Organic chemistry : a short course / 11th ed.

Table Of Contents:
Preface xviii
To the Student 1(5)

Bonding and Isomerism 6(35)

How Electrons Are Arranged in Atoms 6(2)

Ionic and Covalent Bonding 8(3)

Ionic Compounds 8(2)

The Covalent Bond 10(1)

Carbon and the Covalent Bond 11(2)

Carbon--Carbon Single Bonds 13(1)

Polar Covalent Bonds 14(1)

Multiple Covalent Bonds 15(2)

Valence 17(1)

Isomerism 18(1)

Writing Structural Formulas 19(2)

Abbreviated Structural Formulas 21(2)

Formal Charge 23(2)

Resonance 25(1)

Arrow Formalism 26(2)

The Orbital View of Bonding; the Sigma Bond 28(1)

Carbon sp3 Hybrid Orbitals 29(2)

Tetrahedral Carbon; the Bonding in Methane 31(1)

Classification According to Molecular Framework 32(1)

Acyclic Compounds 32(1)

Carbocyclic Compounds 33(1)

Heterocyclic Compounds 33(1)

Classification According to Functional Group 33(8)

Additional Problems 37(4)

Alkanes and Cycloalkanes; Conformational and Geometric Isomerism 41(30)

The Structures of Alkanes 41(2)

Nomenclature of Organic Compounds 43(1)

IUPAC Rules for Naming Alkanes 44(2)

Alkyl and Halogen Substituents 46(2)

Use of the IUPAC Rules 48(1)

Sources of Alkanes 49(1)

A Closer Look at Natural Gas 49(1)

Physical Properties of Alkanes and Nonbonding Intermolecular Interactions 50(2)

A Closer Look At Hydrogen Bonding 51(1)

Conformations of Alkanes 52(2)

Cycloalkane Nomenclature and Conformation 54(4)

Cis--trans Isomerism in Cycloalkanes 58(1)

Summary of Isomerism 59(2)

A Word About Isomers, Possible and Impossible 60(1)

Reactions of Alkanes 61(4)

Oxidation and Combustion; Alkanes as Fuels 61(2)

Halogenation of Alkanes 63(1)

A Word About Methane, Marsh Gas, and Miller's Experiment 64(1)

The Free-Radical Chain Mechanism of Halogenation 65(6)

Reaction Summary 67(1)

Mechanism Summary 67(1)

Additional Problems 67(4)

Alkenes and Alkynes 71(45)

Definition and Classification 71(2)

Nomenclature 73(3)

Some Facts About Double Bonds 76(1)

The Orbital Model of a Double Bond; the Pi Bond 76(3)

Cis--trans Isomerism in Alkenes 79(3)

A Word About The Chemistry of Vision 80(2)

Addition and Substitution Reactions Compared 82(1)

Polar Addition Reactions 82(2)

Addition of Halogens 83(1)

Addition of Water (Hydration) 83(1)

Addition of Acids 84(1)

Addition of Unsymmetric Reagents to Unsymmetric Alkenes; Markovnikov's Rule 84(2)

Mechanism of Electrophilic Addition to Alkenes 86(2)

Markovnikov's Rule Explained 88(2)

Reaction Equilibrium: What Makes a Reaction Go? 90(1)

Reaction Rates: How Fast Does a Reaction Go? 91(3)

Hydroboration of Alkenes 94(1)

Addition of Hydrogen 95(1)

Additions to Conjugated Systems 96(3)

Electrophilic Addition to Conjugated Dienes 96(2)

Cycloaddition to Conjugated Dienes: The Diels--Alder Reaction 98(1)

Free-Radical Additions; Polyethylene 99(2)

Oxidation of Alkenes 101(3)

Oxidation with Permanganate; a Chemical Test 101(1)

Ozonolysis of Alkenes 101(1)

A Word About Ethylene: Raw Material and Plant Hormone 102(1)

Other Alkene Oxidations 103(1)

Some Facts About Triple Bonds 104(1)

The Orbital Model of a Triple Bond 104(1)

Addition Reactions of Alkynes 105(3)

A Word About Petroleum, Gasoline, and Octane Number 106(2)

Acidity of Alkynes 108(8)

A Closer Look At Petroleum 109(1)

Reaction Summary 110(1)

Mechanism Summary 111(1)

Additional Problems 112(4)

Aromatic Compounds 116(30)

Some Facts About Benzene 117(1)

The Kekule Structure of Benzene 118(1)

Resonance Model for Benzene 119(1)

Orbital Model for Benzene 119(1)

Symbols for Benzene 120(1)

Nomenclature of Aromatic Compounds 120(3)

The Resonance Energy of Benzene 123(2)

Electrophilic Aromatic Substitution 125(1)

The Mechanism of Electrophilic Aromatic Substitution 126(4)

Halogenation 127(1)

Nitration 128(1)

Sulfonation 128(1)

Alkylation and Acylation 129(1)

Ring-Activating and Ring-Deactivating Substituents 130(1)

Ortho, Para-Directing, and Meta-Directing Groups 130(5)

Ortho, Para-Directing Groups 131(2)

Meta-Directing Groups 133(2)

Substituent Effects on Reactivity 135(1)

The Importance of Directing Effects in Synthesis 135(1)

Polycyclic Aromatic Hydrocarbons 136(10)

A Word About Polycyclic Aromatic Hydrocarbons and Cancer 137(1)

A Word About C60, an Aromatic Sphere: The Fullerenes 138(2)

A Closer Look At Polycyclic Aromatic Hydrocarbons 140(1)

Reaction Summary 141(1)

Mechanism Summary 142(1)

Additional Problems 142(4)

Stereoisomerism 146(34)

Chirality and Enantiomers 146(2)

Stereogenic Centers; the Stereogenic Carbon Atom 148(4)

Configuration and the R--S Convention 152(5)

The E--Z Convention for Cis--Trans Isomers 157(1)

Polarized Light and Optical Activity 158(4)

A Word About Pasteur's Experiments and the van't Hoff--LeBel Explanation 160(2)

Properties of Enantiomers 162(1)

Fischer Projection Formulas 163(2)

Compounds with More Than One Stereogenic Center; Diastereomers 165(2)

Meso Compounds; the Stereoisomers of Tartaric Acid 167(2)

Stereochemistry: A Recap of Definitions 169(1)

Stereochemistry and Chemical Reactions 170(3)

A Word About Enantiomers and Biological Activity 172(1)

Resolution of a Racemic Mixture 173(7)

A Closer Look At Thalidomide 174(1)

Additional Problems 175(5)

Organic Halogen Compounds: Substitution and Elimination Reactions 180(23)

Nucleophilic Substitution 180(1)

Examples of Nucleophilic Substitutions 181(4)

Nucleophilic Substitution Mechanisms 185(1)

The SN2 Mechanism 185(3)

The SN1 Mechanism 188(2)

The SN1 and SN2 Mechanisms Compared 190(3)

A Word About SN2 Reactions in Nature: Biological Methylations 192(1)

Dehydrohalogenation, an Elimination Reaction; the E2 and E1 Mechanisms 193(1)

Substitution and Elimination in Competition 194(2)

Tertiary Halides 194(1)

Primary Halides 195(1)

Secondary Halides 195(1)

Polyhalogenated Aliphatic Compounds 196(7)

A Word About CFCs, the Ozone Layer, and Trade-Offs 198(1)

A Word About Halogenated Organic Compounds from the Sea 199(1)

Reaction Summary 199(1)

Mechanism Summary 200(1)

Additional Problems 200(3)

Alcohols, Phenols, and Thiols 203(28)

Nomenclature of Alcohols 203(2)

A Word About Industrial Alcohols 205(1)

Classification of Alcohols 205(1)

Nomenclature of Phenols 206(1)

Hydrogen Bonding in Alcohols and Phenols 206(1)

Acidity and Basicity Reviewed 207(3)

The Acidity of Alcohols and Phenols 210(3)

The Basicity of Alcohols and Phenols 213(1)

Dehydration of Alcohols to Alkenes 213(2)

The Reaction of Alcohols with Hydrogen Halides 215(1)

Other Ways to Prepare Alkyl Halides from Alcohols 216(1)

A Comparison of Alcohols and Phenols 217(1)

Oxidation of Alcohols to Aldehydes, Ketones, and Carboxylic Acids 217(3)

A Word About Biologically Important Alcohols and Phenols 219(1)

Alcohols with More Than One Hydroxyl Group 220(1)

Aromatic Substitution in Phenols 221(2)

A Word About Quinones and the Bombardier Beetle 222(1)

Oxidation of Phenols 223(1)

Phenols as Antioxidants 223(1)

Thiols, the Sulfur Analogs of Alcohols and Phenols 224(7)

A Word About Hair, Curly or Straight 225(1)

Reaction Summary 226(1)

Additional Problems 227(4)

Ethers and Epoxides 231(19)

Nomenclature of Ethers 232(1)

Physical Properties of Ethers 233(1)

Ethers as Solvents 233(1)

The Grignard Reagent; an Organometallic Compound 234(3)

Preparation of Ethers 237(2)

A Closer Look at MTBE 238(1)

Cleavage of Ethers 239(2)

A Word About Ether and Anesthesia 240(1)

Epoxides (Oxiranes) 241(2)

A Word About The Gypsy Moth's Epoxide 242(1)

Reactions of Epoxides 243(1)

Cyclic Ethers 244(6)

Reaction Summary 246(1)

Additional Problems 247(3)

Aldehydes and Ketones 250(33)

Nomenclature of Aldehydes and Ketones 251(1)

Some Common Aldehydes and Ketones 252(2)

Synthesis of Aldehydes and Ketones 254(1)

Aldehydes and Ketones in Nature 255(1)

The Carbonyl Group 256(1)

Nucleophilic Addition to Carbonyl Groups: An Overview 257(1)

Addition of Alcohols: Formation of Hemiacetals and Acetals 258(4)

Addition of Water; Hydration of Aldehydes and Ketones 262(1)

Addition of Grignard Reagents and Acetylides 262(3)

Addition of Hydrogen Cyanide; Cyanohydrins 265(1)

Addition of Nitrogen Nucleophiles 266(1)

Reduction of Carbonyl Compounds 267(1)

Oxidation of Carbonyl Compounds 268(2)

Keto--Enol Tautomerism 270(1)

Acidity of α-Hydrogens; the Enolate Anion 271(1)

Deuterium Exchange in Carbonyl Compounds 272(1)

The Aldol Condensation 273(2)

The Mixed Aldol Condensation 275(1)

A Word About Water Treatment and the Chemistry of Enols/Enolates 276(1)

Commercial Syntheses via the Aldol Condensation 276(7)

Reaction Summary 277(2)

Mechanism Summary 279(1)

Additional Problems 279(4)

Carboxylic Acids and Their Derivatives 283(38)

Nomenclature of Acids 283(4)

Physical Properties of Acids 287(1)

Acidity and Acidity Constants 287(2)

What Makes Carboxylic Acids Acidic? 289(1)

Effect of Structure on Acidity; the Inductive Effect Revisited 290(1)

Conversion of Acids to Salts 291(1)

Preparation of Acids 291(5)

Oxidation of Primary Alcohols and Aldehydes 292(1)

Oxidation of Aromatic Side Chains 292(1)

Reaction of Grignard Reagents with Carbon Dioxide 293(1)

Hydrolysis of Cyanides (Nitriles) 293(2)

A Word About Green Chemistry and Ibuprofen: A Case Study 295(1)

A Closer Look At Green Chemistry 296(1)

Carboxylic Acid Derivatives 296(1)

Esters 296(1)

Preparation of Esters; Fischer Esterification 297(1)

The Mechanism of Acid-Catalyzed Esterification; Nucleophilic Acyl Substitution 298(2)

Lactones 300(1)

Saponification of Esters 300(1)

Ammonolysis of Esters 301(1)

Reaction of Esters with Grignard Reagents 302(1)

Reduction of Esters 303(1)

The Need for Activated Acyl Compounds 303(1)

Acyl Halides 304(2)

Acid Anhydrides 306(3)

A Word About Thioesters, Nature's Acyl-Activating Groups 308(1)

Amides 309(2)

A Summary of Carboxylic Acid Derivatives 311(1)

The α-Hydrogen of Esters; the Claisen Condensation 312(9)

Reaction Summary 315(1)

Mechanism Summary 316(1)

Additional Problems 316(5)

Amines and Related Nitrogen Compounds 321(27)

Classification and Structure of Amines 321(2)

Nomenclature of Amines 323(1)

Physical Properties and Intermolecular Interactions of Amines 324(1)

Preparation of Amines; Alkylation of Ammonia and Amines 325(2)

Preparation of Amines; Reduction of Nitrogen Compounds 327(2)

The Basicity of Amines 329(2)

Comparison of the Basicity and Acidity of Amines and Amides 331(2)

Reaction of Amines with Strong Acids; Amine Salts 333(2)

A Word About Alkaloids and the Dart-Poison Frogs 334(1)

Chiral Amines as Resolving Agents 335(1)

Acylation of Amines with Acid Derivatives 336(2)

Quaternary Ammonium Compounds 338(1)

Aromatic Diazonium Compounds 338(3)

Diazo Coupling; Azo Dyes 341(7)

Reaction Summary 343(1)

Mechanism Summary 344(1)

Additional Problems 344(4)

Spectroscopy and Structure Determination 348(32)

Principles of Spectroscopy 349(1)

Nuclear Magnetic Resonance Spectroscopy (NMR) 350(10)

Measuring an NMR Spectrum 351(1)

Chemical Shifts and Peak Areas 352(4)

Spin--Spin Splitting 356(4)

13C NMR Spectroscopy 360(2)

A Word About NMR in Biology and Medicine 362(1)

Infrared Spectroscopy 362(6)

Visible and Ultraviolet Spectroscopy 368(2)

Mass Spectrometry 370(10)

Additional Problems 374(6)

Heterocyclic Compounds 380(21)

Pyridine: Bonding and Basicity 380(2)

Substitution in Pyridine 382(3)

Other Six-Membered Heterocycles 385(3)

Five-Membered Heterocycles: Furan, Pyrrole, and Thiophene 388(2)

Electrophilic Substitution in Furan, Pyrrole, and Thiophene 390(1)

Other Five-Membered Heterocycles: Azoles 391(2)

A Word About Porphyrins: What Makes Blood Red and Grass Green? 392(1)

Fused-Ring Five-Membered Heterocycles: Indoles and Purines 393(8)

A Word About Morphine and Other Nitrogen-Containing Drugs 395(2)

Reaction Summary 397(1)

Mechanism Summary 398(1)

Additional Problems 398(3)

Synthetic Polymers 401(26)

Classification of Polymers 401(1)

Free-Radical Chain-Growth Polymerization 402(5)

Cationic Chain-Growth Polymerization 407(1)

Anionic Chain-Growth Polymerization 408(1)

Stereoregular Polymers; Ziegler--Natta Polymerization 409(2)

A Word About Polyacetylene and Conducting Polymers 411(1)

Diene Polymers: Natural and Synthetic Rubber 411(2)

Copolymers 413(1)

Step-Growth Polymerization: Dacron and Nylon 414(5)

A Word About Degradable Polymers 416(1)

A Word About Aramids, the Latest in Polyamides 417(1)

A Closer Look At Nylon 418(1)

Polyurethanes and Other Step-Growth Polymers 419(8)

Reaction Summary 422(1)

Mechanism Summary 423(1)

Additional Problems 424(3)

Lipids and Detergents 427(21)

Fats and Oils; Triesters of Glycerol 427(4)

Hydrogenation of Vegetable Oils 431(1)

Saponification of Fats and Oils; Soap 431(1)

How Do Soaps Work? 432(1)

Synthetic Detergents (Syndets) 433(4)

A Word About Commercial Detergents 436(1)

Phospholipids 437(1)

Prostaglandins, Leukotrienes, and Lipoxins 438(2)

A Word About Prostaglandins, Aspirin, and Pain 439(1)

Waxes 440(1)

Terpenes and Steroids 440(8)

Reaction Summary 445(1)

Additional Problems 445(3)

Carbohydrates 448(31)

Definitions and Classification 448(1)

Monosaccharides 449(1)

Chirality in Monosaccharides; Fischer Projection Formulas and D,L-Sugars 450(4)

The Cyclic Hemiacetal Structures of Monosaccharides 454(2)

Anomeric Carbons; Mutarotation 456(1)

Pyranose and Furanose Structures 457(1)

Conformations of Pyranoses 458(1)

Esters and Ethers from Monosaccharides 459(1)

Reduction of Monosaccharides 460(1)

Oxidation of Monosaccharides 460(1)

Formation of Glycosides from Monosaccharides 461(2)

Disaccharides 463(4)

Maltose 463(1)

Cellobiose 464(1)

Lactose 464(1)

Sucrose 465(1)

A Word About Sweetness and Sweeteners 466(1)

Polysaccharides 467(4)

Starch and Glycogen 467(2)

Cellulose 469(1)

A Word About Fat Substitutes from Carbohydrates 470(1)

Other Polysaccharides 471(1)

Sugar Phosphates 471(1)

Deoxy Sugars 472(1)

Amino Sugars 472(1)

Ascorbic Acid (Vitamin C) 472(7)

Reaction Summary 474(1)

Additional Problems 475(4)

Amino Acids, Peptides, and Proteins 479(36)

Naturally Occurring Amino Acids 479(4)

A Word About Amino Acid Dating 482(1)

The Acid--Base Properties of Amino Acids 483(3)

The Acid--Base Properties of Amino Acids with More Than One Acidic or Basic Group 486(1)

Electrophoresis 487(1)

Reactions of Amino Acids 488(1)

The Ninhydrin Reaction 489(1)

Peptides 489(3)

A Word About Some Naturally Occurring Peptides 491(1)

The Disulfide Bond 492(1)

Proteins 492(1)

The Primary Structure of Proteins 492(4)

Amino Acid Analysis 493(1)

Sequence Determination 494(1)

Cleavage of Selected Peptide Bonds 495(1)

The Logic of Sequence Determination 496(3)

A Word About Protein Sequencing and Evolution 498(1)

Peptide Synthesis 499(4)

Secondary Structure of Proteins 503(3)

Geometry of the Peptide Bond 503(1)

Hydrogen Bonding 504(1)

The α Helix and the Pleated Sheet 504(2)

Tertiary Structure: Fibrous and Globular Proteins 506(2)

Quaternary Protein Structure 508(7)

Reaction Summary 509(1)

Additional Problems 510(5)

Nucleotides and Nucleic Acids 515(25)

The General Structure of Nucleic Acids 515(1)

Components of Deoxyribonucleic Acid (DNA) 516(1)

Nucleosides 517(2)

Nucleotides 519(1)

The Primary Structure of DNA 520(1)

Sequencing Nucleic Acids 521(2)

A Word About DNA and Crime 522(1)

Laboratory Synthesis of Nucleic Acids 523(1)

Secondary DNA Structure; the Double Helix 523(3)

DNA Replication 526(1)

Ribonucleic Acids; RNA 527(2)

The Genetic Code and Protein Biosynthesis 529(5)

A Word About The Human Genome 531(1)

A Word About Nucleic Acids and Viruses 532(2)

Other Biologically Important Nucleotides 534(6)

Reaction Summary 537(1)

Additional Problems 537(3)

Photo Credits 540(1)

Appendix 541(3)

Table A: Bond energies for the dissociation of selected bonds in the reaction A
X → A . + X . (in kcal/mol) 541(1)

Table B: Bond lengths of selected bonds (in angstroms, A) 541(1)

Table C: Typical acidities of organic functional groups 542(2)
Index/Glossary 544