Perspectives on Structure and Mechanism in Organic Chemistry

by Carroll,Felix A.

• ISBN13: 9780534249489
• ISBN10: 0534249485
• Format: Hardcover
• Copyright: 1997-04-25
• Publisher: Cengage Learning

Summary

Designed to help students not only understand what has been done in the past, but also be able to develop new concepts and to see new relationships in the future, Carroll's text emphasizes the nature and limitations of knowledge in chemistry, the need to question the underlying bases of familiar concepts, and the usefulness of exploring the role of complementary models in the understanding and practice of organic chemistry.

Table of Contents

Chapter 1 Concepts and Models in Organic Chemistry	1	(57)
1.1 Models of Atomic and Molecular Structure	1	(23)
Atoms and Molecules	1	(4)
Molecular Dimensions	5	(4)
Heats of Formation and Reaction	9	(8)
Bonding Models	17	(3)
Electronegativity and Bond Polarity	20	(4)
1.2 Bonding and Molecular Geometry	24	(21)
Complementary Theoretical Models of Bonding	24	(4)
Atomic Energy Levels and Bonding Concepts	28	(1)
The sp -Hybridization Model for Methane	29	(3)
Are There sp -Hybrid Orbitals in Methane?	32	(5)
Valence Shell Electron Pair Repulsion Theory	37	(1)
Variable Hybridization and Molecular Geometry	38	(7)
1.3 Complementary Descriptions of the Double Bond	45	(8)
The x, x Description of Ethene	45	(2)
The Bent Bond Description of Ethene	47	(1)
Predictions of Physical Properties with the Two Models	48	(5)
Conclusion	53	(1)
Problems	54	(4)
Chapter 2 Stereochemistry	58	(61)
2.1 Introduction	58	(3)
2.2 Stereoisomerism	61	(3)
Isomerism	61	(3)
Symmetric, Asymmetric, Dissymmetric, and Nondissymmetric Molecules	64	(11)
Designation of Molecular Configuration	75	(5)
Fischer Projections	80	(4)
Stereochemical Nomenclature	84	(10)
2.3 Manifestations of Stereoisomerism	94	(17)
Optical Activity	94	(5)
Configuration and Optical Activity	99	(2)
Other Physical Properties of Stereoisomers	101	(2)
Stereochemical Relationship of Substituents	103	(4)
Chirotopicity and Stereogenicity	107	(4)
Problems	111	(8)
3 Conformational Analysis and Molecular Mechanics	119	(59)
3.1 Molecular Conformation	119	(7)
3.2 Conformational Analysis	126	(15)
Introduction	126	(1)
Application of Conformational Analysis to Cycloalkanes	133	(2)
Conformational Analysis of Substituted Cyclohexanes	135	(6)
3.3 Molecular Mechanics	141	(20)
3.4 Molecular Strain and Limits to Molecular Stability	161	(12)
Problems	173	(5)
4 Applications of Molecular Orbital Theory and Valence Bond Theory	178	(68)
4.1 Introduction to Molecular Orbital Theory	178	(28)
Huckel Molecular Orbital Theory	178	(14)
Correlation of Physical Properties with Results of HMO Calculations	192	(4)
Other Parameters Generated through HMO Theory	196	(4)
Properties of Odd Alternant Hydrocarbons	200	(5)
The Circle Method	205	(1)
4.2 Aromaticity	206	(18)
Benzene	208	(6)
Aromaticity in small Ring Systems	214	(5)
Larger Annulenes	219	(2)
Dewar Resonance Energy and Absolute Hardness	221	(3)
4.3 Quantitative Methods Using Valence Bond Theory	224	(9)
4.4 Additional Molecular Orbital Methods	233	(8)
Perturbational Molecular Orbital Theory	233	(2)
A Survey of Theoretical Calculations	235	(6)
Problems	241	(5)
5 Reactive Intermediates	246	(70)
5.1 Potential Energy Surfaces, Reaction Coordinate Diagrams and Reactive Intermediates	246	(11)
5.2 Reactive Intermediates with Neutral, Electron Deficient Carbon Atoms	257	(26)
Radicals	257	(18)
Carbenes	275	(8)
5.3 Intermediates with Charged Carbon Atoms	283	(28)
Carbocations	283	(19)
Carbanions	302	(9)
Conclusion	311	(1)
Problems	312	(4)
6 Methods of Studying Organic Reactions	316	(78)
6.1 Molecular Change and Reaction Mechanisms	316	(1)
6.2 Tools to Determine Reaction Mechanisms	317	(15)
Indentification of Reacion Products	317	(1)
Determination of Intermediates	318	(5)
Crossover Experiments	323	(2)
Isotopic Labeling	325	(3)
Stereochemical Studies	328	(1)
Solvent Effects	329	(3)
6.3 Applications of Kinetics in Studying Reaction Mechanisms	332	(7)
6.4 Arrhenius Theory and Transition-State Theory	339	(10)
6.5 Kinetic Isotope Effects	349	(17)
Primary Kinetic Isotope Effects	351	(9)
Secondary Kinetic Isotope Effects	360	(5)
Solvent Isotope Effects	365	(1)
6.6 Substituent Effects and Linear Free Energy Relationships	366	(20)
Substituent Effects	366	(5)
Linear Free Energy Relationships	371	(15)
Problems	386	(8)
7 Acid-Base Catalyzed Reactions	394	(59)
7.1 Acidity and Basicity of Organic Compounds	394	(22)
Acid-Base Measurements in Solution	394	(9)
Acid-Base Reactions in the Gas Phase	403	(8)
Acidity Functions	411	(5)
7.2 Acid and Base Catalysis of Chemical Reactions	416	(5)
Specific Acid Catalysis	417	(1)
General Acid Catalysis	417	(3)
Bronsted Catalysis Law	420	(1)
7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds and Carboxylic Acid Derivatives	421	(28)
Addition to the Carbonyl Group	421	(5)
Enolization of Carbonyl Compounds	426	(5)
Hydrolysis of Acetals	431	(3)
Acid-Catalyzed Hydrolysis of Esters	434	(4)
Alkaline Hydrolysis of Esters	438	(1)
Other Acyl Substitution Reactions	445	(4)
Problems	449	(4)
8 Substitution Reactions	453	(95)
8.1 Introduction	453	(3)
8.2 Nucleophilic Aliphatic Substitution	456	(57)
Designation of Nucleophilic Aliphatic Substitution Reactions	456	(7)
The S 1 Reaction	463	(26)
The S 2 Reaction	489	(17)
Aliphatic Substitution and Single Electron Transfer	506	(7)
8.3 Electrophilic Aromatic Substitution	513	(9)
The SxAr Reaction	513	(4)
Quantitative Measurement of SxAr Rates: Partial Rate Factors	517	(1)
Lewis Structure Bond Models of Reactivity in SxAr Reactions	518	(4)
8.4 Nucleophilic Aromatic and Vinylic Substitution	522	(20)
Nucleophilic Aromatic Substitution	522	(4)
Nucleophilic Vinylic Substitution	526	(4)
Nucleophilic Substitution Involving Benzyne Intermediates	530	(8)
Radical-Nucleophilic Substitution	538	(4)
Concluding Remarks	542	(1)
Problems	543	(5)
9 Addition Reactions	548	(93)
9.1 Introduction	548	(2)
9.2 Addition of Halogens to Alkenes	550	(38)
Electrophilic Addition of Bromine to Alkenes	550	(26)
Addition of Other Halogens to Alkenes	576	(12)
9.3 Other Addition Reactions	588	(49)
Addition of Hydrogen Halides to Alkenes	588	(9)
Hydration of Alkenes	597	(3)
Oxymercuration	600	(6)
Hydroboration	606	(7)
Epoxidation	613	(2)
Electrophilic Addition to Alkynes and Cumulenes	615	(11)
Nucleophilic Addition to Alkenes and Alkynes	626	(5)
Nucleophilic Addition to Carbonyl Compounds	631	(6)
Problems	637	(4)
Chapter 10 Elimination Reactions	641	(69)
10.1 Introduction	641	(4)
10.2 Dehydrohalogenation and Related 1, 2-Elimination Reactions	645	(31)
Potential Energy Surfaces for 1, 2-Elimination	645	(7)
Competition between Substitution and Elimination	652	(3)
Stereochemistry of 1, 2-Elimination Reactions	655	(8)
Regiochemistry of 1, 2-Elimination Reactions	663	(13)
10.3 Other 1, 2-Elimination Reactions	676	(27)
Dehalogenation of Vicinal Dihalides	676	(5)
Dehydration of Alcohols	681	(10)
Deamination of Amines	691	(4)
Pyrolytic Eliminations	695	(8)
Problems	703	(7)
Chapter 11 Concerted Reactions	710	(85)
11.1 Introduction	710	(5)
11.2 Electrocyclic Trasformations	715	(14)
Definitions and Selection Rules	715	(4)
MO Correlation Diagrams	719	(5)
State Correlation Diagrams	724	(5)
11.3 Sigmatropic Reactions	729	(17)
Definitions and Examples	729	(2)
Selection Rules for Sigmatropic Reactions	731	(10)
Further Examples of Sigmatropic Reactions	741	(5)
11.4 Cycloaddition Reactions	746	(16)
Introduction	746	(1)
Ethene Dimerization	746	(5)
The Diels-Alder Reaction	751	(3)
Selection Rules for Cycloaddition Reactions	754	(8)
11.5 Other Concerted Reactions	762	(6)
Cheletropic Reactions	762	(2)
Atom Transfer Reactions	764	(3)
Ene Reactions	767	(1)
11.6 A Generalized Selection Rule for Pericyclic Reactions	768	(4)
11.7 Alternative Conceptual Models for Concerted Reactions	772	(17)
Frontier Molecular Orbital Theory	772	(6)
Huckel and Mobius Aromaticity of Transition Structures	778	(7)
Synchronous and Nonsynchronous Concerted Reactions	785	(4)
Problems	789	(6)
Chapter 12 Photochemistry	795	(82)
12.1 Introduction	795	(27)
Energy and Electronic States	795	(4)
Designation of Spectroscopic Transitions	798	(3)
Photophysical Processes	801	(3)
Selection Rules for Radiative Transitions	804	(2)
Fluorescence and Phosphorescence	806	(5)
Energy Transfer and Electron Transfer	811	(3)
Fundamentals of Photochemical Kinetics	814	(8)
12.2 Properties of Excited States	822	(8)
Acidity and Basicity in Excited States	822	(5)
Bond Angles and Dipole Moments and Excited State Molecules	827	(3)
12.3 Representative Photochemical Reactions	830	(35)
Photochemical Reactions of Carbonyl Compounds	831	(8)
Photochemical Reactions of Alkenes and Dienes	839	(13)
Photochemical Reactions of x, x-Unsaturated Carbonyl Compounds	852	(2)
Photochemical Reactions of Aromatic Compounds	854	(2)
Photosubstitution Reactions	856	(2)
x Bond Photodissociation Reactions	858	(5)
Singlet Oxygen and Organic Photochemistry	863	(2)
12.4 Some Applications of Organic Photochemistry	865	(5)
Problems	870	(7)
References for Selected Problems	877	(7)
Credits	884	(5)
Name Index	889	(18)
Subject Index	907