereochemistry of Reactions	244	(57)
Relative Stabilities of the Monocyclic Alkanes	244	(1)
Conformations of Cyclohexane	245	(8)
The Chair Conformation	245	(3)
Interconversion of Chair Conformations	248	(3)
Boat and Twist-Boat Conformations	251	(2)
Monosubstituted Cyclohexanes: Conformational Analysis	253	(4)
Disubstituted Cyclohexanes	257	(8)
Cis-Trans Isomerism in Disubstituted Cyclohexanes	257	(2)
Conformational Analysis	259	(2)
Use of Planar Structures for Cyclic Compounds	261	(1)
Stereochemical Consequences of the Chair Flip	262	(3)
Cyclopentane, Cyclobutane, and Cyclopropane	265	(3)
Cyclopentane	265	(1)
Cyclobutane and Cyclopropane	266	(2)
Bicyclic and Polycyclic Compounds	268	(7)
Classification and Nomenclature	268	(2)
Cis and Trans Ring Fusion	270	(2)
Trans-Cycloalkenes and Bredt's Rule	272	(1)
Steroids	273	(2)
Relative Reactivities of Stereoisomers	275	(3)
Relative Reactivities of Enantiomers	276	(2)
Relative Reactivities of Diastereomers	278	(1)
Reactions That Form Stereoisomers	278	(5)
Reactions of Achiral Compounds That Give Enantiomeric Products	279	(3)
Reactions That Give Diastereomeric Products	282	(1)
Stereochemistry of Chemical Reactions	283	(18)
Stereochemistry of Addition Reactions	283	(1)
Stereochemistry of Substitution Reactions	284	(2)
Stereochemistry of Bromine Addition	286	(4)
Stereochemistry of Hydroboration-Oxidation	290	(1)
Stereochemistry of Other Addition Reactions	291	(2)
Key Ideas in Chapter 7	293	(1)
Additional Problems	294	(7)
Introduction to Alkyl Halides, Alcohols, Ethers, Thiols, and Sulfides	301	(50)
Nomenclature	302	(8)
Nomenclature of Alkyl Halides	302	(2)
Nomenclature of Alcohols and Thiols	304	(4)
Nomenclature of Ethers and Sulfides	308	(2)
Structures	310	(1)
Effect of Molecular Polarity and Hydrogen Bonding on Physical Properties	311	(5)
Boiling Points of Ethers and Alkyl Halides	311	(2)
Boiling Points of Alcohols	313	(1)
Hydrogen Bonding	313	(3)
Solvents in Organic Chemistry	316	(6)
Classification of Solvents	316	(3)
Solubility	319	(3)
Applications of Solubility and Solvation Principles	322	(6)
Cell Membranes and Drug Solubility	322	(3)
Cation-Binding Molecules	325	(3)
Acidity of Alcohols and Thiols	328	(5)
Formation of Alkoxides and Mercaptides	329	(2)
Polar Effects on Alcohol Acidity	331	(1)
Role of the Solvent in Alcohol Acidity	332	(1)
Basicity of Alcohols and Ethers	333	(1)
Grignard and Organolithium Reagents	334	(4)
Formation of Grignard and Organolithium Reagents	335	(1)
Protonolysis of Grignard and Organolithium Reagents	336	(2)
Industrial Preparation and Use of Alkyl Halides, Alcohols, and Ethers	338	(13)
Free-Radical Halogenation of Alkanes	338	(1)
Uses of Halogen-Containing Compounds	339	(3)
Production and Use of Alcohols and Ethers	342	(3)
Safety Hazards of Ethers	345	(1)
Key Ideas in Chapter 8	346	(1)
Additional Problems	347	(4)
Chemistry of Alkyl Halides	351	(57)
An Overview of Nucleophilic Substitution and -Elimination Reactions	351	(5)
Nucleophilic Substitution Reactions	351	(2)
β-Elimination Reactions	353	(2)
Competition between Nucleophilic Substitution and -Elimination Reactions	355	(1)
Equilibrium in Nucleophilic Substitution Reactions	356	(1)
Reaction Rates	357	(3)
Definition of Reaction Rate	357	(1)
The Rate Law	358	(1)
Relationship of the Rate Constant to the Standard Free Energy of Activation	359	(1)
The SN2 Reaction	360	(11)
Rate Law and Mechanism of the SN2 Reaction	360	(2)
Stereochemistry of the SN2 Reaction	362	(2)
Effect of Alkyl Halide Structure on the SN2 Reaction	364	(2)
Nucleophilicity in the SN2 Reaction	366	(4)
Leaving-Group Effects in the SN2 Reaction	370	(1)
Summary of the SN2 Reaction	371	(1)
The E2 Reaction	371	(11)
Rate Law and Mechanism of the E2 Reaction	371	(1)
Leaving-Group Effects on the E2 Reaction	372	(1)
Deuterium Isotope Effects in the E2 Reaction	372	(2)
Stereochemistry of the E2 Reaction	374	(2)
Regioselectivity of the E2 Reaction	376	(1)
Competition between the E2 and SN2 Reactions: A Closer Look	377	(5)
Summary of the E2 Reaction	382	(1)
The SN1 and E1 Reactions	382	(9)
Rate Law and Mechanism of SN1 and E1 Reactions	383	(1)
Rate-Limiting and Product-Determining Steps	384	(2)
Reactivity and Product Distributions in SN1-E1 Reactions	386	(2)
Stereochemistry of the SN1 Reaction	388	(3)
Summary of the SN1 and E1 Reactions	391	(1)
Summary of Substitution and Elimination Reactions of Alkyl Halides	391	(3)
Carbenes and Carbenoids	394	(14)
α-Elimination Reactions	394	(3)
The Simmons-Smith Reaction	397	(2)
Key Ideas in Chapter 9	399	(1)
Additional Problems	400	(8)
Chemistry of Alcohols and Thiols	408	(47)
Dehydration of Alcohols	408	(3)
Reactions of Alcohols with Hydrogen Halides	411	(3)
Sulfonate and Inorganic Ester Derivatives of Alcohols	414	(8)
Sulfonate Ester Derivatives of Alcohols	415	(3)
Alkylating Agents	418	(1)
Ester Derivatives of Strong Inorganic Acids	419	(1)
Reactions of Alcohols with Thionyl Chloride and Phosphorus Tribromide	420	(2)
Conversion of Alcohols into Alkyl Halides: Summary	422	(1)
Oxidation and Reduction in Organic Chemistry	423	(7)
Oxidation Numbers	423	(4)
Oxidizing and Reducing Agents	427	(3)
Oxidation of Alcohols	430	(3)
Oxidation to Aldehydes and Ketones	430	(3)
Oxidation to Carboxylic Acids	433	(1)
Biological Oxidation of Ethanol	433	(3)
Chemical and Stereochemical Group Equivalence	436	(7)
Chemical Equivalence and Nonequivalence	437	(4)
Stereochemistry of the Alcohol Dehydrogenase Reaction	441	(2)
Oxidation of Thiols	443	(3)
Synthesis of Alcohols	446	(1)
Design of Organic Synthesis	447	(8)
Key Ideas in Chapter 10	449	(1)
Additional Problems	450	(5)
Chemistry of Ethers, Epoxides, Glycols, and Sulfides	455	(42)
Synthesis of Ethers and Sulfides	455	(6)
Williamson Ether Synthesis	455	(2)
Alkoxymercuration-Reduction of Alkenes	457	(1)
Ethers from Alcohol Dehydration and Alkene Addition	458	(3)
Synthesis of Epoxides	461	(3)
Oxidation of Alkenes with Peroxycarboxylic Acids	461	(2)
Cyclization of Halohydrins	463	(1)
Cleavage of Ethers	464	(3)
Nucleophilic Substitution Reactions of Epoxides	467	(6)
Ring-Opening Reactions under Basic Conditions	467	(2)
Ring-Opening Reactions under Acidic Conditions	469	(3)
Reaction of Ethylene Oxide with Grignard Reagents	472	(1)
Preparation and Oxidative Cleavage of Glycols	473	(6)
Preparation of Glycols	474	(3)
Oxidative Cleavage of Glycols	477	(2)
Oxonium and Sulfonium Salts	479	(2)
Reactions of Oxonium and Sulfonium Salts	479	(1)
S-Adenosylmethionine: Nature's Methylating Agent	480	(1)
Neighboring-Group Participation: Intramolecular Reactions	481	(3)
Oxidation of Ethers and Sulfides	484	(1)
The Three Fundamental Operations of Organic Synthesis	485	(12)
Key Ideas in Chapter 11	487	(1)
Additional Problems	488	(9)
Introduction to Spectroscopy: Infrared Spectroscopy and Mass Spectrometry	497	(42)
Introduction to Spectroscopy	497	(5)
Electromagnetic Radiation	497	(3)
Absorption Spectroscopy	500	(2)
Infrared Spectroscopy	502	(3)
The Infrared Spectrum	502	(1)
Physical Basis of IR Spectroscopy	503	(2)
Infrared Absorption and Chemical Structure	505	(7)
Factors That Determine IR Absorption Position	506	(3)
Factors That Determine IR Absorption Intensity	509	(3)
Functional-Group Infrared Absorptions	512	(5)
IR Spectra of Alkanes	512	(1)
IR Spectra of Alkyl Halides	512	(1)
IR Spectra of Alkenes	512	(3)
IR Spectra of Alcohols and Ethers	515	(2)
The Infrared Spectrometer	517	(1)
Introduction to Mass Spectrometry	518	(21)
Production of a Mass Spectrum	518	(2)
Isotopic Peaks	520	(3)
Fragmentation Mechanisms	523	(4)
Odd-Electron Ions and Even-Electron Ions	527	(1)
Identifying the Molecular Ion	528	(1)
The Mass Spectrometer	529	(2)
Key Ideas in Chapter 12	531	(1)
Additional Problems	531	(8)
Nuclear Magnetic Resonance Spectroscopy	539	(67)
An Overview of Proton NMR Spectroscopy	539	(3)
Physical Basis of NMR Spectroscopy	542	(2)
The NMR Spectrum: Chemical Shift and Integral	544	(13)
Chemical Shift	544	(3)
Chemical Shift Scales	547	(1)
Relationship of Chemical Shift to Structure	548	(3)
The Number of Absorptions in an NMR Spectrum	551	(3)
Counting Protons with the Integral	554	(1)
Using the Chemical Shift and Integral to Determine Unknown Structures	555	(2)
The NMR Spectrum: Spin-Spin Splitting	557	(9)
The n + 1 Splitting Rule	557	(4)
Why Splitting Occurs	561	(2)
Solving Unknown Structures with NMR Spectra Involving Splitting	563	(3)
Complex NMR Spectra	566	(7)
Multiplicative Splitting	566	(4)
Breakdown of the n + 1 Rule	570	(3)
Use of Deuterium in Proton NMR	573	(1)
Characteristic Functional-Group NMR Absorptions	574	(7)
NMR Spectra of Alkenes	574	(3)
NMR Spectra of Alkanes and Cycloalkanes	577	(1)
NMR Spectra of Alkyl Halides and Ethers	578	(1)
NMR Spectra of Alcohols	579	(2)
NMR Spectroscopy of Dynamic Systems	581	(3)
Carbon NMR	584	(7)
Solving Structure Problems with Spectroscopy	591	(3)
The NMR Spectrometer	594	(2)
Other Uses of NMR	596	(10)
Key Ideas in Chapter 13	597	(1)
Additional Problems	597	(9)
Chemistry of Alkynes	606	(31)
Nomenclature of Alkynes	606	(2)
Structure and Bonding in Alkynes	608	(3)
Physical Properties of Alkynes	611	(3)
Boiling Points and Solubilities	611	(1)
IR Spectroscopy of Alkynes	611	(1)
NMR Spectroscopy of Alkynes	612	(2)
Introduction to Addition Reactions of the Triple Bond	614	(1)
Conversion of Alkynes into Aldehydes and Ketones	615	(5)
Hydration of Alkynes	615	(3)
Hydroboration-Oxidation of Alkynes	618	(2)
Reduction of Alkynes	620	(3)
Catalytic Hydrogenation of Alkynes	620	(1)
Reduction of Alkynes with Sodium in Liquid Ammonia	621	(2)
Acidity of 1-Alkynes	623	(4)
Acetylenic Anions	623	(3)
Acetylenic Anions as Nucleophiles	626	(1)
Organic Synthesis Using Alkynes	627	(1)
Pheromones	628	(2)
Occurrence and Use of Alkynes	630	(7)
Key Ideas in Chapter 14	631	(1)
Additional Problems	632	(5)
Dienes, Resonance, and Aromaticity	637	(57)
Structure and Stability of Dienes	638	(4)
Structure and Stability of Conjugated Dienes	638	(2)
Structure and Stability of Cumulated Dienes	640	(2)
Ultraviolet Spectroscopy	642	(6)
The UV Spectrum	642	(3)
Physical Basis of UV Spectroscopy	645	(1)
UV Spectroscopy of Conjugated Alkenes	646	(2)
The Diels-Alder Reaction	648	(10)
Reaction of Conjugated Dienes with Alkenes	648	(4)
Effect of Diene Conformation on the Diels-Alder Reaction	652	(2)
Stereochemistry of the Diels-Alder Reaction	654	(4)
Addition of Hydrogen Halides to Conjugated Dienes	658	(6)
1,2-and 1,4-Additions	658	(1)
Allylic Carbocations	659	(2)
Kinetic and Thermodynamic Control	661	(3)
Diene Polymers	664	(2)
Resonance	666	(7)
Drawing Resonance Structures	666	(1)
Relative Importance of Resonance Structures	667	(3)
Use of Resonance Structures	670	(3)
Introduction to Aromatic Compounds	673	(21)
Benzene, a Puzzling ``Alkene''	673	(2)
Structure of Benzene	675	(2)
Stability of Benzene	677	(1)
Aromaticity and the Huckel 4n + 2 Rule	677	(6)
Antiaromatic Compounds	683	(1)
Key Ideas in Chapter 15	684	(1)
Additional Problems	685	(9)
Chemistry of Benzene and Its Derivatives	694	(49)
Nomenclature of Benzene Derivatives	694	(3)
Physical Properties of Benzene Derivatives	697	(1)
Spectroscopy of Benzene Derivatives	698	(6)
IR Spectroscopy	698	(1)
NMR Spectroscopy	699	(3)
CMR Spectroscopy	702	(1)
UV Spectroscopy	703	(1)
Electrophilic Aromatic Substitution Reactions of Benzene	704	(12)
Halogenation of Benzene	704	(2)
Electrophilic Aromatic Substitution	706	(2)
Nitration of Benzene	708	(1)
Sulfonation of Benzene	709	(1)
Friedel-Crafts Alkylation of Benzene	710	(3)
Friedel-Crafts Acylation of Benzene	713	(3)
Electrophilic Aromatic Substitution Reactions of Substituted Benzenes	716	(15)
Directing Effects of Substituents	716	(7)
Activating and Deactivating Effects of Substituents	723	(4)
Use of Electrophilic Aromatic Substitution in Organic Synthesis	727	(4)
Hydrogenation of Benzene Derivatives	731	(1)
Source and Industrial Use of Aromatic Hydrocarbons	732	(11)
Key Ideas in Chapter 16	735	(1)
Additional Problems	735	(8)
Allylic and Benzylic Reactivity	743	(32)
Reactions Involving Allylic and Benzylic Carbocations	744	(4)
Reactions Involving Allylic and Benzylic Radicals	748	(5)
Reactions Involving Allylic and Benzylic Anions	753	(4)
Allylic Grignard Reagents	754	(2)
E2 Eliminations Involving Allylic or Benzylic Hydrogens	756	(1)
Allylic and Benzylic SN2 Reactions	757	(1)
Benzylic Oxidation of Alkylbenzenes	758	(1)
Terpenes	759	(16)
The Isoprene Rule	759	(4)
Biosynthesis of Terpenes	763	(3)
Key Ideas in Chapter 17	766	(1)
Additional Problems	767	(8)
Chemistry of Aryl Halides, Vinylic Halides, and Phenols: Transition-Metal Catalysis	775	(61)
Lack of Reactivity of Vinylic and Aryl Halides Under SN2 Conditions	776	(2)
Elimination Reactions of Vinylic Halides	778	(1)
Lack of Reactivity of Vinylic and Aryl Halides Under SN1 Conditions	779	(2)
Nucleophilic Substitution Reactions of Aryl Halides	781	(7)
Nucleophilic Aromatic Substitution	781	(3)
Substitution by Elimination-Addition: Benzyne	784	(3)
Summary: Nucleophilic Substitution Reactions of Aryl Halides	787	(1)
Transition-Metal Catalyzed Coupling Reactions	788	(19)
Transition Metals and Their Complexes	788	(4)
Oxidation State	792	(1)
The dn Notation	792	(1)
Electron Counting: The 16-and 18-Electron Rules	793	(3)
Fundamental Reactions of Transition-Metal Complexes	796	(6)
The Heck Reaction	802	(3)
Other Examples of Transition-Metal Catalyzed Reactions	805	(2)
Acidity of Phenols	807	(4)
Resonance and Polar Effects on the Acidity of Phenols	807	(2)
Formation and Use of Phenoxides	809	(2)
Oxidation of Phenols to Quinones	811	(4)
Electrophilic Aromatic Substitution Reactions of Phenols	815	(4)
Reactivity of the Aryl-Oxygen Bond	819	(4)
Lack of Reactivity of the Aryl-Oxygen Bond in SN1 and SN2 Reactions	819	(1)
Substitution at the Aryl-Oxygen Bond: The Stille Reaction	820	(3)
Industrial Preparation and Use of Phenol	823	(13)
Key Ideas in Chapter 18	824	(1)
Additional Problems	825	(11)
Chemistry of Aldehydes and Ketones: Carbonyl-Addition Reactions	836	(59)
Nomenclature of Aldehydes and Ketones	838	(4)
Common Nomenclature	838	(2)
Substitutive Nomenclature	840	(2)
Physical Properties of Aldehydes and Ketones	842	(1)
Spectroscopy of Aldehydes and Ketones	843	(8)
IR Spectroscopy	843	(2)
Proton NMR Spectroscopy	845	(1)
Carbon NMR Spectroscopy	846	(1)
UV Spectroscopy	847	(2)
Mass Spectrometry	849	(2)
Synthesis of Aldehydes and Ketones	851	(1)
Introduction to Aldehyde and Ketone Reactions	851	(1)
Basicity of Aldehydes and Ketones	852	(3)
Reversible Addition Reactions of Aldehydes and Ketones	855	(6)
Mechanisms of Carbonyl-Addition Reactions	855	(2)
Equilibria in Carbonyl-Addition Reactions	857	(3)
Rates of Carbonyl-Addition Reactions	860	(1)
Reduction of Aldehydes and Ketones to Alcohols	861	(4)
Reactions of Aldehydes and Ketones with Grignard and Related Reagents	865	(3)
Acetals and Their Use as Protecting Groups	868	(6)
Preparation and Hydrolysis of Acetals	868	(4)
Protecting Groups	872	(2)
Reactions of Aldehydes and Ketones with Amines	874	(5)
Reaction with Primary Amines and Other Monosubstituted Derivatives of Ammonia	874	(3)
Reaction with Secondary Amines	877	(2)
Reduction of Carbonyl Groups to Methylene Groups	879	(2)
The Wittig Alkene Synthesis	881	(3)
Oxidation of Aldehydes to Carboxylic Acids	884	(2)
Manufacture and Use of Aldehydes and Ketones	886	(9)
Key Ideas in Chapter 19	887	(1)
Additional Problems	888	(7)
Chemistry of Carboxylic Acids	895	(39)
Nomenclature of Carboxylic Acids	895	(5)
Common Nomenclature	895	(3)
Substitutive Nomenclature	898	(2)
Structure and Physical Properties of Carboxylic Acids	900	(2)
Spectroscopy of Carboxylic Acids	902	(2)
IR Spectroscopy	902	(1)
NMR Spectroscopy	902	(2)
Acid-Base Properties of Carboxylic Acids	904	(4)
Acidity of Carboxylic and Sulfonic Acids	904	(3)
Basicity of Carboxylic Acids	907	(1)
Fatty Acids, Soaps, and Detergents	908	(2)
Synthesis of Carboxylic Acids	910	(1)
Introduction to Carboxylic Acid Reactions	911	(2)
Conversion of Carboxylic Acids into Esters	913	(5)
Acid-Catalyzed Esterification	913	(3)
Esterification by Alkylation	916	(2)
Conversion of Carboxylic Acids into Acid Chlorides and Anhydrides	918	(4)
Synthesis of Acid Chlorides	918	(2)
Synthesis of Anhydrides	920	(2)
Reduction of Carboxylic Acids to Primary Alcohols	922	(1)
Decarboxylation of Carboxylic Acids	923	(11)
Key Ideas in Chapter 20	926	(1)
Additional Problems	926	(8)
Chemistry of Carboxylic Acid Derivatives	934	(63)
Nomenclature and Classification of Carboxylic Acid Derivatives	934	(6)
Esters and Lactones	934	(2)
Acid Halides	936	(1)
Anhydrides	936	(1)
Nitriles	937	(1)
Amides, Lactams, and Imides	937	(2)
Nomenclature of Substituent Groups	939	(1)
Carbonic Acid Derivatives	939	(1)
Structures of Carboxylic acid Derivatives	940	(2)
Physical Properties of Carboxylic Acid Derivatives	942	(2)
Esters	942	(1)
Anhydrides and Acid Chlorides	942	(1)
Nitriles	943	(1)
Amides	943	(1)
Spectroscopy of Carboxylic Acid Derivatives	944	(5)
IR Spectroscopy	944	(1)
NMR Spectroscopy	945	(4)
Basicity of Carboxylic Acid Derivatives	949	(1)
Introduction to Reactions of Carboxylic Acid Derivatives	950	(1)
Hydrolysis of Carboxylic Acid Derivatives	951	(12)
Hydrolysis of Esters	951	(3)
Hydrolysis of Amides	954	(1)
Hydrolysis of Nitriles	955	(2)
Hydrolysis of Acid Chlorides and Anhydrides	957	(1)
Mechanisms and Reactivity in Nucleophilic Acyl Substitution Reactions	958	(5)
Reactions of Carboxylic Acid Derivatives with Nucleophiles	963	(6)
Reactions of Acid Chlorides with Nucleophiles	963	(3)
Reactions of Anhydrides with Nucleophiles	966	(1)
Reactions of Esters with Nucleophiles	967	(2)
Reduction of Carboxylic Acid Derivatives	969	(8)
Reduction of Esters to Primary Alcohols	969	(1)
Reduction of Amides to Amines	970	(2)
Reduction of Nitriles to Primary Amines	972	(2)
Reduction of Acid Chlorides to Aldehydes	974	(2)
Relative Reactivities of Carbonyl Compounds	976	(1)
Reactions of Carboxylic Acid Derivatives with Organometallic Reagents	977	(3)
Reaction of Esters with Grignard Reagents	977	(1)
Reaction of Acid Chlorides with Lithium Dialkylcuprates	978	(2)
Synthesis of Carboxylic Acid Derivatives	980	(2)
Use and Occurrence of Carboxylic Acids and Their Derivatives	982	(15)
Nylon and Polyesters	982	(2)
Waxes, Fats, and Phospholipids	984	(2)
Key Ideas in Chapter 21	986	(1)
Additional Problems	987	(10)
Chemistry of Enolate Ions, Enols, and α,β-Unsaturated Carbonyl Compounds	997	(72)
Acidity of Carbonyl Compounds	998	(5)
Formation of Enolate Anions	998	(3)
Introduction to Reactions of Enolate Ions	1001	(2)
Enolization of Carbonyl Compounds	1003	(4)
α-Halogenation of Carbonyl Compounds	1007	(7)
Acid-Catalyzed α-Halogenation	1007	(2)
Halogenation of Aldehydes and Ketones in Base: The Haloform Reaction	1009	(2)
α-Bromination of Carboxylic Acids	1011	(1)
Reactions of a-Halo Carbonyl Compounds	1012	(2)
Aldol Addition and Aldol Condensation	1014	(9)
Base-Catalyzed Aldol Reactions	1014	(2)
Acid-Catalyzed Aldol Condensation	1016	(2)
Special Types of Aldol Reaction	1018	(2)
Synthesis with the Aldol Condensation	1020	(3)
Condensation Reactions Involving Ester Enolate Ions	1023	(9)
Claisen Condensation	1024	(3)
Dieckmann Condensation	1027	(1)
Crossed Claisen Condensation	1027	(2)
Synthesis with the Claisen Condensation	1029	(3)
Biosynthesis of Fatty Acids	1032	(3)
Alkylation of Ester Enolate Ions	1035	(8)
Malonic Ester Synthesis	1036	(2)
Direct Alkylation of Enolate Ions Derived from Monoesters	1038	(2)
Acetoacetic Ester Synthesis	1040	(3)
Conjugate-Addition Reactions	1043	(9)
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds	1043	(4)
Conjugate Addition Reactions versus Carbonyl-Group Reactions	1047	(2)
Conjugate Addition of Enolate Ions	1049	(3)
Reduction of α,β-Unsaturated Carbonyl Compounds	1052	(1)
Reactions of α,β-Unsaturated Carbonyl Compounds with Organometallic Reagents	1053	(2)
Addition of Organolithium Reagents to the Carbonyl Group	1053	(1)
Conjugate Addition of Lithium Dialkylcuprate Reagents	1054	(1)
Organic Synthesis with Conjugate-Addition Reactions	1055	(14)
Key Ideas in Chapter 22	1057	(1)
Additional Problems	1058	(11)
Chemistry of Amines	1069	(51)
Nomenclature of Amines	1070	(2)
Common Nomenclature	1070	(1)
Substitutive Nomenclature	1070	(2)
Structure of Amines	1072	(1)
Physical Properties of Amines	1073	(1)
Spectroscopy of Amines	1074	(2)
IR Spectroscopy	1074	(1)
NMR Spectroscopy	1074	(1)
Mass Spectrometry	1075	(1)
Basicity and Acidity of Amines	1076	(7)
Basicity of Amines	1076	(1)
Substituent Effects on Amine Basicity	1076	(5)
Separations Using Amine Basicity	1081	(1)
Acidity of Amines	1082	(1)
Summary of Acidity and Basicity	1082	(1)
Quaternary Ammonium Salts	1083	(1)
Alkylation and Acylation Reactions of Amines	1083	(5)
Direct Alkylation of Amines	1084	(1)
Reductive Amination	1085	(3)
Acylation of Amines	1088	(1)
Hofmann Elimination of Quaternary Ammonium Hydroxides	1088	(4)
Aromatic Substitution Reactions of Aniline Derivatives	1092	(2)
Diazotization: Reactions of Diazonium Ions	1094	(6)
Formation and Substitution Reactions of Diazonium Salts	1094	(3)
Aromatic Substitution with Diazonium Ions	1097	(2)
Reactions of Secondary and Tertiary Amines with Nitrous Acid	1099	(1)
Synthesis of Amines	1100	(8)
Gabriel Synthesis of Primary Amines	1100	(2)
Reduction of Nitro Compounds	1102	(1)
Curtius and Hofmann Rearrangements	1103	(4)
Synthesis of Amines: Summary	1107	(1)
Use and Occurrence of Amines	1108	(12)
Industrial Use of Amines and Ammonia	1108	(1)
Naturally Occurring Amines	1108	(2)
Key Ideas in Chapter 23	1110	(1)
Additional Problems	1111	(9)
Chemistry of Naphthalene and the Aromatic Heterocycles	1120	(52)
Chemistry of Naphthalene	1122	(6)
Physical Properties and Structure	1122	(1)
Nomenclature	1122	(2)
Electrophilic Substitution Reactions	1124	(4)
Introduction to the Aromatic Heterocycles	1128	(7)
Nomenclature	1128	(2)
Structure and Aromaticity	1130	(3)
Basicity and Acidity of the Nitrogen Heterocycles	1133	(2)
Chemistry of Furan, Pyrrole, and Thiophene	1135	(5)
Electrophilic Aromatic Substitution	1135	(3)
Addition Reactions of Furan	1138	(1)
Side-Chain Reactions	1139	(1)
Synthesis of Indoles	1140	(4)
Fischer Indole Synthesis	1140	(2)
Reissert Indole Synthesis	1142	(2)
Chemistry of Pyridine and Quinoline	1144	(17)
Electrophilic Aromatic Substitution	1144	(3)
Nucleophilic Aromatic Substitution	1147	(4)
Pyridinium Salts and Their Reactions	1151	(1)
Side-Chain Reactions of Pyridine Derivatives	1152	(1)
Pyridinium Ions in Biology: Pyridoxal Phosphate	1153	(6)
Skraup Synthesis of Quinolines	1159	(2)
Occurrence of Heterocyclic Compounds	1161	(11)
Key Ideas in Chapter 24	1162	(1)
Additional Problems	1163	(9)
Pericyclic Reactions	1172	(43)
Molecular Orbitals of Conjugated -Electron Systems	1175	(8)
Molecular Orbitals of Conjugated Alkenes	1175	(4)
Molecular Orbitals of Conjugated Ions and Radicals	1179	(3)
Excited States	1182	(1)
Electrocyclic Reactions	1183	(5)
Thermal Electrocyclic Reactions	1183	(2)
Excited-State (Photochemical) Electrocyclic Reactions	1185	(1)
Selection Rules and Microscopic Reversibility	1186	(2)
Cycloaddition Reactions	1188	(4)
Sigmatropic Reactions	1192	(11)
Classification and Stereochemistry	1192	(8)
[3,3] Sigmatropic Reactions	1200	(1)
Summary: Selection Rules for Sigmatropic Reactions	1201	(2)
Summary of the Pericyclic Selection Rules	1203	(1)
Fluxional Molecules	1204	(1)
Formation of Vitamin D	1205	(10)
Key Ideas in Chapter 25	1207	(1)
Additional Problems	1208	(7)
Amino Acids, Peptides, and Proteins	1215	(76)
Nomenclature of Amino Acids and Peptides	1216	(4)
Nomenclature of Amino Acids	1216	(1)
Nomenclature of Peptides	1217	(3)
Stereochemistry of the α-Amino Acids	1220	(1)
Acid-Base Properties of Amino Acids and Peptides	1221	(8)
Zwitterionic Structures of Amino Acids and Peptides	1221	(2)
Isoelectric Points of Amino Acids and Peptides	1223	(4)
Separations of Amino Acids and Peptides Using Acid-Base Properties	1227	(2)
Synthesis and Enantiomeric Resolution of -Amino Acids	1229	(3)
Alkylation of Ammonia	1229	(1)
Alkylation of Aminomalonate Derivatives	1230	(1)
Strecker Synthesis	1230	(2)
Enantiomeric Resolution of α-Amino Acids	1232	(1)
Acylation and Esterification Reactions of Amino Acids	1232	(1)
Determination of Peptide Structure	1233	(13)
Hydrolysis of Peptides: Amino Acid Analysis	1233	(4)
Sequential Degradation of Peptides	1237	(3)
Specific Cleavage of Peptides	1240	(6)
Solid-Phase Peptide Synthesis	1246	(9)
Combinatorial Chemistry	1255	(6)
The Premise of Combinatorial Chemistry	1255	(1)
An Example of Combinatorial Chemistry	1256	(4)
Some Fundamental Ideas of Combinatorial Chemistry	1260	(1)
Structures of Peptides and Proteins	1261	(9)
Primary Structure	1261	(1)
Secondary Structure	1262	(3)
Tertiary and Quaternary Structure	1265	(5)
Enzymes: Biological Catalysts	1270	(9)
The Catalytic Action of Enzymes	1270	(4)
Enzymes as Drug Targets: Enzyme Inhibition	1274	(5)
Occurrence of Peptides and Proteins	1279	(12)
Key Ideas in Chapter 26	1280	(1)
Additional Problems	1281	(10)
Carbohydrates and Nucleic Acids	1291
Classification and Properties of Carbohydrates	1292
Structures of the Monosaccharides	1293
Stereochemistry and Configuration	1293
Cyclic Structures of the Monosaccharides	1297
Mutarotation of Carbohydrates	1302
Base-Catalyzed Isomerization of Aldoses and Ketoses	1306
Glycosides	1308
Ether and Ester Derivatives of Carbohydrates	1311
Oxidation and Reduction Reactions of Carbohydrates	1314
Oxidation to Aldonic Acids	1314
Oxidation to Aldaric Acids	1315
Periodate Oxidation	1317
Reduction to Alditols	1318
Kiliani-Fischer Synthesis	1319
Proof of Glucose Stereochemistry	1320
Which Diastereomer? The Fischer Proof	1320
Which Enantiomer? The Absolute Configuration of D-(+)-Glucose	1325
Disaccharides and Polysaccharides	1326
Disaccharides	1326
Polysaccharides	1329
Nucleosides, Nucleotides, and Nucleic Acids	1333
Nucleosides and Nucleotides	1333
Structures of DNA and RNA	1336
DNA, RNA, and the Genetic Code	1341
Role of DNA and RNA in Protein Synthesis	1341
DNA Modification and Chemical Carcinogenesis	1343
Key Ideas in Chapter 27	1345
Additional Problems	1346
Appendixes	A-1
Appendix I: Substitutive Nomenclature of Organic Compounds	A-1
Appendix II: Infrared Absorptions of Organic Compounds	A-2
Appendix III: Proton NMR Chemical Shifts in Organic Compounds	A-5
Protons within Functional Groups	A-5
Protons Adjacent to Functional Groups	A-5
Appendix IV: 13C NMR Chemical Shifts in Organic Compounds	A-7
Chemical Shifts of Carbons within Functional Groups	A-7
Chemical Shifts of Carbons Adjacent to Functional Groups	A-7
Appendix V: Summary of Synthetic Methods	A-8
Appendix VI: Reactions Used to Form Carbon-Carbon Bonds	A-13
Appendix VII: Typical Acidities and Basicities of Organic Functional Groups	A-14
Acidities of Groups That Ionize to Give Anionic Conjugate Bases	A-14
Basicities of Groups That Protonate to Give Cationic Conjugate Acids	A-15
Credits	C-1
Index	I-1