Structure and reactivity in organic chemistry
著者
書誌事項
Structure and reactivity in organic chemistry
Blackwell Pub., 2008
- pbk.
大学図書館所蔵 件 / 全4件
-
該当する所蔵館はありません
- すべての絞り込み条件を解除する
注記
Includes index
内容説明・目次
内容説明
The jump from an understanding of organic chemistry at lower undergraduate level to that required at postgraduate level or in industry can be difficult. Many advanced textbooks contain a level of detail which can obscure the essential mechanistic framework that unites the huge range of facts of organic chemistry. Understanding this underlying order is essential in any advanced study or application of organic chemistry. Structure and Reactivity in Organic Chemistry aims to bridge that gap.
The text opens with a short overview of the way chemists understand chemical structure, and how that understanding is essential in developing a good knowledge of chemical reactivity and mechanism. The remainder of the text presents a mechanistic classification of modern organic chemistry, developed in the context of synthetic organic chemistry and exemplified by reference to stereoselective synthesis and protecting group chemistry. This approach is intended to illustrate the importance and value of a good grasp of organic reaction mechanisms, which is a prerequisite for a broader understanding of organic chemistry.
Written by an expert educator with a sound understanding of the needs of different audiences, the subject is presented with clarity and precision, and in a highly practical manner. It is relevant to undergraduates, postgraduates and industrial organic chemists.
目次
Preface xi
1 Bonding 1
1.1 Atomic structure 1
1.1.1 The chemical bond 1
1.1.2 The periodic table 1
1.1.3 Valence electrons 3
1.1.4 Lewis structures 3
1.1.5 Conventions for drawing structures 5
1.1.6 Atomic orbital theory 6
1.1.7 Molecular orbital theory 7
1.2 Covalent bonding 10
1.2.1 Bonding in hydrocarbons 11
1.2.2 Bonding in compounds containing heteroatoms 12
1.2.3 Bonding in common functional groups 12
1.2.4 Electronic effects 14
1.2.5 Steric effects 18
1.2.6 Stereoelectronic effects 18
1.2.7 Double bond equivalents 20
2 Structure 21
2.1 Configuration 21
2.1.1 Geometrical isomerism 22
2.1.2 Optical isomerism 23
2.1.3 Representations of stereoisomers 25
2.1.4 Molecules with one stereogenic centre 27
2.1.5 Molecules with more than one stereogenic centre 27
2.1.6 Molecules with more than one stereogenic centre which are not optically active 28
2.1.7 Optically active molecules without stereogenic centres: molecular asymmetry 29
2.1.8 Asymmetric heteroatoms 30
2.2 Conformation 31
2.2.1 Representation of conformers 31
2.2.2 Open-chain compounds 31
2.2.3 Ring compounds 33
2.3 Summary of stereochemical relationships 39
2.4 Naturally occurring chiral compounds 39
2.5 Asymmetric synthesis 41
2.5.1 Enantioselective synthesis 41
2.5.2 Diastereoselective synthesis 43
2.5.3 Methods for the determination of enantiomeric purity 43
3 Reactivity 47
3.1 Thermodynamics 47
3.1.1 Gibbs free energy 47
3.1.2 Enthalpy 48
3.1.3 Entropy 50
3.1.4 Chemical equilibrium 52
3.2 Kinetics 54
3.2.1 Rates of reaction 54
3.2.2 Reactions with competing steps 57
3.2.3 Overcoming activation energy barriers 58
3.3 Reaction mechanism 60
3.3.1 What is reactivity? 60
3.3.2 Lewis acids and bases: 'philicity' 60
3.3.3 Polarisability effects: Hard-Soft Acid-Base theory 61
3.3.4 Curly ('curved') arrows 63
3.4 Classes of reaction mechanism 66
3.4.1 Polar mechanisms 66
3.4.2 Radical mechanisms 67
3.4.3 Pericyclic mechanisms 67
3.4.4 Ligand coupling reaction mechanisms 67
3.5 Principle of microscopic reversibility 68
3.6 Selectivity of reactions 69
3.7 Solvents in organic chemistry 71
3.8 Redox reactions in organic chemistry 72
4 Intermediates 77
4.1 Carbocations 77
4.1.1 Structure 77
4.1.2 Factors stabilising carbocations 77
4.1.3 Generation of carbocations 81
4.1.4 Rearrangements of carbocations 82
4.2 Carbanions 82
4.2.1 Structure 82
4.2.2 Carbanions derived from simple alkanes 84
4.2.3 Factors stabilising carbanions 85
4.3 Carbanions with covalent character 88
4.3.1 Grignard reagents (RMgX) 88
4.3.2 Organolithium reagents (RLi) 89
4.3.3 Organocadmium reagents 89
4.4 Radicals 90
4.4.1 Structure 90
4.4.2 Factors stabilising radicals 90
4.4.3 Generation of radicals 92
4.5 Carbenes 94
4.5.1 Stability and structure 94
4.5.2 Generation of carbenes 95
4.6 Benzynes 96
4.6.1 Stability and structure 96
4.6.2 Generation of benzynes 97
4.7 Ketenes 98
4.7.1 Stability and structure 98
4.7.2 Generation of ketenes 98
5 Acidity and Basicity 99
5.1 Lowry-Bronsted Acid-Base theory 99
5.2 Organic acidity 100
5.2.1 Organic acids 100
5.3 Organic basicity 111
5.3.1 Organic bases 112
6 Nucleophilic Substitution 117
6.1 The S N 1 reaction 117
6.1.1 Factors affecting the S N 1 reaction 118
6.2 The S N 2 reaction 123
6.2.1 Factors enhancing the S N 2 reaction 124
6.3 Synthetic applications of nucleophilic substitution reactions 128
6.3.1 Protecting-group chemistry 128
6.3.2 Stereocontrolled alkylation reactions 131
7 Addition Reactions 139
7.1 Electrophilic addition reactions 139
7.1.1 Addition of halogens 139
7.1.2 Addition of hydrogen halides 141
7.1.3 Addition of hydrogen halides to conjugated dienes 143
7.1.4 Addition of diborane (hydroboration) 143
7.1.5 Addition of hydrogen 147
7.1.6 Addition of oxygen 148
7.1.7 Addition of carbon 153
7.2 Nucleophilic addition reactions 153
7.2.1 Irreversible nucleophilic addition 154
7.2.2 Irreversible nucleophilic conjugate addition 159
7.2.3 Reversible nucleophilic addition 160
7.3 Additions to electron-deficient alkenes 165
7.4 Additions of ketenes 165
7.5 Synthetic applications 166
8 Elimination Reactions 169
8.1 Eliminations 169
8.1.1 E 1 reactions 169
8.1.2 E 1 CB reactions 169
8.1.3 E 2 reactions 170
8.1.4 Eliminations leading to isomeric products 173
8.1.5 Competition between substitution and elimination 175
8.1.6 The leaving group 176
8.2 Oxidation processes 178
8.3 Eliminations leading to carbenes and nitrenes 181
8.4 Eliminations of phosphorus 182
8.5 Eliminations of sulfur and selenium 182
8.6 Eliminations in protecting-group chemistry 184
9 Aromatic Substitution 189
9.1 Aromaticity 189
9.1.1 Benzene 189
9.1.2 Heteroaromatics 189
9.2 Reactions 191
9.2.1 Acidity and basicity 191
9.2.2 Electrophilic aromatic substitution 191
9.2.3 Orientation effects in electrophilic aromatic substitution (S E Ar) 202
9.2.4 o-Lithiation 205
9.2.5 Nucleophilic aromatic substitution 206
9.2.6 Arene chromium tricarbonyl complexes 211
10 Sequential Addition and Elimination Reactions 213
10.1 Addition-elimination reactions 213
10.1.1 Addition of hydride 220
10.1.2 Addition of heteroatom nucleophiles 221
10.1.3 Addition of carbon nucleophiles 222
10.1.4 Addition of phosphorus nucleophiles 225
10.2 Addition-elimination reactions in conjugated systems 230
10.3 Addition-elimination reactions in heterocyclic systems 230
10.4 Addition-elimination reactions in ring-closing metathesis 231
10.5 Addition-elimination reactions in deprotections 234
11 Radical Reactions 237
11.1 Generation 237
11.2 Reactions 237
11.2.1 Termination 237
11.2.2 Propagation 238
11.2.3 Substitution 239
11.2.4 Addition reactions 242
11.2.5 Fragmentation 249
11.2.6 Rearrangement 250
11.3 Synthetic utility 255
12 Ligand Coupling Reactions 263
12.1 Palladium-mediated couplings 263
12.1.1 Palladium-mediated coupling processes 264
12.1.2 Heck coupling 271
12.1.3 Allylic coupling processes 273
12.2 Ligand coupling processes mediated by other elements 275
12.2.1 Copper 276
12.2.2 Magnesium 277
12.2.3 Lead 279
13 Pericyclic Reactions 283
13.1 Molecular orbitals and the FMO approach 283
13.2 Pericyclic reactions 284
13.2.1 Electrocyclic reactions 285
13.2.2 Cycloaddition reactions 287
13.2.3 Sigmatropic reactions 293
13.3 Synthetic applications of pericyclic reactions 296
Index 303
「Nielsen BookData」 より