Advanced Organic Chemistry: Structure and Mechanisms

by Carey, Francis A.

• ISBN13: 9780306462429
• ISBN10: 0306462427
• Format: Hardcover
• Copyright: 2000-05-01
• Publisher: Kluwer Academic Pub

Table of Contents

Chemical Bonding and Structure	1	(74)
Valence Bond Description of Chemical Bonding	2	(11)
Orbital Hybridization	4	(5)
Resonance	9	(4)
Bond Energy, Polarity, and Polarizability	13	(10)
Bond Energies	13	(2)
Electronegativity and Polarity	15	(5)
Polarizability---Hardness and Softness	20	(3)
Molecular Orbital Theory and Methods	23	(8)
Huckel Molecular Orbital Theory	31	(5)
Qualitative Application of Molecular Orbital Theory	36	(10)
Application of Molecular Orbital Theory to Reactivity	46	(8)
Interactions between σ and π Systems---Hyperconjugation	54	(3)
Other Quantitative Descriptions of Molecular Structure	57	(18)
Atom in Molecules	57	(2)
Electron Density Functionals	59	(5)
Modern Valence Bond Approaches	64	(1)
General References	65	(1)
Problems	65	(10)
Principles of Stereochemistry	75	(48)
Enantiomeric Relationships	76	(8)
Diastereomeric Relationships	84	(13)
Stereochemistry of Reactions	97	(8)
Prochiral Relationships	105	(9)
General References	114	(1)
Problems	114	(9)
Conformational, Steric, and Stereoelectronic Effects	123	(64)
Strain and Molecular Mechanics	124	(5)
Conformations of Acyclic Molecules	129	(6)
Conformations of Cyclohexane Derivatives	135	(11)
Carbocyclic Rings Other Than Six-Membered	146	(3)
The Effect of Heteroatoms on Conformational Equilibria	149	(2)
The Anomeric Effect	151	(6)
Conformational Effects on Reactivity	157	(5)
Angle Strain and Its Effect on Reactivity	162	(4)
Relationships between Ring Size and Rate of Cyclization	166	(5)
Torsional and Stereoelectronic Effects on Reactivity	171	(16)
General References	177	(1)
Problems	177	(10)
Study and Description of Organic Reaction Mechanismns	187	(76)
Thermodynamic Data	187	(5)
Kinetic Data	192	(12)
Substituent Effects and Linear Free-Energy Relationships	204	(11)
Basic Mechanistic Concepts: Kinetic versus thermodynamic Control, Hammond's Postulate, the Curtin--Hammett Principle	215	(7)
Kinetic versus Thermodynamic Control	215	(2)
Hammond's Postulate	217	(3)
The Curtin--Hammett Principle	220	(2)
Isotope Effects	222	(3)
Isotopes in Labeling Experiments	225	(1)
Characterization of Reaction Intermediates	226	(2)
Catalysis by Bronsted Acids and Bases	228	(5)
Lewis Acid Catalysis	233	(4)
Solvent Effects	237	(6)
Substituent Effects in the Gas Phase	243	(4)
Stereochemistry	247	(1)
Conclusion	248	(15)
General References	248	(2)
Problems	250	(13)
Nucleophilic Substitution	263	(88)
The Limiting Cases---Substitution by the Ionization (SN1) Mechanism	264	(3)
The Limiting Cases---Substitution by the Direct Displacement (SN2) Mechanism	267	(2)
Detailed Mechanistic Description and Borderline Mechanisms	269	(7)
Carbocations	276	(14)
Nucleophilicity and Solvent Effects	290	(5)
Leaving-Group Effects	295	(3)
Steric and Strain Effects on Substitution and Ionization Rates	298	(2)
Effects of Conjugation on Reactivity	300	(2)
Stereochemistry of Nucleophilic Substitution	302	(7)
Neighboring-Group Participation	309	(7)
Mechanism of Rearrangements of Carbocations	316	(11)
The Norbornyl Cation and Other Nonclassical Carbocations	327	(24)
General References	334	(1)
Problems	335	(16)
Polar Addition and Elimination Reactions	351	(54)
Addition of Hydrogen Halides to Alkenes	352	(6)
Acid-Catalyzed Hydration and Related Addition Reactions	358	(3)
Addition of Halogens	361	(8)
Electrophilic Additions Involving Metal Ions	369	(2)
Additions to Alkynes and Allenes	371	(7)
The E2, E1, and E1cb Mechanisms	378	(5)
Regiochemistry of Elimination Reactions	383	(3)
Stereochemistry of E2 Elimination Reactions	386	(6)
Dehydration of Alcohols	392	(1)
Eliminations Not Involving C--H Bonds	393	(12)
General References	398	(1)
Problems	398	(7)
Carbanions and Other Nucleophilic Carbon Species	405	(44)
Acidity of Hydrocarbons	405	(11)
Carbanions Stabilized by Functional Groups	416	(9)
Enols and Enamines	425	(7)
Carbanions as Nucleophiles in SN2 Reactions	432	(17)
General References	439	(1)
Problems	440	(9)
Reactions of Carbonyl Compounds	449	(60)
Hydration and Addition of Alcohols to Aldehydes and Ketones	449	(7)
Addition--Elimination Reactions of Ketones and Aldehydes	456	(6)
Addition of Carbon Nucleophiles to Carbonyl Groups	462	(8)
Reactivity of Carbonyl Compounds toward Addition	470	(4)
Ester Hydrolysis	474	(5)
Aminolysis of Esters	479	(2)
Amide Hydrolysis	481	(3)
Acylation of Nucleophilic Oxygen and Nitrogen Groups	484	(4)
Intramolecular Catalysis	488	(21)
General References	495	(1)
Problems	496	(13)
Aromaticity	509	(42)
The Concept of Aromaticity	509	(5)
The Annulenes	514	(10)
Aromaticity in Charged Rings	524	(5)
Homoaromaticity	529	(1)
Fused-Ring Systems	530	(10)
Heterocyclic Rings	540	(11)
General References	543	(1)
Problems	543	(8)
Aromatic Substitution	551	(54)
Electrophilic Aromatic Substitution Reactions	551	(6)
Structure--Reactivity Relationships	557	(11)
Reactivity of Polycyclic and Heteroaromatic Compounds	568	(3)
Specific Substitution Mechanisms	571	(18)
Nitration	571	(4)
Halogenation	575	(4)
Protonation and Hydrogen Exchange	579	(1)
Friedel--Crafts Alkylation and Related Reactions	580	(3)
Friedel--Crafts Acylation and Related Reactions	583	(4)
Coupling with Diazonium Compounds	587	(1)
Substitution of Groups Other Than Hydrogen	588	(1)
Nucleophilic Aromatic Substitution by the Addition--Elimination Mechanism	589	(4)
Nucleophilic Aromatic Substitution by the Elimination--Addition Mechanism	593	(12)
General References	597	(1)
Problems	597	(8)
Concerted Pericyclic Reactions	605	(58)
Electrocyclic Reactions	606	(13)
Sigmatropic Rearrangements	619	(17)
Cycloaddition Reactions	636	(27)
General References	651	(1)
Problems	651	(12)
Free-Radical Reactions	663	(80)
Generation and Characterization of Free Radicals	663	(20)
Background	663	(1)
Stable and Persistent Free Radicals	664	(3)
Direct Detection of Radical Intermediates	667	(5)
Sources of Free Radicals	672	(3)
Structural and Stereochemical Properties of Radical Intermediates	675	(5)
Charged Radical Species	680	(3)
Characteristics of Reaction Mechanisms Involving Radical Intermediates	683	(20)
Kinetic Characteristics of Chain Reactions	683	(2)
Structure--Reactivity Relationships	685	(18)
Free-Radical Substitution Reactions	703	(5)
Halogenation	703	(3)
Oxidation	706	(2)
Free-Radical Addition Reactions	708	(6)
Addition of Hydrogen Halides	708	(4)
Addition of Halomethanes	712	(1)
Addition of Other Carbon Radicals	713	(1)
Addition of Thiols and Thiocarboxylic Acids	714	(1)
Halogen, Sulfur, and Selenium Group Transfer Reactions	714	(4)
Intramolecular Free-Radical Reactions	718	(1)
Rearrangement and Fragmentation Reactions of Free Radicals	719	(5)
Rearrangement Reactions	719	(3)
Fragmentation	722	(2)
Electron-Transfer Reactions Involving Transition-Metal Ions	724	(3)
SRN1 Substitution Processes	727	(16)
General References	733	(1)
Problems	734	(9)
Photochemistry	743	(48)
General Principles	743	(4)
Orbital Symmetry Considerations Related to Photochemical Reactions	747	(6)
Photochemistry of Carbonyl Compounds	753	(13)
Photochemistry of Alkenes and Dienes	766	(13)
Photochemistry of Aromatic Compounds	779	(12)
General References	781	(1)
Problems	781	(10)
References to Problems	791	(16)
Index	807