Contents 6-18 Positional Orientation of elimination:Zaitsey's rule 260 6-19 Second-Order Elimination:The E2 Reaction 261 Key Mechanism:The E2 Reaction 262 6-20 Stereochemistry of the E2 Reaction 264 6-21 Comparison of El and E2 Elimination Mechanisms 265 Summary:Elimination Reactions 267 Problem-Solving Strategy:Predic ting Substitutions and Eliminations 267 Summary:Reactions of Alkyl Halides 270 6w27632 7 STRUCTURE AND SYNTHESIS OF ALKENES 281 7-1 Introduction The Orbital Description of the Alkene Double Bond 282 7.5 287 7.6 e of Alkenes 290 7-7 Stability of Alkenes 292 7-8 Physical Properties of Alkenes 298 7-9 Alkene Synthesis by Elimination of Alkyl Halides 300 7-10 Alkene Synthesis by Dehydration of Alcohols 308 ed-Catalyed 7-11 by Hig h-Temperrd Sum ds for nthesis of Alkenes 316 Chanter Glos ary 317 Study Problems 319 8REACTIONS OF ALKENES 323 to Al Key Mechanism:Electrophilic Addition to Alkenes 324 8-3 Addition of Hydrogen Halides to Alkenes 326 8-4 Addition of Water:Hydration of Alkenes 332 8-5 Hydration by Oxymercuration-Demercuration 335 8-6 Alkoxymercuration-Demercuration 337 8-1 Hydroboration of Alkenes 338 8-8 Addition of Ha ogens to Alk es344 8-9 Formation of Halohydrins 347 8-10 Catalytic Hydrogenationo enes to A cnes 352 des 357 9 15 Oxidati ylation 8-16 365 8-17 Olefin Metathesis 369
6-18 Positional Orientation of Elimination: Zaitsev's Rule 260 6-19 Second-Order Elimination: The E2 Reaction 261 Key Mechanism: The E2 Reaction 262 6-20 Stereochemistry of the E2 Reaction 264 6-21 Comparison of E1 and E2 Elimination Mechanisms 265 Summary: Elimination Reactions 267 Problem-Solving Strategy: Predicting Substitutions and Eliminations 267 Summary: Reactions of Alkyl Halides 270 Chapter 6 Glossary 273 Study Problems 276 7 STRUCTURE AND SYNTHESIS OF ALKENES 281 7-1 Introduction 281 7-2 The Orbital Description of the Alkene Double Bond 282 7-3 Elements of Unsaturation 283 7-4 Nomenclature of Alkenes 285 7-5 Nomenclature of Cis-Trans Isomers 287 Summary: Rules for Naming Alkenes 289 7-6 Commercial Importance of Alkenes 290 7-7 Stability of Alkenes 292 7-8 Physical Properties of Alkenes 298 7-9 Alkene Synthesis by Elimination of Alkyl Halides 300 7-10 Alkene Synthesis by Dehydration of Alcohols 308 Key Mechanism: Acid-Catalyzed Dehydration of an Alcohol 309 7-11 Alkene Synthesis by High-Temperature Industrial Methods 311 Problem-Solving Strategy: Proposing Reaction Mechanisms 312 Summary: Methods for Synthesis of Alkenes 316 Chapter 7 Glossary 317 Study Problems 319 8 REACTIONS OF ALKENES 323 8-1 Reactivity of the Carbon-Carbon Double Bond 323 8-2 Electrophilic Addition to Alkenes 324 Key Mechanism: Electrophilic Addition to Alkenes 324 8-3 Addition of Hydrogen Halides to Alkenes 326 8-4 Addition of Water: Hydration of Alkenes 332 8-5 Hydration by Oxymercuration-Demercuration 335 8-6 Alkoxymercuration-Demercuration 337 8-7 Hydroboration of Alkenes 338 8-8 Addition of Halogens to Alkenes 344 8-9 Formation of Halohydrins 347 8-10 Catalytic Hydrogenation of Alkenes 350 8-11 Addition of Carbenes to Alkenes 352 8-12 Epoxidation of Alkenes 355 8-13 Acid-Catalyzed Opening of Epoxides 357 8-14 Syn Hydroxylation of Alkenes 360 8-15 Oxidative Cleavage of Alkenes 362 8-16 Polymerization of Alkenes 365 8-17 Olefin Metathesis 369 Contents ix
Contents Problem-Solving Strategy:Organic Synthesis 372 Summary:Reactions of Alkenes 374 Chapter 8 Glossary 379 Study Problems 382 O ALKYNES 388 9-1 Introduction 388 9-2 Nomenclature of Alkynes 389 9-3 Physical Pro erties of Alkynes 390 9.4 Commercial Importance of Alkynes 390 9-5 Electronic Structure of Alkynes 392 9-6 Acidity of Alkynes:Formation of Acetylide Ions 393 9-7 Synthesis of Alkynes from Acetylides 395 9-8 Synthesis of Alkynes by Elimination Reactions 399 Summary:Syntheses of Alkynes Addition F Summary:Reactions of Alkynes 414 Chapter 9 Glossary 417 Study Problems 418 10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 421 Introduction 42 Structure and Cl sification of Alcohol 2 ture of Alco Physical ies of Al hals Acidity of Alcoh 43 10-7Sy the is of Alcohols:In and Review 434 Summary:Previous Alcohol sv 10-8 Organometallic Reagents for Alcohol Synthesis 436 10-9 Addition of Organometallic Reagents to Carbonyl Compounds 439 Key Mechanism:Grignard Reactions 439 Summary:Grignard Reactions 446 10-10 Side Reactions of Organometallic Reagents:Reduction of Alkyl Halides 447 10-11 Reduction of the Carbonyl Group:Synthesis of 1 and 2 Alcohols 449 Summary:Reactions of LiAlH,and NaBH 452 10-12 Thiols (Mercaptans)455 Chapter 10 Glossary 457 Study Problems 459 11 REACTIONS OF ALCOHOLS 464 11-1 Oxidation State es of Alcohols and Related Functional Groups 46 idizing Alcohols 469
x Contents Problem-Solving Strategy: Organic Synthesis 372 Summary: Reactions of Alkenes 374 Chapter 8 Glossary 379 Study Problems 382 9 ALKYN ES 388 9-1 Introduction 388 9-2 Nomenclature of Alkynes 389 9-3 Physical Properties of Alkynes 390 9-4 Commercial Importance of Alkynes 390 9-5 Electronic Structure of Alkynes 392 9-6 Acidity of Alkynes; Formation of Acetylide Ions 393 9-7 Synthesis of Alkynes from Acetylides 395 9-8 Synthesis of Alkynes by Elimination Reactions 399 Summary: Syntheses of Alkynes 400 9-9 Addition Reactions of Alkynes 40 l 9-10 Oxidation of Alkynes 411 Problem-Solving Strategy: Multistep Synthesis 413 Summary: Reactions of Alkynes 414 Chapter 9 Glossary 417 Study Problems 418 1 Q STRUCTURE AND SYNTHESIS OF ALCOHOLS 421 10-1 Introduction 421 10-2 Structure and Classification of Alcohols 421 10-3 Nomenclature of Alcohols and Phenols 423 10-4 Physical Properties of Alcohols 427 10-5 Commercially Important Alcohols 429 10-6 Acidity of Alcohols and Phenols 431 10-7 Synthesis of Alcohols: Introduction and Review 434 Summary: Previous Alcohol Syntheses 434 10-8 Organometallic Reagents for Alcohol Synthesis 436 10-9 Addition of Organometallic Reagents to Carbonyl Compounds 439 Key Mechanism: Grignard Reactions 439 Summary: Grignard Reactions 446 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 447 10-11 Reduction of the Carbonyl Group: Synthesis of 1 o and 2° Alcohols 449 Summary: Reactions of LiAlH4 and NaBH4 452 Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 453 10-12 Thiols (Mercaptans) 455 Chapter 10 Glossary 457 Study Problems 459 11 REACTIONS OF ALCOHOLS 464 11-1 Oxidation States of Alcohols and Related Functional Groups 464 11-2 Oxidation of Alcohols 466 11-3 Additional Methods for Oxidizing Alcohols 469
Contents xi 11-4 Biological Oxidation of Alcohols 471 11-5 Alcohols as Nucleophiles and Electrophiles:Formation of Tosylates 472 Summary:S.2 Reactions of Tosylate Esters 475 11-6 Reduction of Alcohols 475 11-7 Reactions of Alcohols with Hydrohalic Acids 476 11-8 Reactions of Alcohols with Phosphorus Halides 48 11-9 Reactions of Alcohols with Thionyl Chloride 482 11-10 Dehydration Reactions of Alcohols 484 oposing Reaction Mechanisms 488 iomofAeohois49g 13 ers of In nic Acids 494 11-14 40 Mechanism:The Williamson Ether Synthesis 497 Problem-Solving Strategy:Multiste p Synthesis 499 Summary:Reactions of Alcohols 502 Chapter II Glossary 504 Study Problems 506 INERARED SPECTROSCOPY AND MASS 12 SPECTROMETRY 510 Introduction 510 ctrum5 125 -Active and R Vibrations 515 trum 516 138 ols and amines 524 risti Absortions of Carbonyl Com ounds 525 12-10 Charaeteristic Absomtions ofC-N Bonds 531 12-11 Simplified Summary of IR Stretching Frequencies 532 12-12 Reading and Interpreting IR Spectra(Solved Problems)534 12-13 Introduction to Mass Spectrometry 539 12-14 Determination of the Molecular Formula by Mas B5” 13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 561 13-1 Introduction 561 13-2 Theory of Nuclear Magnetic Resonance 561 13-3 Magnetic Shielding by Electrons 564 13-4 The NMR Spectrometer 566 13-5 The Chemical Shift 567 The Number of Signals 574 Areas of the Peaks 575
11-4 Biological Oxidation of Alcohols 471 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 472 Summary: SN2 Reactions of Tosylate Esters 475 11-6 Reduction of Alcohols 475 11-7 Reactions of Alcohols with Hydrohalic Acids 476 11-8 Reactions of Alcohols with Phosphorus Halides 481 11-9 Reactions of Alcohols with Thionyl Chloride 482 11-10 Dehydration Reactions of Alcohols 484 Problem-Solving Strategy: Proposing Reaction Mechanisms 488 11-11 Unique Reactions ofDiols 491 11-12 Esterification of Alcohols 493 11-13 Esters oflnorganic Acids 494 11-14 Reactions of Alkoxides 497 Key Mechanism: The Williamson Ether Synthesis 497 Problem-Solving Strategy: Multistep Synthesis 499 Summary: Reactions of Alcohols 502 Chapter 11 Glossary 504 Study Problems 506 INFRARED SPECTROSCOPY AND MASS 12 SPECTROMETRY 510 12-1 Introduction 510 12-2 The Electromagnetic Spectrum 511 12-3 The Infrared Region 512 12-4 Molecular Vibrations 513 12-5 IR-Active and IR-Inactive Vibrations 515 12-6 Measurement of the IR Spectrum 516 12-7 Infrared Spectroscopy of Hydrocarbons 519 12-8 Characteristic Absorptions of Alcohols and Amines 524 12-9 Characteristic Absorptions of Carbonyl Compounds 525 12-10 Characteristic Absorptions of C-N Bonds 531 12-11 Simplified Summary ofiR Stretching Frequencies 532 12-12 Reading and Interpreting IR Spectra (Solved Problems) 534 12-13 Introduction to Mass Spectrometry 539 12-14 Determination of the Molecular Formula by Mass Spectrometry 543 12-15 Fragmentation Patterns in Mass Spectrometry 546 Summary: Common Fragmentation Patterns 551 Chapter 12 Glossary 553 Study Problems 554 13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 561 13-1 Introduction 561 13-2 Theory of Nuclear Magnetic Resonance 561 13-3 Magnetic Shielding by Electrons 564 13-4 The NMR Spectrometer 566 13-5 The Chemical Shift 567 13-6 The Number of Signals 574 13-7 Areas of the Peaks 575 Contents xi
x Contents 13-8 Spin-Spin Splitting 578 Problem-Solving Strategy:Drawing an NMR Spectrum 583 13-9 Complex Splitting 587 Stereochemical Nonequivalence of Protons590 13-11 n NMR Spectra 596 13.12 Carbon-13 NMR Sp 601 13.131 ting Carbon NMR Sp ctra 609 13-14 e Imaging 611 Problem-Solving Strategy:Spectroscopy Problems 612 Chapter 13 Glossary 616 Study Problems 618 14 ETHERS,EPOXIDES,AND SULFIDES 625 14-1 Introduction 625 14-2 Physical Properties of Ethers 625 14-3 Nomenclature of Ethers 630 144 Spectroscopy of Ethers 633 14-5 The Williamson Ether Synthesis 635 Synthesis of Ethers by Alkoxymercuration-Demercuration 636 14-7 Industrial Synthesis:Bimolecular Dehydration of Alcohols 637 Summary:Syntheses of Ethers(Review)638 148 Cleavage of Ethers by HBr and HI 638 14- on of Ethers thers 641 1410 eonsorB 1411 ses 647 1413 ed Ring 14-13 Base-Catalyzed Ring ening of Epoxides64 of Epoxides 651 14-14 Orientation of Epoxide Ring Opening 652 14.15 reactions of epoxides with grignard and orea olithium Reagents 654 14.16 Epoxy Resins:The Advent of Modern Glues 655 Sunmmry:Reactions of Epuxides 657 Chapter 14 Glossary 658 Study Problems 660 CoNJUGATED SYSTEMS ORBITAL SYMMETRY 15 AND ULTRAVIOLET SPECTROSCOPY 665 15-1 Introduction 665 of Dienes 665 15-3 Molecular Orbital Picture of a Conjugated System 667 15-4 Allylic Cations 671 15-5 1.2-and 1.4-Addition to Conjugated Dienes 672 15-6 Kinetic versus Thermodynamic Control in the Addition of HBr 1.3-Butadiene 674 Allylic Radical 670 ecular Orbitals of the Allylic System 678
xii Contents 13-8 Spin-Spin Splitting 578 Problem-Solving Strategy: Drawing an NMR Spectrum 583 13-9 Complex Splitting 587 13-10 Stereochemical Nonequivalence of Protons 590 13-11 Time Dependence of NMR Spectroscopy 593 Problem-Solving Strategy: Interpreting Proton NMR Spectra 596 13-12 Carbon-13 NMR Spectroscopy 601 13-13 Interpreting Carbon NMR Spectra 609 13-14 Nuclear Magnetic Resonance Imaging 611 Problem-Solving Strategy: Spectroscopy Problems 612 Chapter 13 Glossary 616 Study Problems 618 14 ETHERS, EPOXIDES, AND SULFIDES 625 14-1 Introduction 625 14-2 Physical Properties of Ethers 625 14-3 Nomenclature of Ethers 630 14-4 Spectroscopy of Ethers 633 14-5 The Williamson Ether Synthesis 635 14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration 636 14-7 Industrial Synthesis: Bimolecular Dehydration of Alcohols 637 Summary: Syntheses of Ethers (Review) 638 14-8 Cleavage of Ethers by HBr and HI 638 14-9 Autoxidation of Ethers 641 Summary: Reactions of Ethers 641 14-10 Sulfides (Thioethers) 642 14-11 Synthesis of Epoxides 644 Summary: Epoxide Syntheses 647 14-12 Acid-Catalyzed Ring Opening of Epoxides 648 14-13 Base-Catalyzed Ring Opening of Epoxides 651 14-14 Orientation of Epoxide Ring Opening 652 14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 654 14-16 Epoxy Resins: The Advent of Modern Glues 655 Summary: Reactions of Epoxides 657 Chapter 14 Glossary 658 Study Problems 660 5 CONJUGATED SYSTEMS, ORBITAL SYMMETRY, 1 AND ULTRAVIOLET SPECTROSCOPY 665 15-1 Introduction 665 15-2 Stabilities of Dienes 665 15-3 Molecular Orbital Picture of a Conjugated System 667 15-4 Allylic Cations 671 15-5 1,2- and 1,4-Addition to Conjugated Dienes 672 15-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene 674 15-7 Allylic Radicals 676 15-8 Molecular Orbitals of the Allylic System 678
Contents 15-9 Electronic Configurations of the allyl radical.cation.and Anion 680 15-10 Sx2 Displacement Reactions of Allylic Halides and Tosylates 681 15-11 The Diels-Alder Reaction 682 Key Mechanism:The Diels-Alder Reacticn 682 15-12 The Diels-Alder as an Example of a Pericyclic Reaction 691 15-13 Ultraviolet Absorption Spectroscopy 694 Chapter 15 Glossary 701 Study Problems 703 16 AROMATIC COMPOUNDS 707 16-1 Introduction:The Discovery of Benzene 707 16-2 The Structure and Properties of Benzene 707 16-3 The Molecular Orbitals of Benzene 711 16-4 The Molecular Orbital Picture of Cyclobutadiene 714 16-5 Aromatic.Antiaromatic,and Nonaromatie Compounds 716 16-6 Htickel's Rule 716 Molecular Orbital Derivation of Huckel's Rule 718 16-9 Aromatic Tons 719 Aromatic Compounds 72 f 16-1 Fused He 16.13 s734 16-14 Physical Pro ies of ber e and Its De ivatives 736 16-15 Spe d73 Chapter 16 Glossary 740 Study Problems 742 17 REACTIONS OF AROMATIC COMPOUNDS 75 17- Aromat Nitration of Be n of Benzene 757 17-5 Nitration of Toluene:The Effect of Alkyl Substitution759 17-6 Activating.Ortho.Para-Directing Substituents 761 Summary:Activating,Ortho.Para-Directors 764 17-7 Deactivating.Meta-Directing Substituents 765 Summary:Deactivating.Meta-Directors 768 17-8 Halogen Substituents:Deactivating.but Ortho.Para-Directing 768 Summary:Directing Effects of Substituents 770 179 Effects of Multiple Substi uents on Electrophilic 17-10 The EriedeL-Cr 17-11 The Friedel-Crafts Acy 777 son of Friedel-Crafts Alkylation and Aeylation 780 17-12 Nucleophilic Aromatic Substitution 782
15-9 Electronic Configurations of the Allyl Radical, Cation, and Anion 680 15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 681 15-11 The Diels-Alder Reaction 682 Key Mechanism: The Diels-Aider Reaction 682 15-12 The Diels-Alder as an Example of a Pericyclic Reaction 691 15-13 Ultraviolet Absorption Spectroscopy 694 Chapter 15 Glossary 701 Study Problems 703 16 AROMATIC COMPOUNDS 707 16-1 Introduction: The Discovery of Benzene 707 16-2 The Structure and Properties of Benzene 707 16-3 The Molecular Orbitals of Benzene 711 16-4 The Molecular Orbital Picture of Cyclobutadiene 714 16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds 716 16-6 Htickel's Rule 716 16-7 Molecular Orbital Derivation of Htickel's Rule 718 16-8 Aromatic Ions 719 16-9 Heterocyclic Aromatic Compounds 725 16-10 Polynuclear Aromatic Hydrocarbons 729 16-11 Aromatic Allotropes of Carbon 731 16-12 Fused Heterocyclic Compounds 733 16-13 Nomenclature of Benzene Derivatives 734 16-14 Physical Properties of Benzene and Its Derivatives 736 16-15 Spectroscopy of Aromatic Compounds 737 Chapter 16 Glossary 740 Study Problems 742 17 REACTIONS OF AROMATIC COMPOUNDS 751 17-1 Electrophilic Aromatic Substitution 751 Key Mechanism: Electrophilic Aromatic Substitution 752 17-2 Halogenation of Benzene 753 17-3 Nitration of Benzene 755 17-4 Sulfonation of Benzene 757 17-5 Nitration of Toluene: The Effect of Alkyl Substitution 759 17-6 Activating, Ortho, Para-Directing Substituents 761 Summary: Activating, Ortho, Para-Directors 764 17-7 Deactivating, Meta-Directing Substituents 765 Summary: Deactivating, Meta-Directors 768 17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing 768 Summary: Directing Effects of Substituents 770 17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 770 17-10 The Friedel-Crafts Alkylation 773 17-11 The Friedel-Crafts Acylation 777 Summary: Comparison of Friedel-Crafts Alkylation and Acylation 780 17-12 Nucleophilic Aromatic Substitution 782 Contents xiii