Preface xvii Acknowledgments xix 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 11 I. Combustion--Heats of Reaction 12 C. On the Nature of the Chemical Bond 17 I. Ionic and Nonpolar Covalent Bonds 17 II.

Polar Covalent Bonds 22 III. Orbital Hybridization 26 IV. Allotropes of Carbon 39 V. Combination of Ionic and Covalent Bonding 40 Notice to the Student 43 Additional Problems 43 Reference 45 2. An Introduction to Spectroscopy and Selected Spectroscopic Methods in Organic Chemistry 46 A. General Introduction 46 B. X-ray Crystallography 49 C. Photon Spectroscopy 50 I.

General Introduction 50 II. UV and VIS Spectroscopy 52 III. IR Spectroscopy 55 IV. Raman Spectroscopy 60 V. Microwave Spectroscopy 60 VI. Magnetic Resonance Spectroscopy 61 a. NMR 61 b. ESR 79 D.

MS 80 I. Creation of Ions in the Mass Spectrometer: The Ionization Chamber 81 II. The Separation of Ions by Mass: The Mass Analyzer 82 III. Detecting the Ions 83 Additional Problems 83 Reference 84 3. Structure: The Nomenclature of Hydrocarbons and the Shape of Things to Come 85 A. Introduction 85 B. Nomenclature and Spectroscopy 86 I. Alkanes 86 a.

Acyclic Alkanes 86 b. Cyclic Alkanes 93 II. Alkenes, Arenes, and Alkynes 97 a. Alkenes 98 b. Arenes 103 c. Alkynes 108 C. Physical and Chemical Properties; Oxidation and Reduction of Hydrocarbons 111 I. The Concept of Homology 111 II.

Oxidation and Reduction 113 a. Oxidation 113 b. Reduction 116 Additional Problems 120 References 123 4. An Introduction to Dynamics 124 A. Introduction 124 B. Review of Some Energy Considerations 126 C. The Barrier between Reactants and Products 128 D. More about the Transition State 130 E.

Rotation about Sigma (σ) Bonds in Acyclic Alkanes, Alkenes, Alkynes, and Alkyl-Substituted Arenes 133 I. Alkanes 133 II. Alkenes, Alkynes, and Arenes 137 F. Conformational Analysis of Medium-Ring Cyclic Alkanes 138 G. The Conservation of Symmetry during Reactions 156 H. The Measurement of Chirality 169 I. The Wave Nature of Light 169 II. Plane-Polarized Light and Handedness 172 III.

Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) 175 Additional Problems 177 5. Classes of Organic Compounds--A Survey: An Introduction to Solvents and to Acids and Bases and to Computational Chemistry 180 A. Introduction 180 B. General Characteristics of Functional Group Placement 182 C. The Functional Groups and Their Names 183 I. Hydrocarbons 183 a. Alkanes 184 b. Alkenes 184 c.

Alkynes 186 d. Arenes 187 II. Alkyl and Aryl Halides 188 III. Alcohols and Phenols 194 IV. Ethers 200 V. Thiols, Thioethers, Disulfi des, and Their Oxides 204 VI. Amines, Hydrazines, and Other Nitrogenous Materials 207 VII. Phosphines, Phosphonium Salts, and Other Phosphorus Derivatives 212 VIII.

An Introduction to Organometallic Compounds 214 IX. Compounds Containing Unsaturated Functional Groups 217 a. Aldehydes 217 b. Ketones 223 c. Nitrogen, Sulfur, and Phosphorus Analogues of Aldehydes and Ketones 227 d. Carboxylic Acids 227 e. Carboxylic Acid Derivatives 232 D. An Introduction to Solvents 254 I.

Protic and Aprotic Solvents 255 II. Polar and Nonpolar Solvents 256 III. Polarizability 257 IV. Choosing a Solvent 257 a. Solvents for Spectroscopy 257 b. Immiscible Liquids 259 c. Organic Compounds that Dissolve in Water 259 d. Phase Transfer Catalysts 261 E.

Acids and Bases 261 I. Brønsted Acids and Bases 262 II. Lewis Acids and Bases 264 III. Hard and Soft Acids and Bases (HSABs) 270 F. Computational Methods 271 I. MM 272 a. Stretching Energy Contribution (Estretch) 272 b. Bending Energy Contribution (Ebend) 272 c.

Stretch-Bend Energy Contribution (Estretch-bend) 272 d. van der Waals Energy Contribution (Evan der Waals) 272 e. Torsional Energy Contribution (Etorsional) 273 f. Dipole Interaction Energy and Dipole Moment Contribution (Edipole) 273 Additional Problems 274 Part II Middleground 277 6. The Reactions of Hydrocarbons: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 291 A. Introduction 291 B. Alkanes 292 I. Oxidation 292 II.

Reduction 295 III. Substitution 296 IV. Rearrangement 301 C. Alkenes 301 I. Oxidation 301 II. Reduction 312 III. Addition 316 a. Electrophilic Addition 317 b.

Nucleophilic Addition to Alkenes, Dienes, and Polyenes 351 c. Radical Addition to Alkenes, Dienes, and Polyenes 354 d. Intermolecular Cheletropic and Other Cycloaddition Reactions 359 IV. Substitution 369 V. Rearrangement 371 D. Alkynes 382 I. Oxidation 382 II. Reduction 385 III.

Addition 386 a. Electrophilic Addition 387 b. Nucleophilic Addition to Alkynes and Conjugated Enynes 394 c. Radical Addition to Alkynes 398 d. Intermolecular Cheletropic and Other Cycloaddition Reactions 398 E. Arenes and Aromaticity: Special Introduction 403 I. Oxidation 413 a. Oxidation of the Aromatic Ring 413 b.

Oxidation of Alkyl Substituents on the Aromatic Ring 419 II. Reduction 420 III. Addition 422 IV. Substitution 424 a. Electrophilic Aromatic Substitution 425 b. Nucleophilic Aromatic Substitution 447 c. Free Radical Substitution 448 Additional Problems 450 7. The Reactions of Alkyl, Alkenyl, and Aryl Halides: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 452 A.

Introduction 452 B. Fluorocarbons 456 I. Freons and Halons 457 II. Polymers of Highly Fluorinated Monomers 459 III. Use of Fluorocarbons to Carry Oxygen 459 C. Oxidation 459 D. Reduction of Alkyl, Alkenyl, and Aryl Halides 462 I. Dehalogenation and Reductions at Carbon 462 a.

Hydrogenolysis 463 b. Substitution of Hydride for Halide 463 c. Radical Replacement of Halogen by Hydrogen 464 d. Reaction of Alkyl, Alkenyl, and Aryl Halides with Metals 466 II. Reductions at Halogen 473 E. Nucleophilic Substitution 476 I. Nucleophiles and Nucleophilicity 480 II. SN1 481 a.

The Kinetics 482 b. Electronegativity Differences 485 c. The Structure of the Alkyl Group 486 d. The Role of the Solvent 487 e. The Substrate Stereochemistry Attending the SN1 Reaction 488 III. SN2 492 a. The Kinetics 495 b. The Stereochemistry of the SN2 Reaction 498 c.

The Nature of the Leaving Group 500 d. The Nature of the Nucleophile 501 e. The Nature of the Solvent 502 IV. The SN2' Reaction 502 V. Nucleophilic Aromatic Substitution 504 a. The Elimination-Addition Pathway (Benzyne) 504 b. The Addition-Elimination Pathway (SNAr Substitution) 506 VI. Electrophilic Aromatic Substitution 506 VII.

Substitution by Carbon 507 VIII. Photochemically Induced Substitution of Vinyl and Aryl Halides 510 F. Addition Reactions 512 I. Addition Reactions to Vinyl Halides 513 G. Elimination Reactions of Alkyl and Alkenyl Halides 517 I. α-Elimination (1,1-Elimination) 519 a. α-Elimination of HX (X = Cl, Br) from Alkyl and Alkenyl Halides 519 b. α-Elimination of X2 (X = Cl) from Alkyl Dihalides 521 II.

β-Elimination (1,2-Elimination) 521 a. β-Elimination of HX (X = F, Cl, Br, I) from Alkyl and Alkenyl Halides 521 b. 1,2- or α,β-Elimination of X2 (X = Cl, Br) from Alkyl and Alkenyl Dihalides 551 III. γ-Elimination (1,3-Elimination) and δ-Elimination (1,4-Elimination) 551 a. γ-Elimination of HX (X = Cl, Br, I) from Alkyl and Alkenyl Halides 551 b. γ-Elimination of X2 (X = Cl, Br, I) from Alkyl Halides 553 c. δ-Elimination of X2 (X = Cl, Br, I) from Alkenyl Halides 553 H. Rearrangement Reactions of Alkyl and Alkenyl Halides 553 Additional Problems 560 References 561 8.

Part I. The Reactions of Alcohols, Enols, and Phenols: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement Part II. Ethers Part III. Selected Reactions of Alkyl and Aryl Thiols and Thioethers 562 Special Introduction to Chapter 8 562 Part I. Alcohols, Enols, and Phenols 566 A. Acidity and Basicity 566 B. Oxidation of Alcohols, Enols, and Phenols 573 I. Introduction 573 II.

Oxidation at the Hydroxyl-Bearing Carbon 574 a. Chemical Oxidation of Alcohols 574 b. Biological Oxidation of Alcohols 594 III. Oxidation at Sites That Do Not Bear Hydroxyl 596 a. Oxidation of Enols 596 b. Oxidation of Phenols 600 c. Oxidation at the Double Bond of Allylic Alcohols 604 C. Reduction of Alcohols, Enols, and Phenols 608 I.

Reduction of Alcohols 608 II. Reduction of Enols and Phenols 613 D. Substitution Reactions of Alcohol, Enols, and Phenols 615 I. Introduction 6.