Organic Chemistry
Intermediate organic chemistry
This book presents key aspects of organic synthesis stereochemistry, functional group transformations, bond formation, synthesis planning, mechanisms, and spectroscopy and a guide to literature searching in a reader-friendly manner. Helps students understand the skills and basics they need to move from introductory to graduate organic chemistry classes Balances synthetic and physical organic chemistry in a way accessible to students Features extensive end-of-chapter problems Updates include new examples and discussion of online resources now common for literature searches Adds sections on protecting groups and green chemistry along with a rewritten chapter surveying organic spectroscopy
Table of contents :
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
