Advanced organic chemistry

Başlık:

Yazar:

Carey, Francis A., 1937-

ISBN:

9780387448978

9780387683461

9780387448992

9780387683508

9780387683546

Ek Yazar:

Carey, Francis A., 1937-

Edition:

5th ed.

Yayım Bilgisi:

New York : Springer, c2007-

Fiziksel Tanım:

v. <A-B> : ill. ; 26 cm.

Contents:

pt. A. Structure and mechanisms -- pt. B. Reactions and synthesis.

Konu Terimleri:

Kimya, organik.

Chemistry, Organic.

Added Author:

Sundberg, Richard J., 1938-

Mevcut:*

Library	Materyal Türü	Barkod	Yer Numarası	Durum
Searching... Pamukkale Merkez Kütüphanesi	Kitap	0052461	QD251.3.C367 2007	Searching... Unknown

Since its original appearance in 1977, Advanced Organic Chemistry has maintained its place as the premier textbook in the field, offering broad coverage of the structure, reactivity and synthesis of organic compounds. As in the earlier editions, the text contains extensive references to both the primary and review literature and provides examples of data and reactions that illustrate and document the generalizations. While the text assumes completion of an introductory course in organic chemistry, it reviews the fundamental concepts for each topic that is discussed.

The two-part fifth edition has been substantially revised and reorganized for greater clarity. Among the changes: Updated material reflecting advances in the field since 2001's Fourth Edition, especially in computational chemistry; A companion Web site provides digital models for study of structure, reaction and selectivity; Solutions to the exercises provided to instructors online.

The material in Part Ais organized on the basis of fundamental structural topics such as structure, stereochemistry, conformation and aromaticity and basic mechanistic types, including nucleophilic substitution, addition reactions, carbonyl chemistry, aromatic substitution and free radical reactions. Together with Part B: Reaction and Synthesis, the two volumes are intended to provide the advanced undergraduate or beginning graduate student in chemistry with a sufficient foundation to comprehend and use the research literature in organic chemistry.

Author Notes

Francis A. Carey is a native of Pennsylvania, educated in the public schools of Philadelphia, at Drexel University (B.S. in chemistry, 1959), and at Penn State (Ph.D. 1963). Following postdoctoral work at Harvard and military service, he was appointed to the chemistry faculty of the University of Virginia in 1966. Prior to retiring in 2000, he regularly taught the two-semester lecture courses in general chemistry and organic chemistry. With his students, Professor Carey has published over forty research papers in synthetic and mechanistic organic chemistry.

Professor Sundberg is primarily engaged in teaching and chemical education. Along with Francis A. Carey he is the author of "Advanced Organic Chemistry. Professor Sundberg is also interested in synthetic methodology in heterocyclic chemistry and is the author of "Indoles" in the Best Synthetic Methods Series (Academic Press, 1996).

Preface	p. v
Acknowledgment and Personal Statement	p. vii
Introduction	p. ix
Chapter 1 Chemical Bonding and Molecular Structure	p. 1
Introduction	p. 1
1.1 Description of Molecular Structure Using Valence Bond Concepts	p. 2
1.1.1 Hybridization	p. 4
1.1.2 The Origin of Electron-Electron Repulsion	p. 7
1.1.3 Electronegativity and Polarity	p. 8
1.1.4 Electronegativity Equalization	p. 11
1.1.5 Differential Electronegativity of Carbon Atoms	p. 12
1.1.6 Polarizability, Hardness, and Softness	p. 14
1.1.7 Resonance and Conjugation	p. 18
1.1.8 Hyperconjugation	p. 22
1.1.9 Covalent and van der Waals Radii of Atoms	p. 24
1.2 Molecular Orbital Theory and Methods	p. 26
1.2.1 The Huckel MO Method	p. 27
1.2.2 Semiempirical MO Methods	p. 32
1.2.3 Ab Initio Methods	p. 32
1.2.4 Pictorial Representation of MOs for Molecules	p. 35
1.2.5 Qualitative Application of MO Theory to Reactivity: Perturbational MO Theory and Frontier Orbitals	p. 41
1.2.6 Numerical Application of MO Theory	p. 50
1.3 Electron Density Functionals	p. 54
1.4 Representation of Electron Density Distribution	p. 57
1.4.1 Mulliken Population Analysis	p. 60
1.4.2 Natural Bond Orbitals and Natural Population Analysis	p. 61
1.4.3 Atoms in Molecules	p. 63
1.4.4 Comparison and Interpretation of Atomic Charge Calculations	p. 70
1.4.5 Electrostatic Potential Surfaces	p. 73
1.4.6 Relationships between Electron Density and Bond Order	p. 76
Topic 1.1 The Origin of the Rotational (Torsional) Barrier in Ethane and Other Small Molecules	p. 78
Topic 1.2 Heteroatom Hyperconjugation (Anomeric Effect) in Acyclic Molecules	p. 81
Topic 1.3 Bonding in Cyclopropane and Other Small Ring Compounds	p. 85
Topic 1.4 Representation of Electron Density by the Laplacian Function	p. 92
Topic 1.5 Application of Density Functional Theory to Chemical Properties and Reactivity	p. 94
T.1.5.1 DFT Formulation of Chemical Potential, Electronegativity, Hardness and Softness, and Covalent and van der Waal Radii	p. 95
T.1.5.2 DFT Formulation of Reactivity-The Fukui Function	p. 97
T.1.5.3 DFT Concepts of Substituent Groups Effects	p. 100
General References	p. 106
Problems	p. 106
Chapter 2 Stereochemistry, Conformation, and Stereoselectivity	p. 119
Introduction	p. 119
2.1 Configuration	p. 119
2.1.1 Configuration at Double Bonds	p. 119
2.1.2 Configuration of Cyclic Compounds	p. 121
2.1.3 Configuration at Tetrahedral Atoms	p. 122
2.1.4 Molecules with Multiple Stereogenic Centers	p. 126
2.1.5 Other Types of Stereogenic Centers	p. 128
2.1.6 The Relationship between Chirality and Symmetry	p. 131
2.1.7 Configuration at Prochiral Centers	p. 133
2.1.8 Resolution-The Separation of Enantiomers	p. 136
2.2 Conformation	p. 142
2.2.1 Conformation of Acyclic Compounds	p. 142
2.2.2 Conformations of Cyclohexane Derivatives	p. 152
2.2.3 Conformations of Carbocyclic Rings of Other Sizes	p. 161
2.3 Molecular Mechanics	p. 167
2.4 Stereoselective and Stereospecific Reactions	p. 169
2.4.1 Examples of Stereoselective Reactions	p. 170
2.4.2 Examples of Stereospecific Reactions	p. 182
2.5 Enantioselective Reactions	p. 189
2.5.1 Enantioselective Hydrogenation	p. 189
2.5.2 Enantioselective Reduction of Ketones	p. 193
2.5.3 Enantioselective Epoxidation of Allylic Alcohols	p. 196
2.5.4 Enantioselective Dihydroxylation of Alkenes	p. 200
2.6 Double Stereodifferentiation: Reinforcing and Competing Stereoselectivity	p. 204
Topic 2.1 Analysis and Separation of Enantiomeric Mixtures	p. 208
T.2.1.1 Chiral Shift Reagents and Chiral Solvating Agents	p. 208
T.2.1.2 Separation of Enantiomers	p. 211
Topic 2.2 Enzymatic Resolution and Desymmetrization	p. 215
T.2.2.1 Lipases and Esterases	p. 216
T.2.2.2 Proteases and Acylases	p. 222
T.2.2.3 Epoxide Hydrolases	p. 224
Topic 2.3 The Anomeric Effect in Cyclic Compounds	p. 227
Topic 2.4 Polar Substituent Effects in Reduction of Carbonyl Compounds	p. 234
General References	p. 239
Problems	p. 240
Chapter 3 Structural Effects on Stability and Reactivity	p. 253
Introduction	p. 253
3.1 Thermodynamic Stability	p. 254
3.1.1 Relationship between Structure and Thermodynamic Stability for Hydrocarbons	p. 256
3.1.2 Calculation of Enthalpy of Formation and Enthalpy of Reaction	p. 257
3.2 Chemical Kinetics	p. 270
3.2.1 Fundamental Principles of Chemical Kinetics	p. 270
3.2.2 Representation of Potential Energy Changes in Reactions	p. 273
3.2.3 Reaction Rate Expressions	p. 280
3.2.4 Examples of Rate Expressions	p. 283
3.3 General Relationships between Thermodynamic Stability and Reaction Rates	p. 285
3.3.1 Kinetic versus Thermodynamic Control of Product Composition	p. 285
3.3.2 Correlations between Thermodynamic and Kinetic Aspects of Reactions	p. 287
3.3.3 Curtin-Hammett Principle	p. 296
3.4 Electronic Substituent Effects on Reaction Intermediates	p. 297
3.4.1 Carbocations	p. 300
3.4.2 Carbanions	p. 307
3.4.3 Radical Intermediates	p. 311
3.4.4 Carbonyl Addition Intermediates	p. 319
3.5 Kinetic Isotope Effects	p. 332
3.6 Linear Free-Energy Relationships for Substituent Effects	p. 335
3.6.1 Numerical Expression of Linear Free-Energy Relationships	p. 335
3.6.2 Application of Linear Free-Energy Relationships to Characterization of Reaction Mechanisms	p. 342
3.7 Catalysis	p. 345
3.7.1 Catalysis by Acids and Bases	p. 345
3.7.2 Lewis Acid Catalysis	p. 354
3.8 Solvent Effects	p. 359
3.8.1 Bulk Solvent Effects	p. 359
3.8.2 Examples of Specific Solvent Effects	p. 362
Topic 3.1 Acidity of Hydrocarbons	p. 368
General References	p. 376
Problems	p. 376
Chapter 4 Nucleophilic Substitution	p. 389
Introduction	p. 389
4.1 Mechanisms for Nucleophilic Substitution	p. 389
4.1.1 Substitution by the Ionization (S[subscript N]1) Mechanism	p. 391
4.1.2 Substitution by the Direct Displacement (S[subscript N]2) Mechanism	p. 393
4.1.3 Detailed Mechanistic Description and Borderline Mechanisms	p. 395
4.1.4 Relationship between Stereochemistry and Mechanism of Substitution	p. 402
4.1.5 Substitution Reactions of Alkyldiazonium Ions	p. 405
4.2 Structural and Solvation Effects on Reactivity	p. 407
4.2.1 Characteristics of Nucleophilicity	p. 407
4.2.2 Effect of Solvation on Nucleophilicity	p. 411
4.2.3 Leaving-Group Effects	p. 413
4.2.4 Steric and Strain Effects on Substitution and Ionization Rates	p. 415
4.2.5 Effects of Conjugation on Reactivity	p. 417
4.3 Neighboring-Group Participation	p. 419
4.4 Structure and Reactions of Carbocation Intermediates	p. 425
4.4.1 Structure and Stability of Carbocations	p. 425
4.4.2 Direct Observation of Carbocations	p. 436
4.4.3 Competing Reactions of Carbocations	p. 438
4.4.4 Mechanisms of Rearrangement of Carbocations	p. 440
4.4.5 Bridged (Nonclassical) Carbocations	p. 447
Topic 4.1 The Role Carbocations and Carbonium Ions in Petroleum Processing	p. 454
General References	p. 459
Problems	p. 459
Chapter 5 Polar Addition and Elimination Reactions	p. 473
Introduction	p. 475
5.1 Addition of Hydrogen Halides to Alkenes	p. 476
5.2 Acid-Catalyzed Hydration and Related Addition Reactions	p. 482
5.3 Addition of Halogens	p. 485
5.4 Sulfenylation and Selenenylation	p. 497
5.4.1 Sulfenylation	p. 498
5.4.2 Selenenylation	p. 500
5.5 Addition Reactions Involving Epoxides	p. 503
5.5.1 Epoxides from Alkenes and Peroxidic Reagents	p. 503
5.5.2 Subsequent Transformations of Epoxides	p. 511
5.6 Electrophilic Additions Involving Metal Ions	p. 515
5.6.1 Solvomercuration	p. 515
5.6.2 Argentation-the Formation of Silver Complexes	p. 520
5.7 Synthesis and Reactions of Alkylboranes	p. 521
5.7.1 Hydroboration	p. 522
5.7.2 Reactions of Organoboranes	p. 526
5.7.3 Enantioselective Hydroboration	p. 529
5.8 Comparison of Electrophilic Addition Reactions	p. 531
5.9 Additions to Alkynes and Allenes	p. 536
5.9.1 Hydrohalogenation and Hydration of Alkynes	p. 538
5.9.2 Halogenation of Alkynes	p. 540
5.9.3 Mercuration of Alkynes	p. 544
5.9.4 Overview of Alkyne Additions	p. 544
5.9.5 Additions to Allenes	p. 545
5.10 Elimination Reactions	p. 546
5.10.1 The E2, E1 and E1cb Mechanisms	p. 548
5.10.2 Regiochemistry of Elimination Reactions	p. 554
5.10.3 Stereochemistry of E2 Elimination Reactions	p. 558
5.10.4 Dehydration of Alcohols	p. 563
5.10.5 Eliminations Reactions Not Involving C-H Bonds	p. 564
General References	p. 569
Problems	p. 569
Chapter 6 Carbanions and Other Carbon Nucleophiles	p. 579
Introduction	p. 559
6.1 Acidity of Hydrocarbons	p. 579
6.2 Carbanion Character of Organometallic Compounds	p. 588
6.3 Carbanions Stabilized by Functional Groups	p. 591
6.4 Enols and Enamines	p. 601
6.5 Carbanions as Nucleophiles in S[subscript N]2 Reactions	p. 609
6.5.1 Substitution Reactions of Organometallic Reagents	p. 609
6.5.2 Substitution Reactions of Enolates	p. 611
General References	p. 619
Problems	p. 619
Chapter 7 Addition, Condensation and Substitution Reactions of Carbonyl Compounds	p. 629
Introduction	p. 629
7.1 Reactivity of Carbonyl Compounds toward Addition	p. 632
7.2 Hydration and Addition of Alcohols to Aldehydes and Ketones	p. 638
7.3 Condensation Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles	p. 645
7.4 Substitution Reactions of Carboxylic Acid Derivatives	p. 654
7.4.1 Ester Hydrolysis and Exchange	p. 654
7.4.2 Aminolysis of Esters	p. 659
7.4.3 Amide Hydrolysis	p. 662
7.4.4 Acylation of Nucleophilic Oxygen and Nitrogen Groups	p. 664
7.5 Intramolecular Catalysis of Carbonyl Substitution Reactions	p. 668
7.6 Addition of Organometallic Reagents to Carbonyl Groups	p. 676
7.6.1 Kinetics of Qrganometallic Addition Reactions	p. 677
7.6.2 Stereoselectivity of Organometallic Addition Reactions	p. 680
7.7 Addition of Enolates and Enols to Carbonyl Compounds: The Aldol Addition and Condensation Reactions	p. 682
7.7.1 The General Mechanisms	p. 682
7.7.2 Mixed Aldol Condensations with Aromatic Aldehydes	p. 685
7.7.3 Control of Regiochemistry and Stereochemistry of Aldol Reactions of Ketones	p. 687
7.7.4 Aldol Reactions of Other Carbonyl Compounds	p. 692
General References	p. 698
Problems	p. 698
Chapter 8 Aromaticity	p. 713
Introduction	p. 713
8.1 Criteria of Aromaticity	p. 715
8.1.1 The Energy Criterion for Aromaticity	p. 715
8.1.2 Structural Criteria for Aromaticity	p. 718
8.1.3 Electronic Criteria for Aromaticity	p. 720
8.1.4 Relationship among the Energetic, Structural, and Electronic Criteria of Aromaticity	p. 724
8.2 The Annulenes	p. 725
8.2.1 Cyclobutadiene	p. 725
8.2.2 Benzene	p. 727
8.2.3 1,3,5,7-Cyclooctatetraene	p. 727
8.2.4 [10]Annulenes-1,3,5,7,9-Cyclodecapentaene Isomers	p. 728
8.2.5 [12], [14], and [16]Annulenes	p. 730
8.2.6 [18]Annulene and Larger Annulenes	p. 733
8.2.7 Other Related Structures	p. 735
8.3 Aromaticity in Charged Rings	p. 738
8.4 Homoaromaticity	p. 743
8.5 Fused-Ring Systems	p. 745
8.6 Heteroaromatic Systems	p. 758
General References	p. 760
Problems	p. 760
Chapter 9 Aromatic Substitution	p. 771
Introduction	p. 771
9.1 Electrophilic Aromatic Substitution Reactions	p. 771
9.2 Structure-Reactivity Relationships for Substituted Benzenes	p. 779
9.2.1 Substituent Effects on Reactivity	p. 779
9.2.2 Mechanistic Interpretation of the Relationship between Reactivity and Selectivity	p. 787
9.3 Reactivity of Polycyclic and Heteroaromatic Compounds	p. 791
9.4 Specific Electrophilic Substitution Reactions	p. 796
9.4.1 Nitration	p. 796
9.4.2 Halogenation	p. 800
9.4.3 Protonation and Hydrogen Exchange	p. 804
9.4.4 Friedel-Crafts Alkylation and Related Reactions	p. 805
9.4.5 Friedel-Crafts Acylation and Related Reactions	p. 809
9.4.6 Aromatic Substitution by Diazonium Ions	p. 813
9.4.7 Substitution of Groups Other than Hydrogen	p. 814
9.5 Nucleophilic Aromatic Substitution	p. 816
9.5.1 Nucleophilic Aromatic Substitution by the Addition-Elimination Mechanism	p. 817
9.5.2 Nucleophilic Aromatic Substitution by the Elimination-Addition Mechanism	p. 821
General References	p. 824
Problems	p. 824
Chapter 10 Concerted Pericyclic Reactions	p. 833
Introduction	p. 833
10.1 Cycloaddition Reactions	p. 834
10.2 The Diels-Alder Reaction	p. 839
10.2.1 Stereochemistry of the Diels-Alder Reaction	p. 839
10.2.2 Substituent Effects on Reactivity, Regioselectivity and Stereochemistry	p. 843
10.2.3 Catalysis of Diels-Alder Reactions by Lewis Acids	p. 848
10.2.4 Computational Characterization of Diels-Alder Transition Structures	p. 851
10.2.5 Scope and Synthetic Applications of the Diels-Alder Reaction	p. 860
10.2.6 Enantioselective Diels-Alder Reactions	p. 865
10.2.7 Intramolecular Diels-Alder Reactions	p. 868
10.3 1,3-Dipolar Cycloaddition Reactions	p. 873
10.3.1 Relative Reactivity, Regioselectivity, Stereoselectivity, and Transition Structures	p. 874
10.3.2 Scope and Applications of 1,3-Dipolar Cycloadditions	p. 884
10.3.3 Catalysis of 1,3-Dipolar Cycloaddition Reactions	p. 886
10.4 [2 + 2] Cycloaddition Reactions	p. 888
10.5 Electrocyclic Reactions	p. 892
10.5.1 Overview of Electrocyclic Reactions	p. 892
10.5.2 Orbital Symmetry Basis for the Stereospecificity of Electrocyclic Reactions	p. 894
10.5.3 Examples of Electrocyclic Reactions	p. 903
10.5.4 Electrocyclic Reactions of Charged Species	p. 906
10.5.5 Electrocyclization of Heteroatomic Trienes	p. 910
10.6 Sigmatropic Rearrangements	p. 911
10.6.1 Overview of Sigmatropic Rearrangements	p. 911
10.6.2 [1,3]-, [1,5]-, and [1,7]-Sigmatropic Shifts of Hydrogen and Alkyl Groups	p. 912
10.6.3 Overview of [3,3]-Sigmatropic Rearrangements	p. 919
10.6.4 [2,3]-Sigmatropic Rearrangements	p. 939
Topic 10.1 Application of DFT Concepts to Reactivity and Regiochemistry of Cycloaddition Reactions	p. 945
Problems	p. 951
Chapter 11 Free Radical Reactions	p. 965
Introduction	p. 965
11.1 Generation and Characterization of Free Radicals	p. 967
11.1.1 Background	p. 967
11.1.2 Long-Lived Free Radicals	p. 968
11.1.3 Direct Detection of Radical Intermediates	p. 970
11.1.4 Generation of Free Radicals	p. 976
11.1.5 Structural and Stereochemical Properties of Free Radicals	p. 980
11.1.6 Substituent Effects on Radical Stability	p. 986
11.1.7 Charged Radicals	p. 988
11.2 Characteristics of Reactions Involving Radical Intermediates	p. 992
11.2.1 Kinetic Characteristics of Chain Reactions	p. 992
11.2.2 Determination of Reaction Rates	p. 995
11.2.3 Structure-Reactivity Relationships	p. 1000
11.3 Free Radical Substitution Reactions	p. 1018
11.3.1 Halogenation	p. 1018
11.3.2 Oxygenation	p. 1024
11.4 Free Radical Addition Reactions	p. 1026
11.4.1 Addition of Hydrogen Halides	p. 1026
11.4.2 Addition of Halomethanes	p. 1029
11.4.3 Addition of Other Carbon Radicals	p. 1031
11.4.4 Addition of Thiols and Thiocarboxylic Acids	p. 1033
11.4.5 Examples of Radical Addition Reactions	p. 1033
11.5 Other Types of Free Radical Reactions	p. 1037
11.5.1 Halogen, Sulfur, and Selenium Group Transfer Reactions	p. 1037
11.5.2 Intramolecular Hydrogen Atom Transfer Reactions	p. 1040
11.5.3 Rearrangement Reactions of Free Radicals	p. 1041
11.6 S[subscript RN]1 Substitution Processes	p. 1044
11.6.1 S[subscript RN]1 Substitution Reactions of Alkyl Nitro Compounds	p. 1045
11.6.2 S[subscript RN]1 Substitution Reactions of Aryl and Alkyl Halides	p. 1048
Topic 11.1 Relationships between Bond and Radical Stabilization Energies	p. 1052
Topic 11.2 Structure-Reactivity Relationships in Hydrogen Abstraction Reactions	p. 1056
General References	p. 1062
Problems	p. 1063
Chapter 12 Photochemistry	p. 1073
Introduction	p. 1073
12.1 General Principles	p. 1073
12.2 Photochemistry of Alkenes, Dienes, and Polyenes	p. 1081
12.2.1 Cis-trans Isomerization	p. 1081
12.2.2 Photoreactions of Other Alkenes	p. 1091
12.2.3 Photoisomerization of 1,3-Butadiene	p. 1096
12.2.4 Orbital Symmetry Considerations for Photochemical Reactions of Alkenes and Dienes	p. 1097
12.2.5 Photochemical Electrocyclic Reactions	p. 1100
12.2.6 Photochemical Cycloaddition Reactions	p. 1109
12.2.7 Photochemical Rearrangements Reactions of 1,4-Dienes	p. 1112
12.3 Photochemistry of Carbonyl Compounds	p. 1116
12.3.1 Hydrogen Abstraction and Fragmentation Reactions	p. 1118
12.3.2 Cycloaddition and Rearrangement Reactions of Cyclic Unsaturated Ketones	p. 1125
12.3.3 Cycloaddition of Carbonyl Compounds and Alkenes	p. 1132
12.4 Photochemistry of Aromatic Compounds	p. 1134
Topic 12.1 Computational Interpretation of Diene and Polyene Photochemistry	p. 1137
General References	p. 1145
Problems	p. 1146
References to Problems	p. 1155
Index	p. 1171

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