Organic Chemistry, Fourth Edition: Structure and Function

by Vollhardt; Schore

• ISBN13: 9780716743743
• ISBN10: 0716743744
• Edition: 4th
• Format: Hardcover
• Copyright: 2002-08-06
• Publisher: W. H. Freeman

Summary

New edition of the acclaimed organic chemistry text that brings exceptional clarity and coherence to the course by focusing on the relationship between structure and function.

Author Biography

K. Peter C. Vollhardt University of California at Berkeley Neil E. Schore University of California at Davis

Table of Contents

Preface: A User's Guide to Organic Chemistry: Structure and Function	xxi
Structure and Bonding in Organic Molecules	1	(49)
The Scope of Organic Chemistry: An Overview	2	(3)
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	(4)
Resonance Forms	18	(4)
Atomic Orbitals: A Quantum Mechanical Description of Electrons around the Nucleus	22	(7)
Molecular Orbitals and Covalent Bonding	29	(3)
Hybrid Orbitals: Bonding in Complex Molecules	32	(5)
Structures and Formulas of Organic Molecules	37	(13)
The Big Picture	40	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	40	(10)
Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules	50	(43)
Kinetics and Thermodynamics of Simple Chemical Processes	51	(5)
Acids and Bases; Electrophiles and Nucleophiles	56	(7)
Functional Groups: Centers of Reactivity	63	(4)
Straight-Chain and Branched Alkanes	67	(1)
Naming the Alkanes	68	(6)
Structural and Physical Properties of Alkanes	74	(3)
Rotation about Single Bonds: Conformations	77	(3)
Rotation in Substituted Ethanes	80	(13)
The Big Picture	84	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	84	(9)
Reactions of Alkanes: Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity	93	(35)
Strength of Alkane Bonds: Radicals	94	(3)
Structure of Alkyl Radicals: Hyperconjugation	97	(1)
Conversion of Petroleum: Pyrolysis	98	(3)
Chlorination of Methane: The Radical Chain Mechanism	101	(6)
Other Radical Halogenations of Methane	107	(2)
Chlorination of Higher Alkanes: Relative Reactivity and Selectivity	109	(4)
Selectivity in Radical Halogenation with Fluorine and Bromine	113	(2)
Synthetic Radical Halogenation	115	(1)
Synthetic Chlorine Compounds and the Stratospheric Ozone Layer	116	(3)
Combustion and the Relative Stabilities of Alkanes	119	(9)
The Big Picture	121	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	121	(7)
Cyclic Alkanes	128	(35)
Names and Physical Properties of Cycloalkanes	129	(2)
Ring Strain and the Structure of Cycloalkanes	131	(4)
Cyclohexane: A Strain-Free Cycloalkane	135	(5)
Substituted Cyclohexanes	140	(4)
Larger Cycloalkanes	144	(1)
Polycyclic Alkanes	145	(2)
Carbocyclic Products in Nature	147	(16)
The Big Picture	153	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	153	(10)
Stereoisomers	163	(46)
Chiral Molecules	165	(4)
Optical Activity	169	(3)
Absolute Configuration: R-S Sequence Rules	172	(5)
Fischer Projections	177	(4)
Molecules Incorporating Several Stereocenters: Diastereomers	181	(4)
Meso Compounds	185	(2)
Stereochemistry in Chemical Reactions	187	(8)
Resolution: Separation of Enantiomers	195	(14)
The Big Picture	197	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	198	(11)
Properties and Reactions of Haloalkanes: Bimolecular Nucleophilic Substitution	209	(34)
Physical Properties of Haloalkanes	209	(3)
Nucleophilic Substitution	212	(2)
Reaction Mechanisms Involving Polar Functional Groups: Using ``Electron-Pushing'' Arrows	214	(2)
A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics	216	(3)
Frontside or Backside Attack? Stereochemistry of the SN2 Reaction	219	(2)
Consequences of Inversion in SN2 Reactions	221	(2)
Structure and SN2 Reactivity: The Leaving Group	223	(2)
Structure and SN2 Reactivity: The Nucleophile	225	(6)
Structure and SN2 Reactivity: The Substrate	231	(12)
The Big Picture	236	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	236	(7)
Further reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination	243	(33)
Solvolysis of Tertiary and Secondary Haloalkanes	243	(2)
Unimolecular Nucleophilic Substitution	245	(3)
Stereochemical Consequences of SN1 Reactions	248	(1)
Effects of Solvent, Leaving Group, and Nucleophile on Unimolecular Substitution	249	(2)
Effect of the Alkyl Group on the SN1 Reaction: Carbocation Stability	251	(3)
Unimolecular Elimination: E1	254	(3)
Bimolecular Elimination: E2	257	(3)
Competition between Substitution and Elimination: Structure Determines Function	260	(3)
Summary of Reactivity of Haloalkanes	263	(13)
The Big Picture	264	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	265	(11)
Hydroxy Functional Group: Alcohols: Properties, Preparation, and Strategy of Synthesis	276	(45)
Naming the Alcohols	277	(1)
Structural and Physical Properties of Alcohols	278	(3)
Alcohols as Acids and Bases	281	(3)
Industrial Sources of Alcohols: Carbon Monoxide and Ethene	284	(1)
Synthesis of Alcohols by Nucleophilic Substitution	285	(1)
Synthesis of Alcohols: Oxidation-Reduction Relation between Alcohols and Carbonyl Compounds	286	(7)
Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis	293	(4)
Organometallic Reagents in the Synthesis of Alcohols	297	(2)
Complex Alcohols: An Introduction to Synthetic Strategy	299	(22)
The Big Picture	306	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	307	(14)
Further Reactions of Alcohols and the Chemistry of Ethers	321	(53)
Reactions of Alcohols with Base: Preparation of Alkoxides	322	(1)
Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols	323	(3)
Carbocation Rearrangements	326	(5)
Organic and Inorganic Esters from Alcohols	331	(3)
Names and Physical Properties of Ethers	334	(3)
Williamson Ether Synthesis	337	(5)
Synthesis of Ethers: Alcohols and Mineral Acid	342	(2)
Reactions of Ethers	344	(2)
Reactions of Oxacyclopropanes	346	(5)
Sulfur Analogs of Alcohols and Ethers	351	(3)
Physiological Properties and Uses of Alcohols and Ethers	354	(20)
The Big Picture	358	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	358	(16)
Using Nuclear Magnetic Resonance Spectroscopy to Deduce Structure	374	(57)
Physical and Chemical Tests	375	(1)
Defining Spectroscopy	375	(3)
Proton Nuclear Magnetic Resonance	378	(5)
Using NMR Spectra to Analyze Molecular Structure: The Proton Chemical Shift	383	(4)
Tests for Chemical Equivalence	387	(4)
Integration	391	(2)
Spin-Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens	393	(8)
Spin-Spin Splitting: Some Complications	401	(7)
Carbon-13 Nuclear Magnetic Resonance	408	(23)
The Big Picture	417	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	417	(14)
Alkenes and Infrared Spectroscopy	431	(43)
Naming the Alkenes	432	(3)
Structure and Bonding in Ethene: The Pi Bond	435	(3)
Physical Properties of Alkenes	438	(1)
Nuclear Magnetic Resonance of Alkenes	439	(5)
Infrared Spectroscopy	444	(5)
Degree of Unsaturation: Another Aid to Identifying Molecular Structure	449	(2)
Catalytic Hydrogenation of Alkenes: Relative Stability of Double Bonds	451	(2)
Preparation of Alkenes from Haloalkenes and Alkyl Sulfonates: Bimolecular Elimination Revisited	453	(4)
Preparation of Alkenes by Dehydration of Alcohols	457	(17)
The Big Picture	459	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	460	(14)
Reactions of Alkenes	474	(59)
Why Addition Reactions Proceed: Thermodynamic Feasibility	475	(1)
Catalytic Hydrogenation	475	(4)
Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides	479	(4)
Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control	483	(2)
Electrophilic Addition of Halogens to Alkenes	485	(3)
The Generality of Electrophilic Addition	488	(3)
Oxymercuration-Demercuration: A Special Electrophilic Addition	491	(3)
Hydroboration-Oxidation: A Stereospecific Anti-Markovnikov Hydration	494	(2)
Diazomethane, Carbenes, and Cyclopropane Synthesis	496	(2)
Oxacyclopropane (Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids	498	(3)
Vicinal Syn Dihydroxylation with Osmium Tetroxide	501	(2)
Oxidative Cleavage: Ozonolysis	503	(2)
Radical Additions: Anti-Markovnikov Product Formation	505	(2)
Dimerization, Oligomerization, and Polymerization of Alkenes	507	(1)
Synthesis of Polymers	508	(6)
Ethene: An Important Industrial Feedstock	514	(1)
Alkenes in Nature: Insect Pheromones	514	(19)
The Big Picture	516	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	516	(17)
Alkynes: The Carbon-Carbon Triple Bond	533	(37)
Naming the Alkynes	534	(1)
Properties and Bonding in the Alkynes	535	(2)
Spectroscopy of the Alkynes	537	(4)
Preparation of Alkynes by Double Elimination	541	(1)
Preparation of Alkynes from Alkynyl Anions	542	(1)
Reduction of Akynes: The Relative Reactivity of the Two Pi Bonds	543	(4)
Electrophilic Addition Reactions of Alkynes	547	(3)
Anti-Markovnikov Additions to Triple Bonds	550	(1)
Chemistry of Alkenyl Halides	551	(1)
Ethyne as an Industrial Starting Material	552	(2)
Naturally Occurring and Physiologically Active Alkynes	554	(16)
The Big Picture	555	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	556	(14)
Delocalized Pi Systems: Investigation by Ultraviolet and Visible Spectroscopy	570	(58)
Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System	571	(3)
Radical Allylic Halogenation	574	(1)
Nucleophilic Substitution of Allylic Halides: SN1 and SN2	575	(2)
Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles	577	(1)
Two Neighboring Double Bonds: Conjugated Dienes	578	(4)
Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control	582	(3)
Delocalization Among More than Two Pi Bonds: Extended Conjugation and Benzene	585	(2)
A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition	587	(9)
Electrocyclic Reactions	596	(6)
Polymerization of Conjugated Dienes: Rubber	602	(4)
Electronic Spectra: Ultraviolet and Visible Spectroscopy	606	(22)
The Big Picture	610	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	611	(12)
Interlude: A Summary of Organic Reaction Mechanisms	623	(5)
Benzene and Aromaticity: Electrophilic Aromatic Substitution	628	(53)
Naming the Benzenes	630	(2)
Structure and Resonance Energy of Benzene: A First Look at Aromaticity	632	(3)
Pi Molecular Orbitals of Benzene	635	(2)
Spectral Characteristics of the Benzene Ring	637	(4)
Polycyclic Aromatic Hydrocarbons	641	(6)
Other Cyclic Polyenes: Huckel's Rule	647	(5)
Huckel's Rule and Charged Molecules	652	(2)
Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution	654	(2)
Halogenation of Benzene: The Need for a Catalyst	656	(2)
Nitration and Sulfonation of Benzene	658	(3)
Friedel-Crafts Alkylation	661	(2)
Limitations of Friedel-Crafts Alkylations	663	(2)
Friedel-Crafts Alkanoylation (Acylation)	665	(16)
The Big Picture	669	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	669	(12)
Electrophilic Attack on Derivatives of Benzene: Substituents Control Regioselectivity	681	(40)
Activation or Deactivation by Substituents on a Benzene Ring	682	(2)
Directing Inductive Effects of Alkyl Groups	684	(4)
Directing Effects of Substituents in Conjugation with Benzene Ring	688	(7)
Electrophilic Attack on Disubstituted Benzenes	695	(3)
Synthetic Strategies toward Substituted Benzenes	698	(5)
Reactivity of Polycyclic Benzenoid Hydrocarbons	703	(3)
Polycyclic Aromatic Hydrocarbons and Cancer	706	(15)
The Big Picture	708	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	708	(13)
Aldehydes and Ketones: The Carbonyl Group	721	(48)
Naming the Aldehydes and Ketones	722	(2)
Structure of the Carbonyl Group	724	(2)
Spectroscopic Properties of Aldehydes and Ketones	726	(2)
Preparation of Aldehydes and Ketones	728	(3)
Reactivity of the Carbonyl Group: Mechanisms of Addition	731	(2)
Addition of Water to Form Hydrates	733	(2)
Addition of Alcohols to Form Hemiacetals and Acetals	735	(2)
Acetals as Protecting Groups	737	(3)
Nucleophilic Addition of Ammonia and Its Derivatives	740	(4)
Deoxygenation of the Carbonyl Group	744	(2)
Addition of Hydrogen Cyanide to Give Cyanohydrins	746	(1)
Addition of Phosphorus Ylides: The Wittig Reaction	747	(4)
Oxidation by Peroxycarboxylic Acids: The Baeyer-Villiger Oxidation	751	(1)
Oxidative Chemical Tests for Aldehydes	752	(17)
The Big Picture	753	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	753	(16)
Enols, Enolates, and the Aldol Condensation: α,β-Unsaturated Aldehydes and Ketones	769	(44)
Acidity of Aldehydes and Ketones: Enolate Ions	770	(1)
Keto-Enol Equilibria	771	(3)
Halogenation of Aldehydes and Ketones	774	(2)
Alkylation of Aldehydes and Ketones	776	(3)
Attack by Enolates on the Carbonyl Function: Aldol Condensation	779	(5)
Crossed Aldol Condensation	784	(1)
Intramolecular Aldol Condensation	785	(3)
Properties of α,β-Unsaturated Aldehydes and Ketones	788	(2)
Conjugate Additions to α,β-Unsaturated Aldehydes and Ketones	790	(2)
1,2- and 1,4-Additions of Organometallic Reagents	792	(3)
Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation	795	(18)
The Big Picture	797	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	798	(15)
Carboxylic Acids	813	(51)
Naming the Carboxylic Acids	814	(1)
Structural and Physical Properties of Carboxylic Acids	815	(3)
NMR and IR Spectroscopy of Carboxylic Acids	818	(2)
Acidic and Basic Character of Carboxylic Acids	820	(3)
Carboxylic Acid Synthesis in Industry	823	(1)
Methods for Introducing the Carboxy Functional Group	823	(4)
Substitution at the Carboxy Carbon: The Addition-Elimination Mechanism	827	(2)
Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides and Anhydrides	829	(3)
Carboxylic Acid Derivatives: Esters	832	(3)
Carboxylic Acid Derivatives: Amides	835	(2)
Reduction of Carboxylic Acids by Lithium Aluminum Hydride	837	(1)
Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction	837	(2)
Biological Activity of Carboxylic Acids	839	(25)
The Big Picture	846	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	846	(18)
Carboxylic Acid Derivatives and Mass Spectrometry	864	(59)
Relative Reactivities, Structures, and Spectra of Carboxylic Acid Derivatives	865	(4)
Chemistry of Alkanoyl Halides	869	(4)
Chemistry of Carboxylic Anhydrides	873	(1)
Chemistry of Esters	874	(6)
Esters in Nature: Waxes, Fats, Oils, and Lipids	880	(2)
Amides: The Least Reactive Carboxylic Acid Derivatives	882	(5)
Amidates and Their Halogenation: The Hofmann Rearrangement	887	(3)
Alkanenitriles: A Special Class of Carboxylic Acid Derivatives	890	(4)
Measuring the Molecular Weight of Organic Compounds: Mass Spectrometry	894	(5)
Fragmentation Patterns of Organic Molecules	899	(5)
High-Resolution Mass Spectrometry	904	(19)
The Big Picture	907	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	907	(16)
Amines and Their Derivatives: Functional Groups Containing Nitrogen	923	(45)
Naming the Amines	924	(1)
Structural and Physical Properties of Amines	925	(4)
Spectroscopy of the Amine Group	929	(3)
Acidity and Basicity of Amines	932	(4)
Synthesis of Amines by Alkylation	936	(3)
Synthesis of Amines by Reductive Amination	939	(3)
Synthesis of Amines from Carboxylic Acids	942	(1)
Quaternary Ammonium Salts: Hofmann Elimination	942	(2)
Mannich Reaction: Alkylation of Enols by Iminium Ions	944	(2)
Nitrosation of Amines	946	(22)
The Big Picture	951	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	951	(17)
Chemistry of Benzene Substituents: Alkylbenzenes, Phenols, and Benzenamines	968	(56)
Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization	969	(4)
Benzylic Oxidations and Reductions	973	(2)
Names and Properties of Phenols	975	(3)
Preparation of Phenols: Nucleophilic Aromatic Substitution	978	(10)
Alcohol Chemistry of Phenols	988	(2)
Electrophilic Substitution of Phenols	990	(4)
An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement	994	(3)
Oxidation of Phenols: Cyclohexadienediones (Benzoquinones)	997	(2)
Oxidation-Reduction Processes in Nature	999	(4)
Arenediazonium Salts	1003	(3)
Electrophilic Substitution with Arenediazonium Salts: Diazo Coupling	1006	(18)
The Big Picture	1008	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	1008	(16)
Enolates and the Claisen Condensation: Synthesis of β-Dicarbonyl Compounds; Acyl Anion Equivalents	1024	(32)
β-Dicarbonyl Compounds: Claisen Condensations	1025	(6)
β-Dicarbonyl Compounds as Synthetic Intermediates	1031	(5)
β-Dicarbonyl Anion Chemistry: Michael Additions	1036	(2)
Alkanoyl (Acyl) Anion Equivalents: Preparation of α-Hydroxyketones	1038	(18)
The Big Picture	1044	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	1044	(12)
Carbohydrates: Polyfunctional Compounds in Nature	1056	(48)
Names and Structures of Carbohydrates	1057	(4)
Conformations and Cyclic Forms of Sugars	1061	(4)
Anomers of Simple Sugars: Mutarotation of Glucose	1065	(1)
Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids	1066	(2)
Oxidative Cleavage of Sugars	1068	(2)
Reduction of Monosaccharides to Alditols	1070	(1)
Carbonyl Condensations with Amine Derivatives	1070	(1)
Ester and Ether Formation: Glycosides	1071	(4)
Step-by-Step Buildup and Degradation of Sugars	1075	(4)
Relative Configurations of the Aldoses: An Exercise in Structure Determination	1079	(2)
Complex Sugars in Nature: Disaccharides	1081	(5)
Polysaccharides and Other Sugars in Nature	1086	(18)
The Big Picture	1091	(1)
Chapter Integration Problem / Important Concepts / Problems / Team Problems / Preprofessional Problems	1091	(13)
Heterocycles: Heteroatoms in Cyclic Organic Compounds	1104	(43)
Naming the Heterocycles	1107	(1)
Nonaromatic Heterocycles	1108	(4)
Structure and Properties of Aromatic Heterocyclopentadienes	1112	(2)
Reactions of the Aromatic Heterocyclopentadienes	1114	(4)
Structure and Preparation of Pyridine: An Azabenzene	1118	(3)
Reactions of Pyridine	1121	(3)
Quinoline and Isoquinoline: The Benzopyridines	1124	(1)
Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature	1125	(22)
The Big Picture	1130	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	1131	(16)
Amino Acids, Peptides, Proteins, and Nucleic Acids: Nitrogen-Containing Polymers in Nature	1147
Structure and Properties of Amino Acids	1148	(6)
Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry	1154	(2)
Synthesis of Enantiomerically Pure Amino Acids	1156	(2)
Peptides and Proteins: Amino Acid Oligomers and Polymers	1158	(9)
Determination of Primary Structure: Amino Acid Sequencing	1167	(5)
Synthesis of Polypeptides: A Challenge in the Application of Protecting Groups	1172	(3)
Merrifield Solid-Phase Peptide Synthesis	1175	(2)
Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin	1177	(2)
Biosynthesis of Proteins: Nucleic Acids	1179	(5)
Protein Synthesis Through RNA	1184	(2)
DNA Sequencing and Synthesis: Cornerstones of Gene Technology	1186
The Big Picture	1191	(1)
Chapter Integration Problems / Important Concepts / Problems / Team Problems / Preprofessional Problems	1192
MCAT® Questions	1	(1)
Answers to Exercises	1	(1)
Photograph Credits	1	(1)
Index	1