Molecular Orbitals and Organic Chamical Reactions Student Edition
Buku ini diterbitkan tahun 2009 John Wiley & Sons Ltd. Buku ini adalah buku edisi Pertama.
Judul: Molecular Orbitals and Organic Chamical Reactions Student Edition
Oleh: Ia Fleming
Penerbit: John Wiley & Sons Ltd
Tahun: 2009
Jumlah Halaman: 378 hal
Penulis:
Ian Fleming
Department of Chemistry,
University of Cambridge, UK.
Lingkup Pembahasan:
Buku ini terdiri atas 8 Bagian utama bagian 1 Teori Molecular Orbital, Bsgian 2 Struktur Molekul Organik, Bagian 3 Bagaimana-Reaksi Kimia Jauh dan Cara Cepat, Bagian 4 Ionic Reaksi-Reaktivitas, Bagian 5 Ionic Reaksi-stereokimia, Bagian 6 Reaksi Pericyclic Thermal, Bagian 7 Reaksi Radikal, dan
Bagian 8 Reaksi fotokimia.
Daftar Isi:
Preface xi
1 Molecular Orbital Theory 1
1.1 The Atomic Orbitals of a Hydrogen Atom 1
1.2 Molecules made from Hydrogen Atoms 2
1.2.1 The H2 Molecule 2
1.2.2 The H3 Molecule 7
1.2.3 The H4 ‘Molecule’ 8
1.3 C—H and C—C Bonds 9
1.3.1 The Atomic Orbitals of a Carbon Atom 9
1.3.2 Methane 12
1.3.3 Methylene 13
1.3.4 Hybridisation 15
1.3.5 C—C _ Bonds and _ Bonds: Ethane 18
1.3.6 C¼C _ Bonds: Ethylene 20
1.4 Conjugation—Hu¨ckel Theory 22
1.4.1 The Allyl System 22
1.4.2 Butadiene 28
1.4.3 Longer Conjugated Systems 31
1.5 Aromaticity 32
1.5.1 Aromatic Systems 32
1.5.2 Antiaromatic Systems 34
1.5.3 The Cyclopentadienyl Anion and Cation 37
1.5.4 Homoaromaticity 37
1.5.5 Spiro Conjugation 38
1.6 Strained _ Bonds—Cyclopropanes and Cyclobutanes 39
1.6.1 Cyclopropanes 39
1.6.2 Cyclobutanes 42
1.7 Heteronuclear Bonds, C—M, C—X and C¼O 42
1.7.1 Atomic orbital energies and electronegativity 43
1.7.2 C—X _ Bonds 43
1.7.3 C—M _ Bonds 47
1.7.4 C¼O _ Bonds 49
1.7.5 Heterocyclic Aromatic Systems 51
1.8 The Tau Bond Model 52
1.9 Spectroscopic Methods 53
1.9.1 Ultraviolet Spectroscopy 53
1.9.2 Photoelectron Spectroscopy 54
1.9.3 Nuclear Magnetic Resonance Spectroscopy 55
1.9.4 Electron Spin Resonance Spectroscopy 56
1.10 Exercises 57
2 The Structures of Organic Molecules 59
2.1 The Effects of _ Conjugation 59
2.1.1 A Notation for Substituents 59
2.1.2 The Effect of Substituents on the Stability of Alkenes 60
2.1.3 The Effect of Substituents on the Stability of Carbocations 65
2.1.4 The Effect of Substituents on the Stability of Carbanions 66
2.1.5 The Effect of Substituents on the Stability of Radicals 67
2.1.6 Energy-Raising Conjugation 69
2.2 Conjugation—Hyperconjugation 69
2.2.1 C—H and C—C Hyperconjugation 70
2.2.2 C—M Hyperconjugation 74
2.2.3 Negative Hyperconjugation 76
2.3 The Configurations and Conformations of Molecules 81
2.3.1 Restricted Rotation in _-Conjugated Systems 82
2.3.2 Preferred Conformations from Conjugation in the _ Framework 89
2.4 Other Noncovalent Interactions 90
2.4.1 The Hydrogen Bond 90
2.4.2 Hypervalency 92
2.4.3 Polar Interactions, and van der Waals and other Weak Interactions 93
2.5 Exercises 95
3 Chemical Reactions—How Far and How Fast 97
3.1 Factors Affecting the Position of an Equilibrium 97
3.2 The Principle of Hard and Soft Acids and Bases (HSAB) 97
3.3 Transition Structures 103
3.4 The Perturbation Theory of Reactivity 104
3.5 The Salem-Klopman Equation 106
3.6 Hard and Soft Nucleophiles and Electrophiles 109
3.7 Other Factors Affecting Chemical Reactivity 110
4 Ionic Reactions—Reactivity 111
4.1 Single Electron Transfer (SET) in Ionic Reactions 111
4.2 Nucleophilicity 114
4.2.1 Heteroatom Nucleophiles 114
4.2.2 Solvent Effects 118
4.2.3 Alkene Nucleophiles 118
4.2.4 The _-Effect 119
4.3 Ambident Nucleophiles 121
4.3.1 Thiocyanate Ion, Cyanide Ion and Nitrite Ion (and the Nitronium Cation) 121
4.3.2 Enolate lons 124
4.3.3 Allyl Anions 125
4.3.4 Aromatic Electrophilic Substitution 129
4.4 Electrophilicity 134
4.4.1 Trigonal Electrophiles 134
4.4.2 Tetrahedral Electrophiles 136
4.4.3 Hard and Soft Electrophiles 137
4.5 Ambident Electrophiles 137
4.5.1 Aromatic Electrophiles 138
4.5.2 Aliphatic Electrophiles 140
4.6 Carbenes 147
4.6.1 Nucleophilic Carbenes 148
4.6.2 Electrophilic Carbenes 149
4.6.3 Aromatic Carbenes 149
4.7 Exercises 151
5 Ionic Reactions—Stereochemistry 153
5.1 The Stereochemistry of the Fundamental Organic Reactions 154
5.1.1 Substitution at a Saturated Carbon 154
5.1.2 Elimination Reactions 156
5.1.3 Nucleophilic and Electrophilic Attack on a _ Bond 158
5.1.4 The Stereochemistry of Substitution at Trigonal Carbon 165
5.2 Diastereoselectivity 167
5.2.1 Nucleophilic Attack on a Double Bond with Diastereotopic Faces 169
5.2.2 Nucleophilic and Electrophilic Attack on Cycloalkenes 175
5.2.3 Electrophilic Attack on Open-Chain Double Bonds with Diastereotopic Faces 178
5.2.4 Diastereoselective Nucleophilic and Electrophilic Attack on Double Bonds Free of
Steric Effects 182
5.3 Exercises 183
6 Thermal Pericyclic Reactions 185
6.1 The Four Classes of Pericyclic Reactions 186
6.2 Evidence for the Concertedness of Bond Making and Breaking 188
6.3 Symmetry-Allowed and Symmetry-Forbidden Reactions 190
6.3.1 The Woodward-Hoffmann Rules—Class by Class 190
6.3.2 The Generalised Woodward-Hoffmann Rule 200
6.4 Explanations for the Woodward-Hoffmann Rules 214
6.4.1 The Aromatic Transition Structure 215
6.4.2 Frontier Orbitals 215
6.4.3 Correlation Diagrams 216
6.5 Secondary Effects 221
6.5.1 The Energies and Coefficients of the Frontier Orbitals of Alkenes and Dienes 222
6.5.2 Diels-Alder Reactions 224
6.5.3 1,3-Dipolar Cycloadditions 242
6.5.4 Other Cycloadditions 252
6.5.5 Other Pericyclic Reactions 259
6.5.6 Periselectivity 263
6.5.7 Torquoselectivity 267
6.6 Exercises 270
7 Radical Reactions 275
7.1 Nucleophilic and Electrophilic Radicals 275
7.2 The Abstraction of Hydrogen and Halogen Atoms 277
7.2.1 The Effect of the Structure of the Radical 277
7.2.2 The Effect of the Structure of the Hydrogen or Halogen Source 278
7.3 The Addition of Radicals to _ Bonds 279
7.3.1 Attack on Substituted Alkenes 279
7.3.2 Attack on Substituted Aromatic Rings 282
7.4 Synthetic Applications of the Chemoselectivity of Radicals 286
7.5 Stereochemistry in some Radical Reactions 287
7.6 Ambident Radicals 290
7.6.1 Neutral Ambident Radicals 290
7.6.2 Charged Ambident Radicals 291
7.7 Radical Coupling 295
7.8 Exercises 296
8 Photochemical Reactions 299
8.1 Photochemical Reactions in General 299
8.2 Photochemical Ionic Reactions 301
8.2.1 Aromatic Nucleophilic Substitution 301
8.2.2 Aromatic Electrophilic Substitution 302
8.2.3 Aromatic Side-Chain Reactivity 303
8.3 Photochemical Pericyclic Reactions and Related Stepwise Reactions 304
8.3.1 The Photochemical Woodward-Hoffmann Rule 304
8.3.2 Regioselectivity of Photocycloadditions 307
8.3.3 Other Kinds of Selectivity in Pericyclic and Related Photochemical Reactions 319
8.4 Photochemically Induced Radical Reactions 321
8.5 Chemiluminescence 323
8.6 Exercises 324
References 327
Index 331
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