Intermediate Organic Chemistry

Content: Preface to the Third Edition xi    Preface to the Second Edition xiii    Preface to the First Edition xv    1 Reading Nomenclature 1    1.1 Acyclic Polyfunctional Molecules 2    1.2 Monocyclic Aliphatic Compounds 3    1.3 Bridged Polycyclic Structures 4    1.4 Fused Polycyclic Compounds 6    1.5 Spiro Compounds 10    1.6 Monocyclic Heterocyclic Compounds 12    1.7 Fused  ]Ring Heterocyclic Compounds 14    1.8 Bridged and Spiro Heterocyclic Compounds 19    Resources 20    Problems 21    References 22    2 Accessing Chemical Information 25    2.1 Databases 25    2.2 Chemical Literature 26    2.3 Synthetic Procedures 29    2.4 Health and Safety Information 30    Problems 32    References 33    3 Stereochemistry 35    3.1 Representations 35    3.2 Vocabulary 37    3.3 Property Differences Among Stereoisomers 40    3.4 Resolution of Enantiomers 44    3.5 Enantioselective Synthesis 47    3.6 Reactions at a Stereogenic Atom 49    3.6.1 Racemization 49    3.6.2 Epimerization 50    3.6.3 Inversion 51    3.6.4 Retention 51    3.6.5 Transfer 52    3.7 Relative and Absolute Configuration 53    3.8 Topism 56    Resources 59    Problems 60    References 65    4 Mechanisms and Predictions 69    4.1 Reaction Coordinate Diagrams and Mechanisms 69    4.2 The Hammond Postulate 71    4.3 Methods for Determining Mechanisms 72    4.3.1 Identification of Products and Intermediates 72    4.3.2 Isotope Tracing 73    4.3.3 Stereochemical Determination 74    4.3.4 Concentration Dependence of Kinetics 75    4.3.5 Isotope Effects in Kinetics 85    4.3.6 Temperature Effects on Kinetics 87    4.3.7 Substituent Effects on Kinetics 90    4.4 Representative Mechanisms 95    4.4.1 Reactions in Basic Solution 96    4.4.2 Reactions in Acidic Solution 100    4.4.3 Free  ]Radical Reactions 103    4.4.4 Molecular Rearrangements 106    Resources 108    Problems 109    References 120    5 Electron Delocalization, Aromatic Character, and Pericyclic Reactions 123    5.1 Molecular Orbitals 124    5.2 Aromatic Character 130    5.3 Pericyclic Reactions 135    5.3.1 Cycloaddition Reactions 137    5.3.2 Electrocyclic Reactions 142    5.3.3 Sigmatropic Reactions 147    Resources 152    Problems 152    References 158    6 Functional Group Transformations 163    6.1 Carboxylic Acids and Related Derivatives 164    6.1.1 Carboxylic Acids 164    6.1.2 Carboxylic Esters 166    6.1.3 Carboxylic Amides 168    6.1.4 Carboxylic Acid Halides 168    6.1.5 Carboxylic Anhydrides 169    6.1.6 Nitriles 169    6.1.7 O rtho Esters 170    6.2 Aldehydes, Ketones, and Derivatives 171    6.2.1 Aldehydes 171    6.2.2 Ketones 174    6.2.3 Imines and Enamines 175    6.2.4 Acetals 175    6.2.5 Vinyl Ethers 177    6.3 Alcohols 179    6.4 Ethers 179    6.5 Alkyl Halides 181    6.5.1 Alkyl Chlorides and Alkyl Bromides 182    6.5.2 Alkyl Iodides 184    6.5.3 Alkyl Fluorides 184    6.6 Amines 185    6.7 Isocyanates 187    6.8 Alkenes 187    6.9 Reductive Removal of Functionality 190    Resources 191    Problems 191    References 198    7 Carbon   Carbon Bond Formation 205    7.1 Carbon   Carbon Single Bond Formation 206    7.1.1 Reactions in Basic Solution 206    7.1.2 Reactions in Acidic Solution 214    7.1.3 O rganometallic Coupling Reactions 217    7.2 Carbon   Carbon Double  ]Bond Formation 218    7.3 Multibond Processes 222    Resources 224    Problems 224    References 230    8 Planning Multistep Syntheses 235    8.1 Retrosynthetic Analysis 235    8.2 Disconnection at a Functional Group or Branch Point 236    8.3 Cooperation for Difunctionality 244    8.4 Ring Closure 250    8.5 Acetylide Alkylation and Addition 253    8.6 T he Diels   Alder Reaction 255    8.7 T he Claisen Rearrangement 259    8.8 Synthetic Strategies 263    8.9 Final Note 265    Resources 266    Problems 266    References 271    9 Physical Influences on Reactions 277    9.1 Unimolecular Reactions 278    9.2 Homogenous Two  ]Component Reactions 279    9.3 Temperature Effects 280    9.4 Pressure Effects 281    9.5 Solvent Effects 282    9.6 Biphasic Reactions 283    9.6.1 Phase Transfer Catalysis 283    9.6.2 Increasing Solubility 286    9.6.3 Increasing Surface Area 287    9.6.4 Ultrasound 287    9.7 Reactions on Chemical Supports 288    9.8 Using Unfavorable Equilibria 291    9.9 Green Chemistry 293    Resources 294    Problems 294    References 295    10 Survey of Organic Spectroscopy 299    10.1 Electromagnetic Radiation 299    10.2 Ultraviolet Spectroscopy 300    10.2.1 Origin of the Signals 300    10.2.2 Interpretation 302    10.2.3 Visible Spectroscopy 302    10.3 Infrared Spectroscopy 303    10.3.1 Origin of the Signals 304    10.3.2 Interpretation 304    10.4 Mass Spectrometry 305    10.4.1 Origin of the Signals 306    10.4.2 Interpretation 307    10.5 N MR Spectroscopy 309    10.5.1 Origin of the Signals 309    10.5.2 Interpretation of Proton NMR Spectra 311    10.6 Carbon NMR Spectra 323    10.6.1 General Characteristics 323    10.6.2 Interpretation of 13C NMR Spectra 325    10.7 Correlation of 1H and 13C NMR Spectra 327    Resources 329    Problems 329    References 333    Appendix A 337    Appendix B 341    Index 347