Organic chemistry 3e by janice g smith

Apago PDF Enhancer smi75625_endppFRONT.indd Periodic Table of the Elements Group number Period number 1A 8A 1 H Hydrogen 1.0079 Li 11 12 Sodium 22.9898 Magnesium 24.3050 Atomic weight 3B 4B 21 22 23 24 25 26 Titanium 47.88 Vanadium 50.9415 Chromium 51.9961 Manganese 54.9380 Iron 55.845 37 38 39 40 41 42 43 44 Zirconium 91.224 Niobium 92.9064 Molybdenum 95.94 Technetium (98) Ruthenium 101.07 72 73 74 75 76 Y Zr Cr 8B Scandium 44.9559 Mn Fe Nb Mo Tc Strontium 87.62 55 56 57 Cesium 132.9054 Barium 137.327 Lanthanum 138.9055 Hafnium 178.49 Tantalum 180.9479 Tungsten 183.84 Rhenium 186.207 Osmium 190.2 87 88 89 104 105 106 107 108 Radium (226) Actinium (227) Dubnium (268) Seaborgium (271) 58 59 Fr Francium (223) Ba La Ra Ac Hf Rf Rutherfordium (267) Lanthanides Ta Db Sg Ce Cerium 140.115 90 Actinides W Th Thorium 232.0381 Pr Re Os Bh Pa Protactinium 231.0359 27 Co Hs 28 7A Helium 4.0026 10 1B 29 C N O F Ne Boron 10.811 Carbon 12.011 Nitrogen 14.0067 Oxygen 15.9994 Fluorine 18.9984 Neon 20.1797 13 14 15 16 17 18 Si P S Silicon 28.0855 Phosphorus 30.9738 30 31 32 33 Zinc 65.41 Gallium 69.723 Germanium 72.64 Arsenic 74.9216 Selenium 78.96 Bromine 79.904 Krypton 83.80 49 50 51 52 53 54 34 35 46 47 48 Rhodium 102.9055 Palladium 106.42 Silver 107.8682 Cadmium 112.411 Indium 114.82 Tin 118.710 Antimony 121.760 Tellurium 127.60 Iodine 126.9045 I Xe 77 78 79 80 81 82 83 84 85 86 Ir Sn Sb Platinum 195.08 Au Gold 196.9665 Hg Mercury 200.59 Thallium 204.3833 Tl Pb Lead 207.2 Bismuth 208.9804 Polonium (209) 109 110 111 112 113 114 115 116 — — — — — Mt Ds Rg Darmstadtium Roentgenium (281) (280) 62 63 Promethium (145) Samarium 150.36 93 Neptunium (237) – – – Bi Te Iridium 192.22 Meitnerium (276) Pt In – Po At Astatine (210) Kr Rn – (288) (293) 64 65 66 67 68 69 70 Europium 151.964 Gadolinium 157.25 Terbium 158.9253 Dysprosium 162.50 Holmium 164.9303 Erbium 167.26 Thulium 168.9342 Ytterbium 173.04 Lutetium 174.967 94 95 96 97 98 99 100 101 102 103 Plutonium (244) Americium (243) Curium (247) Berkelium (247) Einsteinium (252) Fermium (257) Mendelevium (258) Nobelium (259) Np Pu Am Cm Bk Cf Californium (251) (289) Er Radon (222) (284) Dy Ho Xenon 131.29 (285) Nd Pm Sm Eu Gd Tb 36 45 Ag Cd Br Argon 39.948 Nickel 58.693 Copper 63.546 Se Chlorine 35.4527 Ar Aluminum 26.9815 Zn Ga Ge As Sulfur 32.066 Cl 2B Cobalt 58.9332 61 U 6A Cu 60 Uranium 238.0289 5A Ni Hassium (270) 92 4A Al 8B Bohrium (272) Praseodymium Neodymium 140.9076 144.24 91 8B Ru Rh Pd Rubidium 85.4678 Cs Yttrium 88.9059 V 7B Calcium 40.078 Sr Ti 6B Ca Rb Sc 5B 3A B An element K Potassium 39.0983 Holmium 164.9303 Na Mg 20 He Symbol Ho Name Be Beryllium 9.0122 19 4 Lithium 6.941 67 Atomic number 2A Apago PDF Enhancer Key Tm Yb Es Fm Md No 71 Lu Lr Lawrencium (260) 12/2/09 10:14:16 AM smi75625_endppFRONT.indd COMMON FUNCTIONAL GROUPS Type of Compound General Structure Example O O Acid chloride C R Alcohol Cl CH3 R OH R Alkane Cl CH3 OH O O C C H CH3 R H – COCl Aromatic compound – OH hydroxy group Carboxylic acid C O carbonyl group H –– CH3CH3 H C C Alkene Type of Compound H double bond C C H H Alkyl halide R X (X = F, Cl, Br, I) CH3 Br –X halo group Alkyne C C H C C H O O Amide R C N H (or R) H (or R) CH3 C NH2 Apago PDF Enhancer Aldehyde C Functional Group General Structure Example phenyl group R O O C C OH CH3 O Ester Ether Ketone R C R NH2 or R2NH or R3N 12/2/09 10:14:16 AM Anhydride R CH3 NH2 OR CH3 R O R CH3 O CH3 O O R C R CH3 C O carbonyl group triple bond Sulfide R S R CH3 S CH3 – SR alkylthio group – CONH2, – CONHR, – CONR2 Thiol R SH CH3 SH – SH mercapto group – NH2 amino group O O O C C C CH3 CH3 – OR alkoxy group –C N cyano group C O C – COOR CH3 C N O CH3 OCH3 R C N C R C Nitrile O O OH –COOH carboxy group O O Amine Functional Group O O C Thioester R C O SR CH3 C SCH3 – COSR Organic Chemistry Third Edition Apago PDF Enhancer Janice Gorzynski Smith University of Hawai’i at Ma-noa TM smi75625_fm_00i-xxxiv.indd i 11/17/09 11:21:07 AM TM ORGANIC CHEMISTRY, THIRD EDITION Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the Americas, New York, NY 10020 Copyright © 2011 by The McGraw-Hill Companies, Inc All rights reserved Previous editions © 2008 and 2006 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 This book is printed on acid-free paper DOW/DOW ISBN 978–0–07–337562–5 MHID 0–07–337562–4 Vice President & Editor-in-Chief: Marty Lange Vice President, EDP: Kimberly Meriwether-David Director of Development: Kristine Tibbetts Publisher: Ryan Blankenship Senior Sponsoring Editor: Tamara L Hodge Vice President New Product Launches: Michael Lange Senior Developmental Editor: Donna Nemmers Senior Marketing Manager: Todd L Turner Senior Project Manager: Jayne L Klein Lead Production Supervisor: Sandy Ludovissy Senior Media Project Manager: Sandra M Schnee Senior Designer: Laurie B Janssen (USE) Cover Image: ©Amama Images Inc., Alamy Lead Photo Research Coordinator: Carrie K Burger Photo Research: Mary Reeg Supplement Producer: Mary Jane Lampe Compositor: Precision Graphics Typeface: 10/12 Times LT Std Printer: R R Donnelley Apago PDF Enhancer All credits appearing on page or at the end of the book are considered to be an extension of the copyright page Library of Congress Cataloging-in-Publication Data Smith, Janice G Organic chemistry / Janice Gorzynski Smith — 3rd ed p cm Includes index ISBN 978–0–07–337562–5 — ISBN 0–07–337562–4 (hard copy : alk paper) Chemistry, Organic–Textbooks I Title QD253.2.S65 2011 547—dc22 2009034737 www.mhhe.com smi75625_fm_00i-xxxiv.indd ii 11/17/09 11:21:08 AM For Megan Sarah Apago PDF Enhancer smi75625_fm_00i-xxxiv.indd iii 11/17/09 11:21:08 AM About the Author Janice Gorzynski Smith was born in Schenectady, New York, and grew up following the Yankees, listening to the Beatles, and water skiing on Sacandaga Reservoir She became interested in chemistry in high school, and went on to major in chemistry at Cornell University where she received an A.B degree summa cum laude Jan earned a Ph.D in Organic Chemistry from Harvard University under the direction of Nobel Laureate E J Corey, and she also spent a year as a National Science Foundation National Needs Postdoctoral Fellow at Harvard During her tenure with the Corey group she completed the total synthesis of the plant growth hormone gibberellic acid Following her postdoctoral work, Jan joined the faculty of Mount Holyoke College where she was employed for 21 years During this time she was active in teaching organic chemistry lecture and lab courses, conducting a research program in organic synthesis, and serving as department chair Her organic chemistry class was named one of Mount Holyoke’s “Don’tmiss courses” in a survey by Boston magazine After spending two sabbaticals amidst the natural beauty and diversity in Hawai‘i in the 1990s, Jan and her family moved there permanently in 2000 She is currently a faculty member at the University of Hawai‘i at Ma- noa, where she teaches the two-semester organic chemistry lecture and lab courses In 2003, she received the Chancellor’s Citation for Meritorious Teaching Jan resides in Hawai‘i with her husband Dan, an emergency medicine physician She has four children: Matthew and Zachary, age 14 (margin photo on page 163); Jenna, a student at Temple University’s Beasley School of Law; and Erin, an emergency medicine physician and co-author of the Student Study Guide/Solutions Manual for this text When not teaching, writing, or enjoying her family, Jan bikes, hikes, snorkels, and scuba dives in sunny Hawai‘i, and time permitting, enjoys travel and Hawaiian quilting Apago PDF Enhancer The author (far right) and her family from the left: husband Dan, and children Zach, Erin, Jenna, and Matt iv smi75625_fm_00i-xxxiv.indd iv 11/17/09 11:21:09 AM Contents in Brief 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Prologue Structure and Bonding Acids and Bases 54 Introduction to Organic Molecules and Functional Groups 81 Alkanes 113 Stereochemistry 159 Understanding Organic Reactions 196 Alkyl Halides and Nucleophilic Substitution 228 Alkyl Halides and Elimination Reactions 278 Alcohols, Ethers, and Epoxides 312 Alkenes 358 Alkynes 399 Oxidation and Reduction 426 Mass Spectrometry and Infrared Spectroscopy 463 Nuclear Magnetic Resonance Spectroscopy 494 Radical Reactions 538 Conjugation, Resonance, and Dienes 571 Benzene and Aromatic Compounds 607 Electrophilic Aromatic Substitution 641 Carboxylic Acids and the Acidity of the O – H Bond 688 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 721 Aldehydes and Ketones—Nucleophilic Addition 774 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution Substitution Reactions of Carbonyl Compounds at the α Carbon 880 Carbonyl Condensation Reactions 916 Amines 949 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis 1002 Carbohydrates 1027 Amino Acids and Proteins 1074 Lipids 1119 Synthetic Polymers 1148 Appendices A-1 Glossary G-1 Credits C-1 Index I-1 Apago PDF Enhancer 825 v smi75625_fm_00i-xxxiv.indd v 11/17/09 11:21:09 AM Contents Preface xviii Acknowledgments xxiii List of How To’s xxv List of Mechanisms xxvii List of Selected Applications xxx Prologue What Is Organic Chemistry? Some Representative Organic Molecules Ginkgolide B—A Complex Organic Compound from the Ginkgo Tree Structure and Bonding 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 1.13 The Periodic Table Bonding 10 Lewis Structures 12 Lewis Structures Continued 17 Resonance 18 Determining Molecular Shape 23 Drawing Organic Structures 27 Hybridization 32 Ethane, Ethylene, and Acetylene 36 Bond Length and Bond Strength 40 Electronegativity and Bond Polarity 42 Polarity of Molecules 44 L-Dopa—A Representative Organic Molecule 45 Apago PDF Enhancer Key Concepts 46 Problems 47 Acids and Bases 54 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 Brønsted–Lowry Acids and Bases 55 Reactions of Brønsted–Lowry Acids and Bases 56 Acid Strength and pKa 58 Predicting the Outcome of Acid–Base Reactions 61 Factors That Determine Acid Strength 62 Common Acids and Bases 70 Aspirin 71 Lewis Acids and Bases 72 Key Concepts 74 Problems 75 vi smi75625_fm_00i-xxxiv.indd vi 11/17/09 11:21:09 AM Contents vii Introduction to Organic Molecules and Functional Groups 81 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 Functional Groups 82 An Overview of Functional Groups 83 Intermolecular Forces 87 Physical Properties 90 Application: Vitamins 97 Application of Solubility: Soap 98 Application: The Cell Membrane 100 Functional Groups and Reactivity 102 Biomolecules 104 Key Concepts 105 Problems 106 Alkanes 113 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 Alkanes—An Introduction 114 Cycloalkanes 118 An Introduction to Nomenclature 119 Naming Alkanes 120 Naming Cycloalkanes 125 Common Names 127 Fossil Fuels 128 Physical Properties of Alkanes 129 Conformations of Acyclic Alkanes—Ethane 129 Conformations of Butane 134 An Introduction to Cycloalkanes 137 Cyclohexane 138 Substituted Cycloalkanes 141 Oxidation of Alkanes 147 Lipids—Part 149 Apago PDF Enhancer Key Concepts 151 Problems 153 Stereochemistry 159 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 smi75625_fm_00i-xxxiv.indd vii Starch and Cellulose 160 The Two Major Classes of Isomers 162 Looking Glass Chemistry—Chiral and Achiral Molecules 163 Stereogenic Centers 166 Stereogenic Centers in Cyclic Compounds 168 Labeling Stereogenic Centers with R or S 170 Diastereomers 175 Meso Compounds 177 R and S Assignments in Compounds with Two or More Stereogenic Centers 179 Disubstituted Cycloalkanes 180 11/17/09 11:21:11 AM I-17 Index Imines (continued) synthesis of (continued) from nucleophilic addition reactions, 788, 788f reduction of nitriles, 865–866 Iminium ion, 798, 800–801, 801f Immunosuppressants, 837 Indene, 636 Indigo, 988 Inductive effects on acidity, 65–66, 66f, 69f in aliphatic carboxylic acids, 703–704 on basicity of amines, 969, 973t in carbocation stability, 256–257 definition of, 65 electron-donating, 654–656 electron-withdrawing, 65, 654–656 on substituted benzenes, 654–657 -ine (suffix), 230–231 Influenza, 86 Infrared (IR) absorptions/spectra of aldehydes, 780–781, 781f of amines, 955, 955f atom mass and, 478–479, 479f of benzene derivatives, 613 bond strength and, 478–479, 479f, 480 of carboxylic acid derivatives, 835, 835t of carboxylic acids, 693–694, 694f characteristic frequencies, A–10 functional groups and, 478, 479, 479f, 480t, 481–485 of hydrocarbons, 481 important, 479, 480t of ketones, 780–781 of nitriles, 835 of nitrogen-containing compounds, 483 of oxygen-containing compounds, 482 percent s-character and, 480 vibration of bonds and, 476–477, 478–480 wavenumber scale of, 476 Infrared (IR) spectroscopy, 464, 474, 476–487 background on, 476–477 functional group identification, 476, 477 IR inactive vibration, 480 isomers distinguished by, 484 structure determination in, 485–487 vibration modes, 476–477 wavenumber scale, 476 Infrared (IR) spectrum characteristics of, 477–478, 478f fingerprint region, 477, 478, 478f, 479, 479f functional group region, 477, 478, 478f, 479, 479f, 480t Inorganic compounds, Inscribed polygon method for predicting aromaticity, 629–631, 630f, 631f Insecticide, 233, 1012 Inspra See Eplerenone Insulin, 1075, 1105, 1106f Integral, NMR spectrum, 507–508 Intermolecular forces, 87–90 of aldehydes and ketones, 779, 780t boiling point and, 90–92, 91f in carboxylic acids, 692, 693f, 693t dipole–dipole interactions, 89, 90t hydrogen bonding, 89, 90t, 954 ion–ion interactions, 87, 90t melting point and, 92–93 solubility and, 93–96, 94f, 96f van der Waals forces, 87–89, 88f, 90t International Union of Pure and Applied Chemistry, 119 See also IUPAC nomenclature smi75625_index_1218-1246.indd 1234 Intramolecular cyclization, of hydroxy aldehydes, 810, 813 Intramolecular hydrogen bonding, in β-dicarbonyl compounds, 882 Intramolecular malonic ester synthesis, 902 Intramolecular reactions aldol reactions, 926–928, 928f Robinson annulation, 936–939 Friedel–Crafts reactions, 652–653, 653f intramolecular Claisen (Diekmann reaction), 932–933 Inversion of configuration, 263 in alkyl tosylate reactions, 339–340 in SN2 substitution reaction, 246–247, 247f, 263 Invirase See Saquinavir Iodine, polarizability of, 88–89 Iodoform, 894–895 Iodoform test, 894 Iodomethane, polarizability and boiling point of, 91f 1-Iodo-1-methylcyclohexane, 289 Ion(s) anions acetate, 66–67, 67f carbanion, 68, 201–202, 201f cyclopentadienyl, 624–625, 630, 630f definition of, enolate, 21 naked, 241 radical, 436 salt formation, 10–11 solvation by hydrogen bonding, 240 bond formation by, 202 cations carbocation See Carbocation(s) counterions, 55 cyclopentadienyl, 625 definition of, radical, 465 salt formation, 10–11 solvation by ion–dipole interactions, 240, 241, 264–265 spectator ions, 55 tropylium, 625–626, 630, 630f counterions, 55 polyatomic, 16 spectator ions, 55 transport across cell membranes, 100–102, 102f Ion–dipole interactions cation solvation by, 240, 241, 264–265 description of, 94, 94f Ionic bonding, 10–11 Ionic compounds boiling points of, 91 formation of, 10–11 intermolecular forces, 87, 90t melting points of, 93 solubility of, 94, 96f Ionic intermediates, 554 Ionic polymerization, 1153–1156, 1155f Ion–ion interactions, 87, 90t Ionophores, 100–102, 102f IR spectroscopy See Infrared (IR) spectroscopy Iso- (prefix), 120 Isoamyl acetate, 836 Isobutane, 115 p-Isobutylbenzaldehyde, 911 Isobutyl chloride, 231f Isobutylene, 1155 Isobutyl group, 121 Isocyanate, 1162 Isoelectric point (pI), for amino acids, 713, 1078, 1078t Isoleucine isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f, 1077 Isomers constitutional See Constitutional isomers definition of, 17, 162 infrared (IR) spectroscopy of, 484 Lewis structures, 17 ortho and para, 668–669 resonance structures compared, 19 stereoisomers See Stereoisomers types of, 181, 181f Isoniazid, 995 Isooctane combustion of, 148 oxidation of, 196, 206, 216 Isopentane, 127 melting point of, 93 structure, 116 Isopentenyl diphosphate, 1134–1136, 1135f, 1138 Isophorone, 948 Isoprene, 581, 605, 1145, 1159 Isoprene unit, 1132–1138 Isopropyl alcohol, 315 Isopropylamine, 356, 952, 963 Isopropylbenzene oxidation to benzoic acid, 671 structure of, 673 synthesis from benzene, 673 Isopropylcyclopentane, 761 Isopropyl group, 120 3-Isopropyl-4-methylcyclohexanone, 778 Isopropyl methyl ether, 322 Isopropyl 2-methylpentanoate, 833 (R)-Isoproterenol, 768 Isopulegone, 493 Isotactic polymer, 1157–1158 Isotopes, 7, 8f of bromine, 469 of carbon, 7, 8f, 472t of chlorine, 468 definition of, masses of common, 472t of nitrogen, 472t of oxygen, 472t IUPAC nomenclature of alcohols, 314–316, 315f of aldehydes, 776, 777f of alkanes, 121–127, 123f, 126f, 127f of alkenes, 362–363 of alkyl halides, 230–231, 231f of alkynes, 401–402 of benzene derivatives, 610–613 of carboxylic acids, 690–692 of cycloalkanes, 125–127, 126f, 127f of epoxides, 317–318 of ethers, 316–317 of ketones, 777–778, 779f Apago PDF Enhancer Jack-o’-lantern mushroom, 905 Januvia See Sitagliptin cis-Jasmone, 435 Johnson, W S., 928 Joule (J), 40 Juvenile hormones, 721, 745, 745f, 1004 mimics of, 745 Kavain, 364 Keflex See Cephalexin Kekulé, August, 608 Kekulé structures, 608, 609 Kelsey, Frances Oldham, 170 Keratins, 1075 α-keratins, 1107–1108, 1108f Kerosene, composition of hydrocarbons in, 128 Ketal, 804 Ketamine, 191 Ketene, 50 Keto–enol tautomers, 410, 881–883 β-Keto esters as active methylene compounds, 924 conversion to ketones, 903–905 pKa, 886t synthesis of Claisen reaction, 928–932, 929f Michael reaction, 935, 936–937 d-Ketohexoses, 1035, 1036f Ketones See also Carbonyl compounds aldol reactions of, 917–919, 922–923, 925–926 boiling point of, 780t carbohydrates, 812–813 in crossed Claisen reactions, 931 fragmentation pattern in mass spectrum, 471 functional group in, 86t hydration of, 802–804 kinetics of hydrate formation, 803–804 thermodynamics of hydrate formation, 802–803 interesting examples, 783 iodoform test of, 894 IR spectra of, 482, 780–781 melting point of, 780t NMR spectra of, 782, 782f nomenclature, 777–778, 779 common names, 778, 779f IUPAC system, 777–778, 779f nucleophilic addition reactions, 724, 774–813 acid catalyzed, 787 carbanion addition, 789–790 cyanide addition, 790–791 hydride addition, 789 mechanism of, 786–787 nucleophiles in, 787–788, 788f primary amine addition, 797–799, 801f secondary amine addition, 800–801, 801f physical properties, 779, 780t pKa, 886t protecting groups for, 808–809 reactions of aldol reactions, 917–919, 922–923, 925–926 with amines, 975 at α carbon, 785–786 at carbonyl carbon, 785, 786 crossed Claisen reactions, 931 halogenation at α carbon, 892–895, 895f hydration, 802–804 nucleophilic addition reactions, 724, 774–813 with organometallic reagents, 742–745, 745f, 789–790 reactivity of, 724 reduction of, 789–790 to alcohols, 727, 728, 729 of aryl ketones to alkyl benzenes, 672–673 reductive amination to amines, 963–966 to secondary alcohols, 432 solubility of, 780t structure of, 722, 775 synthesis of acetotacetic ester synthesis, 900, 903–905 alcohol oxidation, 447, 448, 450 Friedel–Crafts acylation, 643f, 648, 672–673, 784 hydration of alkynes, 409–412, 784 11/24/09 12:13:36 PM Index hydroboration–oxidation of alkynes, 412–413 hydrolysis of acetals, 807–808 hydrolysis of imines and enamines, 801 oxidation of secondary alcohols, 784 oxidative cleavage of alkenes, 444–446, 785 reactions of acid chlorides with organocuprates, 784 tautomers, 864 unreactivity to nucleophilic substitution, 725 unsymmetrical, alkylation of, 898–899 Wittig reaction, 792–797 Ketoprofen, 70, 191 Ketoses d-ketose family, 1035–1036, 1036f structure, 1028–1029 Keto tautomers, 882–883 Kevlar, 1161, 1174 Kiliani–Fischer synthesis, 1049, 1051–1056 Kinetic enolates, 889–890, 898 Kinetic product, in electrophilic addition reactions of conjugated dienes, 586–588, 587f, 588f Kinetic resolution, of amino acids using enzymes, 1084 Kinetics definition of, 206, 215 E1 elimination reactions, 291, 293t E2 elimination reactions, 285 first-order, 217 rate equations, 216–218 second-order, 217 SN1 substitution reactions, 252, 256t SN2 substitution reactions, 244, 249t Lactams, 827 β-Lactam(s), 311, 827, 838, 856–857 β-Lactam family of antibiotics, 463, 485 Lactase, 219, 220f, 1027, 1058 Lactate dehydrogenase, 733 Lactic acid, 29, 696, 733 copolymerization with glycolic acid, 1161 optical activity of, 183 specific rotation of, 185 Lactide, 1168 Lactols, 809, 810 Lactone(s), 398, 827 macrocyclic, 837 synthesis by esterification of carboxylic acids, 848 Lactose, 812, 1027, 1057–1058 breakdown of, 219, 220f Lactose intolerance, 1027, 1058 Laetrile, 792 Lanolin, 1121 Lanosterol, 1140, 1140f Lard, 369 Latanoprost, 697 Latex, 1159, 1160 Lauric acid, 1122t, 1125 Lavandulol, 747 l (levorotatory) compounds, 183, 1033 LDA See Lithium diisopropylamide (LDA) LDL particles (low density lipoproteins), 862 l-Dopa (levodopa), 6, 45, 191, 1115 LDPE (low-density polyethylene), 561, 1152 Leaving group of alcohols, 324, 330–332, 335–336, 338–339 of carbonyl compounds, 722, 724, 725–726 smi75625_index_1218-1246.indd 1235 of carboxylic acid derivatives, 827, 828, 829t, 838–840 in E2 elimination reactions, 287, 288t in nucleophilic acyl substitution reactions, 827, 838–840 in nucleophilic substitution reactions, 235–236, 264 good, 237t periodic trends in ability, 236–237 poor, 237t reaction rate and, 264 weak bases, 236–238 in terpene biosynthesis, 1134–1137 Le Châtelier’s principle, 327–328, 1042 Lecithin, 1126, 1127f Length, units used to report wavelength, 474 Letrozole, 862 Leucine, 191 isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f Leukotrienes, 1129–1130, 1130t, 1131f biological activity of, 348 leukotriene A4, 348 leukotriene C4, 348, 568 synthesis of, 348 Levonorgestrel, 403 Levorotatory (l) compounds, 183, 1033 Lewis acid, 72–74 alkenes as, 372 borane as, 386 carbocation as, 372 catalyst, 333 Lewis acid–base reactions, 73–74, 235 See also Nucleophilic substitution reactions electrophilic addition, 372 SN1 substitution reactions, 252 Lewis base, 72–74 nucleophile as, 238 tetrahydrofuran (THF) as, 386 Lewis structures, 12–18 of acyclic alkanes, 114–115 condensed formula conversion to, 28–29 drawing of, 12–14 formal charge, 15–16, 17t isomers, 17 molecular shape determination, 23–27 multiple bonds in, 14–15 octet rule exceptions, 17–18 resonance structures, 18–23 skeletal structure conversion to, 29–31 Lexan, 1149f, 1163, 1168 Ligands, in palladium-catalyzed reactions, 1005–1006 Light polarized, 182–183 speed of, 475 Limonene, 50, 446, 1137 (R)-limonene, 367f (S)-limonene, 366 Linalool, 747 Linalyl diphosphate, 1137 Linamarin, 791–792 Lindlar catalyst, 435 Linear molecule, 24, 26f, 44 alkynes, 400 Linen, 858, 858f Linoleic acid, 459, 1122, 1122t as essential fatty acid, 368, 369 melting point, 368t structure, 368f, 368t Linolenic acid, 1122, 1122t as essential fatty acid, 368 melting point, 368t as omega-3 fatty acid, 368 sources of, 369 structure, 368f, 368t Lipases, 853 Lipid bilayer, 100, 101f, 102, 102f, 1126–1127, 1128 Lipids, 149–151, 1119–1147 bonding in, 1120 definition of, 149 eicosanoids, 1129–1132, 1130t, 1131f energy in, 151, 1125 examples of, 150, 150f, 1120f fat-soluble vitamins, 1128, 1129f hydrolysis of, 853–855, 1121 hydrolyzable, 1121 metabolism of, 1125 nonhydrolyzable, 1121 origin of word, 1120 oxidation of, 215, 556–557, 556f phospholipids See Phospholipids solubility of, 149, 1120 steroids See Steroids structure of, 150f terpenes, 1132–1138, 1133f, 1133t, 1135f triacylglycerols See Triacylglycerols unsaturated, oxidation of, 556–557, 556f waxes, 1121 Lipitor See Atorvastatin Lipoprotein, 861f, 862 Lipoxygenase, 348, 1130 Lithium electronegativity value of, 739 valence electrons of, 11 Lithium acetylide, 740–741, 745 Lithium aluminum hydride (LiAlH4), 727–730, 733–738, 738t as reducing agent, 428 reduction of aldehydes and ketones, 789 reduction of alkyl halides, 437–438, 438f reduction of a nitrile, 865 reduction of epoxides, 437–438, 438f reduction of nitriles to primary amines, 962 Lithium diisopropylamide (LDA), 898, 925 enolate formation with, 887–888, 889–890 pKa, 887t preparation of, 888 Lithium dimethylcuprate, 492, 1014 Lithium fluoride, 11 Lithium tri-tert-butoxyaluminum hydride, 734, 735, 738t Lithium tri-sec-butylborohydride, 773 Living polymerization, 1155 Local anesthetic, 673 Local mediators, 1130 Log, 59, 60 London forces, 87 See also van der Waals forces Lone pairs in aromatic heterocycles, 621–623 Brønsted–Lowry bases and, 55–56, 55f in carbanions, 202 in heteroatoms, 82, 103 in Lewis structures, 12–15 of negatively charged carbon atoms, 31 number of, 31 in resonance structures, 19, 21, 67, 576 second-row elements and, 12 Long, Dr Crawford, 320 Loratadine, 615f Lotensin See Benazepril Low density lipoproteins (LDLs), 862 Low-density polyethylene (LDPE), 1152, 1169t Lowest unoccupied molecular orbital (LUMO), 629 Apago PDF Enhancer I-18 LSD, 606, 641 intramolecular Friedel–Crafts acylation in the synthesis of, 653, 653f structure of, 959 synthesis of, 641 LTC4, 1130f LUMO (lowest unoccupied molecular orbital), 629 Lycopene, 571, 581, 598, 598f, 1145 Lycra See Spandex Lyrica See Pregabalin Lynen, Feodor, 1140 Lysergic acid diethyl amide See LSD Lysine, 720 abbreviation for, 711t ionizable side chain of, 1077, 1078t isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f Lysozyme, 1104, 1104f d-Lyxose, 1034, 1035f, 1050 Macrocyclic lactone, 837 Macrolide, 837 Magnesium, electronegativity value of, 739 Magnesium monoperoxyphthalate (MMPP), 438f Magnetic resonance imaging (MRI), 527, 527f Ma huang, 166, 192 Malaria, 289, 974 Maleic acid, 112, 592, 603 Maleic anhydride, 591f Malonic acid, 79, 692 Malonic acid synthesis intramolecular, 902 retrosynthetic analysis of, 902–903 step in, 901–902 Malonic ester synthesis, 900–903 Maltose, 824, 1057 Mandelic acid, 194, 1115 Manganese, in oxidizing agents, 438, 439 Mannose in Fischer proof, 1053–1056 d-mannose, 1035, 1035f, 1051 Haworth projections of, 1039–1040 Manoalide, 1134 Margarine, 432–433 Markovnikov’s rule, 374–375, 374f, 378t, 407, 408, 584 in cationic polymerization, 1153 Mass number, Mass spectrometer features of, 464 high-resolution, 472 schematic of, 464f Mass spectrometry (MS) of alkyl halides, 468–469, 469f of amines, 955, 955f analysis of unknowns using molecular ion, 466–468 base peak, 465 of biomolecules, 474 definition of, 464 electrospray ionization (ESI), 474 features of, 464–466 fragmentation in, 465, 469–472, 470f gas chromatography and, 473–474, 473f, 474f high-resolution, 472 M peak, 465, 468–469 M + peak, 466 M + peak, 468–469 Mass spectrum, 465 Mass-to-charge (m/z) ratio, 464f, 465 Mauveine, 988–989 Maytansine, 1025 mCPBA (meta-chloroperoxybenzoic acid), 438f, 439–441 11/24/09 12:13:37 PM I-19 Index MDMA (3,4-methylenedioxymethamphetamine), 998 Mefloquine, 194 Melamine, 1177 Melanin, 599 Melatonin, 494, 522 Melmac, 1177 Melting point of alcohols, 318t of aldehydes and ketones, 780t of alkanes, 129, 130t of alkenes, 365, 368, 368t of alkyl halides, 232t of alkynes, 402 of amines, 954t of carboxylic acids, 693t definition of, 92 of enantiomers, 182, 184, 184t of epoxides, 318t of ethers, 318t of fats, 369, 1122–1123 intermolecular forces and, 92–93 of monosaccharides, 1036 of oils, 369, 1122–1123 of racemic mixtures, 184, 184t of triacylglycerols, 433f Membrane proteins, 1075 Menthol, 49, 108, 156, 1132–1133 Menthone, 108 Meperidine, 950 Mercapto group, 85t Mercury, in Clemmensen reduction, 672–673 Merrifield method, of peptide synthesis, 1099 Merrifield, R Bruce, 1099 Mescaline, 958, 999 Mesityl oxide, 773 Meso compounds, 177–179 achiral compounds, 178, 180–181, 382, 382f, 592, 1013 carbene addition and, 1013 disubstituted cycloalkanes, 180–181 from epoxidation of alkenes, 440 plane of symmetry, 178 Mestranol, 109, 770 Meta (prefix), 611 Metabolite, 157 Meta director, 657, 658, 661, 663–664, 664f, 665, 666, 668–669, 674 Metal–carbenes, 1017 Metal catalyst, 218–219, 429 Metal hydride reagents reducing agents, 428, 727–731, 733–738, 738t reduction of aldehydes and ketones, 727–729 reduction of nitriles, 865 Metals as catalysts, 218–219 in oxidizing agents, 438–439 Metathesis, 1015–1019, 1016f, 1018f derivation of word, 1015 drawing products of, 1016, 1016f mechanism, 1017 ring-closing (RCM), 1018–1019, 1018f Met-enkephalin, 837 Methamphetamine, 65, 958, 964, 964f Methanal See Formaldehyde Methanamine See Methylamine Methane bonding in, 32–33, 33f combustion of, 148 description, halogenation of, 542f Lewis structure, 13 mass spectrum of, 465–466 molecular formula, 114, 115, 118t molecular shape of, 25 smi75625_index_1218-1246.indd 1236 in natural gas, 128 oxidation of, 427, 427f pKa of, 62, 63 structure of, 114 whole-number mass of, 465 Methanesulfonic acid, 710, 837 Methanethiol, 128 Methanol ether formation by addition to alkenes, 378, 379 hybrid orbitals in, 35 Lewis structure, 14 oxidation of, 451 as polar protic solvent, 240f structure of, 319f toxicity of, 319f Methenolone, 1146 Methionine abbreviation for, 711t isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f synthesis of, 1081f Methoprene, 745 Methoxide, as Brønsted–Lowry base, 55f, 56 p-Methoxybenzoic acid, 706 Methoxychlor, 234 Methoxycyclohexane, conformations of, 209 Methoxy group, 316 Methoxy methyl ether, 819 p-Methoxyphenyl ester, 1117 Methyl acetate, 226 formation of, 243 NMR spectrum of, 524, 526f structure of, 826 Methyl acrylate, 591f Methylamine, 952 as Brønsted–Lowry base, 55f, 56 electrostatic potential plot of, 951, 951f N-Methylaniline, NMR spectrum of, 956, 956f p-Methylaniline basicity of, 970 electrostatic potential plot of, 971f Methyl anthranilate, 875 Methylation, with SAM, 250 Methylbenzene See Toluene Methyl benzoate, synthesis of, 847 (R)-α-Methylbenzylamine, 1082–1084 2-Methyl-1,3-butadiene, 581, 1159 2-Methylbutane, 116, 127 2-Methylbutanenitrile, structure of, 832f 2-Methyl-2-butanol, 325 2-Methylbutanoyl chloride, structure of, 830 (R)-α-Methylbutyrophenone, 909 2-Methyl-CBS-oxazaborolidine, 731 Methyl chloride, electrostatic potential plot for, 44, 44f See also Chloromethane Methyl trans-chrysanthemate, 1023 7-Methyl-1,3,5-cycloheptatriene, 636 3-Methylcycloheptene, 363f Methylcyclohexane, 125, 142, 143f 2-Methyl-1,3-cyclohexanedione, 936 1-Methylcyclohexanol, 352 3-Methylcyclohexanol, 315f cis-3-methylcyclohexanol, 340 trans-4-Methylcyclohexanol, 263 2-Methylcyclohexanone, 412, 925 alkylation of, 898–899 enolates formed from, 889 1-Methylcyclohexene, 760, 1005 3-Methylcyclohexene, 375 stereogenic center, 169 5-Methyl-1,3-cyclopentadiene, 636 2-Methylcyclopentanamine, in Hofmann reaction, 979 Methylcyclopentane, 169 2-Methylcyclopentanecarboxamide, structure of, 831 (3R)-3-Methylcyclopentanone, 790 1-Methylcyclopentene, 363f, 928 Methyl dimethylphosphonate, 537 Methylene, 1014 α-Methylene-γ-butyrolactone, 899 Methylene chloride, 233f Methylenecyclohexane, 365, 796 3,4-Methylenedioxymethamphetamine (MDMA), 998 Methylene group, 117, 365 Methyl ester, 1097 3-Methylfentanyl, 467–468 Methyl α-d-glucopyranoside, 1044, 1048f Methyl group, 121 angular, 1138–1139 as electron-donating group, 657 inductive effect of, 654 as ortho, para director, 657, 662, 666–668 Methyl halides coupling reaction with organocuprates, 1003 SN2 substitution reactions, 248, 262 6-Methyl-6-hepten-2-ol, 363 2-Methylhexanoic acid, synthesis of, 903 5-Methyl-3-hexanol, 315 5-Methyl-4-hexen-1-yne, 402f Methyl 5-hydroxyhexanoate, 808 N-Methylisopropylamine, 952 Methyl ketones, 410 halogenation of, 894–895, 895f synthesis in acetoacetic ester synthesis, 900, 903–905 Methyllithium, 740 Methylmagnesium bromide, 740 Methylmagnesium chloride, 748 Methyl 2-methylbutanoate, 836 N-Methylmorpholine N-oxide (NMO), 444 4-Methyl-2-nonene, 395 Methyl orange, 987, 989–990 3-Methylpentanal, 777f 4-Methyl-1-pentanamine, 953 2-Methylpentane, 163f 3-Methylpentane, 163f 4-Methyl-1,4-pentanediol, 748, 749f, 750 2-Methyl-3-pentanone, 779f 3-Methyl-2-pentanone, 778 3-Methyl-2-pentene, 364 (2E)-3-methyl-2-pentene, 364 (2Z)-3-methyl-2-pentene, 364 4-Methyl-3-penten-2-one, 779 Methylphenidate, 191 1-Methyl-4-phenyl-4-propionoxypiperidine, 467–468 N-Methyl-2-propanamine, 952 2-Methyl-1-propanol, 269 2-Methylpropene, 396, 686, 1014, 1155 2-Methylpropene oxide, 1175 2-[4-(2-Methylpropyl)phenyl]propanoic acid, 119 4-Methylpyridine, 948 Methyltriphenylphosphonium bromide, 794 β-Methylvaleraldehyde, 777f Methyl vinyl ketone, 591f, 936 Metoprolol, 78 Mevalonic acid, 157 Micelles, 99 Michael acceptor, 934 Michael reaction, 934–936, 935f Mifepristone, 403 Mineral oil, 158 Mirror images, 160, 163–165, 177 Apago PDF Enhancer Miscibility, 95 Misoprostol, 1131 Mixed aldol reaction See Crossed aldol reactions MMPP (magnesium monoperoxyphthalate), 438f Molecular formula of acyclic alkanes, 114, 118, 118t of alkenes, 360 of alkyl halides, 229 of alkynes, 400 of amines, 955 of butane, 118t of carbohydrates, 1028 of cycloalkanes, 114, 118 of decane, 118t of eicosane, 118t of ethane, 114, 115, 118t of heptane, 118t of hexane, 118t of methane, 114, 115, 118t of nonane, 118t of octane, 118t of pentane, 118t of propane, 114, 115, 118t Molecular ion, 465, 466–468 Molecular orbitals (MOs), 627–629, 628f antibonding, 627, 628f, 629–630 bonding, 627, 628f, 629–631, 630f, 631f degenerate, 629 highest occupied MO (HOMO), 629 lowest unoccupied MO (LUMO), 629 patterns for cyclic, completely conjugated systems, 631f prediction/determination of relative energies of, 629–631, 630f, 631f Molecular orbital (MO) theory, 627 Molecular recognition, 320 Molecular shape bent, 26, 44 determining bond angle, 24–27, 26f bond length, 23, 23t four groups around an atom, 25–27 linear, 24, 26f, 44 tetrahedral, 25–26, 26f three groups around an atom, 24–25 trigonal planar, 24–25, 26f trigonal pyramid, 26 two groups around an atom, 24 Molecules definition of, 11 polarity of, 44, 45f Molina, Mario, 551 Molozonide, 445 Molybdenum, 1015 Monensin, 812 Monohalogenation, 542 Monomers, 1149 Monosaccharides, 1028–1056 d-aldoses, family of, 1034–1035, 1035f common names of, 1029, 1034 constitutional isomers of, 1029 conversion to esters, 1046–1047 conversion to ethers, 1046–1047 cyclic forms, 1036–1042 anomers, 1037–1042, 1041, 1041f chair form, 1040 drawing glucose as a cyclic hemiacetal, 1037–1038, 1038f furanoses, 1041–1042 Haworth projections, 1038, 1039–1041 three-dimensional representations for d-glucose, 1041, 1041f determining structure of unknown, 1052–1053 11/24/09 12:13:37 PM Index examples of, 1029 Fischer projection formulas of, 1030–1033, 1033f Fischer proof of glucose structure, 1053–1056, 1054f glycosides formation, 1043–1044 hydrolysis, 1044–1045 naturally occurring, 1045 isomers (d and l) of, 1033–1034 d-ketoses, family of, 1035–1036, 1036f melting point of, 1036 physical properties of, 1036 reactions at carbonyl group, 1047–1053 addition or removal of one carbon, 1049–1053 Kiliani–Fischer synthesis, 1049, 1051–1056 oxidation, 1047–1049, 1048f reduction, 1047 Wohl degradation, 1049, 1050 reactions at hydroxy groups, 1046–1047 solubility of, 1036, 1047 stereogenic centers in, 1030–1034 d and l designations, 1033–1034 multiple, 1032 structure of, 1028 sweetness of, 1036 Monosodium glutamate (MSG), specific rotation of, 185 Morphine, 55–56, 597, 845, 957 Morton, Dr William, 320 Motrin See Ibuprofen M peak, in mass spectrum, 465, 468–469 M + peak, in mass spectrum, 466 M + peak, in mass spectrum, 468–469 MPPP, 467–468 MRI (magnetic resonance imaging), 527, 527f MS See Mass spectrometry (MS) MSG (monosodium glutamate), specific rotation of, 185 MTBE See tert-Butyl methyl ether (MTBE) Multiple bond in condensed structures, 27–28 Lewis structures, 14–15 position of, 22 Multiplet, NMR spectrum, 511, 511t, 514, 514f α-Multistriatin, 454, 454f Muscalure, 276, 460 Muscone, 730f Mushroom jack-o’-lantern, 905 Psilocybe, 959 Musk deer, 730 Mutarotation, 1039, 1044, 1057 Mycomycin, 195 Myelin sheath, 1128 Myoglobin, 1074, 1109–1110, 1109f Myrcene, 49, 1132–1133 Myristic acid, 1122t Nabumetone, 906, 941 NADH (nicotinamide adenine dinucleotide), 732–733 NAG (N-acetyl-d-glucosamine), 862, 1061–1062 Nandrolone, 1142 Naphthalene, 614, 621, 683 1-Naphthol, 356 Naprosyn See Naproxen Naproxen, 76, 159, 187, 898 Natta, Giulio, 1158 Natural gas, 128 Natural product, 268 smi75625_index_1218-1246.indd 1237 NBS (N-bromosuccinimide), 383–384 Nelfinavir, 615f Neopentane melting point of, 93 structure, 116 van der Waals forces, 88, 88f Neral, 779, 1145 Nerol, 398 Neryl diphosphate, 1137, 1145 Neurotoxin, 84 Neurotransmitter acetylcholine, 861 dopamine, 958, 959f serotonin, 958 Neutrons, Newman projection, 131–132, 132f, 133f Niacin, 98 Nickel, as catalyst, 219 Nicotinamide adenine dinucleotide (NADH), 732–733 Nicotine, 52, 252, 275, 957, 957f, 973 Niphatoxin B, 416, 416f Nitration of benzene, 643f, 646–647, 669 electrophilic aromatic substitution reactions, 643f, 646–647, 667–668 Nitriles, 862–866 acidity of, 885–886 addition of organometallic reagents, 863, 866 dipole–dipole interactions of, 834 hydrolysis of, 863–864, 1081 infrared (IR) spectra of, 483, 835 NMR spectra of, 836 nomenclature, 832, 832f, 833t physical properties, 834 pKa of, 886, 886t reduction of, 863, 865–866 reduction to primary amines, 962 structure and bonding of, 827, 829, 862–863 synthesis of, 862 Nitrite preservatives, 261 p-Nitroaniline basicity of, 970 electrostatic potential plot of, 971f Nitrobenzene, 643f, 646, 647, 657, 663 reduction to aniline, 673 p-Nitrobenzoic acid, 707 Nitrogen in aromatic heterocycles, 621–624, 623f bonding patterns and formal charge, 17t infrared (IR) absorptions in nitrogencontaining compounds, 483 isotopes, 472t mass of, 472t Nitrogen heterocycles, 953 Nitrogen–nitrogen double bond, 986 Nitrogen rule, 467 Nitro group as electron-withdrawing group, 657 in Friedel–Crafts reactions, 665 as meta director, 657, 663–664, 666, 668, 674 reduction of, 673–674, 962 Nitromethane, 78 Nitronium ion, 646 o-Nitrophenol, 611 Nitrosamines in foods, 261 formation of, 261 N-nitrosamine from primary amines, 981 N-nitrosamine from secondary amines, 980, 981–982 N-Nitrosodimethylamine, 261 Nitrosonium ion, 980–982 N-Nitrosopyrrolidine, 261 o-Nitrotoluene, synthesis from benzene, 669 p-Nitrotoluene, 666 Nitrous acid, reaction of amines with, 980–982 NMO (N-methylmorpholine N-oxide), 444 NMR See Nuclear magnetic resonance (NMR) spectroscopy NMR spectrometers, 496, 496f Noble gases, stability of, 10 Node of electron density, 8–9 Nomenclature, A–3–6 See also Common names; IUPAC nomenclature of acid chlorides, 830, 833, 833t of alcohols, 314–316, 315f of aldehydes, 776–777, 777f, 779 of alkanes, 119–128 common names, 127–128, 128f IUPAC system, 121–127, 123f substituents, 120–121 of alkenes, 362–365 of alkyl halides, 230–231, 231f of alkyl substituents that contain branching, A–3–4 of alkynes, 401–402 of amides, 831–832, 833t of amines, 952–954 of anhydrides, 830, 833t of bicyclic compounds, A–5–6 of carboxylic acids, 690–692, 691t E,Z system, 364 of epoxides, 317–318 of esters, 830–831, 833, 833t of ethers, 316–317 generic name, 119 of ketones, 777–778, 779, 779f of monosaccharides, 1028–1029 of nitriles, 33t, 831–832, 832, 832f, 833t of polyfunctional compounds, A–4–5 systematic name, 119 trade name, 119 Nomex, 1174 Nonactin, 101, 102 Nonane constitutional isomers of, 118t molecular formula, 118t Nonbonded (unshared) electrons, 12 Nonnucleophilic bases, 239 Nonpolar bond, 43 Nonpolar molecule description of, 44, 45f solubility of, 94 Nonreducing sugars, 1048, 1048f, 1058 Nonsteroidal anti-inflammatory drugs (NSAIDs), 1131–1132 Noradrenaline (norepinephrine) structure of, 958 synthesis of, 251, 251f Norethindrone, 97, 192, 402–403, 403f, 1142 Novadex See Tamoxifen Novocain See Procaine Noyori, Ryoji, 1085 NSAIDs (nonsteroidal anti-inflammatory drugs), 150, 1131–1132 Nuclear magnetic resonance (NMR) spectroscopy, 464, 474, 494–537 basis of, 495–497 13 C (carbon), 495, 522–526 See also Carbon NMR H (proton), 495, 497–522 See also Proton NMR medical uses of, 527, 527f nuclear spin in, 495–497 reference signal, 497, 523 Apago PDF Enhancer I-20 scale, 497 signal versus peak, 509 spectrometers, 496, 496f variables in, 496–497 Nucleophiles, 85, 238–242 acetylide anions as, 406 addition to carbonyl groups, 787–788, 788f alkyl halide substitution reactions with, 234 ambident, 888 attack of electron-deficient atoms by, 238 biological, 261 carbanions as, 201, 202 common, table of, 242t enolates as, 888–889, 892 hydroxide, in alcohol synthesis, 322 Lewis base, 73 meaning of term, 73 negatively charged, 242t neutral, 242t opening of epoxide rings, 343–345 organometallic reagents as, 739, 741–742 pi (π) bonds and, 82, 103 reactivity of, 102–103 strength, 239–242 strong, 263 in substitution reactions, 235–236 See also Nucleophilic substitution reactions weak, 263 Nucleophile strength See Nucleophilicity Nucleophilic acyl substitution reactions, 725, 838–858, A–13 biological, 860–862, 861f general reaction of, 881 leaving groups in, 827 mechanism of, 838–839 polyester synthesis, 1161–1162 reactions of acid chlorides, 842–843, 858t reactions of amides, 855–857, 858t reactions of anhydrides, 844–845, 858t reactions of carboxylic acids, 845–850, 846f, 858t conversion to acid chlorides, 845–847, 846f conversion to amides, 846f, 849–850 conversion to cyclic anhydrides, 846f, 847 conversion to esters, 846f, 847–849 reactions of esters, 850–855, 855f, 858t reactivity of carboxylic acids and derivatives in, 839–841 summary of reactions, 857–858, 858t Nucleophilic addition reactions aldehydes and ketones, 724, A–14 aldol reactions See Aldol reactions of carbonyl compounds, 881 Michael reaction, 934–935 of nitriles, 863 organometallic reagents with aldehydes and ketones, 742–745, 745f polyurethane synthesis, 1162 α,β-unsaturated carbonyl compounds, 755–758 Nucleophilicity basicity compared to, 239, 240, 241 periodic trends in, 239, 240, 241 SN1 versus SN2 substitution reactions, 262–264 solvent effects, 240–242 polar aprotic solvents, 241, 241f polar protic solvents, 240, 240f steric effects and, 239 11/24/09 12:13:37 PM I-21 Index Nucleophilic substitution reactions, A–13 acetylide anion reactions with alkyl halides, 414–415 adrenaline synthesis, 228, 251, 251f of alcohols, 323–324, 331–338 alcohol synthesis by, 321–322 of alkyl halides, 234–269 amine formation by, 960–962 bimolecular, 243–244 of carbonyl compounds, 724, 725–726, 881 Claisen reaction, 929–932, 929f components of, 235 crown ether use in, 321, 321f epoxide ring opening reactions, 343–347 equilibrium and, 238 ethers with strong acids, 341–343 ether synthesis by, 321–322 features of, 235–236 first-order rate equation, 243, 244 leaving groups in, 235–238, 237t, 264 mechanisms, 242–269 distinguishing between SN1 and SN2, 262–266, 262f, 265t one-step, 243, 244–245, 249t order of bond breaking and bond making, 242–243, 252 SN1, 252–261, 253f, 255f, 256t, 260f SN2, 244–252, 245f, 247f, 248f, 249f, 249t, 250f, 251f, 268t two-step, 243, 244, 252–253, 256t nucleophile strength (nucleophilicity), 239–242, 262–264 organic synthesis by, 267–269, 268t, 272f in polycarbonate synthesis, 1163 rate-determining step in, 243, 244 second-order rate equation, 243, 244 solvent effects on, 240–242, 241f, 264–265, 265t unimolecular, 244, 252 vinyl halides and, 267 Nucleotides, 104–105, 104f Nucleus, atomic, Nylon history of, 825, 859 nylon 6, 1161, 1170 nylon 6,6, 825, 859, 1149f, 1150, 1160, 1167, 1167f synthesis of, 859, 1160–1161 -o (suffix), 230 Occidentalol, 606 Octane, 1021 constitutional isomers of, 118t molecular formula, 118t Octanenitrile, infrared (IR) spectrum of, 483 Octane rating, of gasoline, 83 4-Octene, 396 1-Octen-3-ol, 769 Octet rule, exceptions to, 17–18 Octinoxate, 30, 852, 947 Octylamine, infrared (IR) spectrum of, 483 Octyl salicylate, 852 1-Octyne, 741 Odor(s) of acetone, 783 of acid chlorides, 842 of aldehydes, 783, 783f of amines, 956–957 of caraway, 188 of esters, 836 of spearmint, 188 OH proton, NMR spectra, 517–518, 518f smi75625_index_1218-1246.indd 1238 -oic acid (suffix), 690, 831 Oil(s), 369 crude, 128 degree of unsaturation, 432 essential, 1132 fatty acid composition, 1123, 1123t fish, 1123 hardening, 1124 hydrogenation of, 432–434, 433f, 1124 melting points of, 369, 1122–1123 oxidation of, 556 partial hydrogenation of, 432–433, 433f rancid, 1124 unsaturated, 369 vegetable, 835, 854, 855, 1123, 1124 Oil of ginger, 367f Oil refinery, 128f Oil spill, 129 Olefin metathesis, 1015–1019, 1016f, 1018f Olefins, 359 See also Alkenes Oleic acid, 358, 485, 1122t melting point, 368t structure, 104f, 368f, 368t triacylglycerol formation, 105 Olestra, 854 Olfactory receptors, 187, 188f Olive oil, 369 Omega carbon, 691 Omega-3 fatty acids, 368 -one (suffix), 777 -onitrile (suffix), 832, 833t Open arrow, 417 Opium, 845 Opsin, 799, 799f Optical activity, 182–183 of chiral compounds, 183 dextrorotatory (d) and levorotatory (l) compounds, 183 enantiomeric excess, 184–185 of racemic mixtures, 183 specific rotation, 184, 185 Optical purity, 184–185 Orajel See Benzocaine Oral contraceptives, 399f, 402–403, 403f Orbitals See also Hybrid orbitals; Molecular orbitals (MOs); specific orbitals description, 8–9 number of electrons in, Order, of a rate equation, 217 Organic chemistry definition of, importance of, 1, 2f Organic halides See also Alkyl halides coupling reaction with organocuprate reagents, 1003–1005 coupling with alkenes (Heck reaction), 1003, 1009–1011 coupling with organoboron reagents (Suzuki reaction), 1003, 1005–1009 Organic molecules aromatic compounds, 607–640 common features of, drawing structures of, 3, 27–31 condensed structures, 27–29, 28f skeletal structures, 27–31, 29f examples of, 2–4 grouping by functional group, 83 shape See Molecular shape solubility of, 94–95 Organic reactions, 196–227 See also specific types of reactions acid–base, 56–58, 61–62 arrows used in describing, 202–203, 202t asymmetric, 452 bimolecular, 217 bond breaking and bond making, 200–203, 201f bond dissociation energy, 203–206, 204t catalysts, 218–219, 219f endergonic, 210 endothermic, 203–204 energy diagrams for, 210–215, 212f, 215f energy of activation, 211–216, 212f, 215f, 219, 219f enthalpy change in, 203–206, 209–210 entropy change in, 209–210 enzymes in, 219–220, 220f equations for, 197, 197f equilibrium constants for, 206–209, 207f, 208t exergonic, 210 exothermic, 203–204, 206 free energy changes in, 206–209, 207f, 208t general types, A–13–14 kinetics of, 215–218 learning details of, 390–391 mechanisms of See Reaction mechanism multistep, 214 oxidation and reduction reactions, 147–148, 148f polar, 201, 201f radical, 201, 201f rate of See Reaction rate sequential, 197 thermodynamics of, 206–209, 207f, 208t types of, 198–199 See also specific types of reactions unimolecular, 217 Organic synthesis alkenes in, 391–392 of aspirin, 268, 269f carbon–carbon bond-forming reactions in, 1002–1026 definition of, 267 halogenation reactions, 548–549 halohydrin use in, 385 by nucleophilic substitution reactions, 267–269, 268t reactions with organometallic reagents, 759–761 retrosynthetic analysis, 417–419 sodium borohydride reductions used in, 730f of taxol, 268 Organoaluminum compounds, 1157 Organoborane definition of, 387 in Suzuki reaction, 1003, 1006–1009 synthesis of, 1007 Organocopper reagents See Organocuprate reagents Organocuprate reagents, 739–740 coupling reactions of, 1003–1005 general features of, 1003–1004 hydrocarbon synthesis in, 1004–1005 stereospecificity of, 1004 preparation of, 740 reactions with α,β-unsaturated carbonyl compounds, 757 reactions with acid chlorides, 752 Organolithium reagents, 739–740 addition to nitriles, 866 in anionic polymerization, 1154 arylborane synthesis, 1007 in ethynylestradiol synthesis, 745 in lithium diisopropylamide preparation, 888 Apago PDF Enhancer reactions with aldehydes and ketones, 742, 789 as base, 741 with esters, 752 with α,β-unsaturated carbonyl compounds, 757 Organomagnesium reagents, 739–740 See also Grignard reagents Organometallic reagents, 739–761 See also specific reagents acetylide anions, 740–741 definition of, 739 organic synthesis with, 759–761 preparation of, 740 protecting groups and, 748–750, 749f reactions acid–base, 748 with acid chlorides, 750–753 with aldehydes, 742–745, 745f, 789–790 as base, 739, 741 with carbon dioxide, 753–754 with carbonyl compounds, 742–745, 748–750, 749f with carboxylic acid derivatives, 750–753 with epoxides, 754–755 with esters, 750–752 with ketones, 742–745, 745f, 789–790 as nucleophile, 739, 741–742 summary of, 758 with α,β-unsaturated carbonyl compounds, 755–758 Organophosphorus reagents, 793–794 Organosodium reagents, 740 Ortho (prefix), 611 Ortho, para activator, 658 Ortho, para deactivator, 658 Ortho, para director, 657–658, 661, 662–663, 664f, 666–668, 669, 984 -ose (suffix), 1029 Oseltamivir, 86, 872 Osmium tetroxide as oxidizing agent, 439 in syn dihydroxylation, 443–444 Osprey, 278 Oxalic acid, 696 Oxaphosphetane, 794 Oxazaborolidine, 731 Oxetane, 772 Oxidation, 147–148, 148f, 426–462 of alcohols, 439f, 447–450, 451 of aldehydes, 726–727, 738–739 of aldoses, 1047–1049 of alkanes, 147–149 of alkenes, 428f, 439f, 444–446 of alkyl benzenes, 671–672 of alkylboranes, 388–389 of alkynes, 428f, 439f, 446–447 of carbonyl compounds, 726–727 carboxylic acid synthesis from alkyl benzenes, 698 from alkynes, 698 from primary alcohols, 698 definition of, 147, 427 dihydroxylation, 442–444 anti, 442, 443 syn, 442, 443–444 energy released by, 206 epoxidation, 439–442, 439f Sharpless, 451–454 stereochemistry of, 440 in synthesis of disparlure, 441, 442f of ethanol, 451 of fatty acids, 853 general scheme for, 427f green chemistry, 450–451 11/24/09 12:13:38 PM Index hydroboration–oxidation reactions, 371f, 385–390, 387f, 388f, 389f, 389t, 412–413 of hydrocarbons, 427, 428f of lipids, 151, 215 oxidative cleavage of alkenes, 444–446 of alkynes, 446–447 in haloform reaction, 894–895, 895f of polycyclic aromatic hydrocarbons (PAHs), 349 reduction, relationship to, 427 of substituted benzenes, 671–672 of unsaturated fatty acids, 1124 of unsaturated lipids, 556–557, 556f Oxidation and reduction reactions, 147–148 Oxidative addition in Heck reaction, 1011 in palladium-catalyzed reactions, 1006, 1008, 1011 in Suzuki reactions, 1008 Oxidative cleavage of alkenes, 444–446 of alkynes, 446–447, 698 in haloform reaction, 894–895, 895f Oxidized state, 147 Oxidizing agents, 438–439 See also specific agents NAD+, 733 peroxyacids, 438, 438f Oxime, 1050 Oxiranes, 317 See also Epoxides 6-Oxoheptanal, 945 -oxy (suffix), 316 Oxycodone, 490 Oxygen bonding patterns and formal charge, 17t in condensed structures, 28 infrared (IR) absorptions in oxygencontaining compounds, 482 isotopes of, 472t mass of, 472t as radical scavenger, 541 Oxytocin, 828, 1089, 1090f, 1105 -oyl (suffix), 779 Ozone destruction of atmospheric, 233, 551–552, 552f as oxidizing agent, 438, 445–447 synthesis of, 551 Ozonide, 445, 447 PABA (para-aminobenzoic acid), 599, 684, 990–991 Pacific yew tree, 268 Padimate O, 599 PAHs See Polycyclic aromatic hydrocarbons (PAHs) Pain relievers, 906 See also Analgesics Palladium-catalyzed reactions, 219 alkene reduction, 429 alkyne reduction, 434–435 general features of, 1005–1006 Heck reaction, 1003, 1009–1011 hydrogenation of aldehydes and ketones, 729 oxidative addition in, 1006, 1008, 1011 in peptide synthesis, 1097–1098 reductive elimination in, 1006, 1008, 1011 Suzuki reactions, 1003, 1005–1009 Palmitic acid, 1122, 1122t Palmitoleic acid, 1122t Palm oil, 1123 Palytoxin, 312, 356 Para (prefix), 611 Paracyclophane, 639 Para red, 989 smi75625_index_1218-1246.indd 1239 Parent ion See Molecular ion Parent name, 120 Parkinson’s disease, treatment of, 6, 45, 191, 958, 959f Paroxetine (Paxil), 78 Patchouli alcohol, 331f, 1145 PCB (polychlorinated biphenyl), 95–96 PCC (pyridinium chlorochromate), 438–439, 448 Peanut butter, 432 PEG (polyethylene glycol), 109, 1157 Penicillamine, 1113 Penicillin(s), 838, 856–857 discovery of, 463 penicillin G, 106, 158, 463, 485 1,4-Pentadiene, 572, 573f hydrogenation of, 583 (3E)-1,3-Pentadiene, hydrogenation of, 583 Pentalene, 635 2-Pentanamine, in E2 elimination reaction, 979–980, 979f Pentane, 466–467 boiling point, 91 constitutional isomers of, 118t melting point of, 93 molecular formula, 118t structure, 116 van der Waals forces, 88, 88f, 90 2,4-Pentanedione, 882, 886, 908, 909 Pentanoic anhydride, 870 3-Pentanol, 746 2-Pentanone, 910 mass spectrum of, 472 preparation from an acid chloride and an organocuprate reagent, 753 3-Pentanone, boiling point of, 91, 91f, 914 Pentanoyl chloride, 492, 870 1-Pentene, 466–467 2-Pentylcinnamaldehyde, 923 1-Pentyne, 466–467 Peptide bonds, 1086, 1088–1089 s-cis conformation, 1088 planar geometry of, 1088–1089 s-trans conformation, 1088–1089 Peptides, 837, 1086–1101 constitutional isomers, 1087 interesting examples, 1089–1090, 1090f N- and C-terminal amino acids, 1087 peptide bond in, 1088–1089 sequencing, 1090–1094 amino acid analysis, 1091 Edman degradation, 1091–1092 partial hydrolysis of peptide, 1092–1093, 1093t simple, 1086–1088 synthesis of, 1094–1101 automated, 1099–1100, 1101f protecting groups in, 1094–1098 solid phase technique, 1099–1100 Percent s-character, 41, 68 bond length and, 582 effect on basicity of amines, 972–973 hybrid orbital in alkenes, 284 infrared (IR) absorption and, 480 Percent transmittance, 477 Perfume, 435 Period, in periodic table, Periodic table, 7–10 bond length trends, 23 element location and bonding type, 10 of elements common in organic chemistry, 8f first-row elements, 8f, organization of, second-row elements, 8f, 9–10 bonding of, 12 exceptions to octet rule, 18 shape arrangements, 24 third-row elements, 18 trends acidity, 63–65 electronegativity, 42, 42f Periodic trends in bond dissociation energies, 204–205 in leaving group ability, 236–237 nucleophilicity, 239, 240, 241 Periplanone B, 486, 925, 925f, 1145 Perkin, William Henry, 988–989 Perlon See Nylon, Nylon Peroxide, as radical initiator, 540 Peroxyacetic acid, 438f, 439 Peroxyacids in epoxidation, 439–441 as oxidizing agents, 438, 438f Peroxy radical, 1151 Pesticide, 233 PET See Polyethylene terephthalate (PET) Petroleum, 113, 128–129, 129f alkenes prepared from, 562 ethylene preparation from, 366 as feedstock of polymer synthesis, 1167 Ph- (abbreviation), 612 PHAs (polyhydroxyalkanoates), 1170–1171 PHB (polyhydroxybutyrate), 1171 PHBV, 1171 α-Phellandrene, 1133f Phenacetin, 877 Phenanthrene, 621, 636, 640 Phenol(s), 151, 227, 611, 717 acidity of, 701, 703f as antioxidants, 557 in aspirin synthesis, 268, 269f Bakelite preparation from, 1165 conjugate base of, 701–702, 702f, 703f formation from anisole, 343 hydroxy group of, 313 naming, 612 pKa of, 701, 703f polyhalogenation of, 665 synthesis from aryl diazonium salts, 982 Phenoxide, 701–702, 702f, 703f Phentermine, 76 Phenylacetaldehyde, 777f, 884 Phenylacetamide, 871 Phenylacetic acid, 871 Phenylacetonitrile, 871 Phenylalanine abbreviation for, 711t N-acetyl, 1086 isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f synthesis of, 1080, 1086 4-Phenyl-2-butanone, 998 Phenylcyclohexane conformations of, 208 phenyl group in, 83 Phenylethanal See Phenylacetaldehyde 2-Phenylethylamine, 965 derivatives of, 958–959 in Hofmann elimination reaction, 978 Phenyl group, 83, 84t, 612 (1E)-1-Phenyl-1-hexene, 1024 Phenyl isothiocyanate, 1091–1092 (1Z,3E)-1-Phenyl-1,3-octadiene, 1009 3-Phenyl-1-propanamine, 995 Phenylpropanoic acid, 195 N-Phenylthiohydantoin (PTH), 1091–1092, 1118 N-Phenylthiourea, 1091–1092 Pheromones, 114, 115, 441, 442f, 454, 454f, 843, 844, 925, 925f, 1008 Phomallenic acid C, 421 Phosgene, 1163 Phosphatidylcholine, 1126 Apago PDF Enhancer I-22 Phosphatidylethanolamine, 1126 Phosphine, in palladium-catalyzed reactions, 1005 Phosphoacylglycerols, 1126–1127, 1127f, 1128f Phosphodiester, 1126, 1127, 1128f Phospholipids in cell membranes, 100, 101f, 102, 102f, 1126–1128 phosphoacylglycerols, 1126–1127, 1127f, 1128f sphingomyelins, 1127–1128, 1128f structure of, 100, 101f, 111, 1126 Phosphoric acid, 1126 Phosphoric acid diester, 1126 Phosphorus, octet rule exceptions in, 18 Phosphorus oxychloride, dehydration of alcohols using, 330–331 Phosphorus tribromide, conversion of alcohols to alkyl halides with, 335, 336–337 Photons, 474–476 Photosynthesis, 1028 Phthalic acid, 672 Phthalimide, 961 Phylloquinone, 98 Physical properties See Boiling point; Melting point; Solubility Pi* (π*) antibonding molecular orbital, 627, 628f Pi (π) bond, 37–40, 38f, 39f, 40f in alkene double bond, 281 in alkenes, 359, 360, 370–373, 391 in alkynes, 299, 300f, 400–401, 405–406 in aromatic compounds, 83, 608, 609 breaking in addition reactions, 199, 359, 370–373, 371f, 378, 379, 380, 383, 390, 391 bromination as test for, 380 Brønsted–Lowry bases and, 55–56, 55f in carbonyl group, 85, 722–723, 724 degrees of unsaturation and, 360 delocalized, 583 formation in elimination reactions, 198, 279–280, 291, 294, 299, 300f in functional groups, 82, 102–103 in Lewis base, 72, 74 in polyenes, 580, 581 radical reactions with, 541, 562 in resonance structure, 67 strength, 359 Pi (π) bonding molecular orbital, 627, 628f Picometer (pm), 23 Pi (π) electrons in aromatic compounds, 613, 617, 618–619, 619t in benzene, 609, 610 Hückel’s rule and, 618–619, 619t, 626–629 in NMR spectroscopy, 505–506, 506t Pinacol, 357 Pinacolone, 357 α-Pinene, 1145 Piperidine basicity of, 972–973, 973t structure, 953 Pitocin See Oxytocin Pivalic acid, 60 pKa values, 59–68, A–1–2 acid strength and, 59–60 of amines, 966, 968–969, 974t for amino acids, 1077, 1078, 1078t of carbonyl compounds, 884–885, 885t, 886t definition, 59 of leaving groups in nucleophilic substitution reactions, 237 logarithmic scale of, 60 11/24/09 12:13:38 PM I-23 Index pKa values (continued) of selected organic compounds, 59t of strong acids, 70 of strong bases, 71 PLA (polylactic acid), 860 Planar carbocation, 377, 1043–1044 Planar double bond, 376–377, 381, 386, 388 Planar molecule benzene, 609–610 Plan B, 403 Plane of symmetry, 165–166, 165f in disubstituted cycloalkanes, 180 of meso compound, 178 Plane-polarized light, 182–183 Plaque, atherosclerotic, 861f, 862 Plastic, polyethylene, 84 Plasticizers, 96, 1165–1166 Platinum, as catalyst, 219 Plavix See Clopidogrel β-Pleated sheet, 1101–1104, 1103f, 1105f, 1107f PMMA [Poly(methyl methacrylate)], 568 Poison ivy, 707 Polar aprotic solvents, 241, 241f, 264, 265, 265t, 287, 288t, 889–890 Polar bond carbon–halogen, 234, 234f description of, 43, 44, 45f Polarimeter, 182 Polarity, of carboxylic acids, 699 Polarizability boiling point and, 91f inductive effects on substituted benzenes, 654 van der Waals forces and, 88–89 Polarized light, 182–183 Polar molecule description, 44, 45f solubility of, 94 Polar protic solvents, 240, 240f, 264–265, 265t, 293t, 890 Polar reactions, 201, 201f Poly- (prefix), 1155 Poly(acrylic acid), 561, 1171 Polyacrylonitrile, 1155f Polyalkylation, 666 Polyamides, 825, 859, 1160–1161 PolyAspirin, 1177 Polyatomic ion, 16 Polycaprolactone, 1177 Polycarbonates, 1163 Polychlorinated biphenyl (PCB), 95–96 Polycyclic aromatic hydrocarbons (PAHs), 349, 614, 614f, 621 Polydioxanone, 1177 Polyenes, 580, 581 ultraviolet absorption, 598 Polyesters, 859–860, 1161–1162 Polyethers, 320, 1156 Poly(ethyl acrylate), 568 Poly(ethyl α-cyanoacrylate), 1155f Polyethylene, 84, 366, 366f, 561, 1149f, 1152–1153, 1158, 1159 Poly(ethylene glycol) (PEG), 109, 1157 Polyethylene terephthalate (PET), 719, 859–860, 1148, 1150f, 1161–1162, 1169t, 1170, 1174 Polyfunctional compounds, nomenclature of, A–4–5 Polyhalogenation, 665 Polyhydroxyalkanoates (PHAs), 1170–1171 Polyhydroxybutyrate (PHB), 1171 Poly(hydroxyethyl methacrylate), 568 Polyhydroxyvalerate, 1171 Polyisobutylene, 568, 1155f Poly(lactic acid) (PLA), 860, 1167–1168 smi75625_index_1218-1246.indd 1240 Polymerization, 560–563 anionic, 1154–1155, 1155f of epoxides, 1156–1157 cationic, 1153–1154, 1155f chain branching in, 1152–1153 coordination, 1159 definition of, 561, 1149 feedstock for, 1166–1167 head-to-tail, 563 ionic, 1153–1156, 1155f living, 1155 radical, 562–563, 1151–1152, 1151f, 1153 Ziegler–Natta, 1157–1159 Polymers, 560–562, 560–563, 1148–1178 alternating, 1156 amorphous regions of, 1164–1165 atatic, 1157–1158 “Big Six,” 1169, 1169t biodegradable, 1170–1171 chain-growth, 1149, 1150–1157 in consumer products, 1149, 1149f copolymers, 1156 crystalline regions of, 1164–1165 definition of, 160, 1149 derivation of word, 1149 green synthesis of, 1166–1169, 1167f, 1168f insoluble, 1099 isotactic, 1157–1158 in medicine and dentistry, 561, 562t molecular weights of, 1150 natural and synthetic fibers, 858–860, 858f nylon, 825, 859, 1149f, 1150, 1160–1161, 1167, 1167f, 1170 physical properties of, 1164–1166 polyesters, 859–860 random, 1156 recycling of, 1148, 1169–1170, 1169t shorthand representation of, 1150, 1150f step-growth, 1150, 1160–1164 stereochemistry of, 1157–1159 structure of, 1149, 1164–1166 syndiotactic, 1157–1158 synthetic, 1148–1178 See also Synthetic polymers Poly(methyl methacrylate) (PMMA), 568 Polypropylene, 562t, 1169t Polysaccharides, 1059–1061 cellulose, 1059–1060 glycogen, 1061 starch, 1060–1061 Polystyrene, 96, 538, 562, 1150f, 1169t preparation from ethylene, 366f Polystyrene derivative, 1099 Polytetrafluoroethylene (Teflon), 562t Poly(trimethylene terephthalate) (PTT), 1167, 1168f Polytulipalin, 946 Polyurethanes, 1162 Poly(vinyl acetate), 562, 1155f preparation from ethylene, 366f Poly(vinyl alcohol), 1176 Poly(vinyl butyral), 1176 Poly(vinyl chloride) (PVC), 109, 232, 562t, 1149, 1165, 1169t preparation from ethylene, 366f p Orbitals description, 8–9 hybridization of, 33–40, 33f–35f, 38f–40f hyperconjugation, 257 overlap of, 572–573, 578–579, 582, 610, 610f 2p orbitals, 9, 32–35, 34f in alkenes, 281 in alkynes, 400, 401, 405 Potassium tert-butoxide, 239 in dehydrohalogenation reactions, 280, 280t Potassium dichromate, 438, 448, 449, 449f Potassium hydroxide, in dehydrohalogenation reactions, 280t Potassium iodide, 10, 983 Potassium permanganate (KMnO4) as oxidizing agent, 71–672, 439, 675, 738 in syn dihydroxylation, 443–444 Potassium propanoate, 692 Potassium sorbate, 696 Precor See Methoprene Prednisone, 783 Prefix, 120 cis, 363 cyclo-, 118, 125 deoxy, 1063 di-, 123 E, 363 epoxy, 317 iso-, 120 meta-, 611 ortho-, 611 para-, 611 R, 170–175, 179–180 S, 170–175, 179–180 sec-, 120 tert-, 120, 121 tetra-, 123 trans, 363 tri-, 123 Z, 363 Pregabalin, 106 Preparations, 697 Prepolymer, 1163–1164, 1164f Preservatives, 261 Primary (1°) alcohols, 390 classification as, 313 conversion to alkyl halides with HX, 332–334, 337t conversion to alkyl halides with phosphorus tribromide, 336, 337t conversion to alkyl halides with thionyl chloride, 335–336, 337t dehydration by E2 mechanism, 327 hydrogen bonding extent, 318 from nucleophilic addition to aldehyde, 735 oxidation to carboxylic acids, 447, 448–450, 698 from reactions of aldehydes with organometallic reagents, 742–743 from reduction of acid chlorides, 734 from reduction of aldehydes, 432, 727, 728, 729 from reduction of carboxylic acid derivatives, 727 from reduction of carboxylic acids, 735 from reduction of esters, 734 from reduction of monosaccharides, 1047 Primary (1°) alkyl halides acetylide anion reactions with, 414–415 classification as, 229–230 E2 elimination reactions, 287, 288, 302f example of, 229f SN2 substitution reactions, 248, 262, 262f, 302f synthesis of, 332, 335, 336 Primary (1°) amides, 827, 831, 834–836, 842, 844, 850 tautomers, 863 Apago PDF Enhancer Primary (1°) amines addition to aldehydes and ketones, 797–799, 799f, 801f amino acids, 1077 from direct nucleophilic substitution, 960–961 Gabriel synthesis, 961–962 IR spectra of, 955, 955f nomenclature, 952 reactions with acid chlorides and anhydrides, 975–976 reactions with aldehydes and ketones, 975 reactions with nitrous acid, 980–981 from reduction of amides, 963 from reduction of nitriles, 962 from reduction of nitro compounds, 962 structure of, 950 synthesis from reduction of nitriles, 865 Primary (1°) carbocations, 256 Primary carbon (1°), 116 Primary hydrogen (1°), 116–117 Primary structure, of proteins, 1101, 1107f Primobolan, 1146 Procaine, 615f Progesterone analogs of, 402, 403 function in body, 1141t structure of, 403, 1120f, 1141t synthesis of, 928 Progestins, 1141 Prograf See FK506 Proline, 719 isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f, 1077 Prontosil, 990 Propanal aldol reaction of, 918–919, 922 enolate formation from, 884 IR spectrum of, 780, 781f NMR spectra of, 782, 782f Propanamide boiling point of, 92 infrared (IR) spectrum of, 483 2-Propanamine, 952 Propane, 224 bromination of, 546–547, 547f chlorination of, 546–548, 548f molecular formula of, 114, 115, 118t as propellant, 551 structure of, 114–115 torsional energy of, 134 Propanedioic acid, 692 1,2-Propanediol, 352 1,3-Propanediol, 352, 1167, 1168f, 1176 1,2,3-Propanetriol, 316 Propanil, 999 Propanoic acid NMR spectra of, 695f pKa of, 77 1-Propanol conversion to butanenitrile, 337–338 IR spectrum of, 477 NMR spectrum of, 524, 526f Proparacaine, 684, 1001 Propene borane addition to, 387 hydrohalogenation, 374 monomers in polymerization, 562t radical halogenation, 552–553 synthesis from propylamine, 977–978 2-Propen-1-ol, 363 Propiolic acid, 77 Propionic acid, structure of, 691t 11/24/09 12:13:39 PM Index Propiophenone, 732 halogenation of, 893–894 Propoxyphene (Darvon), 106, 166–167 Propranolol, 70, 356 Propylamine, conversion to propene, 977–978 Propylbenzene, 227, 673 Propyl group, 120 Prostacyclins, 1129–1130, 1130t, 1131f Prostaglandins, 150, 150f, 215, 1129–1131 analogues, 1131 biological functions, 697 inhibitors of synthesis, 1131–1132 PGA2, synthesis of, 286, 933 PGE1, 768, 1131 PGE2, 1130 PGF2α, 150, 150f, 223, 306, 398, 570, 697, 1120f, 1130f, 1144 PGG2, 570, 697 PGI2, 1130f synthesis of, 697, 1130, 1131f Protecting groups, 748–750 acetals as, 808–809 amide for amines, 977 in amino acid synthesis, 1094–1098 general strategy for using, 749f Proteins, 1086, 1101–1110 See also Peptides amide linkages in, 837, 855–856 conjugated, 1109 fibrous, 1106 globular, 1106 important examples, 1106–1110, 1108f, 1109f membrane, 1075 natural fibers, 858, 858f stability of, 855–856 structure, 1101–1106 primary, 1101, 1107f quaternary, 1105, 1107f secondary, 1101–1104, 1102f, 1103f, 1105f, 1107f tertiary, 1104–1105, 1107f subunits, 1105 Protic solvents, polar, 240, 240f, 264–265, 265t, 293t, 890 Proton acceptor, 55 Protonation in acid-catalyzed ester hydrolysis, 851 in aldehyde/ketone nucleophilic addition reactions, 786–787 of carboxylic acids, 699 in glycoside formation, 1043–1044 in glycoside hydrolysis, 1044 in nucleophilic addition to aldehydes and ketones, 724 tautomerization in acid, 410–412 Proton donor, 55 Proton NMR, 495, 497–522 of aldehydes, 782, 782f of amines, 956, 956f of aromatic compounds, 619–620 of benzene derivatives, 518–519, 519f, 613–614, 613t of carboxylic acid derivatives, 836 of carboxylic acids, 694, 695f characteristic absorptions, A–11–12 chemical shift equation for, 498 predicting values of, 503–504 protons on benzene rings, 505, 506t protons on carbon–carbon double bonds, 505, 506t protons on carbon–carbon triple bonds, 505, 506t scale, 497 values for common bonds, 504t coupled protons, 510 smi75625_index_1218-1246.indd 1241 of cyclohexane conformations, 518 general principles chemical shifts, 497–498 downfield signals, 497–498 reference signal, 497 scale, 497 signal intensity, 497 upfield signals, 497–498 identification of an unknown, 519–522 integrals, 507–508 intensity of signals, 507–508 of ketones, 782 number of signals, 498–502 enantiotopic and diastereotopic protons, 500–502 equivalent protons in alkenes and cycloalkanes, 499–500 general principles, 498–499 OH proton, 517–518, 518f position of signals, 502–504 chemical shift values, 503–504, 504t shielding and deshielding effects, 502–503, 502f, 503f, 506f, 506t regions of spectra, 506, 506f spin–spin splitting, 508–517 in alkenes, 516–517, 516f, 517f common patterns of, 512t complex examples of, 513–515 how a doublet arises, 509–510 how a triplet arises, 510 overview of, 508–509 rules and examples, 510–513 Protons description of, relative acidity of, determining, 69–70 Proton transfer reaction aspirin and, 71–72 description of, 56–58 Proventil See Albuterol Proximity effect, 587 Prozac See Fluoxetine d-Pscicose, 1036f Pseudoephedrine, 65, 192, 966, 999 Psilocin, 958–959 Psilocybe mushroom, 959 PTH (N-phenylthiohydantoin), 1091–1092 PTT See Poly(trimethylene terephthalate) Puffer fish, 589, 589f Purification procedures extraction, 707–709, 708f, 709f Purine, 635, 1063–1064 Putrescine, 956–957 PVC See Poly(vinyl chloride) Pyran, 1037 Pyranose ring, 1037, 1056 Pyrethrin I, 106, 1012, 1023 Pyridine, 71, 369–370, 621–622, 687, 842 alcohol conversion to alkyl tosylates in, 338–340, 341f basicity of, 972–973, 973t, 974t conversion of alcohols to alkyl halides, 335–336 conversion of monosaccharides to esters using, 1046 dehydration of alcohols using, 330–331 electrostatic potential plot of, 622, 623f structure of, 953 Pyridinium chlorochromate (PCC), 438–439, 448 Pyridoxine, 109 Pyrimidine, 1063–1064 α-Pyrone, 635 Pyrrole, 622, 636, 687, 995 basicity of, 972, 973t, 974t electrostatic potential plot of, 622, 623f structure of, 953 Pyrrolidine, structure of, 953, 995 Pyruvic acid, 733 Qinghao, 389 Quantum, 474 Quartet, NMR spectrum, 511t, 512t, 518 Quaternary ammonium salt See also Ammonium salt in Hofmann elimination reaction, 977–978 synthesis of, 960–961 Quaternary carbon (4°), 116 Quaternary structure, of proteins, 1105, 1107f Quiana, 1174 Quinine, 194 as natural alkaloid, 957 source of, 289 structure of, 624, 975 synthesis of, 288, 289f, 896, 896f Quinoline, 435 Quintet, NMR spectrum, 511t Quinuclidine, 277 R (prefix), 170–175, 179–180 Racemic mixture (racemate), 183–184, 184t of alcohols from hydroboration– oxidation of alkenes, 389 alkene halogenation, 381 of alkyl chlorides, 334 of amino acids, separation of, 1081–1084, 1082f in carbene addition, 1014 in enolate alkylation, 898 from epoxidation of alkenes, 440 in epoxide ring opening reactions, 344 formation by hydrohalogenation, 376 halogenation reactions and, 381, 549–550 in hydride reduction of ketones, 730 SN1 substitution reactions and, 254–255, 255f Racemic switch, 187 Racemization at α carbon of carbonyl compounds, 891 definition of, 254 in SN1 substitution reactions, 254–255, 255f Radiation electromagnetic, 474–476, 475f infrared, 476–477 RF (radiofrequency), 495–496, 527 ultraviolet, 599 Radical(s) bond formation from, 202 definition of, 539 as electrophile, 202 as reactive intermediate, 201–202, 201f resonance-stabilized, 555 stability of, 539–540, 540f Radical anion, 436 Radical cation, 465 Radical inhibitor, 541 Radical initiator, 540 Radical intermediates, 539, 554, 558 Radical polymerization, 1151–1152 chain branching in, 1153 chain termination in, 1152 monomers used in, 1151, 1151f Radical reactions, 201, 201f, 538–570 See also specific reactions of alkanes, 541–551 of alkenes, 541, 558–560 applications of antioxidants, 557 oxidation of unsaturated lipids, 556–557, 556f ozone destruction by CFCs, 551–552, 552f carbon–hydrogen bond, reaction of radical with, 540–541 double bonds, addition to, 541, 558–560 Apago PDF Enhancer I-24 general features of, 540–541 halogenation at allylic carbon, 552–555 bromination, 553–554 product mixtures in, 555 halogenation of alkanes, 541–551 of achiral starting material, 549–550, 549t bromination, 546–547, 547f of chiral starting material, 549t, 550 chlorination, 544–548, 544f, 545f, 548f, 549–551 energy changes during, 544, 544f, 545f mechanism of, 542–544 in organic synthesis, 548–549 stereochemistry of, 549–551, 549t halogenation of alkyl benzenes, 669–671 inhibitors of, 541 polymerization, 560–563, 562t two radicals reacting with each other, 541 Radical scavenger, 541 Radical substitution reaction, 541, A–13 Randomness, entropy as measure of, 209 Rate constant (k), 216–217 Rate-determining step in chlorination of ethane, 544, 545f, 548 E1 elimination reactions, 292 electrophilic additions, 373, 373f, 374 in halogenation reactions, 546–548 bromination, 547 chlorination, 548 halogenation of alkenes, 382 in a multistep mechanism, 214–215, 217 in nucleophilic substitution reactions, 243, 244 rate equation for, 217 SN1 substitution reactions, 260 Rate equation, 216–218 first-order, 217, 243, 244 for nucleophilic substitution reactions, 243–244 second-order, 217, 243, 244 Rate law, 216–218 RCM (ring-closing metathesis), 1018–1019, 1018f Reaction arrow, 197, 202t curved, 201, 202, 202t double, 202t Reaction coordinate, 210, 211, 212f, 215f Reaction mechanism bond cleavage, 200–202 bond formation, 202 concerted, 200 definition of, 200 energy diagram for a two-step, 213–215, 215f rate equations and, 216–218 stepwise, 200, 213–215, 217 Reaction rate catalysts and, 218–219, 219f concentration effect on, 216, 217–218 of endothermic reactions, 212f, 259 energy of activation (Ea) and, 215–217 of exothermic reactions, 212f, 259 nucleophilic substitution reactions, 264–265 rate-determining step, 214–215, 217 temperature effect on, 216 Reactions See Organic reactions Reactive intermediate carbanion, 201–202, 201f carbocation, 201–202, 201f, 252–253, 330 description of, 200 radicals, 201–202, 201f synthetic intermediate compared, 392 11/24/09 12:13:39 PM I-25 Index Reactivity, functional groups and, 102–104 Reactivity–selectivity principle, 546 Reagent, 197, 197f Rebaudioside A, 1045 Receptors, chiral, 187 Recycling of polymers, 1148, 1169–1170, 1169t Red seaweed (Asparagopsis taxiformis), 232 Reduced state, 147 Reducing agents, 428 See also specific agents chiral, 731 metal hydride reagents, 428, 727–731, 733–738, 738t NADH, 732–733 Reducing sugars, 1048, 1048f, 1057 Reduction, 147–148, 148f, 426–462 of acid chlorides and esters, 734–735 of alkenes, 427, 428–432, 428f of alkyl halides, 437–438, 438f of alkynes, 427, 428f, 434–437, 437f to alkanes, 428f, 434–435 to cis alkenes, 434, 435 to trans alkenes, 434, 436 of amides to amines, 736–737, 963 of aryl ketones to alkyl benzenes, 672–673 asymmetric, 731 of carbonyl compounds, 726–738 biological, 732–733 carboxylic acids and derivatives, 733–738 by catalytic hydrogenation, 729 enantioselective, 731–733, 732f with metal hydride reagents, 728–729, 730f, 738t stereochemistry of, 729–731 of the carbonyl group of monosaccharides, 1047 Clemmensen, 672 definition of, 147, 427 dissolving metal, 428, 436 of epoxides, 437–438, 438f general scheme for, 427f of hydrocarbons, 427, 428f hydrogenation, 429–434 of ketones to amines, 963–966 of nitriles, 863, 865–866 of nitriles to amines, 962 of nitro groups, 673–674 oxidation, relationship to, 427 of polar C–X sigma (σ) bonds, 437–438 of triple bonds, 437–437, 437f Wolff–Kishner, 672 Reductive amination, of aldehydes and ketones to amines, 963–966 Reductive elimination in Heck reaction, 1011 in palladium-catalyzed reactions, 1006, 1008, 1011 in Suzuki reactions, 1008 Refining, 128–129, 129f Refrigerant, 233 Regioselectivity of alcohol dehydrations, 325 of E1 elimination reactions, 293 of E2 elimination reactions, 289, 296 of electrophilic addition of hydrogen halides, 374 of epoxide ring opening reactions, 345–346 of halohydrin formation, 384–385, 385t of Hofmann elimination, 979 of hydroboration, 387 Reserpine, 879 Resolution, of amino acids, 1081–1084, 1082f smi75625_index_1218-1246.indd 1242 Resolving agent, 1082 Resonance, 18–23 of allylic carbocations, 574–575, 574f allyl type, 575–576 benzene, 609 examples of, 575–577 theory/principles, 18 usage of term, 574 Resonance delocalization, 67 Resonance effects on acidity, 66–67, 67f, 69f on basicity of amines, 973t electron-donating, 654–656 electron-withdrawing, 654–656 on substituted benzenes, 654–657 Resonance hybrid, 18, 22–23 of benzene, 609 drawing, 22 electron delocalization, hybridization, and geometry, 578–579 major contributor to, 577–578 minor contributors to, 577–578 Resonance stabilization, of carboxylic acids, 701–702, 702f, 703f Resonance-stabilized allyl carbocation, 574–575, 574f, 575f Resonance-stabilized carbocation, 584–585, 587 in electrophilic aromatic substitution reaction, 643 in glycoside formation, 1043–1044 in glycoside hydrolysis, 1044 Resonance-stabilized radical, 555 Resonance structures, 18–23, 574–579 of acetate, 701, 703f acidity and, 66–67 of allyl radical, 553 of benzylic radical, 669 of carboxylic acid derivatives, 828 cations with positive charge adjacent to lone pair, 576 conjugated allyl carbocation, 574 of conjugated dienes, 582, 583 double bond conjugated, 576 major contributor, 577–578, 582 minor contributors, 577–578, 582 with one atom more electronegative than the other, 576, 577 drawing, 19–22 of enolates, 884 of enols, 883–884 isomers compared to, 19 of naphthalene, 621 of phenoxide, 701–702, 702f, 703f stability of, 577–578 of substituted benzenes, 654–655 three atom allyl system, 575–576, 577 of α,β-unsaturated carbonyl compound, 934 of Wittig reagent, 793 Retention of configuration in conversion of alcohols to alkyl tosylates, 338–339, 340 in oxidation of alkylboranes, 388–389 in SN2 substitution reactions, 246 Retention time, in gas chromatography, 473–474 Retinal, 799, 799f Retinol, 97 Retro Diels–Alder reaction, 595–596 Retrosynthetic analysis, 392, 417–419 in acetoacetic ester synthesis, 904 in benzene derivative synthesis, 985 of Diels–Alder product, 595 of disparlure, 441 of Grignard products, 746–748 of Heck reaction, 1010 organometallic reagent reactions, 760–761 in substituted benzene syntheses, 674, 675–677 synthesis of m-bromoaniline from benzene, 674 using aldol reaction, 920–921 using malonic ester synthesis, 902–903 Wittig reaction, 795–796 RF radiation, 495–496, 527 R group, 82, 120 identity in SN2 substitution reactions, 248–249, 249t Rhodium, 1085 Rhodopsin, 799, 799f Ribbon diagrams, 1104 α-d-Ribofuranose, 1042, 1062 β-d-Ribofuranose, 1042 Ribonucleosides, 1063–1064 Ribonucleotides, 1064 d-Ribose, 1034, 1035f, 1063 d-Ribulose, 1036f Rimantadine, 966 Ring-closing metathesis (RCM), 1018–1019, 1018f Ring-flipping, 140–141, 141f Ring formation, in Robinson annulation, 936–939 Ring-opening metathesis polymerization (ROMP), 1022 Ritalin See Methylphenidate RNA, 1064, 1065f Robinson, Sir Robert, 936 Robinson annulation, 936–939 Rocaltrol See Calcitriol Rofecoxib, 1132 Row, in periodic table, Rowland, F Sherwood, 551 RU 486, 403 Rubber, 1149f, 1159–1160, 1159f Rubbing alcohol, 319f Ruthenium, 1015 Apago PDF Enhancer S (prefix), 170–175, 179–180 Saccharide, origin of word, 1028 Saccharin, 1058, 1059f Safflower oil, 369 Safrole, 998 Salicin, 71, 195, 696, 1045 Salicylamide, 874 Salicylates, 71 Salicylic acid, 696, 873 Salmeterol, 347, 347f, 732f, 772 Salsolinol, 820 Salts Brønsted–Lowry bases and, 55 of carboxylic acids, 696 formation of, 10–11 negatively charged nucleophile, 235 SAM (S-Adenosylmethionine), 250 SAMe, 250 Samuelsson, Bengt, 697 Sandmeyer reaction, 983 Santalbic acid, 401 Saponification, 851, 854–855 Saponins, 98 Saquinavir, 195 Saran, 1156 Saturated fats, 369 Saturated fatty acid, 358 Saturated hydrocarbons, 114 Saytzeff rule, 289 SBR (styrene–butadiene rubber), polymerization of, 1156 Sch38516, 1018f s-character, of hybrid orbitals, 68 Schiff base, 797 Schrock, Richard, 1015 s-cis conformation, 580 Scombroid fish poisoning, 622 Seashells, chiral helical, 166 Seaweed, 232 Sebacic acid, 1177 Sebacoyl chloride, 1177 sec- (prefix), 120 Secondary (2°) alcohols, 390 classification as, 313 conversion to alkyl halides with HX, 332–334, 337t conversion to alkyl halides with phosphorus tribromide, 336, 337t conversion to alkyl halides with thionyl chloride, 335–336, 337t dehydration by E1 mechanism, 326 hydrogen bonding extent, 318 oxidation to ketones, 447, 448, 450 from reactions of aldehydes with organometallic reagents, 742–743 from reduction of ketones, 432, 727, 728, 729 Secondary (2°) alkyl halides acetylide anion reactions with, 414–415 classification as, 229–230 E1 elimination reactions, 292, 303f E2 elimination reactions, 287, 302f–303f example of, 229f SN1 substitution reactions, 255, 262, 262f, 303f SN2 substitution reactions, 248, 262, 262f, 302f synthesis of, 332, 335, 336 Secondary (2°) amides, 827, 831–832, 834–836, 842, 844, 850 Secondary (2°) amines addition to aldehydes and ketones, 800–801, 801f from direct nucleophilic substitution, 960 IR spectra of, 955, 955f nomenclature, 952–953 proline, 1077 reactions with acid chlorides and anhydrides, 975–976 reactions with aldehydes and ketones, 975 reactions with nitrous acid, 981–982 from reduction of amides, 963 structure of, 950 Secondary carbon (2°), 116 Secondary hydrogen (2°), 116–117 Secondary structure, of proteins, 1101–1104, 1102f, 1103f, 1105f, 1107f Second-order kinetics, 217 of E2 elimination reactions, 285 in nucleophilic substitution reactions, 243–244 Second-order rate equation, 217, 243, 244 L-Selectride, 773 Selective serotonin reuptake inhibitors (SSRIs), 958 Separation, of amino acids, 1081–1084 Separatory funnel, 707, 708f Septet, NMR spectrum, 511t, 513 Serevent See Salmeterol Serine abbreviation for, 711t isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f Serotonin, 874, 958 Sertraline, 615f, 653 Sex hormones, 1141–1142, 1141t See also specific hormones Sex pheromone, 486, 1002 Sextet, NMR spectrum, 511t, 515f 11/24/09 12:13:39 PM Index Sharpless epoxidation, 451–454, 1085 Sharpless, K Barry, 452 Sharpless reagent, 452 Shell, of electrons, 8–9 Shielding effects, in NMR, 502–503, 502f, 503f, 506f, 506t 1,2-Shifts, 328–330 Shikimic acid, 86 Sickle cell anemia, 1110 Sickle cell hemoglobin, 1110 Side chain, of amino acid, 1075, 1077, 1078t Sigma (σ) bond, 32, 33, 36–40, 38f, 39f, 40f in alkanes, 83 in alkenes, 281, 359, 428–429 in alkynes, 400–401 breaking in addition reactions, 199 carbon–oxygen, 313 formation in addition reactions, 370, 371, 371f, 372 formation in elimination reactions, 198 functional groups that contain C–Z σ bonds, 84, 85t hyperconjugation, 257 inductive effect and, 65, 256 length in conjugated dienes, 581–582 radical reactions with, 540 rotation around, 129 in substitution reactions, 198, 242 Sildenafil, 615f Silent Spring, 233 Silk, 858, 858f binding of dyes to, 989–990 structure of, 1104, 1105f Silver(I) oxide in aqueous ammonium hydroxide, 738 as oxidizing agent, 439 Silyl ether, 749 Simmons, H E., 1014 Simmons–Smith reaction, 1014–1015 Simmons–Smith reagent, 1015 Simvastatin, 170, 581, 581f, 1140, 1141f α-Sinensal, 723 Singlet, NMR spectrum, 508, 511t, 518 Sirenin, 1024 Sitagliptin, 624 Six-membered ring, synthesis of in aldol reaction, 928 in Dieckmann reaction, 933 in Robinson annulation, 936–939 Skeletal structures, 29–31, 29f with charged carbon atoms, 31 Smith, R D., 1014 SN1 substitution reactions, 252–261 alcohol conversion to alkyl halide, 332–334 alkyl halide identity in, 262, 262f applications of, 261 carbocation stability, 256–258 Hammond postulate and, 258–261 hyperconjugation and, 257–258 inductive effects and, 256–257 E1 elimination reaction compared, 294, 300–304, 302f–303f E2 elimination reaction compared, 300–304, 302f–303f energy diagram for, 253, 253f, 260f ethers with strong acids, 341–342 features of, 252 kinetics of, 252, 256t leaving group in, 264 nucleophile strength in, 262–264 racemization in, 254–255, 255f rate-determining step, 260 R group in, 255–256, 256t SN2 reactions compared, 262–266, 262f, 265t, 300–304, 302f–303f smi75625_index_1218-1246.indd 1243 solvent effects on, 264–265 stereochemistry, 253–255, 255f, 256t transition state in, 253, 253f, 264 two-step mechanism for, 252–253, 256t SN2 substitution reactions, 244–252 in acetoacetic ester synthesis, 904, 905 acetylide anion reactions with alkyl halides, 414–415 acetylide anion reaction with epoxides, 416–417 alcohol conversion to alkyl halides, 336–337 with HX, 332–334 with phosphorus tribromide, 336–337 with thionyl chloride, 335–336 alcohol synthesis from alkyl halides, 321–322 alkyl halide identity in, 262, 262f alkyl halide with ammonia or amine, 960–961 alkyl tosylate reactions, 339–340 applications of, 250–252, 250f, 251f in automated peptide synthesis, 1099 backside attack in, 245–247, 263 direct enolate alkylation, 897 E1 elimination reactions compared, 300–304, 302f–303f E2 elimination reactions compared, 300–304, 302f–303f energy diagrams for, 245, 245f, 249f epoxide ring opening reactions, 343–345 epoxide synthesis from halohydrin, 323 epoxy resin synthesis, 1163 ethers with strong acids, 341–342 ether synthesis from alkyl halides, 321–322 features of, 244, 249t frontside attack in, 245–246 of α-halo acids with ammonia, 1078–1079, 1081f of α-halo carbonyl compounds, 896, 896f kinetics of, 244, 249t leaving group in, 264 in malonic ester synthesis, 901 nitrile synthesis, 862 nucleophile strength in, 262–264 one-step mechanism for, 244–245, 249t organic synthesis, 267, 268t, 269 reduction of alkyl halides, 437–438, 438f reduction of epoxides, 437–438, 438f R group in, 248–249, 249t SN1 reactions compared, 262–266, 262f, 265t, 300–304, 302f–303f solvent effects on, 264–265 stereochemistry of, 245–248, 247f, 249t steric hindrance and, 248–249, 248f, 249t transition state, 245, 245f, 246, 247f, 264 Soap, 98–99, 99f, 851, 854–855 Sodium, in dissolving metal reductions, 428, 436 Sodium acetate, 93, 692 Sodium amide, for alkyne synthesis by dehydrohalogenation, 299, 300f Sodium benzoate, 696, 708 Sodium bisulfite, 443–444 Sodium borohydride, 428, 727–731, 730f, 738, 738t, 789, 1047 Sodium chloride, 10–11 Sodium cyanoborohydride, for reductive amination of aldehydes and ketones, 964 Sodium dichromate, 438, 448 Sodium ethoxide, 322 in dehydrohalogenation reactions, 280t Sodium hydroxide in dehydrohalogenation reactions, 280, 280t use in extraction procedure, 707–708, 709f Sodium hypochlorite, 451 Sodium iodide, 983 Sodium methoxide, 322 in dehydrohalogenation reactions, 280t Sodium nitrite, 261 Sodium salicylate, 696 Sodium trichloroacetate, 1023 Soft coral (Capnella imbricata), 416 Solanine, 1045 Solid phase technique, of amino acid synthesis, 1099–1100 Solubility, 93–96 of alcohols, 318t of aldehydes and ketones, 780t of alkanes, 129, 130t of alkenes, 365 of alkynes, 402 of amines, 954t of carboxylic acids, 693t definition of, 93 of enantiomers, 182 of epoxides, 318t of ethers, 318t intermolecular forces and, 93–96, 94f “like dissolves like,” 94 of lipids, 149, 1120 of monosaccharides, 1036, 1047 Solute, 93 Solvent effects, on nucleophilic substitution reactions, 240–242, 240f, 241f, 264–265, 265t Solvents, 93 alkyl halides, 232 in E1 elimination reactions, 293t in E2 elimination reactions, 287, 288t for extraction procedure, 707–709, 708f, 709f liquid, 197 nonpolar, 94 nucleophilicity and, 240–242, 265 organic, 94 polar, 94 polar aprotic, 241, 241f, 264, 265, 265t, 287, 288t, 889–890 polar protic, 240, 240f, 264–265, 265t, 293t, 890 s Orbitals description, 8–9 hybridization of, 33–40, 33f–35f, 38f–40f 1s orbital, 9, 32 2s orbital, 9, 32–34, 34f Sorbitol, 179, 180, 1047 d-Sorbose, 1036f Sorona, 1167, 1168f Spam, 261 Spandex, 1162 Spearmint, odor of, 188 Specific rotation, 184, 185 Spectator ions, 55 Spectrometer, NMR, 496, 496f Spectroscopy, 465 Spermaceti wax, 1121 Spermine, 950 SPF rating (sun protection factor), 599 Sphingomyelins, 1127–1128, 1128f Sphingosine, 1127 sp hybrid orbitals, 34–35, 34f, 38–39, 40f in alkynes, 400, 401, 405 percent s-character, 41, 68 Apago PDF Enhancer I-26 sp2 hybrid orbitals, 34–35, 34f, 37, 39f, 40f, 257, 267, 313, 365 in alkenes, 281, 283–284, 359 of alkyl halides, 229, 229f, 267 in aromatic heterocycles, 621–623, 623f carbon radical, 539 carboxy group, 689 percent s-character, 41, 68 sp3 hybrid orbitals, 33–34, 33f, 35, 35f, 36, 36f, 39f, 40f, 242, 313, 365 in acyclic alkanes, 114 in alkenes, 283–284 of alkyl halides, 229, 229f in nucleophilic substitution reactions, 235–236 percent s-character, 41, 68 Spiriva See Tiotropium bromide Spiro ring system, A–6 Splenda See Sucralose Squalene, 157, 459, 1133f, 1135–1136, 1135f, 1140, 1140f Squalene oxide, 1140, 1140f Stachyose, 1072 Staggered conformation, 131–137, 132f, 133f, 134f, 136f, 295, 295f Stanozolol, 639, 1142 Starch hydrolysis of, 160, 161, 161f, 319, 320f, 1061 structure of, 160–161, 161f, 162f, 1060–1061 Stearic acid, 358, 1122, 1122t melting point, 368t structure, 368f, 368t Stearidonic acid, 368–369, 457 Step-growth polymers, 1150, 1160–1164 epoxy resins, 1163–1164, 1164f polyamides, 1160–1161 polycarbonates, 1163 polyesters, 1161–1162 polyurethanes, 1162 Stepwise reaction, 200 Stereocenter See Stereogenic centers Stereochemistry, 129, 159–195 of addition reactions, 371, 376–378, 377f, 378t of carbonyl reduction, 729–731 chemical properties of enantiomers, 186–188 chiral and achiral molecules, 163–166, 165f diastereomers, 175–177, 185–186, 186f of Diels–Alder reaction, 592 of dienophiles, 592 of dihydroxylation, 442–444 of disubstituted cycloalkanes, 180–181 of E2 elimination reactions, 295–298, 295f of electrophilic addition reactions, 376–378, 378t of enolate alkylation, 898 of epoxidation, 440 of halogenation reactions, 381–383, 549–551, 549t of halohydrin formation, 384–385, 385t of hydroboration–oxidation reactions, 388–389, 389t meso compounds, 177–179, 177f physical properties of stereoisomers, 182–186, 184t, 186f polymer, 1157–1159 reactions of organometallic reagents, 744 of SN2 substitution reactions, 245–248, 247f, 249t of SN1 substitution reactions, 253–255, 255f, 256t 11/24/09 12:13:39 PM I-27 Index Stereochemistry (continued) of starch and cellulose, 160–162, 161f, 162f stereogenic centers, 166–180, 168f, 172f Stereogenic centers, 166–180 in amines, 951–952 in amino acids, 710–711, 1075, 1077 on carbon atoms not part of ring, 166–167 in cyclic compounds, 168–170 definition of, 164 in diastereomers, 175–177 drawing enantiomers, 168, 168f formation from hydrohalogenation, 376, 377 halogenation reactions and, 549–551 inversion of configuration around, 246–247, 247f labeling with R or S, 170–175, 172f, 175f, 179–180 in meso compounds, 177–179 in monosaccharides, 1030–1034 number in a molecule, 165 priority assignment, 170–174, 172f retention of configuration around, 246 tetrahedral, 164–165, 166, 168, 169, 178 Stereoisomers See also Enantiomers in alkenes, 360t chemical properties of, 186–188 cis, 144–147 configuration of, 162 of conjugated dienes, 580 constitutional isomers compared, 163f of cycloalkanes, 144–147 definition of, 144 diastereomers, 175–177, 177f, 185–186, 186f disubstituted cycloalkanes, 180–181 enantiomers, 164 of monosaccharides, 1032–1036, 1034f nomenclature for alkenes, 363–364 number of, maximum, 175 physical properties of, 182–186, 184t, 186f starch and cellulose, 160–162 trans, 144–147 Stereoselective reaction dissolving metal reduction of alkynes, 436 of E2 elimination reactions, 290 Stereospecific reactions carbene addition, 1013–1014 coupling reactions with organocuprates, 1004 definition of, 382 epoxidation, 440 halogenation of alkenes, 382 Heck reaction, 1009–1010 Simmons–Smith reaction, 1015 Suzuki reaction, 1006 Steric effects, nucleophilicity and, 239 Steric hindrance, 239 in alcohols, 318 in hydroboration reactions, 387 SN2 substitution reactions and, 248–249, 248f, 249t Steric strain, 135, 136t, 138, 239 Steroids, 1138–1142 adrenal cortical, 1142 anabolic, 1142 cholesterol See Cholesterol sex hormones, 1141–1142, 1141t structure of, 1138–1139, 1139f synthesis in Diels–Alder reaction, 596–597 smi75625_index_1218-1246.indd 1244 Stone, Reverand Edmund, 71 Strain angle, 137–139, 314 Baeyer strain theory, 137 steric, 135, 136t, 138, 239 torsional, 133–134, 136t, 137, 138 s-trans conformation, 580 Strecker synthesis, 1080–1081, 1081f Strong electrostatic interactions, in ionic compounds, 87 Strychnine, 1084 Styrene, 538, 562, 671, 1016, 1016f, 1021 polymerization of, 1150f, 1151, 1153, 1156 structure of, 1150f, 1151f Styrene–butadiene rubber (SBR), 1156 Substituents, naming, 120–121, 611–612 naming aromatic rings as, 612 Substitution reactions, A–13 alcohols, 323–324, 331–338 allylic, 554 of aryl diazonium salts, 982–986 at α-carbon of carbonyl compounds, 880–906 description of, 198 electrophilic aromatic See Electrophilic aromatic substitution reactions Heck reaction, 1003, 1009–1011 nucleophilic, 235–269 radical, 541 Substrate, 219–220, 220f Succinic acid, 692 Sucralose, 1058, 1059f Sucrose, 109, 157, 1058, 1058f olestra synthesis from, 854 stereogenic centers, 170 structure of, 1058f Sudafed, 65 See also Pseudoephedrine Suffix, 120 -adiene, 362 -al, 776 -aldehyde, 777 -amide, 831–832, 833t -amine, 952–953 -ane, 117, 120, 121, 127, 362 -ate, 692, 830–831, 833t -carbonyl chloride, 830, 833t -carboxylic acid, 830 -dioic acid, 692 -diol, 315 -ene, 362 -enol, A–5 -enone, A–5 -enyne, A–5 -ic acid, 691, 830, 831, 832 -ide, 231 -ine, 230–231 -o, 230 -oic acid, 690, 831 -one, 777 -onitrile, 832, 833t -ose, 1029 -oxy, 316 -oyl, 779 -yl, 120, 316 -yl chloride, 833, 833t, 860 -ylic acid, 831 -yne, 401 Sugar, simple, 104–105 See also Monosaccharides Sugars See also Carbohydrates amino, 1061–1062 nonreducing, 1048, 1048f, 1058 reducing, 1048, 1048f, 1057 simple See Monosaccharides Sulfa drugs, 990–991 Sulfamethoxazole, 991f Sulfanilamide, 990–991 Sulfide (functional group), 85t Sulfisoxazole, 991f Sulfonate anion, 710 Sulfonation of benzene, 643f, 646–647 electrophilic aromatic substitution reaction, 643f, 646–647 Sulfonic acids, 709–710 Sulfur in fossil fuels, 70 octet rule exceptions in, 18 Sulfuric acid, 70 dehydration of alcohols in, 325–330, 327f in epoxide ring opening reactions, 345 in nitration and sulfonation reactions of benzene, 646–647 Sulfur nucleophile, 348 Sulfur oxides, 70 Sulfur trioxide, 646–647 Sunscreen, 30, 599 Supercoil, 1108, 1108f Superhelix, 1108–1109 Surface area boiling point and, 91f van der Waals forces and, 88, 88f Suzuki reaction, 1002, 1003, 1005–1009, 1008f Sweeteners, artificial, 1058, 1059f, 1090 Sweetness, of monosaccharides, 1036 Sweet’n Low See Saccharin Symbol, atomic, Symmetrical anhydrides, 826–827, 830 Symmetry melting points and, 93 plane of, 165–166, 165f, 178 Syn additions, 371, 377, 378t, 386, 388–389, 434, 440, 442, 442f, 443–444, 1013 Syndiotactic polymer, 1157–1158 Syn periplanar geometry, 295, 295f Synthetic intermediate, 392 Synthetic polymers, 560–562, 1148–1178 amorphous regions of, 1164–1165 atatic, 1157–1158 “Big Six,” 1169, 1169t biodegradable, 1170–1171 chain-growth, 1149, 1150–1157 in consumer products, 1149, 1149f crystalline regions of, 1164–1165 disposal of, 1169–1171 green synthesis of, 1166–1169, 1167f, 1168f isotactic, 1157–1158 molecular weights of, 1150 nylon, 825, 859 physical properties of, 1164–1166 plasticizer addition to, 1165–1166 polyesters, 859–860 recycling of, 1148, 1169–1170, 1169t shorthand representation of, 1150, 1150f step-growth, 1150, 1160–1164 stereochemistry of, 1157–1159 structure of, 1149, 1164–1166 syndiotactic, 1157–1158 thermoplastics, 1165 thermosetting, 1165 Systematic name, 119 See also IUPAC nomenclature of amines, 952–953 Apago PDF Enhancer 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), 646f Tacrine, 975 Tacrolimus See FK506 Tagamet See Cimetidine d-Tagatose, 1036f Talose d-talose, 1035f, 1050 Wohl degradation, 1050 Tamiflu, 86 Tamoxifen, 880, 899 Tandem ring-opening–ring-closing metathesis, 1026 Target compound, 417 Tartaric acid, stereoisomers of, 185–186, 186f Tautomerization in acid, 410–411, 883 of amides, 863–864 in base, 883 of carbonyl compounds, 863–864, 881–883, 893 mechanism of, 883 Tautomers definition of, 410 enol, 410–412, 864, 882–883 keto, 410–412, 864, 882–883 Taxol, 170, 268, 726 Taxotere, 876 TBDMS (tert-butyldimethylsilyl), 749, 750 Teflon See Polytetrafluoroethylene (Teflon) Temperature, reaction rate and, 216 Teratogen, 169 Terephthalic acid, 860, 1148, 1150f, 1161, 1176 Terpenes, 1132–1138 biosynthesis of, 1134–1138, 1135f classes of, 1133t examples of, 1133f locating isoprene units in, 1132–1134, 1133f rubber, 1159 α-Terpinene, 1138 α-Terpineol, 398, 1137 tert- (prefix), 120, 121 Tertiary (3°) alcohols classification as, 313 conversion to alkyl halides with HX, 332–334, 337t dehydration by E1 mechanism, 326 hydrogen bonding extent, 318 from reaction of esters and acid chlorides with organometallic reagents, 750–752 from reaction of ketones with organometallic reagents, 742–743 Tertiary (3°) alkyl halides acetylide anion reaction with, 414 classification as, 229–230 E1 elimination reactions, 292, 294, 302f E2 elimination reactions, 287, 288, 302f example of, 229f SN1 substitution reactions, 255, 262, 262f, 302f synthesis of, 332, 334–335 Tertiary (3°) amides, 827, 831–832, 842, 844, 850 enolates formation from, 885–886 Tertiary (3°) amines from direct nucleophilic substitution, 960 IR spectra of, 955, 955f nomenclature, 952–953 reactions with acid chlorides and anhydrides, 975–976 from reduction of amides, 963 structure of, 950 Tertiary carbon (3°), 116 Tertiary hydrogen (3°), 116–117 Tertiary structure, of proteins, 1104–1105, 1107f 11/24/09 12:13:40 PM Index Testosterone, 1141t Tetra- (prefix), 123 Tetrabutylammonium fluoride, 749 Tetrachloromethane, 232 Tetrafluoroethylene, monomers in polymerization, 562t Tetrahalide, 409 Tetrahedral arrangement, 25–26, 26f Tetrahedral geometry, of acyclic alkanes, 114–115 Tetrahedral oxygen, 314 Tetrahedral stereogenic center, 164–165, 166, 169, 178 Tetrahedrane, 138 Tetrahydrocannabinol (THC) mass spectrum of, 474, 474f structure of, 70 Tetrahydrofuran (THF), 317, 888, 889–890, 898 complexed with borane, 386 as solvent, 241f, 341 Tetrahydrogestrinone, 1142 α-Tetralone, 653 2,3,4,6-Tetra-O-methyl-d-galactose, 1073 Tetramethyl α-d-glucopyranose, 1048f Tetramethylsilane (TMS), 497, 523 Tetravalent carbon, 4, 25, 27 Tetrodotoxin, synthesis of, 589, 589f Thalidomide, 169 THC See Tetrahydrocannabinol (THC) Thermodynamic enolates, 890–891, 899 Thermodynamic product, in electrophilic addition reactions of conjugated dienes, 586–588, 587f, 588f Thermodynamics, 206–209, 207f, 208t of hydrate formation, 802–803 Thermoplastics, 1165 Thermosetting polymers, 1165 THF See Tetrahydrofuran (THF) Thiazolinone, 1091–1092, 1118 Thioester, 860–861 Thiol (functional group), 85t Thionyl chloride conversion of alcohols to alkyl halides with, 335–336 conversion of carboxylic acids to acid chlorides, 846–847, 846f Three-dimensional representation, of acyclic alkanes, 114–115 Threonine, 719 isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f, 1077 Threose, 190 d-threose, 1034, 1034f, 1035f l-threose, 1034, 1034f Thrombin, 1075 Thromboxanes, 1129–1130, 1130t, 1131f Thymine, 1063–1064, 1065f Thymol, 529, 638 Tiotropium bromide, 321 Titanium(IV) isopropoxide, 452 Toads (Bufo), 958 Tobacco, 614f Tobramycin, 1062 Tollens reagent, 738, 1048 Toluene, 108 in BTX mixture, 614 electrophilic aromatic substitution reaction, 657, 662 oxidation to benzoic acid, 671 structure of, 611 synthesis by Friedel–Crafts alkylation, 675 Toluene 2,6-diisocyanate, 1162 p-Toluenensulfonate See Tosylate p-Toluenesulfonic acid (TsOH), 70, 709–710, 804 smi75625_index_1218-1246.indd 1245 dehydration of alcohols to alkenes in, 325, 331f p-Toluenesulfonyl chloride (TsCl), 338–340, 340, 341f p-Toluidine basicity of, 970 electrostatic potential plot of, 971f Torsional energy, 133–134 Torsional strain, 133–134, 136t, 137, 138 Tosic acid, 710 Tosylate, 338–340, 341f Tosyl group, 338, 710 TPA (thermal polyaspartate), 1171 Trade name, 119 Trans diaxial geometry, 296–298, 296f Trans dihalide, 409 Trans fats, 433 Trans geometry alkenes, 359, 360t, 363 cycloalkenes, 359 Trans isomers of 2-butene, 282–283, 282f of cycloalkanes, 144–147 definition of, 144, 282, 377 of disubstituted cycloalkanes, 180 Transition state definition of, 210–211 drawing structure of, 211 of E1 elimination reactions, 292, 292f of E2 elimination reactions, 285–286, 286f, 287, 289, 295 in energy diagrams, 210–215, 215f four-centered, 386 in halogenation reactions, 546–548, 547f, 548f Hammond postulate and, 258–261, 259f, 260f, 546–547 SN1 substitution reactions, 264 SN2 substitution reactions, 264 in two-step reactions, 213–215, 215f Trans protons, 516, 517f Tri- (prefix), 123 Triacylglycerols, 1122–1125 combustion of, 1125 common fatty acids in, 1122t degrees of unsaturation in, 432 energy storage in, 1125 fats and oils, 369 formation of, 105 hydrogenation of, 432–434, 433f, 1124 hydrolysis of, 367, 853, 854–855, 1124 melting point of, 1122–1123 mixed, 1122 olestra as a substitute for, 854 oxidation of, 556, 556f, 1124 physical properties of, 369 saponification of, 854–855 saturated, 853, 853f, 1122–1123, 1122t, 1123f simple, 1122 structure of, 366–367, 853, 853f, 1120f, 1122–1123, 1122t, 1123f, 1128f unsaturated, 1122–1123, 1122t, 1123f, 1124 Trialkylborane, 387, 387f Triarylphosphine, 1009 1,3,5-Tribromobenzene, synthesis of, 984, 984f Tributyltin hydride, 570 Trichlorofluoromethane, 3, 233, 551 Trichloromethane, 232 2,4,5-Trichlorophenoxyacetic acid herbicide (2,4,5-T), 646f Tricyclohexylphosphine, 1005 Trienes, 362 Triethylamine, 71, 277, 952, 1009 1,2,4-Triethylcyclopentane, 127f Trifluoroacetic acid, for removal of Boc protecting group, 1096 2,2,2-Trifluoroethanol, 65–66, 66f Trifluoromethanesulfonic acid, 710 Trigonal planar carbocation, 253–254, 376 Trigonal planar carbon radical, 539 Trigonal planar double bond, 281 Trigonal planar molecule, 24–25, 26, 26f carbonyl group, 722–723 carboxy group, 689 Trigonal pyramidal molecule amines, 950–951 Trihalomethanes, 1012 Trimethylamine, 956 electrostatic potential plot of, 951, 951f Trimethyl borate, 1007 1,3,5-Trimethylcyclohexane, 156 2,5,5-Trimethylcyclohexanecarboxylic acid, 690 2,5,5-Trimethylcyclohexanol, 315f 2,3,5-Trimethyl-2-hexene, 362 1,3,6-Tri-O-methyl-d-fructose, 1073 2,3,4-Tri-O-methyl-d-glucose, 1073 2,2,4-Trimethylpentane, combustion of, 148 2,3,5-Trimethyl-4-propylheptane, 123f Triols, 315 Tripeptide, 1086–1088 Triphenylene, 640 Triphenylphosphine, 793, 1005 Triphenylphosphine oxide, 792, 794 Triple bonds in alkynes, 83, 84t, 400–401 bond length and bond strength, 41, 41t components of carbon–carbon, 39 as functional group, 83, 84t Lewis structure, 15 NMR spectra of, 505, 506f, 506t reduction of, 434–437, 437f Triple helix, of collagen, 1108–1109, 1109f Triplet, NMR spectrum, 509, 510, 511t, 512, 512t, 515f, 518 Tri(o-tolyl)phosphine, 1005 Triynes, 401 Tropylium cation, 625–626 Truvia See Rebaudioside A Trypsin, 1093, 1093t Tryptophan, 720 isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f TsCl (p-Toluenesulfonyl chloride), 338–340, 341f TsOH See p-Toluenesulfonic acid (TsOH) Tuberculosis, 250 Tulipalin A, 946 Tungsten, 1015 ar-Turmerone, 926 Twistoflex, 614–615 Two-step reaction mechanism, 213–215, 215f, 217 TXA2, 1130f Tylenol See Acetaminophen Tyrian purple, 988 Tyrosine isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f Tyvek, 1170 Apago PDF Enhancer Ultraviolet light absorption by conjugated dienes, 597–599, 598f skin damage from, 599 I-28 Undecane, 114 Unimolecular elimination See E1 elimination reactions Unimolecular reaction in nucleophilic substitution reactions, 244, 252 organic reactions, 217 Unknown analysis using mass spectrometry, 466–468 using 1H NMR to identify an, 519–522 α,β-Unsaturated carbonyl compounds, 755–758 1,2-addition to, 755–756 1,4-addition to, 755–756 in Michael reaction, 934–936, 935f resonance structures, 934 in Robinson annulation, 936–939 synthesis of in dehydration of aldol product, 919–920, 922, 924f from α-halo carbonyl compounds, 896 Unsaturated fatty acid See Fatty acids, unsaturated Unsaturation, degrees of in alkenes, 431–432 benzene, 608 calculation of, 360–361, 431–432 hydrogenation data and, 431–432 in triacylglycerols, 432 Uracil, 1063–1064, 1065f Urethanes, 1162, 1175 Urushiols, 707 Valdecoxib, 1132 Valence bond theory, 627 Valence electrons, 10–16, 17t, 32 Valence shell electron pair repulsion (VSEPR) theory, 24 Valeric acid, structure of, 691t Valine isoelectric point for, 1078t pKa values for, 1078t structure of, 1076f Valinomycin, 101 Valium See Diazepam Valproic acid, 78, 910 Vancomycin, 111 van der Waals forces, 87–89, 88f, 90t in alkanes, 129 surface area and, 88, 88f Vane, John, 697 Vanillin, 30, 529, 783f Vanilloids, Varenicline, 995 Vasopressin, 1089, 1090f, 1105 Vasotec See Enalapril Vegetable oil, 835, 854, 855 partial hydrogenation of, 432–433, 433f Venlafaxine, 748, 773 Ventolin See Albuterol β-Vetivone, 913, 915, 943 Viagra See Sildenafil Vibration of bonds, infrared spectroscopy and, 476–477, 478–480 Vicinal dibromide, 404, 405 Vicinal dihalides, 299, 379 alkyne synthesis from, 404–405 Vinegar, 695 Vinyl acetate NMR spectrum of, 517f polymerization of, 1152, 1155f structure of, 1151f Vinylboranes, 1007, 1009 trans vinylborane, 1006–1007 Vinyl bromide, 1009 Vinyl carbanion, 436 Vinyl carbocation, 407, 408 11/24/09 12:13:40 PM I-29 Index Vinyl chloride bond strength, 51 monomers in polymerization, 562t polymerization of, 1149, 1156 structure of, 1149, 1151f 1-Vinylcyclohexene, 365 Vinyl group, 365 Vinyl halides, 229, 229f, 267 coupling reactions with alkenes, 1009–1011 organoboranes, 1006–1007 organocuprates, 1003–1004 reactivity of, 650 synthesis in hydrohalogenation of alkynes, 406–407 Vinylidene chloride, polymerization of, 1156 Vinyl iodide, 1010–1011 Vioxx See Rofecoxib Viracept See Nelfinavir Vitamin(s), 97–98 definition of, 97, 1128 fat-soluble, 97, 149, 1128, 1129f origin of term, 97 water-soluble, 97–98 Vitamin A, 97–98, 331f β-carotene conversion to, 97–98 deficiency, 97, 1129f electrostatic potential plot of, 1128, 1129f role in the body, 1129f solubility, 97 sources, 1128, 1129f structure, 97, 282, 1129f, 1134 Vitamin B3, 98 Vitamin B6, 109 Vitamin C (ascorbic acid), 80, 81, 568 solubility of, 98 sources of, 98 structure of, 98, 836 Vitamin D3, 581 deficiency, 1129f role in the body, 1129f sources of, 1128 structure of, 282, 1129f Vitamin E, 109 as antioxidant, 557 deficiency, 1129f electrostatic potential plot of, 1128, 1129f as radical scavenger, 541 role in the body, 1129f sources of, 1128 structure of, 557, 1129f Vitamin K (phylloquinone), 98 deficiency, 1129f role in the body, 1129f sources of, 1128 structure of, 1129f VSEPR (valence shell electron pair repulsion) theory, 24 Vulcanization, 1159, 1159f Wald, George, 799 Walden, Dr Paul, 246 Walden inversion, 246 Wang resin, 1118 Water as achiral molecule, 164 electrophilic addition of, 378–379, 390 electrostatic potential plot for, 45f hybrid orbitals in, 35, 35f hydration of alkynes, 406f, 409–412 hydrogen bonding, 89 as Lewis base, 73 Markovnikov addition of, 410 molecular shape of, 26, 26f nucleophilicity of, 73, 263 pKa of, 59t, 62, 63 as polar molecule, 44 removing from reaction mixture using Dean–Stark trap, 804, 805f as solvent, 94–96, 240, 240f, 264 in extraction procedure, 707, 708f Wavelength definition of, 474 electromagnetic spectrum and, 474–476, 475f length units for, 474 Wavenumber, 476 Waxes, 150, 150f, 1121 Wedges, in Fischer projection formula, 1032 Wellbutrin See Bupropion Williamson ether synthesis, 322 Willow tree, 71 Wittig, Georg, 792 Wittig reaction mechanism of, 794 retrosynthetic analysis using, 795–796 Wittig reagent, 792–797 Wohl degradation, 1049, 1050 Wolff–Kishner reduction, 672 Wood alcohol, 319f See also Methanol Wool binding of dyes to, 989–990 structure of, 858, 858f Xalatan See Latanoprost X-ray crystallography, 1053 m-Xylene, 667 p-Xylene, 614 d-Xylose, 1034, 1035f d-Xylulose, 1036f -yl (suffix), 120, 316, 779 -yl chloride (suffix), 833, 833t, 860 -ylic acid (suffix), 831 Ylide, 793 -yne (suffix), 401 Zaitsev rule, 288–291, 293, 297, 980 Z configuration, of double bonds, 368 Zidovudine See AZT (azidodeoxythymidine) Ziegler, Karl, 1158 Ziegler–Natta catalysts, 1157–1158, 1160 Zigzag skeletal structures, 137 Zileuton, 348 Zinc in Clemmensen reduction, 672–673 conversion of ozonide to carbonyl compounds, 445 Zinc chloride, 333 Zinc–copper couple, 1014–1015 Zingerone, 50 Zingiberene, 367f, 459, 601, 1133f Z isomer, 364 Zocor See Simvastatin Zoloft See Sertraline Zuclomiphene, 394 Zwitterion, 80, 711–712, 1077 Zyban See Bupropion Zyflo See Zileuton Apago PDF Enhancer smi75625_index_1218-1246.indd 1246 11/24/09 12:13:40 PM Common Abbreviations, Arrows, and Symbols Abbreviations Ac BBN BINAP Boc bp Bu CBS reagent DBN DBU DCC DET DIBAL-H DMF DMSO ee Et Fmoc HMPA HOMO IR LDA LUMO mmCPBA Me MO mp MS MW NBS NMO NMR opPCC Ph ppm Pr RCM ROMP TBDMS THF TMS Ts TsOH UV acetyl, CH3CO – 9-borabicyclo[3.3.1]nonane 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl tert-butoxycarbonyl, (CH3)3COCO – boiling point butyl, CH3CH2CH2CH2 – Corey–Bakshi–Shibata reagent 1,5-diazabicyclo[4.3.0]non-5-ene 1,8-diazabicyclo[5.4.0]undec-7-ene dicyclohexylcarbodiimide diethyl tartrate diisobutylaluminum hydride, [(CH3)2CHCH2]2AlH dimethylformamide, HCON(CH3)2 dimethyl sulfoxide, (CH3)2S –– O enantiomeric excess ethyl, CH3CH2 – 9-fluorenylmethoxycarbonyl hexamethylphosphoramide, [(CH3)2N]3P –– O highest occupied molecular orbital infrared lithium diisopropylamide, LiN[CH(CH3)2]2 lowest unoccupied molecular orbital meta m-chloroperoxybenzoic acid methyl, CH3 – molecular orbital melting point mass spectrometry molecular weight N-bromosuccinimide N-methylmorpholine N-oxide nuclear magnetic resonance ortho para pyridinium chlorochromate phenyl, C6H5 – parts per million propyl, CH3CH2CH2 – ring-closing metathesis ring-opening metathesis polymerization tert-butyldimethylsilyl tetrahydrofuran tetramethylsilane, (CH3)4Si tosyl, p-toluenesulfonyl, CH3C6H4SO2 – p-toluenesulfonic acid, CH3C6H4SO3H ultraviolet Apago PDF Enhancer smi75625_endppBACK.indd 12/2/09 10:13:14 AM Arrows reaction arrow equilibrium arrows double-headed arrow, used between resonance structures full-headed curved arrow, showing the movement of an electron pair half-headed curved arrow (fishhook), showing the movement of an electron retrosynthetic arrow no reaction Symbols hν ∆ δ+ δ– λ ν ~ ν HA B: :Nu– E+ X [ ]‡ [O] [H] smi75625_endppBACK.indd dipole light heat partial positive charge partial negative charge wavelength frequency wavenumber Brønsted–Lowry acid Brønsted–Lowry base nucleophile electrophile halogen bond oriented forward bond oriented behind partial bond transition state oxidation reduction Apago PDF Enhancer 12/2/09 10:13:14 AM ... 11/17/09 11:21:48 AM Prologue What is organic chemistry? Some representative organic molecules Ginkgolide B—A complex organic compound from the ginkgo tree Organic chemistry You might wonder how a discipline... smi75625_001-005prologue.indd 10/15/09 9:02:47 AM Ginkgolide B—A Complex Organic Compound from the Ginkgo Tree Figure Ginkgolide B O HO OH O O O O OH CH3 C(CH3)3 O O ginkgolide B • Hydrogen atoms bonded to ring... including inorganic, physical, and analytical chemistry, and newer fields such as bioinorganic chemistry, physical biochemistry, polymer chemistry, and materials science Organic chemistry was singled