ORGANIC CHEMISTRY. Fifth Edition. Stanley H. Pine

Transcription

1 ORGANIC CHEMISTRY Fifth Edition Stanley H. Pine Professor of Chemistry California State University, Los Angeles McGraw-Hill, Inc. New York St. Louis San Francisco Auckland Bogota Caracas Lisbon London Madrid Mexico Milan Montreal New Delhi Paris San Juan Singapore Sydney Tokyo Toronto

2 Contents 1 What is Organic Chemistry? The Chemistry of Carbon Compounds A Historical Perspective Contemporary Organic Chemistry 6 2 Bonding in Organic Molecules Bonding Structural Formulas of Organic Molecules Electronegativity and Dipoles Quantum Mechanics and Atomic Orbitals Molecular Orbitals and Bonding Hybrid Orbitals Bond Angles Bond Energies and Distances Summary Supplementary Problems 46 3 Classes and Nomenclature of Organic Compounds Functional Groups Hydrocarbons Heteroatom Functional Groups Supplementary Problems 89 ix

3 X Contents 4 Characteristic Reactions of Organic Compounds Acids and Bases Reactions of Organic Compounds Oxidation and Reduction Summary Supplementary Problems Reaction Mechanism The Reaction Mechanism Reaction Energetics Reaction Kinetics Summary Supplementary Problems The Shapes of Molecules Stereochemistry Representations of Three-Dimensional Molecules Conformations of Acyclic Compounds Conformations of Cyclic Compounds Geometrical Isomerism Chirality and Optical Activity Summary Supplementary Problems Structural Effects on Reactivity Resonance Structural Effects on Acidity and Basicity The Resonance Method Aromatic Compounds Some Consequences of Resonance Summary Supplementary Problems Nucleophilic Additions to the Carbonyl Group Aldehydes and Ketones Reactivity of the Carbonyl Group Cyanide as the Nucleophile The Cyanohydrin Reaction Oxygen or Sulfur as the Nucleophile Acetals, Ketals and Hydrates 223

4 Contents xi 8-4 Hydride as the Nucleophüe Reduction Carbon as the Nucleophüe Organometallic Compounds Nitrogen as the Nucleophüe Nucleophilic Addition to Carbonyl Analogs Summary Supplementary Problems Nucleophilic Substitutions on the Carbonyl Group The Carboxylic Acid Family Reactivity in the Carboxylic Acid Family Oxygen or Sulfur as the Nucleophüe Esters and Carboxylic Acids Nitrogen as the Nucleophüe Amides Acyl Halides and Anhydrides Hydride as the Nucleophüe Reduction Carbon as the Nucleophüe Organometallic Reagents Enantiomer Resolution Nucleophilic Substitution on Derivatives of Sulfuric and Phosphoric Acids Summary Supplementary Problems Nucleophilic Substitutions at Saturated Carbon The Reaction Mechanism Stereochemistry of Nucleophilic Substitution The Variables in Nucleophilic Substitution Summary Supplementary Problems The Scope of Nucleophilic Substitution Nucleophüe Substrate Combinations Halide as the Nucleophüe Haloalkanes Competing Reactions Oxygen and Sulfur as the Nucleophiles Alcohols, Ethers, and Sulfides Nitrogen and Phosphorus as the Nucleophiles Amines Neighboring Group Participation Hydride, Nitrile, and Organometallic Nucleophiles Summary Supplementary Problems 391

5 XÜ Contents 12 The Alpha Carbanion Nucleophilic-Electrophilic Reactivity of Carbonyl Compounds Enols and Enolate Anions Addition-Dehydration The Aldol Reaction Ester Condensation Fragmentation of Beta-Dicarbonyl Compounds Alkylation of Enolate Anions Other Stabilized Carbanions and Carbon Nucleophiles Summary Supplementary Problems Nucleophilic Additions and Substitutions in Synthesis Available Reactions Experimental Considerations The Strategy of Synthesis Synthesis Examples Summary Supplementary Problems Elimination Reactions Alkenes and Alkynes The Reaction Mechanism Elimination Versus Substitution The Direction of Elimination Stereochemistry Formation of Alkenes Formation of Alkynes Other Double and Triple Bonds Summary Supplementary Problems Electrophilic Additions to Unsaturated Carbon The Mechanism of Electrophilic Addition Direction and Stereochemistry of Addition Additions to Alkenes and Alkynes Transition Metal Organometallics Summary Supplementary Problems 569

6 Contents xiü 16 Additions to Conjugated Compounds Conjugated Dienes Double Bonds Conjugated with Carbonyl Groups Pericyclic Reactions Summary Supplementary Problems The Mechanism of Electrophilic Aromatic Substitution Characteristics of Cyclic Polyenes Mechanism and Orientation in Electrophilic Aromatic Substitution Quantitative Correlations of Substituent Effects Summary Supplementary Problems The Scope oi Aromatic Substitutions Electrophilic Aromatic Substitution Reactions Heteroatoms as the Electrophiles Electrophilic Aromatic Substitution Reactions Carbon Electrophiles Nucleophilic Aromatic Substitutions Synthesis with Aromatic Compounds Summary Supplementary Problems Polycyclic and Heterocyclic Aromatic Compounds Polycyclic Aromatic Compounds Heterocyclic Aromatic Compounds Summary Supplementary Problems Organic Synthesis Design of a Synthesis Reaction Patterns Stereochemistry 741

7 Xiv Contents 20-4 Applications and Examples Summary Supplementary Problems Carbohydrates and Nucleosides Characteristics and Properties of Carbohydrates Chemistry of Monosaccharides Oligosaccharides and Polysaccharides Nucleosides and Nucleotides Sunlight, Carbohydrates, and Energy Summary Supplementary Problems Ämino Acids and Proteins Amino Acids Peptides Proteins, Enzymes, and Biosynthesis Summary Supplementary Problems Lipids Glycerol Derivatives Terpenes Steroids Prostaglandins Pheromones Summary Supplementary Problems Free Radicals History Characteristics of Free Radicals Reactions Detection of Free Radicals Summary Supplementary Problems 940

8 Contents XV 25 Natural and Synthetic Polymers Structural Characteristics Preparation of Synthetic Polymers Fibers Summary Supplementary Problems Molecular Rearrangements Rearrangement to an Electron-Deficient Atom Free-Radical and Anionic Rearrangements Orbital Symmetry Considerations Summary Supplementary Problems Photochemistry and Electrochemistry Principles of Photochemistry Photochemical Reactions Principles of Electrochemistry Electrochemical Reactions Summary Supplementary Problems 1057 APPENDIX: Spectroscopic Methods 1062 A-l Electromagnetic Radiation 1064 A-2 Nuclear Magnetic Resonance Spectroscopy 1065 A-3 Infrared Spectroscopy 1095 A-4 Ultraviolet and Visible Spectroscopy 1113 A-5 Mass Spectrometry 1120 A-6 Spectroscopic Solution of Structural Problems 1132 A-7 Supplementary Problems 1139 Index 1157