Table Of Content

I Marye Anne Fox James K.Whitesell A B B Periodic Table of the Elements i Group Qa.t IA Key 1 0079 atomicmass 12.011 2.2 electronegativity 2.5 electronic [He]2s22p2 configuration H C symbol atomic i 6 number Hydrogen II name Carbon 6.941 901218 10 1 5 [He^s2 Li Be 3 4 Lithium Beryllium 22.98977 24.305 1.0 1.2 [Ne]3s [Ne]3s2 Na Mg 11 12 VII Sodium Magnesium IIIB IVB VB VI VII 390983 40.08 44.9559 47.88 50.9415 51.996 54.9380 55.847 58.9332 0.9 1.0 1.2 1.3 1.5 1.6 1.6 1.6 1.7 [Ar]4s [Ar]4s2 [Ar]3d4s2 [Ar]3d24s2 [Ar)3d34s2 (Ar]3d54s [Ar]3d54s2 [Ar^s2 [Ar]3d74s2 JX Ca SC Ti V Cr Mn Fe CO 19 20 21 22 23 24 25 26 27 Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt 85.4678 87.62 88.9059 91.22 92.9064 95.94 98.906 101.07 102.9055 0.9 1.0 1.1 1.2 1.2 1.3 1.4 1.4 1.5 [Krj5s [Kr)5s2 [Kr)4d5s2 [Kr]4d25s2 [Kr]4rf45s [Kr]4d55s [Kr]4c/65s [Kr]4d75s [Kr]4de5s Rb br Y ZA Nb MO TC RU Rh 37 38 39 40 41 42 43 44 45 Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium 132.9054 137.33 138.9055 178.49 180.9479 183.85 186.207 190.2 192.22 0.9 1.0 1.1 1 2 1.3 1.4 1.5 1.5 1.6 [Xe]6s [Xe]6s-' [Xe]5d6s2 [Xe]4r145d26s2 [Xe]4f~,45d36s2 [XWe]4/K5d46s2 [Xe]4/'45d56s2 [Xe]4f,45d66s2 [Xe)4r'45dV CS Ba La Hf Ta Re OS Ir 55 56 57 72 73 74 75 76 77 Cesium Barium Lanthanium Hafnium Tantalum Tungsten Rhenium Osmium Iridium (223) 226.0254 227.0278 (261) (262) (263) 0.9 1.0 1.0 [Rn]7s [RnRs2 {Rr\$d7s* [Rn]5f"6d27s2 [Rn]5f,46d47s2 Fr Ra tAC Unqio4 Unpio5 Unhioe 87 se 89 Francium Radium Actinium Unnilquadium Unnilpentium Unnilhexium 140.12 140.9077 144.24 145 150.4 151.96 157.25 1.1 1.1 1.1 1.1 1.1 1.0 1.1 [XeHfts2 [Xe)4f36s2 [Xe]4f46s2 [Xe]4/56s2 [Xe]4/66s2 [Xe]4/76s2 [Xe]4r75d6s2 *Lai Ce Pr Nd Pm Sm EU G(l 58 59 60 61 62 63 64 6 Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium 232.0381 231.0359 238.029 237.0482 (244) (243) (247) 1.1 1.1 1.2 1.2 1.2 1.2 =1.2 [Rn)6d27s2 [Rnl'^ctfs2 [Rn)5f36cr7s2 [Rn]5f6o7s2 [RnjSr^s2 [RnJSrVs2 [Rn]5r76d7s2 tActinides Th Pa U Np PU Am Cm 90 91 92 93 94 95 96 7 Thorium Protactinium Uranium Neptunium Plutonium Americium Curium A Noble Gases The elements shown incolor are those that commonly 4.0026 undergobonding with carbon. 1s2 He 2 IIIA IVA VA VIA VII Helium 10.81 12.011 14.0067 15.9994 18.9984 20.179 2.0 2.5 3.1 3.5 4.1 [He]2s22p [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p4 B C N O F Ne 5 , 7 . . 10 Boron Carbon Nitrogen Oxygen Fluoride Neon 26.9815 28.0855 30.97376 32.06 35.453 39.948 1.5 1.7 2.1 2.4 2.8 [Ne]3s23p [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6 Al Si H P D CI Ar ,3 ,5 16 ,7 is IB MB 1 Aluminum Silicon Phosphorus Sulfur Chloride Argon 58.70 63.546 65.38 69.72 72.59 74.9216 78.96 79.904 83.80 1.8 1.8 1.7 1.8 2.0 2.2 2.5 2.7 [Ar]3d84s2 [Ar]3d'°4s [Ar]3d'°4s2 [Ar)3d,04s24p [Ar]3d'°4s24p2 [Ar]3d,04s24p3 [Ar]3d'°4s24p4 [Ar]3d'°4s24p5 [Ar]3d,04s24p6 Ni 28 CU 29 Zll 30 VJcl 31 Ge 32 AS 33 Se 34 Br ~5 .Kr 36 Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton 106.4 107.868 112.41 114.82 ,18.69 121.75 127.60 126.9045 131.30 1.4 1.4 1.5 1.5 1.7 1.8 2.0 2.2 [Kr]4d'° [Kr]4d,05s [Kr]4d,05s2 [Kr]4d'°5s25p [Kr]4d'°5s25p2 [Kr)4d,05s25p3 [Kr]4d105s25p4 [Kr]4d,05s25p5 [Kr]4d,05s25p6 Pd Ag Cd In Sn Sb Te Xe 46 47 48 49 50 51 52 1 53 54 Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon 195.09 196.9665 200.59 204.37 207.2 208.9804 (209) (210) (222) 1.4 1.4 1.5 1.4 1.6 1.7 1.8 2.0 (Xe]4/145d96s [Xe]4r"45d,06s [Xe]4f,45d'°6s2 [Xel4^'45cf' 6s26p [Xe]4r5d'°6s26p2 [Xe]4f45d,06s26p3 [Xe)4i"45o"°6s26p4 [Xe]4/'45d,06sV [Xe]4f,45d,06s26p6 Pt AU Hg Tl Pb Bi PO At Rn 78 79 80 8, 82 83 84 85 se Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon 158.9254 162.50 164.9304 167.26 168.9342 173.04 174.967 1.1 1.1 1.1 1.1 1.1 1.1 1.1 [Xe]4/96s2 [Xe]4/,06s2 [Xe]4f""6s2 [Xe]4f,26s2 [Xe]4f,36s2 [Xe]4f146s2 [Xe]4/'45d6s2 Tb Dy HO Er Tm Yb Lu 65 ee 67 68 69 70 71 Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium (247) (251) (254) (257) (258) 259 260 =1.2 =1.2 =1.2 =1.2 =1.2 [Rn]5f*7s2 [Rn]5f,07s2 [Rn]5/"7s2 [Rn]5f,27s2 [Rn]5f'37s2 [Rn]5/'47s2 [Rn]5f,46d7s2 Bk ES Fm Mdioi NO Lr 97 V^I 98 99 100 102 103 Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium ORGANIC CHEMISTRY Reproduction ofa woodblockprint, in theauthors'col- lection,froma bookpublished in 1497 in Basel, Switzer- land,depictingan alchemist (standingat the right)and his twoassistants,oneworkingat the "fumehood" and theother takinga samplefrom thecask. Thealchemist is holdinga retort,an all-in-onedistillation apparatus in which thelongsnoutservesas thecondenser. (Another retort is in use in thefumehood,anda thirdone is on thefloor.) ORGANIC CHEMISTRY Marye Anne Fox James K. Whitesell The University ofTexas Austin, Texas Jones and Bartlett Publishers Boston London Editorial, Sales, and Customer Service Offices Jones and Bartlett Publishers One Exeter Plaza MA Boston, 02116 617-859-3900 800-832-0034 Jones and Bartlett Publishers International PO Box 1498 London W6 7RS England Copyright © 1994byJones and Bartlett Publishers, Inc. All rights reserved. No part ofthe material protected by this copyright notice may bereproduced or utilized in any form, electronic ormechanical, including photocopying, recording, orby anyinformation storageand retrieval system, without written permission from the copyright owner. Library ofCongress Cataloging-in-Publication Data Fox, MaryeAnne, 1947- Organic chemistry / MaryeAnne Fox,James K. Whitesell. p. cm. Includesbibliographical references and index. ISBN 0-86720-207-6 1. Chemistry, Organic. 2. Biochemistry. I. Whitesell,James K. II. Title. QD251.2.F69 1994 547—dc20 93-43800 CIP Acquisitions: ArthurC. Bartlett, David E. Phanco Developmental Editor: Patricia Zimmerman Production Editor: JudySongdahl Manufacturing Buyer: Dana L. Cerrito Design: Nancy Blodget Illustrations: Sarah Mittelstadt Bean Typesetting: TheClarinda Company CoverDesign: Marshall Henrichs Printing and Binding: Rand McNally Cover Printing: John P. PowCompany Cover: Opiatedrugs such as morphine are effective in relieving painbecause they bind to the samesite in the central nervous system as do theenkephalins. Theimage on the coveris ofcrystals ofan enkephalin, viewed between crossed polarizers so as tobringout the vivid rainbowdisplay ofcolors. (Photograph ©Dr. Dennis Kunkel/PhototakeNYC) Printed in the United States ofAmerica 98 97 96 95 94 10 9 8 7 6 5 4 3 2 Brief Contents Chapter 1 Structure and Bonding in Alkanes 1 Chapter 2 Alkenes, Arenes, and Alkynes 21 Chapter Functional Groups Containing Heteroatoms 59 Chapter Chromatography and Spectroscopy 109 Chapter Stereochemistry 155 Chapter Understanding Organic Reactions 193 Chapter Mechanisms ofOrganic Reactions 227 Chapter 8 Nucleophilic Substitutions at sp -Hybridized Carbon 267 Chapter 9 Elimination Reactions 303 Chapter 10 Electrophilic Addition to Carbon-Carbon Multiple Bonds 331 Chapter 11 Electrophilic Substitution ofAromatic Molecules 369 Chapter 12 Addition and Substitution by Heteroatomic Nucleophiles at sp -Hybridized Carbon 401 Chapter 13 Addition and Substitution by Carbon Nucleophiles at sp -Hybridized Carbon 451 Chapter 14 Skeletal-Rearrangement Reactions 477 Chapter 15 Multistep Syntheses 505 Chapter 16 Polymeric Materials 541 Chapter 11 Structures and Reactions ofNaturally Occurring Compounds Containing Oxygen Functional Groups 581 vi BriefContents Chapter 18 Structures and Reactions ofNaturally Occurring Compounds Containing Nitrogen Functional Groups 613 Chapter 19 Noncovalent Interactions and Molecular Recognition 651 Chapter 20 Catalyzed Reactions 681 Chapter 21 Cofactors for Biological Redox Reactions 713 Chapter 22 Energy Storage in Organic Molecules 745 Chapter 23 Molecular Basis for Drug Action 789