Organic chemistry 7e by francis a carey

M cGraw-Hill offers various tools and technology to support the seventh edition of Organic Chemistry You can order supplemental study materials by contacting your bookstore or the McGraw-Hill Customer Service Department at 1-800-338-3987 Solutions Manual CPS eInstruction ISBN-13: 978-0-07-304788-1 • ISBN-10: 0-07-304788-0 The Classroom Performance System’s Written by Robert C Atkins (James Madison University) and Francis A Carey, the Solutions Manual provides step-by-step solutions to guide students through the reasoning behind solving each problem in the text There is also a self-test at the end of each chapter designed to assess the student’s mastery of the material (CPS) eInstruction brings interactivity into the classroom or lecture hall It is a wireless response system that gives the instructor and students immediate feedback from the entire class The wireless response pads are essentially remotes that are easy to use and engage students CPS allows instructors to motivate student preparation, promote interactivity and active learning, and receive immediate feedback to assess student understanding Questions covering the content of the Organic Chemistry text and formatted in the CPS eInstruction software are available on the Organic Chemistry ARIS™ site McGraw-Hill Higher Education Apago PDF Enhancer car47872_fm_i-xxxii 11/24/06 23:09 Page i CONFIRMING PAGES S e v e n t h E d i t i o n Francis A Carey University of Virginia Apago PDF Enhancer Boston Burr Ridge, IL Dubuque, IA New York San Francisco St Louis Bangkok Bogotá Caracas Kuala Lumpur Lisbon London Madrid Mexico City Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei Toronto car47872_fm_i-xxxii 11/15/06 18:32 Page ii CONFIRMING PAGES ORGANIC CHEMISTRY, SEVENTH EDITION Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the Americas, New York, NY 10020 Copyright © 2008 by The McGraw-Hill Companies, Inc All rights reserved No part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior written consent of The McGraw-Hill Companies, Inc., including, but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning Some ancillaries, including electronic and print components, may not be available to customers outside the United States E This book is printed on recycled, acid-free paper containing 10% postconsumer waste DOW/DOW ISBN 978–0–07–304787–4 MHID 0–07–304787–2 Publisher: Thomas D Timp Senior Sponsoring Editor: Tamara Good-Hodge Developmental Editor: Jodi Rhomberg Senior Marketing Manager: Todd Turner Senior Project Manager: Gloria G Schiesl Senior Production Supervisor: Kara Kudronowicz Lead Media Project Manager: Judi David Executive Producer: Linda Meehan Avenarius Senior Designer: David W Hash Cover/Interior designer: Elise Lansdon (USE) Cover Image: Nanotube supplied by Dr Dirk Guldi of the University of Erlangen (Germany) and Dr Maurizio Prato of the University of Trieste (Italy) Senior Photo Research Coordinator: John C Leland Photo Research: Mary Reeg Supplement Producer: Tracy L Konrardy Compositor: Techbooks Typeface: 10.5/12 Times Printer: R R Donnelley Willard, OH Apago PDF Enhancer The credits section for this book begins on page C-1 and is considered an extension of the copyright page Library of Congress Cataloging-in-Publication Data Carey, Francis A., 1937Organic chemistry / Francis A Carey.—7th ed p cm Includes index ISBN 978-0-07-304787-4—ISBN 0-07-304787-2 (hard copy : alk paper) Chemistry, Organic I Title QD251.3.C37 2008 547—dc22 2006031901 www.mhhe.com car47872_fm_i-xxxii 11/24/06 23:10 Page iii CONFIRMING PAGES This edition is dedicated to my colleague and friend Bob Atkins, who is not only the lead author of our Solutions Manual but who also has contributed generously of his time, knowledge, and common sense throughout the seven editions of this text Apago PDF Enhancer car47872_fm_i-xxxii 11/22/06 17:19 Page iv CONFIRMING PAGES About the Cover Chemists are increasingly concerned with preparing compounds designed to have particular properties The compound featured on the cover is the creation of Dr Dirk Guldi of the University of Erlangen (Germany) and Dr Maurizio Prato of the University of Trieste (Italy) The cylindrical object is a form of carbon known as a nanotube.* About percent of the carbons of this nanotube are linked to molecules of the organometallic “sandwich” compound ferrocene.† On irradiation with visible light, ferrocene transfers an electron to the nanotube, generating a charge-separated species Thus, nanotubes that bear appropriate attached groups hold promise as materials suitable for devices, such as solar cells, that are capable of converting sunlight to electricity Apago PDF Enhancer *For more about carbon nanotubes, see pages 432–433 † For more about ferrocene, see page 600 iv car47872_fm_i-xxxii 11/15/06 18:32 Page v CONFIRMING PAGES About the Author Francis A Carey, a native of Philadelphia, was educated at Drexel University (B.S in chemistry, 1959) and Penn State (Ph.D., 1963) Following postdoctoral work at Harvard and military service, he served on the faculty of the University of Virginia from 1966 until retiring as Professor Emeritus in 2000 In addition to this text, Professor Carey is coauthor (with Robert C Atkins) of Organic Chemistry: A Brief Course and (with Richard J Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava Apago PDF Enhancer v car47872_fm_i-xxxii 11/15/06 18:32 Page vi CONFIRMING PAGES Brief Contents List of Important Features xix Preface xxv Acknowledgments xxxi 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Introduction Structure Determines Properties Alkanes and Cycloalkanes: Introduction to Hydrocarbons 58 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 102 Alcohols and Alkyl Halides 138 Structure and Preparation of Alkenes: Elimination Reactions 182 Addition Reactions of Alkenes 224 Stereochemistry 276 Nucleophilic Substitution 318 Alkynes 354 Conjugation in Alkadienes and Allylic Systems 382 Arenes and Aromaticity 420 Reactions of Arenes: Electrophilic Aromatic Substitution 470 Spectroscopy 516 Organometallic Compounds 578 Alcohols, Diols, and Thiols 620 Ethers, Epoxides, and Sulfides 662 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 700 Enols and Enolates 752 Carboxylic Acids 790 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 825 Ester Enolates 880 Amines 908 Aryl Halides 964 Phenols 990 Carbohydrates 1022 Lipids 1064 Amino Acids, Peptides, and Proteins 1106 Nucleosides, Nucleotides, and Nucleic Acids 1162 Synthetic Polymers 1200 Apago PDF Enhancer Glossary G-1 Credits C-1 Index I-1 vi car47872_fm_i-xxxii 11/15/06 18:32 Page vii CONFIRMING PAGES Contents List of Important Features xix Preface xxv Acknowledgments xxxi I N T R O D U C T I O N The Origins of Organic Chemistry Berzelius, Wöhler, and Vitalism The Structural Theory Electronic Theories of Structure and Reactivity The Influence of Organic Chemistry Computers and Organic Chemistry Challenges and Opportunities Where Did the Carbon Come From? C H A P T E R Structure Determines Properties 1.1 1.2 1.3 1.4 1.5 Atoms, Electrons, and Orbitals Ionic Bonds 12 Covalent Bonds, Lewis Structures, and the Octet Rule 14 Double Bonds and Triple Bonds 16 Polar Covalent Bonds and Electronegativity 16 Electrostatic Potential Maps 19 1.6 1.7 1.8 1.9 Apago PDF Enhancer Structural Formulas of Organic Molecules 19 Formal Charge 22 Resonance 24 The Shapes of Some Simple Molecules 29 Molecular Modeling 30 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 Molecular Dipole Moments 32 Curved Arrows and Chemical Reactions 33 Acids and Bases: The Arrhenius View 35 Acids and Bases: The Brønsted–Lowry View 36 What Happened to pKb? 40 How Structure Affects Acid Strength 41 Acid–Base Equilibria 45 Lewis Acids and Lewis Bases 48 Summary 49 Problems 52 Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures 57 C H A P T E R Alkanes and Cycloalkanes: Introduction to Hydrocarbons 2.1 2.2 2.3 2.4 2.5 58 Classes of Hydrocarbons 59 Electron Waves and Chemical Bonds 60 Bonding in H2: The Valence Bond Model 61 Bonding in H2: The Molecular Orbital Model 63 Introduction to Alkanes: Methane, Ethane, and Propane 64 Methane and the Biosphere 65 2.6 2.7 2.8 2.9 2.10 2.11 sp3 Hybridization and Bonding in Methane 66 Bonding in Ethane 68 Isomeric Alkanes: The Butanes 68 Higher n-Alkanes 68 The C5H12 Isomers 69 IUPAC Nomenclature of Unbranched Alkanes 71 What’s In a Name? Organic Nomenclature 72 vii car47872_fm_i-xxxii 11/15/06 18:32 Page viii viii CONFIRMING PAGES CONTENTS 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 Applying the IUPAC Rules: The Names of the C6H14 Isomers 73 Alkyl Groups 74 IUPAC Names of Highly Branched Alkanes 76 Cycloalkane Nomenclature 77 Sources of Alkanes and Cycloalkanes 78 Physical Properties of Alkanes and Cycloalkanes 80 Chemical Properties: Combustion of Alkanes 82 Oxidation–Reduction in Organic Chemistry 85 Thermochemistry 86 2.20 2.21 2.22 2.23 sp2 Hybridization and Bonding in Ethylene 89 sp Hybridization and Bonding in Acetylene 91 Which Theory of Chemical Bonding Is Best? 92 Summary 93 Problems 97 Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes 100 C H A P T E R Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 3.1 3.2 102 Conformational Analysis of Ethane 104 Conformational Analysis of Butane 107 Molecular Mechanics Applied to Alkanes and Cycloalkanes 109 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 Conformations of Higher Alkanes 110 The Shapes of Cycloalkanes: Planar or Nonplanar? 110 Small Rings: Cyclopropane and Cyclobutane 111 Cyclopentane 112 Conformations of Cyclohexane 112 Axial and Equatorial Bonds in Cyclohexane 113 Conformational Inversion (Ring Flipping) in Cyclohexane 115 Conformational Analysis of Monosubstituted Cyclohexanes 116 Disubstituted Cycloalkanes: cis–trans Stereoisomers 119 Enthalpy, Free Energy, and Equilibrium Constant 120 3.12 3.13 3.14 3.15 3.16 Apago PDF Enhancer Conformational Analysis of Disubstituted Cyclohexanes 121 Medium and Large Rings 125 Polycyclic Ring Systems 125 Heterocyclic Compounds 128 Summary 129 Problems 132 Descriptive Passage and Interpretive Problems 3: Cyclic Forms of Carbohydrates 137 C H A P T E R Alcohols and Alkyl Halides 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 Functional Groups 139 IUPAC Nomenclature of Alkyl Halides 141 IUPAC Nomenclature of Alcohols 142 Classes of Alcohols and Alkyl Halides 142 Bonding in Alcohols and Alkyl Halides 143 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces 144 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides 148 Mechanism of the Reaction of Alcohols with Hydrogen Halides 149 Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism 154 Structure, Bonding, and Stability of Carbocations 155 Effect of Alcohol Structure on Reaction Rate 158 Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The SN2 Mechanism 159 Other Methods for Converting Alcohols to Alkyl Halides 160 Halogenation of Alkanes 161 Chlorination of Methane 162 Structure and Stability of Free Radicals 162 Mechanism of Methane Chlorination 167 Halogenation of Higher Alkanes 168 From Bond Enthalpies to Heats of Reaction 169 4.19 Summary 173 Problems 176 Descriptive Passage and Interpretive Problems 4: More About Potential Energy Diagrams 180 138 car47872_fm_i-xxxii 11/15/06 18:32 Page ix CONFIRMING PAGES CONTENTS C H A P T E R Structure and Preparation of Alkenes: Elimination Reactions 5.1 5.2 182 Alkene Nomenclature 183 Structure and Bonding in Alkenes 185 Ethylene 186 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5.17 5.18 5.19 Isomerism in Alkenes 187 Naming Stereoisomeric Alkenes by the E–Z Notational System 188 Physical Properties of Alkenes 189 Relative Stabilities of Alkenes 191 Cycloalkenes 195 Preparation of Alkenes: Elimination Reactions 196 Dehydration of Alcohols 197 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule 198 Stereoselectivity in Alcohol Dehydration 199 The E1 and E2 Mechanisms of Alcohol Dehydration 200 Rearrangements in Alcohol Dehydration 202 Dehydrohalogenation of Alkyl Halides 205 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides 207 Anti Elimination in E2 Reactions: Stereoelectronic Effects 209 Isotope Effects and the E2 Mechanism 210 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides 211 Summary 213 Problems 217 Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions 222 C H A P T E R Addition Reactions of Alkenes 6.1 6.2 6.3 6.4 6.5 6.6 224 Hydrogenation of Alkenes 225 Heats of Hydrogenation 226 Stereochemistry of Alkene Hydrogenation 229 Electrophilic Addition of Hydrogen Halides to Alkenes 229 Regioselectivity of Hydrogen Halide Addition: Markovnikov’s Rule 231 Mechanistic Basis for Markovnikov’s Rule 233 Apago PDF Enhancer Rules, Laws, Theories, and the Scientific Method 235 6.7 6.8 6.9 6.10 6.11 6.12 6.13 6.14 6.15 6.16 6.17 6.18 6.19 6.20 6.21 6.22 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes 235 Free-Radical Addition of Hydrogen Bromide to Alkenes 236 Addition of Sulfuric Acid to Alkenes 239 Acid-Catalyzed Hydration of Alkenes 241 Thermodynamics of Addition–Elimination Equilibria 243 Hydroboration–Oxidation of Alkenes 246 Stereochemistry of Hydroboration–Oxidation 248 Mechanism of Hydroboration–Oxidation 248 Addition of Halogens to Alkenes 251 Stereochemistry of Halogen Addition 251 Mechanism of Halogen Addition to Alkenes: Halonium Ions 252 Conversion of Alkenes to Vicinal Halohydrins 254 Epoxidation of Alkenes 255 Ozonolysis of Alkenes 257 Introduction to Organic Chemical Synthesis 259 Reactions of Alkenes with Alkenes: Polymerization 260 Ethylene and Propene: The Most Important Industrial Organic Chemicals 265 6.23 Summary 266 Problems 269 Descriptive Passage and Interpretive Problems 6: Some Unusual Electrophilic Additions 274 C H A P T E R Stereochemistry 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 Molecular Chirality: Enantiomers 277 The Chirality Center 279 Symmetry in Achiral Structures 281 Optical Activity 282 Absolute and Relative Configuration 284 The Cahn–Ingold–Prelog R–S Notational System 285 Fischer Projections 288 Properties of Enantiomers 290 276 ix car47872_ndx_I1-I26 11/22/06 16:18 Page I-17 CONFIRMING PAGES INDEX preparation, 593–594, 610 reactions with alkenyl, alkyl, and aryl halides, 593–595, 612 Lithium hydride, electrostatic potential map, 19 Living polymer, 1214–1216, 1221–1222, 1224 Locant, numerical prefix in IUPAC nomenclature, 73 London dispersion forces See van der Waals forces Lovastatin, 1091 Low-density lipoprotein (LDL), 1091 Low-density polyethylene (LDPE), 1207, 1208 Lowry, Thomas M., 36 Luciferin, 456 Lycopene, 559, 1094 Lynen, Feodor, 1088 L-Lysine, 1113 electrophoresis, 1117–1118 isoelectric point, 1116 structure and electrostatic potential map, 1111 D-Lyxose, 1027 Macrolide antibiotics, 812 Macromolecule, 1201 Magnesium, reaction of with alkyl and aryl halides, 583–584, 610 Magnetic field induced, and nuclear shielding, 521–529 strength, 519–521 Magnetic resonance imaging (MRI), 540–541 MALDI See Matrix-assisted laser desorption ionization mass spectrometry Maleic anhydride, 405, 412, 839 (S)-Malic acid, 294, 304–305, 804 Malonic acid, 792 acidity, 802 decarboxylation, 815–817, 820 Malonic ester synthesis, 892–894, 899 Malonyl coenzyme A, 879, 1067, 1070–1073, 1086 Maltase, 1043 Maltose, 1043 Mandelic acid, 792 D-Mannose, 1027 conversion to D-fructose, 1051 epimerization, 1050 L-Mannose, 1050 Markovnikov, Vladimir, 232 Markovnikov’s rule, 232 in addition to alkenes, 231–235 to alkynes, 368–369, 371, 376 Mass spectrometer, 560 Mass spectrometry, 517, 559–563, 568–569 alcohols, 648 aldehydes and ketones, 738 amines, 946 carboxylic acid derivatives, 867 carboxylic acids, 818 ethers, 687 and gas chromatography, 564–565 peptides, 1136 phenols, 1010 thiols, 648 Matrix-assisted laser desorption ionization mass spectrometry (MALDI), 1136 Mauveine, Mayo, Frank R., 237 Maxam, Allan, 1187 Mechanisms, 4–5 acetal formation, 719, 1041 AdE3, 369 aldol addition, 758 Baeyer-Villiger oxidation, 735 biosynthesis amino acids by transamination, 1124–1126 cholesterol, 1087–1090 fatty acids, 1070–1073 terpenes, 1082–1087 Birch reduction, 435 borohydride reduction of aldehydes and ketones, 627 branching in polyethylene via intramolecular and intermolecular hydrogen transfer, 1212–1213, 1224 carboxypeptidase-catalyzed hydrolysis, 1151 cationic polymerization of 2-methylpropene, 1217 chlorination of methane, 167–168 chromic acid oxidation, 639–640 Claisen condensation, 883–884 Claisen rearrangement, 1006–1007 cyanohydrin formation, 716 cyclopropanation of alkenes, 597 DCCI-promoted peptide bond formation, 1142 decarboxylation of malonic acid, 815 dehydration of alcohols, 200–201, 216 dehydrohalogenation of alkyl halides, 207–213, 216, 217 Dieckmann cyclization, 886 Diels-Alder reaction, 403 dimerization of 2-methylpropene, 261–262 DNA replication, 1178–1180 Edman degradation, 1134–1135 electrophilic addition to alkenes, 229–236, 240 to 1,3-cyclopentadiene, 400–401 electrophilic aromatic substitution, 471–474, 504 bromination, of benzene, 478 Friedel-Crafts acylation, of benzene, 482 Friedel-Crafts alkylation, of benzene, 479 nitration, of benzene, 474–476 sulfonation, of benzene, 477 elimination E1, 200–201, 211–213, 217 E2, 200–201, 207–211, 215, 216, 339–342 formation of dibromocarbene from tribromomethane, 597 enamine formation, 728 enol conversion to ketone, 370 enolization, 764, 765 epoxidation, 257, 597 epoxide ring opening, 679, 680 esterification, 809–810 ether cleavage, 673 ether formation, 634 formation of a lithium dialkylcuprate, 594 free-radical addition of hydrogen bromide to alkenes, 236–239, 268 glycosidation, 1042 halogenation addition to alkenes, 252–254, 301–303 ␣, of aldehydes and ketones, 768–772, 773 allylic, of alkenes, 389–392 bromination, of benzene, 478 chlorination, of methane, 167–168 halohydrin formation, 254–255 hydration aldehydes and ketones, 713–715 alkenes, 241–243 alkynes, 370 hydride reduction of aldehydes and ketones, 627 hydroboration-oxidation, 248–250 hydrogenation of alkenes, 227, 603 hydrogen halide addition to alkenes, 229–236, 293 to alkynes, 369 hydrolysis acid anhydrides, 840–841 acyl chlorides, 838 allylic halide, 385–388 amides, 857–860 enzyme-catalyzed, of peptides, 1151 esters, 844–848 nitriles, 863–865 saponification, 848–851 imine formation, 723 nitration of benzene, 474–476 nucleophilic acyl substitution, 829–830, 834–836, 868–870 nucleophilic alkyl substitution SN1, 154–155, 175, 330–336, 346 table SN2, 159–160, 175, 323–328, 346 table nucleophilic aromatic substitution addition-elimination, 512–515, 971–973, 981 elimination-addition, 974–978, 982 olefin metathesis, 606 polymerization of ethylene coordination polymerization, 608–609 free-radical polymerization, 261–263 polymerization of styrene anionic, 1214, 1221–1222 free-radical, 445 proton transfer, 149–151 Apago PDF Enhancer I-17 reaction of alcohols with hydrogen halides, 149–155, 158–160, 344–345, 347 reaction of esters with amines, 853 reduction of alkynes by sodium in ammonia, 367 Wittig reaction, 730 Meisenheimer, Jacob, 985 Meisenheimer complex, 985 Melatonin, 877 Mendel, Gregor, 1163, 1173 Menthol, 177, 314–315, 1081 Menthyl chloride, 220 Mercaptans See Thiols 6-Mercaptopurine, 1165–1166 Mercurinium ion, 618 Mercury (II) oxide, 371 Merlic, Craig A., 551 Merrifield, R Bruce, 1143–1145, 1227 See also Solid-phase peptide synthesis Mesityl oxide, 775 Meso stereoisomer, 297–298 Messenger RNA See Ribonucleic acid, messenger Meta (m) directing groups, 488–489, 491 table, 493–496, 506, 507 disubstituted aromatic compounds, 428–429 Metal-ammonia reduction of alkynes, 367–368, 375 arenes See Birch reduction Metal-ion complexes of ethers, 667–668 Metallocenes, 600, 613 Metallocarbenes, 605 Metathesis See Olefin methathesis Methane, 64–67 acidity, 39, 41, 360, 585 bonding, 68, 93 chemical shifts (1H and 13C), 544 chlorination, 162, 167–169 clathrates, 65 conversion to acetylene, 356 electrostatic potential map, 30 natural occurrence, 65 physical properties, 64 pKa, 39, 41 structure, 15, 64 VSEPR and molecular geometry, 31 Methanesulfonic acid, 342 Methanethiol electrostatic potential map, 645 pKa, 39 Methanogens, 65 Methanoic acid See Formic acid Methanol, 142, 622 bond distances and bond angles, 143 chemical shifts (1H and 13C), 544 13 C NMR, 945 dehydrogenation, 709 dipole moment, 143 electrostatic potential map, 144, 645 esterification, 808–811 industrial preparation, 621 nitration, 637 pKa, 39, 42 properties, 622 car47872_ndx_I1-I26 11/22/06 16:18 Page I-18 I-18 CONFIRMING PAGES INDEX Methanide ion, 360 Methine group, 68 L-Methionine, 684–685 isoelectric point, 1115–1116 and protein biosynthesis, 1183–1184 structure and electrostatic potential map, 1110 Methionine enkephalin, 1128 Methyl alcohol, 142 See also Methanol Methyl acetate UV absorption, 867 Methyl acrylate, 1215 Methylalumoxane (MAO), 608 Methylamine basicity, 914 chemical shifts (1H and 13C), 544 13 C NMR, 945 electrostatic potential map, 909 reaction with benzaldehyde, 923 structure and bonding, 911–912 Methyl benzoate in mixed Claisen condensation, 887 preparation, 635, 808–811 Methyl bromide nucleophilic substitution in, 323–326 reaction with triphenylphosphine, 731 2-Methylbutane, 81 See also Isopentane 2-Methyl-2-butanol dehydration, 198 preparation, 241 3-Methyl-2-butanol preparation, 247 reaction with hydrogen chloride, 345 2-Methyl-2-butene acid catalyzed hydration, 241, 624 hydroboration-oxidation, 247 hydrogenation, 226 preparation, 198, 206, 211–212 reaction with hydrogen halides, 232, 239 3-Methyl-2-butenyl diphosphate See Dimethylallyl diphosphate 3-Methyl-2-butenyl diphosphate See Isopentenyl diphosphate 3-Methylbutyl acetate See Isoamyl acetate Methyl cation, 155–156, 158 Methyl chloride, 146 See also Chloromethane H chemical shift, 524 Methyl 2-cyanoacrylate, polymerization of, 1215–1216 Methylcyclohexane, conformations, 116-118 2-Methylcyclohexanol, dehydration, 198 1-Methylcyclopentene addition of hydrogen chloride, 232 hydroboration-oxidation, 248–250 Methylene chloride See also Dichloromethane H chemical shift, 524 Methylenecyclohexane, 728 Methylene group, 68, 185 Methylenetriphenylphosphorane, 728, 731 electrostatic potential map, 729 1-Methylethyl group, 75 See also Isopropyl group Methyl fluoride chemical shifts carbon, 544 proton, 524 electrostatic potential map, 581 Methyl ␣-D-glucopyranoside, 1041–1042 tetra-O methyl ether, 1052–1053 Methyl ␤-D-glucopyranoside, 1041–1042 Methyl group, 68 Methyl hexanoate, infrared spectrum, 556 Methyl iodide See also Iodomethane nucleophilic substitution, 329, 374, 763 reaction with amines, 931 Methyllithium, 585 electrostatic potential map, 581 Methylmagnesium halides, reaction with butanal, 611 cyclopentanone, 587 methyl 2-methylpropanoate, 593 1-phenyl-1-propanone, 591 Methyl methacrylate See Methyl 2-methylpropenoate Methyl 2-methylpropenoate hydrolysis, 847–848 Methyl migration in alcohol dehydration, 202–205 in cholesterol biosynthesis, 1088–1089 Methyl nitrate, 637 2-Methylpentane, 73 bromination, 172 3-Methylpentane, 73 2-Methylpropanal acidity and pKa, 39, 756 H NMR, 736–737 reaction with tertbutylamine, 740 2-Methylpropane, 73 See also Isobutane acidity, 585 bond dissociation enthalpies, 166, 436 chemical shifts 13 C, 544 H, 525, 544 chlorination, 171 Methyl propanoate H NMR spectrum, 866–867 in mixed Claisen condensation, 887 2-Methylpropanoic acid, alkylation via dianion, 904 2-Methyl-2-propanol, 148 See also tert-Butyl alcohol acid-catalyzed dehydration, 197 2-Methylpropene See also Isobutene; Isobutylene addition of hydrogen bromide to, 232 addition of methanol to, 669–670 bromohydrin formation, 254 dimerization, 261–262 dipole moment, 189 heat of combustion, 192 hydration, 241–242, 245 polymerization, 1216–1217 preparation, 197 1-Methylpropyl group, 75 See also sec-Butyl group 2-Methylpropyl group, 75 See also Isobutyl group N- Methylpyrrolidone, 861 Methyl radical intermediate in chlorination of methane, 167–168 structure and stability, 163 Methyl red, 942 Methyl salicylate, 842, 994 Methyltrioctylammonium chloride, 921 Methyl vinyl ketone reaction with diethyl malonate, 894–895 in Robinson annulation, 778, 782 Mevalonic acid, 812, 1082, 1086, 1097 Mevalonolactone, 812, 824 Micelle, 798–799, 849 Michael, Arthur, 778 Michael reaction, 778, 894–895, 899 See also Conjugate addition; ␣, ␤-Unsaturated carbonyl compounds Microscopic reversibility, 243 Microwaves, 518, 573 Miescher, Johann, 1173 Migratory aptitude, 734 Mitscherlich, Eilhardt, 422 MM3, 109 Models See Molecular models Molar absorptivity, 557 Molecular dipole moments See Dipole moment Molecular formula, 20, 50, 55, 563–566 Molecular ion, 560 Molecular models and modeling, 30, 109 Molecular orbitals allyl cation, 416 [10]annulene, 450 and anomeric effect, 1037 benzene, 427, 448–449 and bimolecular nucleophilic substitution, 325, 442 chapter 10, chapter 11 bonding and antibonding, 63–64 1,3-butadiene, 408 cyclobutadiene, 448–449 cycloheptatrienyl cation, 452–453 cis, trans-1,3-cyclooctadiene, 558 cyclooctatetraene, 448–449 cyclopentadienide anion, 454 ethylene, 407 frontier, 407 highest occupied (HOMO), 407, 558 hydrogen, 63–64 lowest unoccupied (LUMO), 407, 558 ␲ and ␲*, 407–408, 558–559 ␴ and ␴*, 63–64 Apago PDF Enhancer Moncado, S., 1153 Monensin, 669 Monomer, 261, 1202 Monosaccharide, 1023 See also Carbohydrates Monoterpene, 1080 Morphine, 919 Morpholine, 740 MRI See Magnetic resonance imaging Mullis, Kary B., 1188 Multiplets See also Spin-spin splitting in 13C NMR spectra, 546, 568 in 1H NMR spectra, 532–539, 567 Murad, F., 1153 Mutarotation, 1035–1036, 1055 Myoglobin, 1153 Myosin, 1147 Myrcene, 1079 Myristic acid, 1069 ␯ (symbol for frequency), 518 n (prefix), 68, 71 n ϩ splitting rule, 532–533, 538 NAD, NADϩ, NADH, NADPH See Nicotinamide adenine dinucleotide Nanotubes, 433 Naphthalene, 421, 430 electrophilic aromatic substitution in, 502 2-Naphthol, nitrosation, 999 Naproxen, 604, 1078 Natta, Giulio, 263, 607–609, 613 Natural gas, 64, 65 Neomenthol, 177 Neomenthyl chloride, 220 Neopentane, 69 See also 2, 2-Dimethylpropane Neopentyl group, 75 See also 2,2-Dimethylpropyl group Neopentyl halides, nucleophilic substitution in, 328 Neoprene, 5, 404 Neryl diphosphate, 1084 Neurotransmitters, 920, 1122–1123 Newman, Melvin S., 104 Newman projections, 104–105, 108, 113 Nickel carbonyl, 599 Nickel, hydrogenation catalyst, 225–226, 425 Nicotinamide adenine dinucleotide coenzyme in epoxidation of alkenes, 682 fatty acid biosynthesis, 1072–1073 formation of acetyl coenzyme A, 1066 oxidation of alcohols, 640–643 reduction of pyruvic acid, 732–733 structure, 642 Nicotine, 55, 292, 919 NIH shift, 697–699 car47872_ndx_I1-I26 11/22/06 16:18 Page I-19 CONFIRMING PAGES INDEX Ninhydrin, 1120 Nirenberg, Marshall, 1195 Nitration acetanilide, 934 acetophenone, 501 benzaldehyde, 493–494, 923 benzene, 472, 474–476, 501 p-tert-butyltoluene, 499 chlorobenzene, 496 p-cresol, 999 fluorobenzene, 505 p-isopropylacetanilide, 933 p-methylbenzoic acid, 499 phenol, 490 toluene, 484–488, 501 (trifluoromethyl)benzene, 485, 488–489 m-xylene, 499 Nitric acid formal charges in, 23 nitration of arenes by, 474–476 oxidation carbohydrates, 1048 p-xylene, 805 pKa, 38, 44 reaction with alcohols, 637–638, 650 resonance in, 27 Nitric oxide See Nitrogen monoxide Nitriles See also Cyanohydrins ␣-amino, as intermediates in Strecker synthesis, 1118 hydrolysis, 806–807, 819, 863–865 infrared absorption, 866 nomenclature, 831 preparation of from alkyl halides, 321, 340, 807, 863 from aryl diazonium salts, 940, 952 by dehydration of amides, 862–863 reaction with Grignard reagents, 864–866 reduction, 926, 948 m-Nitroaniline, diazotization, 940, 950, 951 o-Nitroaniline, diazotization, 952 p-Nitroaniline basicity, 916, 917 bromination, 950 preparation, 934 Nitrobenzene electrophilic aromatic substitution in, 495, 967 preparation, 472, 474-476, 501 Nitrogen monoxide, 1153, 1169 Nitrogen rule, 563 Nitro group electron-withdrawing effect, 495, 973, 996 reduction, 926–927, 949 Nitronium cation, 474–476 m-Nitrophenol acidity, 995, 996 preparation, 951, 998 o-Nitrophenol acidity, 995 intramolecular hydrogen bonding, 993 reaction with acetic anhydride, 1001–1002, 1011 butyl bromide, 1012 p-Nitrophenol acidity, 995 esters, in peptide bond formation, 1141, 1143 Nitrosamines, 935–936 Nitrosation amines, 935–937, 950–952 phenols, 999 N-Nitrosodimethylamine, 935-936 N-Nitrosonornicotine, 936 N-Nitrosopyrrolidine, 936 Nitrous acid, 935–942 See also Nitrosation Nobel, Alfred, 637 Noble gas electron configuration, 12 Nodal properties p orbitals, 11 ␲ orbitals and pericyclic reactions, 407–410 Nomenclature common names alcohols, 142 alkanes, 71 alkenes, 183–185 alkenyl groups, 184 alkyl groups, 74–75, 96 carboxylic acids, 820 functional class, 141–142, 173 historical development, 72 IUPAC acid anhydrides, 830 acyl halides, 830 alcohols, 142, 173 aldehydes, 701–703, 738–739 alkadienes, 395 alkanes, 71–78, 95–96 table alkenes, 183–185, 213 alkyl groups, 74–75, 96 table alkyl halides, 141–142, 173 alkynes, 357 amides, 830–831 amines, 909–911, 947 benzene derivatives, 428–430 bridged bicyclic ring systems, 127–128 carboxylic acids, 791–793 cycloalkanes, 77–78, 96 table diols, 630–631 epoxides, 255, 664 esters, 830–831 ethers, 663–664 ␤-keto esters, 883 ketones, 703–704, 738–739 lactones, 811–813 nitriles, 831 organometallic compounds, 580, 610 polymers, 1202, 1223 sulfides, 664 thiols, 644 stereochemical notation cis and trans, 119 D-L, 288, 1025–1028, 1054 erythro and threo, 296 E-Z, 188–190, 214 R-S, 285–288 substitutive, 141–142, 173 Nomex, 1218 Nonsteroidal antiinflammatory drugs, 1078 Norepinephrine, 684–685, 1123 Norethindrone, 1093 Noyori, Ryoji, 604, 632 NSAIDs See Nonsteroidal antiinflammatory drugs Nuclear magnetic resonance spectra carbon 1-chloropentane, 542 m-cresol, 545 3-heptanone, 738 methanol, 945 methylamine, 945 1-phenyl-1-pentanone, 546–547 proton benzyl alcohol, 539 2-butanone, 737 chloroform, 523 1-chloropentane, 542 p-cresol, 1009, 1010 1,1-dichloroethane, 533 dipropyl ether, 686–687 ethyl acetate, 866–867 ethyl bromide, 535 isopropyl chloride, 536 methoxyacetonitrile, 530 4-methylbenzyl alcohol, 945, 946 4-methylbenzylamine, 945, 946 2-methylpropanal, 737 methyl propanoate, 866–867 m-nitrostyrene, 538–539 4-phenylbutanoic acid, 817 2-phenylethanol, 648 2,3,4-trichloroanisole, 537 Nuclear magnetic resonance spectroscopy, 517 carbon, 541–550, 567–568 alcohols, 647 aldehydes and ketones, 736–738 amines, 945 in biosynthetic studies, 1087 carboxylic acid derivatives, 866–867 carboxylic acids, 817–818 chemical shifts, 543–545, 575–577 ethers, 686–687 thiols, 647 and magnetic field strength, 519–521 proton, 519–541, 566–567 alcohols, 539–540, 567, 647–648, 652 aldehydes and ketones, 736–737 amines, 945, 946 carboxylic acid derivatives, 866–867 carboxylic acids, 817–818 chemical shift, 521–525, 566 and conformations, 540–541, 567 ethers and epoxides, 686–687, 691 interpretation, 530–532 nuclear shielding, 521–524 phenols, 1009–1010 Apago PDF Enhancer I-19 spin-spin splitting, 532–539, 567–567 thiols, 647 two dimensional (2D NMR), 547–550, 568 Nuclear spin states, 519–520 Nucleic acids, 1173–1174 See also Deoxyribonucleic acid; Ribonucleic acid Nucleophiles, 49, 153–155, 159–160, 319–322 relative reactivity, 328–330 solvation and reactivity, 330, 337–338 Nucleophilic acyl substitution, 828–879 and acetyl coenzyme A, 877, 1066 acid anhydrides, 839–841, 869 acyl chlorides, 836–839, 868 amides, 857–860, 870 esters, 844–852, 869 general mechanism, 829–830, 834–836, 868 thioesters, 876–879, 1066 Nucleophilic addition to aldehydes and ketones, 710–733, 739–740 to ␣,␤-unsaturated aldehydes and ketones, 775–778, 782, 894–895, 899 Nucleophilic alkyl substitution See also SN1, SN2 alcohols,149–160 alkyl halides, 319–342, 731, 806–807, 863, 889–894 alkyl p-toluenesulfonates, 342–344, 347 allylic halides, 385–389, 410, 645, 891 benzylic halides, 440–442 crown ether catalysis, 667–668 enzyme-catalyzed, 331 epoxides, 676–681 ␣-halo carboxylic acids, 813–814 phase-transfer catalysis, 921–922 Nucleophilic aromatic substitution, 512–515, 968–978, 981–982, 997, 1004–1005 Nucleosides, 1166–1168 Nucleosomes, 1177–1178 Nucleotides, 1167–1170, 1172–1173, 1192 See also Deoxyribonucleic acid; Ribonucleic acid Nylon, 5, 1218 Octadecanoic acid, 792 Octane, relative stability of isomers, 84–85 Octane number of gasoline, 79 2-Octanol, 345, 587 Octet rule, 14, 49–50 Off-resonance decoupling, 546 Oil of wintergreen See Methyl salicylate Oils See Fats Olah, George A., 82 car47872_ndx_I1-I26 11/22/06 16:18 Page I-20 I-20 CONFIRMING PAGES INDEX Olefin, 186 See also Alkenes Olefin methathesis, 605–608, 1210 ␣-Olefins See Linear ␣-olefins Oleic acid, 188, 792, 804, 1069 Oligomer, 1205 Oligonucleotide(s), 1173 synthesis of, 1195–1199 Oligosaccharide, 1024 Opsin, 726 Optical activity, 282–284, 307 and chemical reactions, 292–295, 302, 308, 324–325, 334–335, 343–344, 345, 774 Optical purity, 283 Optical resolution See Resolution Orbital hybridization model for bonding, 66–67, 92–93 sp acetylene and alkynes, 91–92, 97, 357–359, 373 allenes, 398–399 sp2 alkadienes, 396–398 aniline, 912–913 benzene, 426 carbocations, 152–153, 155–158, 175 carbenes, 598 ethylene and alkenes, 89–90, 97, 185–187, 214 formaldehyde, 704–705 free radicals, 163 sp3 alkyl halides, 143 ethane, 68, 94 methane, 66–67, 93 methanol, 143 methylamine, 912 Orbital symmetry, and Diels-Alder reaction, 408–410 Orbitals atomic, 10–12, 49 hybrid orbitals, 66–67, 89–90, 91–92, 92–93 molecular See Molecular orbitals Organic chemistry definition and historical background, 2–6 Organic Structure Elucidation, 551 Organoboranes, 246–250 Organocopper compounds See Lithium diorganocuprates Organolithium reagents basicity, 584–586, 611 preparation, 581–582, 610, 1018–1021 reaction with aldehydes and ketones, 586–588, 611, 612, 624 epoxides, 629–630 nitriles, 864–866 Organomagnesium compounds See Grignard reagents Organometallic compounds, 578–619 See also Grignard reagents; Lithium diorganocuprates; Organolithium reagents; Organozinc compounds Organozinc compounds, 595–596, 610 Ortho (o), disubstituted organic compounds, 428–429 Ortho-para directing groups, 484–488, 490–493, 491 table, 496–498 Osmium tetraoxide, 631, 649 Oxalic acid, 55, 802 Oxane, 634, 664 Oxaphosphetane, 729–730 Oxazole, 456 Oxidation See also Dihydroxylation; Epoxidation; Ozonolysis alcohols, 638–644, 651, 707–710, 805 aldehydes, 733–734, 741, 805 alkylbenzenes, 438–440, 461, 805 biological, 281, 431, 439, 640–643 carbohydrates, 1047–1049, 1056 ketones, 734–736, 742 phenols, 1007–1009, 1012 vicinal diols, 643–644, 651 Oxidation-reduction in organic chemistry, 85–88, 94 Oximes, 724 Oxirane, 664 See also Ethylene oxide Oxolane, 664 See also Tetrahydrofuran Oxonium ion, 37 See also Hydronium ion Oxo process See Hydroformylation Oxygen biological storage and transport, 1152–1153 isotopic labels, 808, 847–848, 849–850 Oxymercuration, 617–619 Oxytocin, 1128–1130 Ozone, bonding in, 24–25, 257 Ozonide, 257 Ozonolysis alkenes, 257–259, 268, 708 alkynes, 372–373 1,3- and 1,4-Pentadiene, relative stabilities, 395–396 2,3-Pentadiene, enantiomers, 399 Pentane, 71, 81 conformation, 110 n-Pentane, 68 See also Pentane 2,4-Pentanedione ␣-alkylation, 763 enol content, 766–767 pKa, 39, 755 Pentanenitrile hydrogenation, 926 preparation, 921–922 1-Pentanol esterification, 650 reaction with thionyl chloride, 174 3-Pentanol, dehydration, 199 3-Pentanone cyanohydrin, 739 mass spectrum, 738 Pentyl azide, 922 Peptide(s), 1127–1194 See also Proteins amino acid analysis, 1130–1131 classification, 1107 end-group analysis, 1132–1135 hydrolysis, 1131 mapping, 1136 structure, 1107, 1127–1130 synthesis, 1137–1145 Peptide bond, 1107 geometry, 1127–1128 preparation, 1141–1145 Pericyclic reactions, 403, 1007 Periodic acid cleavage carbohydrates, 1053–1054, 1057 vicinal diols, 643–644, 651 Periodic tables, 580, inside back cover anti- and syn-Periplanar, 210 Perkin, William Henry, Peroxide effect, 237 Peroxides initiators of free-radical reactions, 237–238, 438, 1209, 1210 intermediates in icosanoid biosynthesis, 1076–1079 by oxidation of ethers, 672 Peroxyacetic acid, 256–256, 267, 674–675, 690 Peroxybenzoic acid, 734–736 Petrochemicals, 5, 186 Petroleum, 78–79 PGE1, PGE2, PGF1␣, PGG2, and PGH2 See Icosanoids Phase-transfer catalysis, 921–922, 947 ␣-Phellandrene, 1081 Phenacetin, 1015 Phenanthrene, 430 Phenol(s), 990–1021 acidity and pKa, 39, 47, 994–996, 1011 13 C chemical shifts, 1009 electrostatic potential maps, 991, 993 formation, in Claisen rearrangement, 1006–1007, 1012 hydrogen bonding, 993–994 naturally occurring, 998–999 nomenclature, 428, 991–992 Apago PDF Enhancer Palladium acetate, catalyst in Heck reaction, 986–989 hydrogenation catalyst, 225–226 Lindlar, 365–366, 375 Palmitic acid, 1069 Papain, 1131 Para (p), disubstituted organic compounds, 428–429 Paraffin hydrocarbon, 82 See also Alkanes Partial rate factors, 486–487, 489, 497, 511 Pasteur, Louis, 303 Pauli exclusion principle, 10 Pauling, Linus, 4, 17 electronegativity scale, 18 and orbital hybridization, 66–67 and peptide structure, 1145–1146 PCBs See Polychlorinated biphenyls PCC See Pyridinium chlorochromate PCR See Polymerase chain reaction PDC See Pyridinium dichromate Pedersen, Charles J., 667 Penicillin, 861–862 physical properties, 993–994 preparation from aryl diazonium salts, 938–939, 951, 998, 1011 benzenesulfonic acid, 997 chlorobenzene, 967, 997 cumene, 997 reactions O-alkylation, 1004, 1012 azo coupling, 1000 bromination, 999, 1000 carboxylation, 1002–1003, 1011–1012 electrophilic aromatic substitution, 490, 999–1000 esterification, 1001, 1002, 1011–1012 Friedel-Crafts acylation, 1000, 1001 Friedel-Crafts alkylation, 999 Kolbe-Schmitt reaction, 1002–1003, 1011–1012 nitration, 490, 999 nitrosation, 999 oxidation, 1007–1009, 1012 sulfonation, 999 resonance in, 993 spectroscopic analysis, 1009–1010 structure and bonding, 992–993 Phenylacetic acid ␣-halogenation, 813 preparation, 807 L-Phenylalanine, 1109 N-benzyloxycarbonyl derivative, 1138–1139 conversion to L-tyrosine, 697–699 isoelectric point, 1115–1116 in PKU disease, 1126 structure and electrostatic potential map, 1110 Phenylalanylglycine, synthesis of, 1137–1141, 1143 Phenyl benzoate, Fries rearrangement, 1002 2-Phenyl-2-butanol, 591, 637 2-Phenylethanol, 623, 636 H NMR spectrum, 648 1-Phenylethylamine, resolution, 304–305 Phenyl group, 430 Phenylhydrazine, reaction, with aldehydes and ketones, 724 Phenyl isothiocyanate, 1134–1135 Phenylketonuria (PKU disease), 1126 Phenyllithium, 582 Phenylmagnesium bromide carboxylation, 807 preparation, 583, 968 reaction with 2-butanone, 591 1,2-epoxypropane, 679 ethyl benzoate, 611 methanol, 584 2-Phenylpropene, dihydroxylation of, 649 Phenylpyruvic acid, 1125–1126 Phenylthiohydantoin, 1134–1135 car47872_ndx_I1-I26 11/22/06 16:18 Page I-21 CONFIRMING PAGES INDEX Pheromone aggregating cockroach, 69, 71 European elm bark beetle, 655 alarm ant, 707 bees, 707 sex attractant boll weevil, 217 boll worm moth, 874 codling moth, 218 female gypsy moth, 256 female house fly, 188, 379 female Japanese beetle, 842 female tiger moth, 99 female winter moth, 746 greater wax moth, 707 honeybee, 218 male Oriental fruit moth, 842 Mediterranean fruit fly, 217 Western pine beetle, 744 Phosphatidic acid, 1073–1074 Phosphatidylcholine, 1074–1075 Phosphines as nucleophiles, 731 optically active, 307, 604 Phosphoglucose isomerase, 1051 Phosphoglycerides, 1074 Phospholipid bilayer, 1074–1075 Phospholipids, 1073–1075 Phosphoric acid catalyst for alcohol dehydration, 197, 198, 202 esters, 638, 1167–1170 Phosphorous acid, esters, 638 Phosphorus pentoxide, 863 Phosphorus tribromide, reaction with alcohols, 160–161, 174 Phosphorus ylides See Ylides Phosphorylation, 1169, 1171 Photochemical initiation addition of hydrogen bromide to alkenes, 239, 287 free-radical reactions, 169, 239, 268 Photon, 518 Photosynthesis, 1028 Phthalhydrazide, 925 Phthalic acid See 1, 2-Benzenedicarboxylic acid Phthalic anhydride, 839, 840 Phthalimide, potassium salt of in Gabriel synthesis, 924–925, 948 Physical properties See entry under specific compound class Physostigmine, 953 Phytane, 74 Picrocrocin, 1095 Pinacol rearrangement, 658–661 ␣-Pinene, 1085 hydroboration-oxidation, 248 hydrogenation, 229–230 ␤-Pinene, 1085 Piperidine, 129, 837, 917, 929 pKa, 36 See also Acidity pKb, 40 See also Basicity PKU disease See Phenylketonuria Planck, Max, 518 Planck’s constant, 518 Plane of symmetry, 281–282 in meso- 2,3-butanediol, 297–298 cis-1,2-dibromocyclopropane, 298 Plane-polarized light, 282–284 Platinum, hydrogenation catalyst, 225–226, 266,425, 623 Pleated ␤-sheet, 1146 PLP See Pyridoxal phosphate Poison ivy, allergens, 1016 Polar covalent bonds See Bonds, polar covalent Polarimeter, 282–284 Polarizability,146 Polar solvents, 320, 337 Polyacrylonitrile, 1202 Polyamides, 1204, 1217–1218, 1224 Polyamines, 920 Polycarbonates, 1219–1220, 1225 Polychlorinated biphenyls, 986 Polycyclic hydrocarbons aliphatic, 125–128 aromatic, 430–431, 502 Polyesters, 1218–1220, 1225 Polyethers, 667–668 Polyethylene, 261–263, 264, 265, 607–609, 613 high-density (HDPE), 1207, 1208 low-density (LDPE), 1207, 1208 Poly(ethylene glycol), 1202 Poly(ethylene oxide), 1202 Poly(ethylene terephthalate), 1208, 1218–1219 Poly(glycolic acid), 1219 Polyisobutylene, 1216–1217 Polyisoprene, 264, 404 Polyketides, 1101–1105 Poly(lactic acid), 1219 Polymer(s), 260–264, 268, 1200–1229 See also Polymerization classification, 1203–1209, 1223 copolymers, 1221–1223, 1225 crystallinity, 1206–1207 definition, 1201 dienes, 404, 1210 glass transition and melting temperature, 1207 living, 1214–1216, 1224 nomenclature, 1202, 1223 polyamides, 1217–1218, 1224–1225 polycarbonates, 1219–1220, 1225 polyesters, 1218–1220, 1225 polyurethanes, 1220–1221, 1225 recycling, 1208 repeating unit in, 1202 stereoregular, 305–306, 309, 607–609, 613 vinyl, 264 Polymerase chain reaction (PCR), 1188–1191 Polymerization anionic, 1214–1216,1224 cationic, 261–262, 1216–1217, 1224 condensation, 1225 coordination, 263, 305–306, 404, 607–609, 613 free-radical, 261–263, 1211–1213, 1223–1224 Polymer-supported chemical reactions, 1227–1229 See also Combinatorial synthesis; Oligonucelotide synthesis; Solid-phase synthesis Poly(methyl methacrylate), 1207 Polynucleotides, 1172 See also Nucleic acids Polyolefin, 1203 Polypeptide, 1107 See also Peptides; Proteins Polypropylene, 264, 265, 1208 stereoregular, 305–306, 609, 1207 Polysaccharide, 1024, 1044, 1045–1047, 1055 Polystyrene, 264, 265, 445, 1210 See also Solid-phase synthesis by anionic polymerization, 1214 recycling, 1208 Polytetrafluoroethylene, 1202 See also Teflon Polyurethanes, 265, 1220–1221, 1225 Poly(vinyl alcohol), 875 Poly(vinyl chloride), 184, 264, 265, 1202 recycling, 1208 Porphyrin, 1152 Potassium tert-butoxide base in elimination reactions, 205, 363, 597, 598 Potassium dichromate See also Chromic acid oxidation of alcohols, 638, 639 oxidation of aldehydes, 733–734, 805 Potassium permanganate oxidation of alcohols, 638, 805 oxidation of aldehydes, 805 oxidation of alkylbenzenes, 438–439, 461, 805 Potential energy, 84 diagrams, 150–155 addition of hydrogen bromide to 1,3–butadiene, 402 bimolecular elimination (E2), 209 bimolecular nucleophilic substitution (SN2), 324 branched versus unbranched alkanes, 85 carbocation formation, 152 carbocation rearrangement, 203 conformations of 1,3-butadiene, 397–398 conformations of cyclohexane, 116 conformations of butane, 108 conformations of ethane, 106 electrophilic aromatic substitution, 474, 487, 489 hydration of aldehydes and ketones, 714 and Markovnikov’s rule, 233 proton transfer, 151 reaction of tert-butyl alcohol with hydrogen chloride, 155 unimolecular nucleophilic substitution (SN1), 155, 332 and heat of combustion, 84–85, 119, 192 and heat of hydrogenation, 227 Apago PDF Enhancer I-21 Pott, Sir Percivall, 431 Preferred IUPAC name (PIN), 72 Prelog, Vladimir, 189 Prenols and prenyl groups, 1084 Priestley, Joseph, 404 Principal quantum number, 10 Primary carbon, 74 Pristane, 98 Prochirality, 292–294, 316–317 Progesterone, 1093 L-Proline, 1108, 1109 isoelectric point, 1115–1116 structure and electrostatic potential map, 1110 Prontosil, 943 1,3-Propadiene See Allene Propagation step, 167–168, 176, 238, 437 Propanal, 705 Propane attractive forces in, 144 bond dissociation enthalpies in, 165 chemical shifts 13 C, 544 H, 524 conformational analysis, 109 dehydrogenation, 186, 196 dipole moment, 144, 913 in natural gas, 64 2-Propanol, 142 See also Isopropyl alcohol Propanolol, 693–694 Propene, 183 addition of sulfuric acid to, 240 allylic chlorination, 390–391 bond dissociation enthalpy, 389, 436 bond distances in, 186, 385, 396 dipole moment, 191 epoxidation, 292–293 heat of hydrogenation, 228, 395–396 hydration rate, 242 as industrial chemical, 186, 265, 372 polymerization, 263, 305–306, 609 structure, 186 Propylene, 183 See also Propene Propylene glycol, 631 Propylene oxide, 265 See also 1, 2-Epoxypropane Propyl group, 75 Propyl radical, 165 Prostacyclins, 1077 Prostaglandins, 141, 791, 1076–1079 Prosthetic group, 1152 Protease inhibitors, 1185 Protecting groups acetals as, 721–722 for amino acids, 1138–1141 for arylamines, 933–934 for DNA bases, 1195 Proteins amino acid analysis, 1130–1131 biosynthesis, 1227 hydrolysis, 1131 structure primary, 1130–1136, 1155 quaternary, 1153–1154, 1156 car47872_ndx_I1-I26 11/22/06 16:18 Page I-22 I-22 CONFIRMING PAGES INDEX Proteins—Cont secondary, 1145–1148, 1156 tertiary, 1148–1152, 1156 synthesis, 1137–1145 Protic solvents, 337 Proton magnetic resonance spectra See Nuclear magnetic resonance spectra Proton magnetic resonance spectroscopy See Nuclear magnetic resonance spectroscopy Proton-transfer reactions See Acid-base reactions Pseudoionone, 1101 Purcell, Edward, 519 Purine(s), 456, 1163–1166, 1191 hydrogen bonding in, 1174 nucleosides of, 1166–1168, 1191 nucleotides, 1167–1170, 1172 polynucleotides, 1172, 1192 Putrescine, 920 Pyramidal inversion, 306–307 Pyranose forms of carbohydrates, 1029, 1032–1035, 1055 Pyrethrins, 1098 Pyridine, 455 acylation catalyst, 636–636, 837 basicity, 40, 917 bonding in, 457–458 electrophilic aromatic substitution in, 502–504 electrostatic potential map, 457 pKa of conjugate acid, 38, 40 Pyridinium chlorochromate (PCC), 638, 651, 708 Pyridinium dichromate (PDC), 638, 651, 707–708 Pyridoxal 5Ј-phosphate, 725 coenzyme in amino acid reactions decarboxylation, 1121–1122 racemization, 1123 transamination, 1122–1126 Pyridoxamine 5Ј-phosphate, 1125–1126 Pyrimidine(s), 1163–1166, 1191 hydrogen bonding in, 1174 nucleosides of 1166–1168, 1191 nucleotides, 1167–1170, 1192 polynucleotides, 1172, 1192 Pyrocatechol, 992, 1006 (S)-Pyroglutamic acid, 1159–1162 Pyrrole, 455 bonding in, 457–458 electrophilic aromatic substitution in, 502–504 electrostatic potential map, 457 Pyrrolidine, 129 acylation, 923 enamine, 728, 930 Pyrrolysine, 1108 Pyruvic acid acetyl coenzyme A from, 1066 biological reduction, 732–733 biosynthesis, 643, 1065 conversion to L-alanine, 1124–1126 Quantized energy states, 519 Quantum, 518 Quantum numbers, 10 Quaternary ammonium salts, 911 hydroxides, Hofmann elimination, 931–933, 950 as phase-transfer catalysts, 921–922, 947 preparation, 924, 931 Quaternary carbon, 75 Quaternary structure proteins, 1153–1154 Quinine, 919 Quinoline, 455 Quinones, 1007–1009, 1012 Racemic mixture, 283, 292, 307 resolution, 303–305, 309 Racemization and chair-chair interconversion, 300 via enol, 774 in SN1 reactions, 334–335 Radio waves, 518 Random coil, 1147–1148 Rare gas See Noble gas Rate constant, 158 Rate-determining step, 154 Rate of reaction See also Substituent effects and carbocation stability, 155–159, 331–333 effect of catalyst, 226 effect of temperature, 107, 158 Rearrangement alcohol dehydration, 202–205, 216 allylic, 386–388, 401, 410 Baeyer-Villiger oxidation, 734–736, 843 Claisen rearrangement, 1006–1007, 1012 electrophilic addition to alkenes, 235–236 Friedel-Crafts alkylation, 480, 506 Fries rearrangement, 1002 NIH shift, 697–699 pinacol rearrangement, 658–661 reactions of alcohols with hydrogen halides, 345, 347 SN1 reactions, 335–336 Recycling codes, 1208 Red Dye #40, 943–944 Reduction, 85–88 See also Hydrogenation; Hydrogenolysis aldehydes and ketones, 622–623, 625–628, 630, 649, 710 amides, 927–928, 949 aryl diazonium salts, 940–942, 952 azides, 926, 948 Birch reduction, 433–436, 460 carbohydrates, 1047, 1056 carbonyl groups, agents for, 649 table carboxylic acids, 628–629, 649, 707, 808 Clemmensen, 483–484, 501, 710 esters, 629, 649 imines, 928–929 metal-ammonia reduction of alkynes, 367–368 nitriles, 926, 948 nitro groups, 926–927, 949 Wolff-Kishner, 484, 710 Reductive amination, 928–929, 949 Refining of petroleum, 78–79 Reforming, in petroleum refining, 79 Regioselectivity addition of bromine to 1, 3-butadiene, 403 addition of hydrogen halides to 1,3-butadiene, 400–402 allylic halogenation, 389–392, 411 dehydration of alcohols, 198–199, 215, 399, 412, 443 dehydrohalogenation of alkyl halides, 206–207, 215, 399, 443 electrophilic addition to alkenes, 233–235, 240, 241–243, 246–250, 254–255, 266–267 electrophilic aromatic substitution, 484–504 enolate formation, 787–789 epoxide ring opening, 676–681, 719–720 Hofmann elimination, 931–933, 950 hydration of alkynes, 370–371, 376 hydroboration-oxidation, 246–250, 267 and Markovnikov’s rule, 233–235, 266, 267 nucleophilic aromatic substitution, 512–515 and regiospecificity, 303 and Zaitsev’s rule, 198–200, 215 Relative configuration, 284 Repeating unit of polymer, 1202 Resolution, 303–305, 309 kinetic, 305, 331 Resonance, 4, 24–29, 51 aldehydes and ketones, 494, 705 allyl anion, 393 allylic carbocations, 384–385 allyl radical, 389 amides, 833–834 aniline, 913 and anomeric effect, 1037 benzene, 424 benzylic carbocations, 441 benzylic radicals, 436 carboxylic acid derivatives, 832–834 cyclohexadienyl anions, 971–973 cyclohexadienyl cations, 473, 485–489, 492, 493, 494, 497, 502 enolate ions, 754, 755, 882 formic acid, 793 ␤-keto ester enolates, 883 p-nitroaniline, 917 ozone, 24–25, 257 phenol, 993 phenoxide anions, 994, 996, 1003 protonated benzoic acid, 810–811 protonated ketone, 713 purines and pyrimidines, 1164–1165 rules for, 27–28 table thioesters, 877 ␣,␤-unsaturated carbonyl compounds, 775 Apago PDF Enhancer Resonance energy [18]annulene, 451 anthracene and phenanthrene, 430 benzene, 425–426, 459 cycloctatetraene, 447 conjugated dienes, 395–396 1,3,5-hexatriene, 426 naphthalene, 430 Resorcinol, 992 acylation, 1001 Restriction enzymes, 1186 Retention of configuration, 249–250 in acylation of alcohols, 637 in Baeyer-Villiger oxidation, 734–736 in ester hydrolysis, 850 Retinal, 726 Retinol, 726 Retro-aldol cleavage, 1051–1052 Retrosynthetic analysis acetoacetic ester synthesis, 891 Grignard synthesis of alcohols, 589–592, 611 malonic ester synthesis, 893 Simmons-Smith reaction, 596 Wittig reaction, 730–731 Reverse transcriptase, 1185 L-Rhamnonolactone, 1056 L-Rhamnose, 1056 Rhodium, hydrogenation catalyst, 225–226 Rhodopsin, 726 Ribavarin, 1167 9-␤-D-Ribofuranosyladenine See Adenosine 1-␤-D-Ribofuranosyluracil See Uridine Ribonuclease, 1144, 1147–1148 Ribonucleic acid (RNA), 1172, 1180–1184 messenger (mRNA), 1180–1182, 1183, 1193 polymerase, 1180 purine and pyrimidine bases in, 1166–1168 ribosomal (rRNA), 1183 transfer (tRNA), 1182–1183, 1193 D-Ribose, 1028, 1027 cyanohydrin, 1056 2-deoxy, 1038, 1057 furanose and pyranose forms, 137, 1029–1035, 1035, 1055 Ribosome and rRNA, 1183 Ribozyme, 1183 D-Ribulose, 1038 Rickets, 1092 Ring flipping See Ring inversion Ring inversion cyclohexane, 115–116, 131–132, 540–541 substituted cyclohexanes, 116–119, 121–125, 131–132 Ring-opening metathesis, 607, 1210 RNA, mRNA, rRNA, and tRNA See Ribonucleic acid RNA World, 1184 Roberts, John D., 975 Roberts, Irving, 808–809 Robinson, Sir Robert, 4, 424, 909 Robinson annulation, 778, 782 car47872_ndx_I1-I26 11/22/06 16:18 Page I-23 CONFIRMING PAGES INDEX Rotamer, 104 See also Conformation Rotational energy barrier alkenes, 188 amides, 833–834 butane, 107–108 conjugated dienes, 397–398 ethane, 106–107 R-S-notational system, 285–288, 307–308 Rubber, 404 Rubbing alcohol, 142 See also Isopropyl alcohol Ruzicka, Leopold, 1082 S (symbol for entropy), 120 Sabatier, Paul, 226, 583 Sabinene, 1100 Saccharic acids See Aldaric acids Saccharin, 1045 Safranal, 1095 Saffron, 1095 Salicylic acid, 792 acetylation, 1002 acidity, 36, 1003 synthesis, 1002–1003 Salt bridge, 1149–1150 Samuelsson, Bengt, 1076 Sandmeyer reactions, 938, 940, 952, 967 Sanger, Frederick, 1130, 1132–1134, 1186–1187 Sanger’s reagent See 1-Fluoro-2, 4-dinitrobenzene ␣-Santonin, 1098 Saponification, 848–851 Sawhorse diagrams, 104–105 Saytzeff See Zaitsev Schiemann reaction, 938, 940, 951 Schiff’s base, 722, 740 See also Imines Schrock, Richard R., 605 Schrödinger, Erwin, 9, 1175 Schrödinger equation See Wave equation Scientific method, 235 Secondary carbon, 74–75 Secondary structure, 1145–1148 Selectivity See Regioselectivity; Stereoselective reactions Selenocysteine, 1108 Selenolactonization, 826–827 ␣-Selinene, 1080, 1081 Semicarbazide, 724 Semicarbazones, 724 Sequence rule alkene stereochemistry, 188–190, 214 R-S notation, 285–288, 307–308 L-Serine, 1109, 1110 isoelectric point, 1115–1116 structure and electrostatic potential map, 1111 Serotonin, 877, 920 Sesquiterpene, 1080 Sesterpene, 1080 Sex attractant See Pheromone, sex attractant Sex hormones, 1093, 1097 Shared-electron pair bond See Covalent bond Sharpless, K Barry, 632, 674–675 Shielding of nuclei in NMR spectroscopy, 521–525, 543–545 See also Chemical shift Sialic acids, 1039–1040 Sickle-cell anemia, 1154 Sigma bond, 62 Sigmatropic rearrangement, 1007 Sildenafil, 1169 Silk, 1146 Silver oxide, 931, 1007, 1012 Simmons, Howard E., 595 Simmons-Smith reaction (reagent), 595–596 Sinigrin, 1040 Sites of unsaturation See Index of hydrogen deficiency SI units, 13, 25 Skew-boat conformation of cyclohexane, 113–114, 131 Smalley, Richard, 432 Smith, Bradley D., 551 Smith, Ronald D., 595 SN1 mechanism, 154–155, 175, 330–332, 346 table SN2 mechanism, 159–160, 175, 323–328, 346 table Squaric acid, 57 Soap, 799, 849 Sodium, reaction with alkynes, 367–368, 375 arenes, 433–436, 460 Sodium acetylide, 350, 579 preparation, 362 reaction with alkyl halides, 350, 361–363 cyclohexanone, 589 Sodium alkoxides as bases in elimination reactions, 205, 339–342 preparation, 205 in Williamson ether synthesis, 670–672, 689 Sodium amide as base, 361–364, 374, 588 reaction with aryl halides, 974–978 Sodium borohydride reduction aldehydes and ketones, 625–628, 649, 710 aryl diazonium ions, 941 carbohydrates, 1047, 1056 Sodium cyanoborohydride, 929 Sodium dichromate See also Chromic acid; Potassium dichromate oxidation of alcohols, 639, 651 oxidation of alkylbenzenes, 438–439, 461, 501 Sodium 1-dodecyl sulfate (SDS), 799, 1117–1118 Sodium ethoxide as base, 882 acetoacetic ester synthesis, 889–891 Claisen and Dieckmann condensations, 883–887 elimination reactions, 205, 339–342 malonic ester synthesis, 892–894 reaction with epoxides, 678 Sodium hypochorite, 641 Sodium iodide, 322 Sodium lauryl sulfate, 799 See also Sodium dodecyl sulfate Sodium metaperiodate, 683 Sodium methoxide reaction with aryl halides, 969–973 Sodium stearate, 798 Solid-phase synthesis and chemically modified polymers, 1227–1229 of oligonucleotides, 1195–1199 of peptides, 1143–1145 Solvation and nucleophilicity, 330 Solvent effects, and rate of nucleophilic substitution, 337–339, 346 Solvolysis alkyl halides, 328–336 allylic halides, 385–389, 410 benzylic halides, 440–441 Somatostatin, 1158 Sondheimer, Franz, 451 Sorbitol, 653, 1047 Space-filling models, 30, 327 Spandex, 1221 Specific rotation, 283 Spectral Data Base System, 551 Spectrometer, 519 mass, 559–560 nuclear magnetic resonance, 521–522 Spectroscopy, 516–577 See also Mass spectrometry 13 C NMR, 541–550, 567–568 general principles, 518, 566 H NMR, 519–541, 566–567 infrared, 550–557, 568 ultraviolet-visible, 557–559, 568 Web sites, 551 Speed of light, 518 Spermaceti, 1075 Spermidine, 920 Spermine, 920 Spin density, 163 in allyl radical, 389 in benzyl radical, 436 in methyl radical, 164 Spin-spin coupling, 534 Spin-spin splitting in 19F NMR, 572 in 1H NMR, 532–539, 567 n ϩ1 rule, 532–533, 538 Spiro compounds, 125–127, 132 Spiropentane, 126 Splitting diagrams doublet of doublets, 536–538 quartet, 534 triplet, 535 Spontaneous reaction, 244 Squalene, 55, 682, 1080, 1081, 1088–1089, 1097 Squalene 2,3-epoxide, 682 in cholesterol biosynthesis, 1088, 1089 Staggered conformation, 104–106, 130 Standard state, 244, 1170 Stanozolol, 1094 Starch, 1045–1047 Apago PDF Enhancer I-23 Staudinger, Hermann, 1201–1202 Stearic acid, 792, 1069 Stearolic acid, 356 Step-growth polymer, 1203, 1204–1205 Sterculic acid, 195 Stereocenter See Chirality center Stereochemistry, 276–317 and chemical reactions See also Stereoselective reactions; Stereospecific reactions bimolecular nucleophilic substitution (SN2), 324–325, 343–344, 346 ester hydrolysis, 305, 850 hydrogenation of alkenes, 229, 302 that produce chiral molecules, 292–295, 309 that produce diastereomers, 301–303, 309 unimolecular nucleophilic substitution (SN1), 334–335, 346 Fischer projection formulas ␣-amino acids, 1113–1114, 1154 carbohydrates, 1024–1025, 1027, 1054 chiral molecules, 288–290, 308 two chirality centers, 295–298, 309 notational systems See also Stereoisomers cis and trans, 119, 187–188, 214 D and L, 288, 1025–1028, 1054, 1113–1114 E and Z, 188–190, 214 erythro and threo, 296 R and S, 285–288, 307–308 Stereoelectronic effects bimolecular elimination, 209–210, 216 nucleophilic substitution, 325 Stereogenic axis See Chirality axis Stereogenic center See Chirality center Stereoisomers, 19–20, 119–125, 132 alkenes, 187–190, 214 diastereomers, 295–305, 308, 309 enantiomers, 277–295, 308 endo and exo, 732 epimers, 1050 maximum number, 299–301, 309 Stereoregular polymers, 305–306, 309, 608–609 Stereoselective reactions, 229, 302–303 addition to carbonyl groups, 732–733 alcohol dehydration, 199 dehydrohalogenation of alkyl halides, 206 enolate formation, 787–789 enzyme-catalyzed hydration of fumaric acid, 294 epoxidation, 674–675 hydrogenation of alkenes, 229, 302–303 metal-ammonia reduction of alkynes, 367–368, 375 car47872_ndx_I1-I26 11/22/06 16:18 Page I-24 I-24 CONFIRMING PAGES INDEX Stereospecific reactions, 301–303 Baeyer-Villiger oxidation, 734–736 bimolecular (E2) elimination, 209–210 bimolecular nucleophilic substitution (SN2), 324–325, 343–344, 346 table Diels-Alder reaction, 406 dihydroxylation of alkenes, 631–632, 681 epoxidation of alkenes, 255–257, 267, 302, 674–675 epoxide formation from bromohydrins, 675–676 epoxide ring opening, 679, 681 halogen addition to alkenes, 251, 267, 301–303 halogen addition to alkynes, 372 Hofmann elimination, 932–933 hydroboration of alkenes, 248–250, 267 hydrogenation of alkenes, 229, 303 hydrogenation of alkynes, 365–366, 375 Simmons-Smith reaction, 595–596 Steric effects, 107–109 bimolecular nucleophilic substitution (SN2), 326–328, 346 cyclohexane derivatives, 117 electrophilic aromatic substitution, 499 Hofmann elimination, 932–933 hydration of aldehydes and ketones, 711–714 hydroboration of alkenes, 249 hydrogenation of ␣-pinene, 229 sodium borohydride reduction, 732–733 and stability of isomeric alkenes, 191–196, 214, 228 and stereoselectivity, 302–303, 732–733 Steric hindrance, 107–109, 229–230, 732 bimolecular nucleophilic substitution (SN2), 326–328, 346 Steric strain, 106, 107–109, 193–194, 195–196 Steroids, 136, 299–300, 1087–1093 Strain See Angle strain; Torsional strain; van der Waals strain Strain energy minimization, 109 Strecker, Adolf, 1118 Strecker synthesis, 1118 Stretching vibrations and infrared spectroscopy, 550 Strong acids and bases definitions, 36, 46–47 Structural formulas Fischer projections, 288–290, 308, 1024–1025, 1027, 1054, 1113–1114, 1154 Lewis dot structures, 14 Newman projections, 104–105, 108 organic molecules, 19–22 sawhorse, 104–105 wedge-and-dash, 29, 104–105 Structural isomers See Constitutional isomers Structural theory, Styrene, 428 addition of bromine, 443 addition of hydrogen bromide, 445, 461 anionic polymerization, 1214–1215 industrial preparation, 265, 422, 443, 480 polymers, 264, 445, 1143–1144, 1203 copolymer with 1,3–butadiene, 404, 1215, 1222–1223 Substituent effects See also Field effect; Inductive effect; Steric effects on acidity carboxylic acids, 799–802 phenols, 995–996 on basicity of amines, 914–919 on equilibrium, hydration of aldehydes and ketones, 711–714 Hammett equation, 466–469 on rate acid-catalyzed hydration, 242–243 bimolecular nucleophilic substitution (SN2), 326–328, 346, 388, 441–442 bromine addition to alkenes, 253 epoxidation, 256–257 nucleophilic aromatic substitution, 512–515, 968–973 unimolecular elimination, 211–213 unimolecular nucleophilic substitution (SN1), 158–159, 330–333, 346, 386, 440–441 on rate and regioselectivity in electrophilic aromatic substitution, 484–504, 973 on stability aldehydes and ketones, 706 alkenes, 191–194, 214 carbocations, 155–158, 175, 386, 440–441 carbon-carbon triple bonds, 365 free radicals, 162–167, 175, 432, 436 Substitution reactions, 48, 149–160, 318–353 aryl diazonium salts, 938–942, 951–952 electrophilic aromatic, 471–512 free radical alkanes, 161–172 allylic, 389–392, 411 benzylic, 436–438, 461 nucleophilic acyl, 828–879 aliphatic, 154–155, 158–160, 318–353 allylic, 385–389, 410 aromatic, 512–515 968–978, 981–982, 1004–1005 benzylic, 440–442, 460 Substitutive nomenclature, 141–142, 173 Succinic acid, 196 Succinic anhydride, 483 Succinimide, 390, 438 Sucrose, 1023, 1044 octaacetate, 1057 Sucralose, 1045 Sulfa drugs, 943 Sulfanilamide, 943 Sulfenic acids, 646 Sulfhydryl group, 644 Sulfides alkylation, 684–685, 691 oxidation, 683–684, 691 preparation, 645, 682–683, 691 Sulfinic acids, 646 Sulfonate esters nucleophilic substitution reactions, 342–344, 347 preparation, 342, 347, 633 Sulfonation benzene, 472, 476–477 benzenesulfonic acid, 495 2,6-dimethylphenol, 999 1,2,4,5-tetramethylbenzene, 505 Sulfones, 683, 691 Sulfonic acids, 342, 472, 646 Sulfonium salts, 684–685, 691 Sulfoxides See also Dimethyl sulfoxide as solvent optically active, 307 preparation, 683–684, 691 Sulfuric acid See also Sulfonation addition to alkenes, 239–241, 266 as catalyst, 197, 241–243, 260–261, 267, 476 Fischer esterification, 635 esters, 638 pKa, 38 Sulfur trioxide, 476 Supercoiled DNA, 1177–1178 Syndiotactic polymer, 305–306, 309 Synthon, 890 Systéme International d’Unités See SI unit Apago PDF Enhancer 2,4,5-T See 2,4,5Trichlorophenoxyacetic acid Talaromycin A, 744 D-Talose, 1027 Tariric acid, 356 Tartaric acids, 303 Tautomerism See Keto-enol tautomerism Teflon, 262, 264, 1202 Terephthalic acid See 1,4Benzenedicarboxylic acid Termination step, 168 in alkene polymerization, 1210–1211 Terpenes, 1079–1087, 1097 biosynthesis, 1082–1087 classification, 1080 and isoprene rule, 1079–1082 ␣-Terpineol, 1084 Tertiary carbon, 74–75 Tertiary structure, 1148–1152 Tesla, Nikola, 520 Tesla, unit of magnetic field strength, 520 Testosterone, 1093 Tetrachloromethane, 146, 162 See also Carbon tetrachloride Tetrafluoroethylene, 262, 264 Tetrahedral geometry sp3 hybridization, 67 VSEPR, 29–32, 51 Tetrahedral intermediate, 809, 830, 834–835 Claisen condensation, 884 Dieckmann cyclization, 886 Fischer esterification, 809–811, 820 hydrolysis of acid anhydrides, 840–841 acyl chlorides, 836, 838 amides, 857–859 esters, 846–848, 851, 869 reaction of esters with ammonia, 853 ⌬9-Tetrahydrocannabinol, 998, 1070 Tetrahydrofuran, 129, 664 See also Oxolane acid-catalyzed cleavage, 673 complex with borane, 247 as solvent, 583 Tetrahydropyran, 664, 665 See also Oxane Tetrahymanol, 1098 Tetramethylsilane, 523, 524, 543 electrostatic potential map, 517 Tetrapeptide, 1107 Tetraterpene, 1080 Thalidomide, 291 Theobromine, 1165 Thermochemistry, 86 Thermodynamic control addition of hydrogen bromide to 1,3-butadiene, 401–402 addition to ␣,␤-unsaturated aldehydes and ketones, 775–777 enolate formation, 787–789 Fries rearrangement, 1002 glycoside formation, 1042 Kolbe-Schmitt reaction, 1002–1003 Thermodynamics and addition-elimination equilibria, 243–246 bioenergetics, 1170–1172 and conformational equilibria, 120 Thermoplastic polymer, 1203 properties, 1207 Thermosetting polymer, 1203 properties, 1209 Thiazole, 456 Thiirane, 664 Thioesters acetyl coenzyme A, 877, 1066–1067 nucleophilic acyl substitution in, 876–879 resonance in, 877 Thiols acidity, 39, 644–645, 651, 683 conjugate addition to ␣, ␤-unsaturated carbonyl compounds, 776 car47872_ndx_I1-I26 11/22/06 16:18 Page I-25 CONFIRMING PAGES INDEX oxidation, 646, 651 NMR spectra, 647 physical properties, 644 preparation, 645 Thionyl chloride, 23–24 reactions with alcohols, 160–161, 174, 633 carboxylic acids, 482, 808, 836 Thiophene, 455, 504 Threo, stereochemical prefix, 296 L-Threonine, 1112 isoelectric point, 1115–1116 structure and electrostatic potential map, 1111 D-Threose, 1026 L-Threose, 1026 Thromboxanes, 1077 Thymidine, 1168 Thymine, 855, 1166, 1173–1174 Thymol, 998 Thyroxine, 292, 968 Tin, reduction of nitro groups by, 926–927, 949 Titanium(IV) isopropoxide, 674–675 Toluene, 421, 422 benzylic chlorination, 437 bond dissociation enthalpy, 436 nitration, 484–488, 501 oxidation, 439 physical properties, 994 p-Toluenesulfonic acid as acid catalyst, 720 acidity, 343 esters preparation, 342, 347, 633 nucleophilic aliphatic substitution in, 342–344, 347 nucleophilic aromatic substitution in, 997 p-Toluenesulfonyl chloride, reaction with alcohols, 342, 347, 633 o-Toluidine, 940 Torsional strain, 105, 129 cycloalkanes, 112–114 eclipsed conformation of butane, 107–109, 109 eclipsed conformation of ethane, 105–106 Torsion angle, 104 Tosylates See p-Toluenesulfonic acid, esters s-Trans conformation, 397–398 Transamination, 1122–1126 Transcription, 1179, 1181–1182, 1193 Transfer RNA See Ribonucleic acid, transfer Transition metal organometallic compounds, 599–602, 613 Transition state and activation energy, 106–107 addition of bromine to alkenes, 252 bimolecular elimination (E2), 208–209 bimolecular nucleophilic substitution (SN2), 159–160, 324–325, 345, 346 electrostatic potential map, 319 bond rotation in ethane, 106–107 carbocation rearrangement, 203 conversion of primary alcohols to primary alkyl halides, 159–160, 175, 345 Diels-Alder reaction, 403 double-bond rotation, 188 epoxide ring opening, 679, 680 free-radical halogenation, 170 nucleophilic capture of carbocation, 153, 332 oxonium ion dissociation, 151–152, 155, 158–159 proton transfer, 150–151, 155 unimolecular nucleophilic substitution (SN1), 154–155, 332 Translation, 1179, 1183–1184 Tranylcypromine, 953 Triacylglycerols See Glycerol, esters Tribromomethane See also Bromoform dibromocarbene from, 597–598 Trichloroacetic acid, 800 Trichloromethane, 146, 162 See also Chloroform 2,4,5-Trichlorophenol, 1005 2,4,5-Trichlorophenoxyacetic acid, 1005 cis-9-Tricosene, 379 Triethylamine, 915 Trifluoroacetic acid, 819 acidity, 43–44 2,2,2-Trifluoroethanol, 43 p-(Trifluoromethyl)aniline, 916 (Trifluoromethyl)benzene, nitration, 484–485, 488–489 Triglycerides See Glycerol, esters Trigonal planar geometry and sp2 hybridization, 89–90, 152–153, 185–186, 426, 704–705 and VSEPR, 31 Trigonal pyramidal geometry, 29 Trimer, 261 Trimethylamine, 914 H chemical shift, 524 2,2,4-Trimethylpentane, 261 chlorination, 180 Trimethyl phosphate, 638 Trimethyl phosphite, 638 Trimyristin, 849 Trinucleotide, 1172 Triose phosphate isomerase, 1052 Tripeptide, 1107 Triphenylamine,916 Triphenylmethyl perchlorate, 441 Triphenylphosphine, 731 Triple bond, 16, 91–92, 97, 355, 357–359 See also Bonds in benzyne, 976–977 Tristearin, 842, 1067–1068 Tris(triphenylphosphine)rhodium chloride See Wilkinson’s catalyst Triterpenes, 1080 biosynthesis, 682, 1084, 1087–1090 Trityl See Triphenylmethyl Trivial names See Common names Tropane, 909 Tropylium cation See Cycloheptatrienyl cation Trypsin, 1131 L-Tryptophan, 1109 isoelectric point, 1115–1116 structure and electrostatic potential map, 1110 Twist-boat See Skew boat conformation of cyclohexane Tyrian purple, 5, 55, 968 L-Tyrosine, 1112, 1123, 1122 formation from L-phenylalanine, 697–699 isoelectric point, 1115–1116 structure and electrostatic potential map, 1110 Ubiquinone, 1008 Ultraviolet-visible spectroscopy, 517, 557–559, 568 alcohols, 648 aldehydes and ketones, 738 amines, 945 carboxylic acids and derivatives, 817, 867 ethers and epoxides, 687 phenols, 1010 Unimolecular elementary step, 151, 154 elimination, 200–201, 211–213, 216, 217 nucleophilic substitution, 154–155, 175, 330–336 ␣,␤-Unsaturated aldehydes and ketones conjugate addition to, 775–777, 781–782, 894–895, 899 electron delocalization in, 774–775 preparation, 759–763, 780 Uracil, 1166 Urea, 2–3 Urey, Harold C., 808–809 Uridine, 1168 Uronic acids, 1047, 1048 Apago PDF Enhancer Valence-bond theory, 61–62, 92, 93 Valence electrons, 11 and Lewis structures, 14–16, 20–21, 23–24 Valence-shell electron pair repulsion and molecular geometry, 29–32, 51 L-Valine, 1109 isoelectric point, 1115–1116 structure and electrostatic potential map, 1110 L-Vancosamine, 1040 van der Waals forces attractive, 80–82 and stability of isomeric alkanes, 85 and protein structure, 1149–1150 repulsive, 81, 107–109, 113, 117 See also van der Waals strain stereoisomers, 119, 121, 193–194, 214 I-25 van der Waals radius, 81, 107, 109 van der Waals strain, 107–109, 129 See also Steric effects; Steric hindrance; Steric strain alkenes, 193–194, 214 [10]annulene, 451 axial substituents in cyclohexane, 116–119, 132 boat conformation of cyclohexane, 113 butane, 107–109, 130 SN2 reactions, 326–328 in stereoisomers, 119, 121, 193–194, 214 Vane, John, 1076 Vanillin, 998 Van’t Hoff, Jacobus, 277, 282 Venter, J Craig, 1188 Vetiver and ␤-vetivone, 127 Vernolepin, 812 Vibrations of methylene group, 550 Vicinal coupling, 534, 567 Vicinal dihalides See Dihaloalkanes, vicinal Vicinal diols, 630–631 cyclic acetals from, 720, 721 preparation, 630–632 reaction with periodic acid, 643–644, 651 Vicinal halohydrins See Halohydrins Vinyl acetate, 372 Vinyl chloride, 52, 184, 191, 264, 265, 372, 583, 1202 Vinyl group, 184 Vinyl halides See Alkenyl halides; Vinyl chloride Vinylic, 383–384 chapter 13 Vinylidene chloride, 1203 Vinyllithium, 588 Vinylmagnesium chloride, 583 Visible light, 518 Vision, chemistry of, 725–726 Vitalism, 2–3 Vitamin, 909 A, 726, 1081 B6, 725 B12, 601–602 C See Ascorbic acid D3, 1092 K, 1008–1009 von Baeyer, Adolf, 110–111 VSEPR See Valence-shell electron pair repulsion Vulcanization, 404, 1201, 1207 Wallach, Otto, 1079 Water acidity and pKa, 36, 39, 41, 360, 585 bond angles, 29–31 as a Brønsted acid, 37 as a Brønsted base, 37, 45–46 dipole moment, 143 solubility of alcohols in, 147 VSEPR and molecular geometry, 29–31 Watson, James D., 1174–1177 Wave equation, Wave function, 9, 49 car47872_ndx_I1-I26 11/22/06 16:18 Page I-26 I-26 CONFIRMING PAGES INDEX Wavelength, 518 Wavenumber, 551 Waxes, 1075 WebSpectra, 551 Wedge-and-dash structural formulas, 29, 104–105 Whitmore, Frank C., 201 Wilkins, Maurice, 1175 Wilkinson, Geoffrey, 602 Wilkinson’s catalyst, 602–603 Williamson, Alexander, 670 Williamson ether synthesis, 670–672, 689, 1004 intramolecular, 675 Willstätatter, Richard, 446 Wittig, Georg, 728 Wittig reaction, 728–732, 740 Wöhler, Friederich, 2–3 Wolff-Kishner reduction, 484, 710 Wood alcohol, 142, 622 Woodward, Robert B., 410, 655 Woodward-Hoffmann rules, 410 Wool, 1147 Wurtz, Charles-Adolphe, Xanthophylls, 1096 X-ray crystallography and structure carbohydrates, 1033–1034, 1036 nucleic acids, 1174, 1175 peptides, 1127, 1145–1146 vitamin B12, 601–602 X-rays, 518 m-Xylene, 428–429 nitration, 499 o-Xylene, 428–429 Birch reduction, 460 p-Xylene, 428–429 Friedel-Crafts acylation, 498 oxidation, 805 D-Xylonic acid, 1048 1027 furanose and pyranose forms, 137, 1032 oxidation, 1048 L-Xylulose, 1038 D-Xylose, Yellow #5 and Yellow #6, 944 Yields in chemical reactions, 148 Ylides, 728–732 Z (abbrevation for benzyloxycarbonyl group), 1139 Z (stereochemical prefix), 188–190, 214 Z (symbol for atomic number), Zaitsev, Alexander M., 198 Apago PDF Enhancer Zaitsev’s rule, 198–199, 206, 215 Zeaxanthyn, 1094 Zidovudine, 1185 Ziegler, Karl, 263, 607–609 Ziegler-Natta catalyst, 263, 404, 607–609 Zigzag conformations of alkanes, 110 Zinc in carboxypeptidase A, 1150–1152 in Clemmensen reduction, 483–484, 501 in hydrolysis of ozonides, 258 in synthesis of cyclopropanes, 595 Zirconium, bis-cyclopentadiene complex, 600 catalyst in alkene polymerization, 608–609, 1210 Zusammen, (Z), 188–190, 214 Zwitterion, 1114–1115, 1198 ISBN: 0073047872 Author: Carey Title: Organic Chemistry Back endsheets Color: Pages: 4,5 Be 2A (2) Mg 12 20 Ca Sc 21 3B (3) Ti 22 4B (4) V 23 5B (5) Cr 24 6B (6) Mn 25 7B (7) Fe 26 (8) Co 27 8B (9) TRANSITION ELEMENTS Sr 38 Y 39 Zr 40 Nb 41 Mo 42 56 Ba 57 La 72 Hf 73 Ta W 74 Re 75 (98) Tc 43 Rh 45 Actinides Lanthanides Ra (226) Fr 88 (223) 87 76 Os Ir 77 61 91 13 93 94 (242) (237) Pu 238.0 Np U 92 Ne 10 F 4.003 7A (17) Si 14 P 15 S 16 17 Cl 18 Ar Ga 31 Ge 32 As 33 Se 34 Br 35 Kr 36 26.98 28.09 30.97 32.07 35.45 39.95 Al 47 Ag 46 Pd Cd 48 In 49 Sn 50 Sb 51 Te 52 79 Au 78 Pt 80 Hg Tl 81 82 Pb 83 Bi (277) Hs 108 (268) Mt 109 Eu 63 Gd 64 Rg (272) 66 Dy Ds 65 Tb 111 (281) 110 Ho 67 (285) 112 Er 68 Tm 69 (289) 114 Yb 70 84 I 53 Xe 54 95 (243) Am 96 (247) Cm 98 Cf (251) *When two names are cited, either one is acceptable in IUPAC nomenclature 97 Bk (247) (258) (257) H2C (252) 101 Md 100 (CH3)2CHCH2 Fm 99 Es (259) No 102 85 (210) At 86 (222) Rn Lu 71 As of late 2006, elements 112,114, and 116 have not (292) been named 116 (209) Po (260) Lr 103 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0 Sm 62 CH3CHCH2 (CH3)3CCH2 (231) Pa (267) Bh 107 CH3 H2C 232.0 Th 90 Pm 60 (145) Pr (266) Sg 106 Nd Ce 59 (262) Db 105 INNER TRANSITION ELEMENTS (263) Rf 104 140.1 140.9 144.2 58 (227) Ac 89 O 6A (16) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3 Ru 44 N 5A (15) 132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 Cs 55 85.47 87.62 88.91 91.22 92.91 95.94 Rb 37 Zn 30 2B (12) C 4A (14) He 8A (18) 10.81 12.01 14.01 16.00 19.00 20.18 B 3A (13) MAIN–GROUP ELEMENTS 63.55 65.41 69.72 72.61 74.92 78.96 79.90 83.80 29 Cu 28 1B (11) Ni (10) 39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 K 19 22.99 24.31 Na 11 6.941 9.012 Li 1.008 H Metals (main-group) Metals (transition) Metals (inner transition) Metalloids Nonmetals Periodic Table of the Elements Apago PDF Enhancer 1A (1) MAIN–GROUP ELEMENTS CONFIRMING PAGES SOME COMMONLY ENCOUNTERED GROUPS H2C Group Name* CH3CH2CH2 Propyl or n-propyl (CH3)2CH 1-Methylethyl or isopropyl CH3CH2CH2CH2 Butyl or n-butyl CH3CHCH2CH3 1-Methylpropyl or sec-butyl (CH3)3C 1,1-Dimethylethyl or tert-butyl 2-Methylpropyl or isobutyl (CH3)3CCH2 2,2-Dimethylpropyl or neopentyl CH Ethenyl or vinyl O H2C CHCH2 2-Propenyl or allyl C CCH3 1-Methylvinyl or isopropenyl Group HOCH2 CH3 (CH3)2CH O 10 HC O Period 12 HOC CH (CH3)3C 21 F 22 HS O 23 Cl 11 CH3C 24 Br 25 I Name* O CH3C Ethanoyl or acetyl Phenyl CH2 O H 13 CH3OC 14 HSCH2 CH3CH2 15 H2N 16 HO 17 CH3O 18 CH3CH2O O 19 HCO O 20 CH3CO Phenylmethyl or benzyl Benzenecarbonyl or benzoyl COMMONLY ENCOUNTERED GROUPS LISTED IN ORDER OF INCREASING RANK IN THE CAHN–INGOLD–PRELOG SYSTEM ISBN: 0073047872 Author: Carey Title: Organic Chemistry Back endsheets Color: Pages: 4,5 7 Be 2A (2) Mg 12 20 Ca Sc 21 3B (3) Ti 22 4B (4) V 23 5B (5) Cr 24 6B (6) Mn 25 7B (7) Fe 26 (8) Co 27 8B (9) TRANSITION ELEMENTS Metals (main-group) Metals (transition) Metals (inner transition) Metalloids Nonmetals Sr 38 Y 39 Zr 40 Nb 41 Mo 42 56 Ba 57 La 72 Hf 73 Ta W 74 Re 75 (98) Tc 43 Rh 45 Actinides Lanthanides Ra (226) Fr 88 (223) 87 76 Os Ir 77 61 91 93 94 (242) (237) Pu 238.0 Np U 92 Ne 10 F 4.003 7A (17) P 15 S 16 17 Cl 18 Ar Ga 31 Ge 32 As 33 Se 34 Br 35 Kr 36 26.98 28.09 30.97 32.07 35.45 39.95 Si 14 47 Ag 46 Pd Cd 48 In 49 Sn 50 Sb 51 Te 52 79 Au 78 Pt 80 Hg Tl 81 82 Pb 83 Bi (277) Hs 108 Rg (272) 66 Dy Ds Eu 63 65 Tb 64 111 (281) 110 (268) Mt 109 Gd Ho 67 (285) 112 Er 68 Tm 69 (289) 114 Yb 70 84 I 53 Xe 54 95 (243) Am 96 (247) Cm 98 Cf (251) *When two names are cited, either one is acceptable in IUPAC nomenclature 97 Bk (247) (258) (257) H2C (252) 101 Md 100 (CH3)2CHCH2 Fm 99 Es (259) No 102 85 (210) At 86 (222) Rn Lu 71 As of late 2006, elements 112,114, and 116 have not (292) been named 116 (209) Po (260) Lr 103 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0 Sm 62 CH3CHCH2 (CH3)3CCH2 (231) Pa (267) Bh 107 CH3 H2C 232.0 Th 90 Pm 60 (145) Pr (266) Sg 106 Nd Ce 59 (262) Db 105 INNER TRANSITION ELEMENTS (263) Rf 104 140.1 140.9 144.2 58 (227) Ac 89 O 6A (16) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3 Ru 44 13 Al 132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 Cs 55 85.47 87.62 88.91 91.22 92.91 95.94 Rb 37 Zn 30 2B (12) N 5A (15) He 8A (18) 63.55 65.41 69.72 72.61 74.92 78.96 79.90 83.80 29 Cu 28 Ni (10) 1B (11) C 4A (14) MAIN–GROUP ELEMENTS 10.81 12.01 14.01 16.00 19.00 20.18 B 3A (13) Periodic Table of the Elements 39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 K 19 22.99 24.31 Na 11 6.941 9.012 Li 1.008 H 1A (1) MAIN–GROUP ELEMENTS CONFIRMING PAGES SOME COMMONLY ENCOUNTERED GROUPS H2C Group Name* CH3CH2CH2 Propyl or n-propyl (CH3)2CH 1-Methylethyl or isopropyl CH3CH2CH2CH2 Butyl or n-butyl CH3CHCH2CH3 1-Methylpropyl or sec-butyl (CH3)3C 1,1-Dimethylethyl or tert-butyl 2-Methylpropyl or isobutyl (CH3)3CCH2 2,2-Dimethylpropyl or neopentyl CH Ethenyl or vinyl O H2C CHCH2 2-Propenyl or allyl C CCH3 1-Methylvinyl or isopropenyl Group HOCH2 CH3 (CH3)2CH O 10 HC O Period 12 HOC CH (CH3)3C 21 F 22 HS O 23 Cl 11 CH3C 24 Br 25 I Name* O CH3C Ethanoyl or acetyl Phenyl CH2 Apago PDF Enhancer O H 13 CH3OC 14 HSCH2 CH3CH2 15 H2N 16 HO 17 CH3O 18 CH3CH2O O 19 HCO O 20 CH3CO Phenylmethyl or benzyl Benzenecarbonyl or benzoyl COMMONLY ENCOUNTERED GROUPS LISTED IN ORDER OF INCREASING RANK IN THE CAHN–INGOLD–PRELOG SYSTEM CONFIRMING PAGES THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY Example Acceptable Name(s) of Example Characteristic Reaction Type Alkanes CH3CH3 Ethane Free-radical substitution of hydrogen by halogen Alkenes H2C Ethene or ethylene Electrophilic addition to double bond Alkynes HC Ethyne or acetylene Electrophilic addition to triple bond Hydrocarbons Dienes THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY Example Acceptable Name(s) of Example Characteristic Reaction Type Ethanoyl chloride or acetyl chloride Nucleophilic acyl substitution Ethanoic anhydride or acetic anhydride Nucleophilic acyl substitution Ethyl ethanoate or ethyl acetate Nucleophilic acyl substitution N-Methylethanamide or N-methylacetamide Nucleophilic acyl substitution Carboxylic acid derivatives CH2 CH H2C CHCH CH2 Arenes 1,3-Butadiene Benzene O Acyl halides O O Acid anhydrides Electrophilic addition to double bonds Electrophilic aromatic substitution CH3CCl CH3COCCH3 O Esters CH3COCH2CH3 O Halogen-substituted derivatives of hydrocarbons Amides CH3CNHCH3 Alkyl halides CH3CH2Cl Chloroethane or ethyl chloride Nucleophilic substitution; elimination Alkenyl halides H2C Chloroethene or vinyl chloride Electrophilic addition to double bond; elimination Aryl halides C6H5Cl Chlorobenzene Electrophilic aromatic substitution; nucleophilic aromatic substitution Amines CH3CH2NH2 Ethanamine or ethylamine Nitrogen acts as a base or as a nucleophile Nitriles CH3C Ethanenitrile or acetonitrile Nucleophilic addition to carbon–nitrogen triple bond Nitro compounds C6H5NO2 Nitrobenzene Reduction of nitro group to amine CHCl Apago PDF Enhancer Nitrogen-containing organic compounds N Oxygen-containing organic compounds Alcohols CH3CH2OH Ethanol or ethyl alcohol Dehydration; conversion to alkyl halides; esterification Phenols C6H5OH Phenol Electrophilic aromatic substitution Ethers CH3CH2OCH2CH3 Ethoxyethane or diethyl ether Cleavage by hydrogen halides Epoxides H2C Epoxyethane or ethylene oxide or oxirane Nucleophilic ring opening Ethanal or acetaldehyde Nucleophilic addition to carbonyl group 2-Propanone or acetone Nucleophilic addition to carbonyl group Ethanoic acid or acetic acid Ionization of carboxyl; esterification CH2 O O Aldehydes CH3CH O Ketones CH3CCH3 O Carboxylic acids ISBN: 0073047872 Author: Carey Title: Organic Chemistry CH3COH Front endsheets Color: Pages: 2,3 Sulfur-containing organic compounds Thiols CH3CH2SH Ethanethiol Oxidation to a sulfenic, sulfinic, or sulfonic acid or to a disulfide Sulfides CH3CH2SCH2CH3 Diethyl sulfide Alkylation to a sulfonium salt; oxidation to a sulfoxide or sulfone CONFIRMING PAGES THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY Example Acceptable Name(s) of Example Characteristic Reaction Type Alkanes CH3CH3 Ethane Free-radical substitution of hydrogen by halogen Alkenes H2C Ethene or ethylene Electrophilic addition to double bond Alkynes HC Ethyne or acetylene Electrophilic addition to triple bond Hydrocarbons Dienes THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY Example Acceptable Name(s) of Example Characteristic Reaction Type Ethanoyl chloride or acetyl chloride Nucleophilic acyl substitution Ethanoic anhydride or acetic anhydride Nucleophilic acyl substitution Ethyl ethanoate or ethyl acetate Nucleophilic acyl substitution N-Methylethanamide or N-methylacetamide Nucleophilic acyl substitution Ethanamine or ethylamine Nitrogen acts as a base or as a nucleophile Carboxylic acid derivatives CH2 CH H2C CHCH CH2 Arenes 1,3-Butadiene Benzene O Acyl halides O O Acid anhydrides Electrophilic addition to double bonds Electrophilic aromatic substitution CH3CCl CH3COCCH3 O Esters CH3COCH2CH3 O Halogen-substituted derivatives of hydrocarbons Amides CH3CNHCH3 Alkyl halides CH3CH2Cl Chloroethane or ethyl chloride Nucleophilic substitution; elimination Alkenyl halides H2C Chloroethene or vinyl chloride Electrophilic addition to double bond; elimination Aryl halides C6H5Cl Chlorobenzene Electrophilic aromatic substitution; nucleophilic aromatic substitution Amines CH3CH2NH2 Nitriles CH3C Nitro compounds C6H5NO2 CHCl Nitrogen-containing organic compounds N or Apago PDF Ethanenitrile Enhancer acetonitrile Oxygen-containing organic compounds Alcohols CH3CH2OH Ethanol or ethyl alcohol Dehydration; conversion to alkyl halides; esterification Phenols C6H5OH Phenol Electrophilic aromatic substitution Ethers CH3CH2OCH2CH3 Ethoxyethane or diethyl ether Cleavage by hydrogen halides Epoxides H2C Epoxyethane or ethylene oxide or oxirane Nucleophilic ring opening Ethanal or acetaldehyde Nucleophilic addition to carbonyl group 2-Propanone or acetone Nucleophilic addition to carbonyl group Ethanoic acid or acetic acid Ionization of carboxyl; esterification CH2 O O Aldehydes CH3CH O Ketones CH3CCH3 O Carboxylic acids ISBN: 0073047872 Author: Carey Title: Organic Chemistry CH3COH Front endsheets Color: Pages: 2,3 Nucleophilic addition to carbon–nitrogen triple bond Nitrobenzene Reduction of nitro group to amine Sulfur-containing organic compounds Thiols CH3CH2SH Ethanethiol Oxidation to a sulfenic, sulfinic, or sulfonic acid or to a disulfide Sulfides CH3CH2SCH2CH3 Diethyl sulfide Alkylation to a sulfonium salt; oxidation to a sulfoxide or sulfone M cGraw-Hill offers various tools and technology to support the seventh edition of Organic Chemistry You can order supplemental study materials by contacting your bookstore or the McGraw-Hill Customer Service Department at 1-800-338-3987 Solutions Manual CPS eInstruction ISBN-13: 978-0-07-304788-1 • ISBN-10: 0-07-304788-0 The Classroom Performance System’s Written by Robert C Atkins (James Madison University) and Francis A Carey, the Solutions Manual provides (CPS) eInstruction brings interactivity into the classroom or lecture hall It is a wireless Apago PDF Enhancer step-by-step solutions to guide students through the reasoning behind solving each problem in the text There is also a self-test at the end of each chapter designed to assess the student’s mastery of the material response system that gives the instructor and students immediate feedback from the entire class The wireless response pads are essentially remotes that are easy to use and engage students CPS allows instructors to motivate student preparation, promote interactivity and active learning, and receive immediate feedback to assess student understanding Questions covering the content of the Organic Chemistry text and formatted in the CPS eInstruction software are available on the Organic Chemistry ARIS™ site McGraw-Hill Higher Education ... undergraduates Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava Apago PDF Enhancer... Phase-Transfer Catalysts 921 Reactions That Lead to Amines: A Review and a Preview 922 Preparation of Amines by Alkylation of Ammonia 923 The Gabriel Synthesis of Primary Alkylamines 924 Preparation of Amines... Biochemical Reactions of Alkanes 100 C H A P T E R Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 3.1 3.2 102 Conformational Analysis of Ethane 104 Conformational Analysis of Butane