BROWN IVERSON ANSLYN FOOTE Organic Chemistry SEVENTH EDITION CpeIefL OL&SUIG
7th edition Organic Chemistry William H.Brown Beloit College Brent L.Iverson University of Texas,Austin Eric V.Anslyn Christopher S.Foote University of Califomia,Los Angeles Bruce M.Novak University of Texas at Dallas WADWORTH Australia Brazil Japan·Korea Mexico·Singapore Spain-United KingdomUnited State
Organic Chemistry William H. Brown Beloit College Brent L. Iverson University of Texas, Austin Eric V. Anslyn University of Texas, Austin Christopher S. Foote University of California, Los Angeles Chapter 29 was originally contributed by Bruce M. Novak University of Texas at Dallas 7th edition Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Dedication This Seventh Edition is dedicated to the memory of our dear friend and colleague,Christopher Foote.Chris's insights,encouragement,and dedication to this project can never be replaced.His kind and nurturing spirit lives on in all who are lucky enough to have known him
Dedication This Seventh Edition is dedicated to the memory of our dear friend and colleague, Christopher Foote. Chris’s insights, encouragement, and dedication to this project can never be replaced. His kind and nurturing spirit lives on in all who are lucky enough to have known him. Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
ABOUT THE AUTHORS William H.Brown is an Emeritus Professor of Chemistry at Beloit College, where he has twice been named Teacher of the Year.His teaching responsibilities included organic chemistry,advanced organic chemistry,and special topics in phar macology and drug synthesis.He received his Ph.D.from Columbia University under the direction of Gilbert Stork and did postdoctoral work at the California Institute of Technology and the University of Arizona. Brent L.Iverson received his B.S.from Stanford University and his Ph.D. from the Califoria Institute of Technology.He is a University Distinguished Teaching Professor at the University of Texas at Austin as well as a respected researcher.Brent's research spans the interface of organic chemistry and molecular biology.His group has developed several patented technologies,including an effective treatment for anthrax. Eric V.Anslyn received his B.S.from Califomia State University,Northridge,and his Ph.D.from the Califomia Institute of Technology.He is the Nomman Hackerman Professor and a University Distinguished Teaching Professor at the University of Texas at Austin.Eric's research focuses on the physical and bioorganic chemistry of synthetic and natural receptors and catalysts. Christopher S.Foote received his B.S.from Yale University and his Ph.D. from Harvard University.His scholarly credits include Sloan Fellow;Guggenheim Fellow;ACS Baekland Award;ACS Cope Scholar;Southern Califomia Section ACS Tolman Medal;President,American Society for Photobiology;and Senior Editor, Accounts of chemical research.He was a professor of chemistry at ucla
Unless otherwise noted all art on this page © Cengage Learning 2013 William H. Brown is an Emeritus Professor of Chemistry at Beloit College, where he has twice been named Teacher of the Year. His teaching responsibilities included organic chemistry, advanced organic chemistry, and special topics in pharmacology and drug synthesis. He received his Ph.D. from Columbia University under the direction of Gilbert Stork and did postdoctoral work at the California Institute of Technology and the University of Arizona. Brent L. Iverson received his B.S. from Stanford University and his Ph.D. from the California Institute of Technology. He is a University Distinguished Teaching Professor at the University of Texas at Austin as well as a respected researcher. Brent’s research spans the interface of organic chemistry and molecular biology. His group has developed several patented technologies, including an effective treatment for anthrax. Eric V. Anslyn received his B.S. from California State University, Northridge, and his Ph.D. from the California Institute of Technology. He is the Norman Hackerman Professor and a University Distinguished Teaching Professor at the University of Texas at Austin. Eric’s research focuses on the physical and bioorganic chemistry of synthetic and natural receptors and catalysts. Christopher S. Foote received his B.S. from Yale University and his Ph.D. from Harvard University. His scholarly credits include Sloan Fellow; Guggenheim Fellow; ACS Baekland Award; ACS Cope Scholar; Southern California Section ACS Tolman Medal; President, American Society for Photobiology; and Senior Editor, Accounts of Chemical Research. He was a Professor of Chemistry at UCLA. About the Authors Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents in Brief 1.Covalent Bonding and Shapes of Molecules /1 2 Alkanes and Cycloalkanes /65 3.Stereoisomerism and Chirality /117 4.Acids and Bases/157 5.Alkenes:Bonding,Nomenclature,and Properties /191 Primer I Reaction Mechanisms 213 6.Reactions of Alkenes 221 7.Alkynes /275 8. Haloalkanes,Halogenation,and Radical Reactions /305 9.Nucleophilic Substitution and B-Elimination /341 10.Alcohols/401 11.Ethers,Epoxides,and Sulfides /451 12.Infrared Spectroscopy/491 13. Nuclear Magnetic Resonance Spectroscopy /512 14.Mass Spectrometry /557 15.An Introduction to Organometalic Compounds/579 16.Aldehydes and Ketones /600 17.Carboxvlic Acids 669 Primer Il Carboxylic Acid Derivative Reaction Mechanisms /701 18.Functional Derivatives of Carboxylic Acids /704 19.Enolate Anions and Enamines/763 20.Dienes,Coniugated Systems.and Pericyclic Reactions/831 21.Benzene and the Concept of Aromaticity 873 22. Reactions of Benzene and Its Derivatives/926 23.Amines 967 24. Catalytic Carbon-Carbon Bond Formation /1021 25.Carbohydrates /1058 26.Lipids 1093 27.Amino Acids and Proteins /1120 28.Nucleic Acids /1156 29.Organic Polymer Chemistry /1180 UhesohewitnotedaaftomhisgeeCeg3geleamig2013
Unless otherwise noted all art on this page © Cengage Learning 2013 v 1. Covalent Bonding and Shapes of Molecules / 1 2. Alkanes and Cycloalkanes / 65 3. Stereoisomerism and Chirality / 117 4. Acids and Bases / 157 5. Alkenes: Bonding, Nomenclature, and Properties / 191 Primer I Reaction Mechanisms / 213 6. Reactions of Alkenes / 221 7. Alkynes / 275 8. Haloalkanes, Halogenation, and Radical Reactions / 305 9. Nucleophilic Substitution and b-Elimination / 341 10. Alcohols / 401 11. Ethers, Epoxides, and Sulfides / 451 12. Infrared Spectroscopy / 491 13. Nuclear Magnetic Resonance Spectroscopy / 512 14. Mass Spectrometry / 557 15. An Introduction to Organometallic Compounds / 579 16. Aldehydes and Ketones / 600 17. Carboxylic Acids / 669 Primer II Carboxylic Acid Derivative Reaction Mechanisms / 701 18. Functional Derivatives of Carboxylic Acids / 704 19. Enolate Anions and Enamines / 763 20. Dienes, Conjugated Systems, and Pericyclic Reactions / 831 21. Benzene and the Concept of Aromaticity / 873 22. Reactions of Benzene and Its Derivatives / 926 23. Amines / 967 24. Catalytic Carbon-Carbon Bond Formation / 1021 25. Carbohydrates / 1058 26. Lipids / 1093 27. Amino Acids and Proteins / 1120 28. Nucleic Acids / 1156 29. Organic Polymer Chemistry / 1180 Contents in Brief Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents in Brief Appendices: 1.Thermodynamics and the Equilibrium Constant /A-1 2.Major Classes of Organic Acids /A-2 3.Bond Dissociation Enthalpies /A-3 4.Characteristic 1H-NMR Chemical Shifts /A-4 5.Characteristic 13C-NMR Chemical Shifts /A-5 Characteristic Infrared Absorption Frequencies/A-6 7.Electrostatic Potential Maps /A-7 8.Summary of Stereochemical Terms /A-8 9.Summary of the Rules of Nomenclature /A-11 10.Common Mistakes in Arrow Pushing /A-18 11.Organic Chemistry Road Maps/Insert Glossary Index
Unless otherwise noted all art on this page © Cengage Learning 2013 Contents in Brief vi Appendices: 1. Thermodynamics and the Equilibrium Constant / A-1 2. Major Classes of Organic Acids / A-2 3. Bond Dissociation Enthalpies / A-3 4. Characteristic 1 H-NMR Chemical Shifts / A-4 5. Characteristic 13C-NMR Chemical Shifts / A-5 6. Characteristic Infrared Absorption Frequencies / A-6 7. Electrostatic Potential Maps / A-7 8. Summary of Stereochemical Terms / A-8 9. Summary of the Rules of Nomenclature / A-11 10. Common Mistakes in Arrow Pushing / A-18 11. Organic Chemistry Road Maps / Insert Glossary Index Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents Covalent Bonding and Shapes of Molecules 1 Electronic Structure of Atoms 2 1.2 Lewis Model of Bonding 7 HOW TO Quickly Figure Out Formal Charge 14 HOWTO Draw Lewis Structures from Condensed Structural Formulas 16 1.3 Functional Groups 17 1.4 Bond Angles and Shapes of Molecules 22 15 Polar and Nonpolar Molecules 25 MCAT PRACTICE:PASSAGE AND QUESTIONS Fullerenes 26 1.6 Quantum or Wave Mechanics 27 1.7 A Combined Valence Bond and Molecular Orbital Theory Approach to Covalent Bonding 31 CONNECTIONS TO BIOLOGICAL CHEMISTRY Phosphoesters 38 HOWTO Quickly Recognize the Hybridization and Geometry of Atoms 43 1.8 Resonance 43 HOWTO Draw Curved Arrows and Push Electrons in Creating Contributing Structures 44 1.9 Molecular Orbitals for Delocalized Systems 49 MCAT PRACTICE:PASSAGE AND QUESTIONS VSEPR and Resonance 52 1.10 Bond Lengths and Bond Strengths in Alkanes,Alkenes,and Alkynes 53 Summary54·Problems57 2 Alkanes and Cycloalkanes 65 2.1 The Structure of Alkanes 66 2.2 Constitutional lsomerism in Alkanes 67 2.3 Nomenclature of Alkanes and the IUPAC System 70 2.4 Cycloalkanes 75 2.5 Conformations of Alkanes and Cycloalkanes 78 HOW TO Draw Alternative Chair Conformations of Cyclohexane 89 Unessisotelartnhn3
Unless otherwise noted all art on this page © Cengage Learning 2013 vii 1 Covalent Bonding and Shapes of Molecules 1 1.1 Electronic Structure of Atoms 2 1.2 Lewis Model of Bonding 7 HoW To Quickly Figure Out Formal Charge 14 HoW To Draw Lewis Structures from Condensed Structural Formulas 16 1.3 Functional Groups 17 1.4 Bond Angles and Shapes of Molecules 22 1.5 Polar and Nonpolar Molecules 25 MCAT PrACTICE: PASSAgE And QuESTIonS Fullerenes 26 1.6 Quantum or Wave Mechanics 27 1.7 A Combined Valence Bond and Molecular Orbital Theory Approach to Covalent Bonding 31 ConnECTIonS To BIoLogICAL CHEMISTry Phosphoesters 38 HoW To Quickly Recognize the Hybridization and Geometry of Atoms 43 1.8 Resonance 43 HoW To Draw Curved Arrows and Push Electrons in Creating Contributing Structures 44 1.9 Molecular Orbitals for Delocalized Systems 49 MCAT PrACTICE: PASSAgE And QuESTIonS VSEPR and Resonance 52 1.10 Bond Lengths and Bond Strengths in Alkanes, Alkenes, and Alkynes 53 Summary 54 • Problems 57 2 Alkanes and Cycloalkanes 65 2.1 The Structure of Alkanes 66 2.2 Constitutional Isomerism in Alkanes 67 2.3 Nomenclature of Alkanes and the IUPAC System 70 2.4 Cycloalkanes 75 2.5 Conformations of Alkanes and Cycloalkanes 78 HoW To Draw Alternative Chair Conformations of Cyclohexane 89 Contents Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents 2.6 Cis,Trans Isomerism in Cycloalkanes and Bicycloalkanes 91 HOW TO Convert Planar Cyclohexanes to Chair Cyclohexanes 93 MCAT PRACTICE:PASSAGE AND QUESTIONS Tetrodotoxin 98 2.7 Physical Properties of Alkanes and Cycloalkanes99 2.8 Reactions of Alkanes 102 2.9 Sources and Importance of Alkanes 104 CHEMICAL CONNECTIONS Octane Rating:What Those Numbers at the Pump Mean 106 Summary 107.Problems 109 3 Stereoisomerism and Chirality 117 3.1 Chirality-The Handedness of Molecules 118 3.2 Stereoisomerism 119 HOWTO Draw Chiral Molecules 120 3.3 Naming Chiral Centers-The R,S System 124 HOW TO Assign R or S Configuration to a Chiral Center 126 3.4 Acyclic Molecules with Two or More Stereocenters 127 HOWTO Quickly Draw and Recognize Enantiomers and Diastereomers 133 3.5 Cyclic Molecules with Two or More Chiral Centers 133 3.6 Tying All the Terminology Together 136 3.7 Optical Activity-How Chirality Is Detected in the Laboratory 138 3.8 The Significance of Chirality in the Biological World 142 CONNECTIONS TO BIOLOGICAL CHEMISTRY Chiral Drugs 143 MCAT PRACTICE:PASSAGE AND QUESTIONS Amino Acid Stereochemistry 144 3.9 Separation of Enantiomers-Resolution 145 Summary 148.Problems 151 4 Acids and Bases 157 4.1 Arrhenius Acids and Bases 157 4.2 Bronsted-Lowry Acids and Bases 158 4.3 Acid Dissociation Constants,pK,and the Relative Strengths of Acids and Bases 164 4.4 The Position of Equilibrium in Acid-Base Reactions 166 HOWTO Calculate the Constants for Acid-Base Reactions 167 CONNECTIONS TO BIOLOGICAL CHEMISTRY The lonization of unctional Groups at Physiological pH 168 4.5 Thermochemistry and Mechanisms of Acid-Base Reactions 169 4.6 Molecular Structure and Acidity 173 MCAT PRACTICE:PASSAGE AND QUESTIONS Acid-Base Equilibria 178 4.7 Lewis Acids and Bases 179 Summary 181 Problems 184 Unless otherwise noted all art on this pageCengage Learning 2013
Unless otherwise noted all art on this page © Cengage Learning 2013 Contents viii 2.6 Cis,Trans Isomerism in Cycloalkanes and Bicycloalkanes 91 HoW To Convert Planar Cyclohexanes to Chair Cyclohexanes 93 MCAT PrACTICE: PASSAgE And QuESTIonS Tetrodotoxin 98 2.7 Physical Properties of Alkanes and Cycloalkanes 99 2.8 Reactions of Alkanes 102 2.9 Sources and Importance of Alkanes 104 CHEMICAL ConnECTIonS Octane Rating: What Those Numbers at the Pump Mean 106 Summary 107 • Problems 109 3 Stereoisomerism and Chirality 117 3.1 Chirality—The Handedness of Molecules 118 3.2 Stereoisomerism 119 HoW To Draw Chiral Molecules 120 3.3 Naming Chiral Centers—The R,S System 124 HoW To Assign R or S Configuration to a Chiral Center 126 3.4 Acyclic Molecules with Two or More Stereocenters 127 HoW To Quickly Draw and Recognize Enantiomers and Diastereomers 133 3.5 Cyclic Molecules with Two or More Chiral Centers 133 3.6 Tying All the Terminology Together 136 3.7 Optical Activity—How Chirality Is Detected in the Laboratory 138 3.8 The Significance of Chirality in the Biological World 142 ConnECTIonS To BIoLogICAL CHEMISTry Chiral Drugs 143 MCAT PrACTICE: PASSAgE And QuESTIonS Amino Acid Stereochemistry 144 3.9 Separation of Enantiomers—Resolution 145 Summary 148 • Problems 151 4 Acids and Bases 157 4.1 Arrhenius Acids and Bases 157 4.2 Brønsted-Lowry Acids and Bases 158 4.3 Acid Dissociation Constants, pKa, and the Relative Strengths of Acids and Bases 164 4.4 The Position of Equilibrium in Acid-Base Reactions 166 HoW To Calculate the Equilibrium Constants for Acid-Base Reactions 167 ConnECTIonS To BIoLogICAL CHEMISTry The Ionization of Functional Groups at Physiological pH 168 4.5 Thermochemistry and Mechanisms of Acid-Base Reactions 169 4.6 Molecular Structure and Acidity 173 MCAT PrACTICE: PASSAgE And QuESTIonS Acid-Base Equilibria 178 4.7 Lewis Acids and Bases 179 Summary 181 • Problems 184 Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents Alkenes:Bonding,Nomenclature,and Properties 191 5.1 Structure of Alkenes 193 HOWTO Calculate the Index of Hydrogen Deficiency193 5.2 Nomenclature of Alkenes 196 5.3 Physical Properties of Alkenes 202 CHEMICAL CONNECTIONS The Case of the lowa and New York Strains of the European Comn Borer 202 5.4 Naturally Occurring Alkenes-Terpene Hydrocarbons 203 DLOGICAL CHEMISTRY The Importance Summary 206 Problems 207 Primer I Reaction Mechanisms 213 6 Reactions of Alkenes 221 6.1 Reactions of Alkenes-An Overview 221 6.2 Organic Reactions Involving Reactive Intermediates 223 6.3 Electrophilic Additions 225 6.4 Hydroboration-Oxidation 244 6.5 Oxidation 248 HOW TO Write a Balanced Halt-Reaction 251 6.6 Reduction 253 CONNECTIONS TO BIOLOGICAL CHEMISTRY Tans Fatty Acids: What They Are and How to Avoid Them 256 6.7 Molecules Containing Chiral Centers as Reactants or Products 257 Summary 262.Problems 266 7 Alkynes 275 7.1 Structure of Alkynes 275 72 Nomenclature of Alkynes 276 7.3 Physical Properties of Alkynes 278 7.4 Acidity of 1-Alkynes 278 7.5 Preparation of Alkynes 279 7.6 Electrophilic Addition to Alkynes 282 7.7 Hydration of Alkynes to Aldehydes and Ketones 284 7.8 Reduction of Alkynes 289 .9 Organic Synthesis 291 Summary 295.Problems 298 Unessisotel artnpe3 ix
Unless otherwise noted all art on this page © Cengage Learning 2013 Contents ix 5 Alkenes: Bonding, Nomenclature, and Properties 191 5.1 Structure of Alkenes 193 HoW To Calculate the Index of Hydrogen Deficiency 193 5.2 Nomenclature of Alkenes 196 5.3 Physical Properties of Alkenes 202 CHEMICAL ConnECTIonS The Case of the Iowa and New York Strains of the European Corn Borer 202 5.4 Naturally Occurring Alkenes!Terpene Hydrocarbons 203 ConnECTIonS To BIoLogICAL CHEMISTry The Importance of Cis Double Bonds in Fats Versus Oils 205 Summary 206 • Problems 207 Primer I Reaction Mechanisms 213 6 Reactions of Alkenes 221 6.1 Reactions of Alkenes—An Overview 221 6.2 Organic Reactions Involving Reactive Intermediates 223 6.3 Electrophilic Additions 225 6.4 Hydroboration-Oxidation 244 6.5 Oxidation 248 HoW To Write a Balanced Half-Reaction 251 6.6 Reduction 253 ConnECTIonS To BIoLogICAL CHEMISTry Trans Fatty Acids: What They Are and How to Avoid Them 256 6.7 Molecules Containing Chiral Centers as Reactants or Products 257 Summary 262 • Problems 266 7 Alkynes 275 7.1 Structure of Alkynes 275 7.2 Nomenclature of Alkynes 276 7.3 Physical Properties of Alkynes 278 7.4 Acidity of 1-Alkynes 278 7.5 Preparation of Alkynes 279 7.6 Electrophilic Addition to Alkynes 282 7.7 Hydration of Alkynes to Aldehydes and Ketones 284 7.8 Reduction of Alkynes 289 7.9 Organic Synthesis 291 Summary 295 • Problems 298 Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Contents 8 -Haloalkanes,Halogenation,and Radical Reactions 305 8.1 Structure 306 8.2 Nomenclature 306 8.3 Physical Properties of Haloalkanes 307 8.4 Preparation of Haloalkanes by Halogenation of Alkanes 311 8.5 Mechanism of Halogenation of Alkanes 315 CHEMICAL CONNECTIONS Freons 318 8.6 Allylic Halogenation 322 8.7 Radical Autoxidation 327 MCAT PRACTICE:PASSAGE AND QUESTIONS Antioxidants 328 8.8 Radical Addition of HBr to Alkenes 330 Summary 333.Problems 335 9Nucleophilic Substitution and B-Elimination 341 9.1 Nucleophilic Substitution in Haloalkanes 343 .2 Mechanisms of Nucleophilic Aliphatic Substitution 344 9.3 Experimental Evidence for S.,1 and S.2 Mechanisms 348 9.4 Analysis of Several Nucleophilic Substitution Reactions 364 9.5 B-Elimination 366 9.6 Mechanisms of B-Elimination 368 9.7 Experimental Evidence for E1 and E2 Mechanisms 370 9.8 Substitution Versus Elimination 376 9.9 Analysis of Several Competitions Between Substitutions and Eliminations 380 MCAT PRACTICE:PASSAGE AND QUESTIONS Solvents and Solvation 383 9.10 Neighboring Group Participation 383 CONNECTIONS TO BIOLOGICAL CHEMISTRY Mustard Gases and the Treatment of Neoplastic Diseases 386 Summary 387 Problems 391 10 Alcohols 401 10.1 Structure and Nomenclature of Alcohols 402 10.2 Physical Properties of Alcohols 404 CONNECTIONS TO BIOLOGICAL CHEMISTRY The Importance of Hydrogen Bonding in Drug-Receptor Interactions 406 10.3 Acidity and Basicity of Alcohols 408 10.4 Reaction of Alcohols with Active Metals 409 Unless otherwise noted all art on this pageCengage Learning 2013
Unless otherwise noted all art on this page © Cengage Learning 2013 Contents x 8 Haloalkanes, Halogenation, and Radical Reactions 305 8.1 Structure 306 8.2 Nomenclature 306 8.3 Physical Properties of Haloalkanes 307 8.4 Preparation of Haloalkanes by Halogenation of Alkanes 311 8.5 Mechanism of Halogenation of Alkanes 315 CHEMICAL ConnECTIonS Freons 318 8.6 Allylic Halogenation 322 8.7 Radical Autoxidation 327 MCAT PrACTICE: PASSAgE And QuESTIonS Antioxidants 328 8.8 Radical Addition of HBr to Alkenes 330 Summary 333 • Problems 335 9 Nucleophilic Substitution and b-Elimination 341 9.1 Nucleophilic Substitution in Haloalkanes 343 9.2 Mechanisms of Nucleophilic Aliphatic Substitution 344 9.3 Experimental Evidence for SN1 and SN2 Mechanisms 348 9.4 Analysis of Several Nucleophilic Substitution Reactions 364 9.5 b-Elimination 366 9.6 Mechanisms of b-Elimination 368 9.7 Experimental Evidence for E1 and E2 Mechanisms 370 9.8 Substitution Versus Elimination 376 9.9 Analysis of Several Competitions Between Substitutions and Eliminations 380 MCAT PrACTICE: PASSAgE And QuESTIonS Solvents and Solvation 383 9.10 Neighboring Group Participation 383 ConnECTIonS To BIoLogICAL CHEMISTry Mustard Gases and the Treatment of Neoplastic Diseases 386 Summary 387 • Problems 391 10 Alcohols 401 10.1 Structure and Nomenclature of Alcohols 402 10.2 Physical Properties of Alcohols 404 ConnECTIonS To BIoLogICAL CHEMISTry The Importance of Hydrogen Bonding in Drug-Receptor Interactions 406 10.3 Acidity and Basicity of Alcohols 408 10.4 Reaction of Alcohols with Active Metals 409 Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it