Prologue xix Acknowledgments xxi About the Companion Website xxiii Part I Background 1 1. An Introduction to Structure and Bonding 5 A. The Sources of Carbon Compounds 5 I. How Do We Know a Material is Pure? 6 B. More About Hydrocarbons: Heats of Combustion and Reaction 9 I. Combustion: Heats of Reaction 9 C. On The Nature of the Chemical Bond 12 I. Ionic and Nonpolar Covalent Bonds 12 II.
Polar Covalent Bonds: Mixing Orbitals and Molecular Orbitals 17 III. The Use of Orbital Hybridization and Molecular Orbitals 21 a. Summary Comment on Bonding Models 37 IV. Allotropes of Carbon 37 V. Combination of Ionic and Covalent Bonding 37 Notice to the Student 41 Problems 41 Notes and References 44 2. An Introduction to Spectroscopy and Selected Spectroscopic Methods in Organic Chemistry 49 A. General Introduction. The Electromagnetic Spectrum 49 B.
X?Ray Crystallography 51 C. Photon Spectroscopy 52 I. General Introduction 52 II. Ultraviolet and Visible Spectroscopy 54 III. Infrared Spectroscopy 56 IV. Raman Spectroscopy 58 V. Microwave Spectroscopy 58 VI. Magnetic Resonance Spectroscopy 59 a.
Nuclear Magnetic Resonance (NMR) 59 1. The Chemical Shift 62 2. Multiplicity (The Coupling Constant: Spin-Spin Splitting) 65 3. The Integrated Area 66 4. Expansion of the Principle 67 5. NMR in Two Dimensions 69 6. Double Resonance 70 7. 13C, 19F, and 31P NMR Spectroscopy 72 b.
Electron Spin Resonance (ESR) Spectroscopy or Electron Paramagnetic Resonance (EPR) Spectroscopy 74 D. Mass Spectrometry 75 I. Creation of Ions in the Mass Spectrometer: The Ionization Chamber 76 II. The Separation of Ions by Mass: The Mass Analyzer 76 III. Detecting the Ions 77 Problems 77 Notes and References 78 3. Structure: The Nomenclature of Hydrocarbons and the Shape of Things to Come 83 A. Introduction 83 B. Nomenclature and Spectroscopy 84 I.
Alkanes in Two and Three Dimensions 84 a. Acyclic Alkanes 84 b. Cyclic Alkanes 89 II. Alkenes, Arenes, and Alkynes in Two and Three Dimensions 92 a. Alkenes 93 b. Arenes 97 c. Alkynes 102 C. Physical and Chemical Properties: Oxidation and Reduction of Hydrocarbons 104 I.
The Concept of Homology 105 II. Oxidation and Reduction 105 a. Oxidation 105 b. Reduction 108 Problems 112 Notes and References 115 4. An Introduction to Dynamics 119 A. Introduction 119 B. Review of Some Energy Considerations 120 C. The Barrier Between Reactants and Products 121 D.
More About the Transition State 123 E. Rotation About Sigma (Σ) Bonds in Acyclic Alkanes, Alkenes, Alkynes, and Alkyl?Substituted Arenes 126 I. Alkanes 126 II. Alkenes, Alkynes, and Alkyl?Substituted Arenes 129 F. Conformational Analysis of Medium?Ring Cyclic Alkanes 131 G. The Conservation of Symmetry During Reactions 146 H. The Measurement of Chirality 156 I. The Wave Nature of Light 156 II.
Plane?Polarized Light and Handedness 157 III. Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) 160 Problems 162 Notes and References 165 5. Classes of Organic Compounds: A Survey Along with an Introduction to Solvents, Acids and Bases, and to More About Computational Chemistry 173 A. Introduction 173 B. General Characteristics of Functional Group Placement 175 C. The Functional Groups, Their Names, and Some Physical and Spectroscopic Properties 176 I. Hydrocarbons 176 a. Alkanes 176 b.
Alkenes 176 c. Alkynes 178 d. Arenes 178 II. Alkyl and Aryl Halides 179 III. Alcohols and Phenols 183 IV. Ethers 190 V. Thiols, Thioethers, and Disulfides and Their Oxides 193 VI. Amines, Hydrazines, and Other Nitrogenous Materials 196 VII.
Phosphines, Phosphonium Salts, and Other Phosphorus Derivatives 199 VIII. An Introduction to Organometallic Compounds 201 IX. Compounds Containing Unsaturated Functional Groups 204 a. Aldehydes 204 b. Ketones 210 c. Nitrogen, Sulfur, and Phosphorus Analogues of Aldehydes and Ketones 212 d. Carboxylic Acids 213 e. Carboxylic Acid Derivatives 217 1.
Carboxylic Acid Halides (Acyl Halides) 218 2. Carboxylic Acid Anhydrides 219 3. Carboxylic Acid Esters and Lactones 221 4. Amides, Lactams, Imides, Hydroxamic Acids, and Ureas 227 5. Nitriles 236 D. An Introduction to Solvents 237 I. Protic and Aprotic Solvents 238 II. Polar and Nonpolar Solvents 238 III.
Polarizability 239 IV. Choosing a Solvent 240 a. Solvents for Spectroscopy 240 1. Solvents for UV Spectroscopy 240 2. Solvents for IR and Raman Spectroscopy 240 3. Solvents for NMR Spectroscopy 240 b. Immiscible Liquids 241 c. Organic Compounds That Dissolve in Water 241 d.
Phase Transfer Catalysts 242 E. Acids and Bases 242 I. Brønsted Acids and Bases 243 II. Lewis Acids and Bases 245 III. Hard and Soft Acids and Bases (HSAB) 248 F. Computational Methods 250 I. Molecular Mechanics 251 a. Stretching Energy Contribution (Estretch) 251 b.
Bending Energy Contribution (Ebend) 251 c. Stretch?Bend Energy Contribution (Estretch?bend) 251 d. Van der Waals Energy Contribution (Evan der Waals) 252 e. Torsional Energy Contribution (Etorsional) 252 f. Dipole Interaction Energy and Dipole Moment Contribution (Edipole) 252 Problems 253 Notes and References 255 Part II Middleground 261 6. The Reactions of Hydrocarbons: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 271 A. Introduction 271 B. Alkanes 271 I.
Oxidation 271 II. Reduction 276 III. Substitution 276 IV. Rearrangement 280 C. Alkenes 280 I. Oxidation 280 II. Reduction 286 III. Addition 292 a.
Electrophilic Addition 294 1. The Stereochemistry of Electrophilic Addition 295 2. The Regiochemistry of Electrophilic Addition 298 3. The Kinetics of Electrophilic Addition 311 4. Cationic Polymerization: Electrophilic Addition in the Absence of a Reactive Nucleophile 315 5. Electrophilic Addition to Dienes and Polyenes 317 6. Special Cases: The Oxo and Ritter Reactions 321 b. Nucleophilic Addition to Alkenes, Dienes, and Polyenes 323 c.
Radical Addition to Alkenes, Dienes, and Polyenes 327 d. Intermolecular Cheletropic and Other Cycloaddition Reactions 329 IV. Substitution 340 V. Rearrangements 343 D. Alkynes 353 I. Oxidation 353 II. Reduction 354 III. Addition 355 a.
Electrophilic Addition 356 b. Nucleophilic Addition to Alkynes and Conjugated Ene?Ynes 362 c. Radical Addition to Alkynes 365 d. Intermolecular Cheletropic and Other Cycloaddition Reactions 365 E. Arenes and Aromaticity: Special Introduction 370 I. Oxidation 377 a. Oxidation of the Aromatic Ring 377 b. Oxidation of Alkyl Substituents on the Aromatic Ring 381 II.
Reduction 382 III. Addition 384 IV. Substitution 385 a. Electrophilic Aromatic Substitution 386 b. Nucleophilic Aromatic Substitution 405 c. Free Radical Substitution 405 Problems 407 Notes and References 410 7. The Reactions of Alkyl, Alkenyl, and Aryl Halides: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 423 A. Introduction 423 B.
Fluorocarbons 426 I. Freons and Halons 427 II. Polymers of Highly Fluorinated Monomers 428 III. Use of Fluorocarbons to Carry Oxygen 428 C. Oxidation 428 D. Reduction of Alkyl, Alkenyl, and Aryl Halides 430 I. Dehalogenation and Reductions at Carbon 430 a. Hydrogenolysis 431 b.
Substitution of Hydride for Halide 431 c. Radical Replacement of Halogen by Hydrogen 431 d. Reaction of Alkyl, Alkenyl, and Aryl Halides with Metals 433 1. Organomercurials 433 2. Organomagnesium Compounds (Grignard Reagents) 434 3. Alkyl, Alkenyl, and Aryl Lithium Reagents 437 II. Reductions at Halogen 439 E. Nucleophilic Substitution 440 I.
Nucleophiles and Nucleophilicity 441 II. Substitution, Nucleophilic, Unimolecular (SN1) 442 a. The Kinetics 443 b. Electronegativity Differences 446 c. The Structure of the Alkyl Group 447 d. The Role of the Solvent 448 e. The Substrate Stereochemistry Attending the SN1 Reaction 449 III. Substitution, Nucleophilic, Bimolecular (SN2) 452 a.
The Kinetics 454 b. The Stereochemistry Attending the SN2 457 c. The Nature of the Leaving Group 459 d. The Nature of the Nucleophile 459 e. The Nature of the Solvent 460 IV. The SN2' Reaction 460 V. Nucleophilic Aromatic Substitution 460 a. The Elimination-Addition Pathway (Benzyne) 461 b.
The Addition-Elimination Pathway (SNAr Substitution) 462 VI. Electrophilic Aromatic Substitution 463 VII. Substitution by Carbon 464 VIII. Photochemically Induced Substitution of Vinyl and Aryl Halides 468 F. Addition Reactions 468 I. Addition Reactions to Vinyl and Allyl Halides 469 G. Elimination Reactions of Alkyl and Alkenyl Halides 473 I. α?Elimination (1,1?E.