Encyclopedia of Physical Science and Technology – Organic Chemistry

Robert A. Meyers (Editor)978-0122274107

Nine years has passed since the 1992 second edition of the encyclopedia was published. This completely revised third edition, which is a university and professional level compendium of chemistry, molecular biology, mathematics, and engineering, is refreshed with numerous articles about current research in these fields. For example, the new edition has an increased emphasis on information processing and biotechnology, reflecting the rapid growth of these areas. The continuing Editor-in-Chief, Robert Meyers, and the Board prepared a new topical outline of physical science and technology to define complete coverage. Section editors are either Nobel Laureates or editors of key journals in their fields. Additional Board members representing the global scientific community were also recruited.

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Table of contents :
Cover Table……Page 1
Table of Contents……Page 2
Glossary……Page 3
Production of Acetylene and Commodity Chemicals……Page 4
Acetylene Production on a World Basis……Page 5
Replacement Process: Ammoxidation of Propylene……Page 6
Replacement Process: Oxychlorination of Ethylene……Page 7
Vinylidene Fluoride (Vinylidene Difluoride)……Page 8
Reppe Products……Page 9
Applications of Reppe Products……Page 10
Butane-1,4-Diol and Tetrahydrofuran: Large-Volume Polymer Uses……Page 11
Linalool (3,7-Dimethylocta-1,6-dien-3-ol)……Page 12
Corrosion Inhibitors……Page 13
Processes for Acetylene Production……Page 14
Reppe Process for 2-Butyne-1,4-Diol and Propargyl Alcohol (1-Propyn-3-ol)……Page 16
Sodium and Lithium Acetylides in Liquid Ammonia……Page 17
Potassium Hydroxide–Acetylene–Organic Solvent Route……Page 18
Grignard Route……Page 19
Use of Liquid Acetylene as Solvent and Reactant……Page 20
Flavor and Fragrance Compounds and Vitamins A and E……Page 21
Barban……Page 25
Cyclic Carbonates from Alkynol– Alkynediol–Carbon Dioxide Reactions……Page 27
Arylacetylenes from Methylbutynol and Aromatic Compounds……Page 29
Acetylene-Capped Polyimide Polymers……Page 30
Acetylene Research in Russia……Page 31
Reactions of Triads: S8–KOH–DMSO, Se8–KOH–DMSO, Te–KOH–HMPA……Page 32
Vinylox (2-Vinyloxyethoxymethyl Oxirane)……Page 33
References……Page 36
Glossary……Page 38
History of Alkaloids……Page 39
Occurrence……Page 40
Physical and Chemical Features of Alkaloids……Page 41
Structure Elucidation……Page 42
Classification……Page 43
Heterocyclic Alkaloids……Page 44
Putrescine, Spermidine, and Spermine Alkaloids……Page 46
Biosynthesis……Page 47
Chemotaxonomy……Page 49
In Natural Sources……Page 51
Alkaloid Structures in Drug Design……Page 52
References……Page 54
Glossary……Page 55
Carboxylic……Page 56
Multiple Sites of Chemical Conjugation: Mathematics of Random Labeling……Page 57
Methods……Page 58
Separation and Analysis in vitro……Page 59
References……Page 60
Glossary……Page 61
Historical Background……Page 62
Monosaccharides……Page 63
Oligosaccharides……Page 64
Polysaccharides……Page 65
Configuration……Page 66
Cyclic structures and anomeric configuration…….Page 67
Conformation……Page 69
Reactions of Monosaccharides……Page 72
Reactions of the Carbonyl Group……Page 73
Nucleophilicity Quotient of Monosaccharides……Page 76
Nucleophilic Substitution Reactions of the Anomeric Carbon Atom……Page 77
Displacement of OH groups by OR groups……Page 78
Nucleophilic displacement of OR groups…….Page 79
Nucleophilic Attacks by Hydroxyl Groups……Page 80
Formation of ethers…….Page 81
Cyclic acetals…….Page 82
Heterolytic oxidations…….Page 83
Borohydrides and diborane…….Page 85
Oligosaccharides……Page 86
Reducing power…….Page 87
Monosaccharide sequence in trisaccharides…….Page 89
Monosaccharide sequence in tetrasaccharides…….Page 91
By enzymatic hydrolysis…….Page 92
By NMR spectroscopy…….Page 93
Chemical Methods of Oligosaccharide Synthesis……Page 94
Synthesis of Oligosaccharides on Fixed Beds of Polymers……Page 96
Reactions……Page 98
Structure……Page 99
Starch……Page 100
Chemically modified starch…….Page 102
Cellulose……Page 103
Mannans and Galactomannans……Page 104
Synthesis of Oligonucleotides……Page 105
Block Synthesis of Oligonucleotides……Page 106
References……Page 108
Glossary……Page 109
Definition……Page 110
Creation of a “Vacant Site” and Coordination of the Substrate……Page 111
β-Elimination and De-Insertion……Page 112
Oxidative Addition……Page 113
Cyclometallation……Page 114
Oxidative Addition……Page 115
Activation by Lewis Acids……Page 116
Wilkinson’s Catalyst……Page 117
Enantioselective hydrogenation…….Page 118
Asymmetric Isomerization……Page 120
Monsanto Acetic Acid Process……Page 121
Introduction……Page 122
Rhodium-Based Hydroformylation……Page 123
Ligand Effects……Page 124
Two-Phase Hydroformylation: Water-Soluble Catalysts……Page 125
Purification and metathesis…….Page 126
Synthesis……Page 127
The Cossee-Arlman Mechanism……Page 128
Homogeneous Catalysts……Page 129
Mechanistic Explanations……Page 130
Allylic Alkylation……Page 131
Cross Coupling……Page 132
Heck Reaction……Page 133
Wacker-type Reactions……Page 134
Introduction……Page 135
The Chemistry……Page 136
Process Description……Page 137
Alkene Metathesis……Page 138
Cyclopropanation……Page 139
Polyesters……Page 140
References……Page 141
Glossary……Page 143
Origin of Fossil Fuels……Page 144
Properties for Utilization……Page 145
Combustion of Coal……Page 146
Fixed Bed Combustion……Page 148
Pulverized Coal Combustion……Page 149
Fluidized Bed Combustion……Page 150
Behavior of Ash in Boiler Furnaces……Page 151
During the Combustion Control Method……Page 152
Nitrogen Oxides……Page 153
NOx Control Technologies……Page 154
Gasification Reactions……Page 155
Major Gasification Processes……Page 156
Indirect Liquefaction……Page 158
Liquid Fuels……Page 159
Combustion of Liquid Fuels……Page 160
Environmental Challenges for Liquid Fuel Utilization……Page 162
See also the Following Articles……Page 163
References……Page 164
Glossary……Page 165
Comparison with Carbocyclic Compounds……Page 166
Nomenclature and Numbering of Heterocycles……Page 167
Occurrence and Isolation……Page 168
Melting and Boiling Points……Page 169
Tautomerism……Page 170
Conformation……Page 172
Electrophilic Attack……Page 173
Electrocyclic Reactions……Page 174
Use of Heterocycles in Synthesis……Page 175
Synthesis of Heterocycles……Page 176
Synthesis……Page 177
Properties and Importance……Page 178
Naturally Occurring Five-Membered Heterocycles……Page 179
Six-Membered Rings with One Heteroatom……Page 181
Quinolines, Isoquinolines, and Their Derivatives……Page 182
Nucleic Acids……Page 184
Properties……Page 185
See also the Following Articles……Page 186
References……Page 187
Glossary……Page 188
Structural Formulas……Page 189
Valence Angles……Page 190
Molecular Mechanics……Page 192
Resonance (Mesomerism)……Page 193
Qualitative Molecular Orbital Model of Electronic Structure……Page 194
Atomic Orbitals……Page 195
Orbital Interactions……Page 196
Delocalized Bonds……Page 198
Construction of Potential Energy Surfaces……Page 199
Motions on the Surfaces……Page 200
Chemical Reactions……Page 201
Reaction Coordinate Diagrams……Page 202
The Valence–Bond Method……Page 203
The Molecular Orbital Method……Page 204
Molecular Properties……Page 205
Thermal Reactions……Page 206
References……Page 209
Glossary……Page 211
Reactions of Alkanes and Alkenes……Page 212
Addition of Water to Alkenes……Page 213
Amination……Page 214
Mannich Reaction……Page 215
Introduction of Sulfur……Page 216
Alkyl Halides……Page 217
Epoxides……Page 218
Grignard and Related Reagents……Page 219
Natural Product Synthesis……Page 220
Prostaglandins……Page 221
Asymmetric Synthesis……Page 223
Hydroboration……Page 224
Asymmetric Syntheses with Enolates……Page 225
Directed Aldol Reactions……Page 226
Biomimetic Polyene Cyclization……Page 227
Guest–Host Inclusion Enzyme Models……Page 228
References……Page 229
Glossary……Page 230
Crown Ethers……Page 231
Naturally Occurring Macrocycles……Page 233
Tetraaza Macrocycles……Page 234
Complexation of Organic Cations……Page 235
Selective Ion Separations……Page 236
Supramacrocycles: Self-Assembly and Molecular Machines……Page 237
Synthesis of Macrocyclic Compounds……Page 238
References……Page 241
With Metal Carbon Bonds……Page 242
With Metal Hydrogen Bonds……Page 243
With Metal Carbon Bonds……Page 244
Typical Reaction Types……Page 247
Applications in Catalysis……Page 248
Organometallic Species in Biology……Page 250
References……Page 251
Glossary……Page 252
Introduction/History……Page 253
Membrane Diffusion-Controlled Systems……Page 254
Osmotic Systems……Page 256
Important Controlled Release Products……Page 258
Transdermal Systems……Page 260
Targeted Drug Delivery……Page 262
See also the following Articles……Page 263
References……Page 264
Glossary……Page 265
Covalent Bonding……Page 266
Resonance……Page 267
Atomic Orbitals……Page 268
Hybrid Orbitals……Page 269
Molecular Orbital Theory……Page 270
Conformations about Single Bonds……Page 271
Isomerism about Double Bonds……Page 272
Stereoisomerism from Stereo Centers……Page 273
Cyclic Compounds……Page 274
Chemical Equilibrium……Page 275
The Transition State……Page 276
Electron Pushing……Page 278
Inductive Effects……Page 279
Delocalization Effects……Page 280
Steric Effects……Page 281
Stereochemistry and Reactivity……Page 282
Methodology of Mechanistic Studies……Page 283
Kinetic Order……Page 284
Solvent Effects……Page 285
Isotope Effects……Page 286
Regiochemical and Stereochemical Studies……Page 287
Labeling and Crossover Experiments……Page 288
Reactive Intermediates……Page 289
Computation and Structure……Page 290
Pericyclic Reactions……Page 291
Proton Exchange……Page 293
Alpha-Haloketones……Page 294
Linear Free Energy Relationships……Page 295
References……Page 297
Glossary……Page 298
History. Optical Activity……Page 299
Stereoisomerism of Alkenes and Cyclanes……Page 300
Properties of Stereoisomers……Page 301
Separation (Resolution) and Racemization of Enantiomers……Page 302
Structure, Configuration, Notation……Page 304
Determination of Configuration……Page 305
Chirality in Absence of Chiral Centers……Page 306
Conformation……Page 307
Cycloalkanes and their Conformations……Page 308
Chiroptical Properties. Enantiomeric Purity……Page 310
Prochirality……Page 311
References……Page 312