Making Everything Easier!T Organic Chemistry ll FOR DUMMIES Learn to: Understand the physical and chemical properties of organic compounds Observe from a macro-scopic and micro-scopic view Grasp chemical and organic reactions Follow along and ace your Organic Chemistry ll course John T.Moore,EdD Richard H.Langley,PhD Professors of Chemistry and coauthors of Biochemistry For Dummies
John T. Moore, EdD Richard H. Langley, PhD Professors of Chemistry and coauthors of Biochemistry For Dummies Learn to: • Understand the physical and chemical properties of organic compounds • Observe from a macro-scopic and micro-scopic view • Grasp chemical and organic reactions • Follow along and ace your Organic Chemistry II course Organic Chemistry II Making Everything Easier!™ Open the book and find: • A review of Organic Chemistry I • Clear descriptions of organic reactions • Spectroscopy of aromatic compounds and carbonyls • All you need to know about amines • An explanation of the infamous Grignard reaction • Hints for working with synthesis and roadmaps • Surefire ways to fail the course (and how to avoid them!) • Ten tips for increasing your exam scores John T. Moore, EdD, is Regents Professor of Chemistry at Stephen F. Austin State University in Nacogdoches, Texas. He is the author of Chemistry For Dummies. Richard H. Langley, PhD, teaches chemistry at Stephen F. Austin State University. Langley and Moore are coauthors of Biochemistry For Dummies. $19.99 US / $23.99 CN / £14.99 UK ISBN 978-0-470-17815-7 Science/Chemistry/Organic Chemistry Go to Dummies.com® for videos, step-by-step examples, how-to articles, or to shop! Your plain-English guide to understanding chemical reactions and tackling tests with ease Whether you’re confused by carbocations or baffled by biomolecules, this straightforward, easy-to-read guide demystifies Organic Chemistry II. From appreciating aromatic compounds to comprehending carbonyls, you’ll discover what you need to know about organic reactions in order to master the course and score high on your exams! • Get comfortable with the course — follow your coursework alongside the book, as it corresponds to a typical second semester college-level organic chemistry class • Refresh your knowledge of key topics — from mechanisms to alcohol and ethers, from conjugated unsaturated systems to electrophiles and nucleophiles, get prepped for Organic II • Grasp carbonyl group basics — get an overview of structure, reactivity, and spectroscopy before delving deeper into aldehydes and ketones, enols and enolates, and carboxylic acids and their derivatives • Ace advanced topics — take a closer look at nitrogen compounds, organometallic compounds, the Claisen Condensation and its variations, and biomolecules, such as carbohydrates, lipids, and proteins Organic Chemistry II Moore Langley spine=.7680
Organic Chemistry lI For Dummies Published by hing,Inc. Hob0keh,07030-5774 www.wiley.com Copyright2010 by Wiley Publishing,Inc.,Indianapolis,Indiana Published simultaneously in Canada No part of this publication may be reprodu ced.storedinaretiealsystemortransmtieaptrgoemal ed under sec ons the 1976United States Copyright Act.without either the prior written 23.78750-8400.9786 eawuesttoheR Street.Hoboken.NJ07030.C201)748-6011.fax (201)748-6008.or onlineat www.wiley.com/go/permissions. Trademarks:Wiley.the wiley Publishing l o.For Dummies.the dummies man loeo.a referer ce for the Rest of Us!The Di Making Everything ermis or vendor mentioned in this book ng. LIMIT OF LIABILITY/DISCLAIMER OF WARRANTY:THE PUBLISHER AND THE AUTHOR MAKE NO OUT LIN OR AR PURP RRANT Y MAY BE CONTAINED HEREIN MAY NOT BE SUITABLE FOR EVERY SITUATION.THIS WORK IS SOLD WITH THE R THE PURLISHER NOR T TION OR WEBSITE IS REFERRED TO IN THIS AS A CITATION AND/OR A POTEN TIAL SOURCE WHEN IT IS READ. For technical support.please visit www.wilev.com/techsupport. Wiley also blishes its books in a variety of electronic formats.Some not be available in electronic books. content that appears in print may Library of Congress Control Number:2010926849 ISBN978-0470-17815- Manufactured in the United States of America 10987654321 國
Organic Chemistry II For Dummies® Published by Wiley Publishing, Inc. 111 River St. Hoboken, NJ 07030-5774 www.wiley.com Copyright © 2010 by Wiley Publishing, Inc., Indianapolis, Indiana Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 646-8600. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http:// www.wiley.com/go/permissions. Trademarks: Wiley, the Wiley Publishing logo, For Dummies, the Dummies Man logo, A Reference for the Rest of Us!, The Dummies Way, Dummies Daily, The Fun and Easy Way, Dummies.com, Making Everything Easier, and related trade dress are trademarks or registered trademarks of John Wiley & Sons, Inc. and/ or its affi liates in the United States and other countries, and may not be used without written permission. All other trademarks are the property of their respective owners. Wiley Publishing, Inc., is not associated with any product or vendor mentioned in this book. LIMIT OF LIABILITY/DISCLAIMER OF WARRANTY: THE PUBLISHER AND THE AUTHOR MAKE NO REPRESENTATIONS OR WARRANTIES WITH RESPECT TO THE ACCURACY OR COMPLETENESS OF THE CONTENTS OF THIS WORK AND SPECIFICALLY DISCLAIM ALL WARRANTIES, INCLUDING WITHOUT LIMITATION WARRANTIES OF FITNESS FOR A PARTICULAR PURPOSE. NO WARRANTY MAY BE CREATED OR EXTENDED BY SALES OR PROMOTIONAL MATERIALS. THE ADVICE AND STRATEGIES CONTAINED HEREIN MAY NOT BE SUITABLE FOR EVERY SITUATION. THIS WORK IS SOLD WITH THE UNDERSTANDING THAT THE PUBLISHER IS NOT ENGAGED IN RENDERING LEGAL, ACCOUNTING, OR OTHER PROFESSIONAL SERVICES. IF PROFESSIONAL ASSISTANCE IS REQUIRED, THE SERVICES OF A COMPETENT PROFESSIONAL PERSON SHOULD BE SOUGHT. NEITHER THE PUBLISHER NOR THE AUTHOR SHALL BE LIABLE FOR DAMAGES ARISING HEREFROM. THE FACT THAT AN ORGANIZATION OR WEBSITE IS REFERRED TO IN THIS WORK AS A CITATION AND/OR A POTENTIAL SOURCE OF FURTHER INFORMATION DOES NOT MEAN THAT THE AUTHOR OR THE PUBLISHER ENDORSES THE INFORMATION THE ORGANIZATION OR WEBSITE MAY PROVIDE OR RECOMMENDATIONS IT MAY MAKE. FURTHER, READERS SHOULD BE AWARE THAT INTERNET WEBSITES LISTED IN THIS WORK MAY HAVE CHANGED OR DISAPPEARED BETWEEN WHEN THIS WORK WAS WRITTEN AND WHEN IT IS READ. For general information on our other products and services, please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. at 317-572-3993, or fax 317-572-4002. For technical support, please visit www.wiley.com/techsupport. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Library of Congress Control Number: 2010926849 ISBN: 978-0-470-17815-7 Manufactured in the United States of America 10 9 8 7 6 5 4 3 2 1 01_178157-ffirs.indd iv 5/28/10 9:44 AM
About the Authors John T.Moore,EdD,grew up in the foothills of western North Carolina.He attended the University of North Carolina-Asheville where he received his bachelor's degree in chemistry.He earned his master's degree in chemistry from Furman University in Greenville,South Carolina.After a stint in the United States Army,he decided to try his hand at teachi ng.In 1971 he joined the chemistry faculty of Stephen F.Austin St te University in Nacogdoches, Teicrfig9 part ti stry.In 1985 he went back to schoo receive is doctor rom as &M ith on le past s evera for Kids i The n.In 2003 his by Wil (Broadway)and Chemis Essentials For Dum 1 by mies (s cooking and making custom knife handles from exotic woods. Richard H.Langley,PhD,grew up in southwestern Ohio.He attended Miami University in Oxford,Ohio,where he received bachelor's degrees in chemistry and in mineralogy and a master's degree in chemistry.His next stop was the University of Nebraska in Lincoln,Nebraska,where he received his doctorate in chemistry.Afterwards he took a postdoctoral position at Arizona State University in Tempe,Arizona,followed by a visit nt professor position the Ur versity of Wiscon e move ate niversity.For the past s He and oders for ave ne free espons portion of th em try ave ed on se g proje cts,in tep raw-H C my fo n publishe enjoys je ng an
About the Authors John T. Moore, EdD, grew up in the foothills of western North Carolina. He attended the University of North Carolina–Asheville where he received his bachelor’s degree in chemistry. He earned his master’s degree in chemistry from Furman University in Greenville, South Carolina. After a stint in the United States Army, he decided to try his hand at teaching. In 1971 he joined the chemistry faculty of Stephen F. Austin State University in Nacogdoches, Texas, where he still teaches chemistry. In 1985 he went back to school part time and in 1991 received his doctorate in education from Texas A&M University. For the past several years he has been the co-editor (along with one of his former students) of the “Chemistry for Kids” feature of The Journal of Chemical Education. In 2003 his fi rst book, Chemistry For Dummies, was published by Wiley, soon to be followed by Chemistry Made Simple (Broadway) and Chemistry Essentials For Dummies (Wiley). John enjoys cooking and making custom knife handles from exotic woods. Richard H. Langley, PhD, grew up in southwestern Ohio. He attended Miami University in Oxford, Ohio, where he received bachelor’s degrees in chemistry and in mineralogy and a master’s degree in chemistry. His next stop was the University of Nebraska in Lincoln, Nebraska, where he received his doctorate in chemistry. Afterwards he took a postdoctoral position at Arizona State University in Tempe, Arizona, followed by a visiting assistant professor position at the University of Wisconsin–River Falls. In 1982 he moved to Stephen F. Austin State University. For the past several years he and John have been graders for the free-response portion of the AP Chemistry Exam. He and John have collaborated on several writing projects, including 5 Steps to a Five AP Chemistry and Chemistry for the Utterly Confused (both published by McGraw-Hill). Rich enjoys jewelry making and science fi ction. 01_178157-ffirs.indd v 5/28/10 9:44 AM
Dedication nderful daugh d the t o most wone the world,Zane and Sadie.I love you guys. Rich:I dedicate this book to my mother. Authors'Acknowledgments We would not have had the opportunity to write this book without th for k ur agent Grace Freed e would also like support assistance in th e ea thi ran o he like ito Klein and Joe Burnell. Many thanks to our colleagues Russell Franks and Jim Garrett who helped with suggestions and ideas.Rich would also like to acknowledge Danica Dizon for her suggestions,ideas,and inspiration.Thanks to all of the people at Wiley publishing who help bring this project from concept to publication
Dedication John: I dedicate this book to my wife, Robin; sons, Matthew and Jason; my wonderful daughter-in-law, Sara; and the two most wonderful grandkids in the world, Zane and Sadie. I love you guys. Rich: I dedicate this book to my mother. Authors’ Acknowledgments We would not have had the opportunity to write this book without the encouragement of our agent Grace Freedson. We would also like to thank Chrissy Guthrie for her support and assistance in the early portion of this project and to Sarah Faulkner who helped us complete it. We would also like to thank our copy editor, Caitie Copple, and our technical editors, Susan Klein and Joe Burnell. Many thanks to our colleagues Russell Franks and Jim Garrett who helped with suggestions and ideas. Rich would also like to acknowledge Danica Dizon for her suggestions, ideas, and inspiration. Thanks to all of the people at Wiley publishing who help bring this project from concept to publication. 01_178157-ffirs.indd vii 5/28/10 9:44 AM
Publisher's Acknowledgments 货 Some of the people who helped bring this book to market include the following: aa0eapmaraad Composition serpices Project Coordinator:Patrick Redmond Proiect Editors:Sarah Faulkner Layout and Graphics:Nikki Gately Christina guthrie Proofreaders:Laura Albert,Sossity R.Smith Indexer:Sharon Shock Copy Editor:Caitlin Copple Special Help Jennifer Tebbe Assistant Editor:Erin Calligan Mooney Senior Editorial Assistant:David Lutton Technical Editors:Susan J.Klein,PhD. Joe C.Burnell.PhD Editorial Manager:Christine Meloy Beck Cover Photos: ©Havwiremedia I Dreamstime.com/©iStock Cartoons:Rich Tennant (www.the5thwave.com) Publishing and Editorial for Consumer Dummies Diane Graves Steele,Vice President and Publisher,Consumer Dummies Kristin Ferguson-Wagstaffe,Product Development Director,Consumer Dummies Ensley Eikenburg,Associate Publisher.Trave Kelly Regan,Editorial Director.Trave Publishing for Technology Dummies Andy Cummings,Vice President and Publisher,Dummies Technology/General User Composition Services Debble Stalley,Director of Composition Services
Publisher’s Acknowledgments We’re proud of this book; please send us your comments at http://dummies.custhelp.com. For other comments, please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. at 317-572-3993, or fax 317-572-4002. Some of the people who helped bring this book to market include the following: Acquisitions, Editorial, and Media Development Project Editors: Sarah Faulkner, Christina Guthrie Senior Acquisitions Editor: Lindsay Sandman Lefevere Copy Editor: Caitlin Copple Assistant Editor: Erin Calligan Mooney Senior Editorial Assistant: David Lutton Technical Editors: Susan J. Klein, PhD, Joe C. Burnell, PhD Editorial Manager: Christine Meloy Beck Editorial Assistants: Jennette ElNaggar, Rachelle S. Amick Cover Photos: © Haywiremedia | Dreamstime.com/ © iStock Cartoons: Rich Tennant (www.the5thwave.com) Composition Services Project Coordinator: Patrick Redmond Layout and Graphics: Nikki Gately Proofreaders: Laura Albert, Sossity R. Smith Indexer: Sharon Shock Special Help Jennifer Tebbe Publishing and Editorial for Consumer Dummies Diane Graves Steele, Vice President and Publisher, Consumer Dummies Kristin Ferguson-Wagstaffe, Product Development Director, Consumer Dummies Ensley Eikenburg, Associate Publisher, Travel Kelly Regan, Editorial Director, Travel Publishing for Technology Dummies Andy Cummings, Vice President and Publisher, Dummies Technology/General User Composition Services Debbie Stailey, Director of Composition Services 01_178157-ffirs.indd viii 5/28/10 9:44 AM
Contents at a Glance Introduction... Part 1:Brushing up on Important Organie Chemistry I Concepts. Chapter 1:Organic Chemistry II:Here We Go Again!9 Chapter 2:Remembering How We Do It:Mechanisms. .17 Chapter 3:Alcohols and Ethers:Not Just for Drinking and Sleeping. 31 Chapter 4:Conjugated Unsaturated Systems... .53 Chapter 5:"Seeing"Molecules:Spectroscopy Revisited67 Part 11:Discovering Aromatic (And Not So Aromatic)Compounds..79 Chapter 6:Introducing Aromatics... 81 Chapter 7:Aromatic Substitution Part I:Attack of the Electrophiles... 93 .111 Part I11:Carbonyls:Good Alcohols Gone Bad..........121 Chapter 9:Comprehending Carbonyls.............. .123 Chapter 10:Aldehydes and Ketones .137 Chapter 11:Enols and Enolates... 161 Chapter 12:Carboxylic Acids and Their Derivatives .187 Part IV:Advanced Topics (Every Student's Nightmare)219 Chapter 13:Amines and Friends. 221 Chapter 14:Metals Muscling In:Organometallics... 249 Chapter 15:More Reactions of Carbonyl Compounds.. 261 Chapter 16:Living Large:Biomolecules.. …281
Contents at a Glance Introduction ................................................................ 1 Part I: Brushing Up on Important Organic Chemistry I Concepts ....................................... 7 Chapter 1: Organic Chemistry II: Here We Go Again! ....................................................9 Chapter 2: Remembering How We Do It: Mechanisms ................................................17 Chapter 3: Alcohols and Ethers: Not Just for Drinking and Sleeping ........................31 Chapter 4: Conjugated Unsaturated Systems...............................................................53 Chapter 5: “Seeing” Molecules: Spectroscopy Revisited ............................................67 Part II: Discovering Aromatic (And Not So Aromatic) Compounds ........................................... 79 Chapter 6: Introducing Aromatics .................................................................................81 Chapter 7: Aromatic Substitution Part I: Attack of the Electrophiles .......................93 Chapter 8: Aromatic Substitution Part II: Attack of the Nucleophiles and Other Reactions ...........................................................................111 Part III: Carbonyls: Good Alcohols Gone Bad ............. 121 Chapter 9: Comprehending Carbonyls ........................................................................123 Chapter 10: Aldehydes and Ketones ...........................................................................137 Chapter 11: Enols and Enolates ...................................................................................161 Chapter 12: Carboxylic Acids and Their Derivatives ................................................187 Part IV: Advanced Topics (Every Student’s Nightmare) .............................................. 219 Chapter 13: Amines and Friends ..................................................................................221 Chapter 14: Metals Muscling In: Organometallics .....................................................249 Chapter 15: More Reactions of Carbonyl Compounds ..............................................261 Chapter 16: Living Large: Biomolecules ......................................................................281 02_178157-ftoc.indd ix 5/28/10 9:44 AM
Part U:Pulling It All Together30g Chapter 17:Overview of Synthesis Strategies.... 31 Chapter 18:Roadmaps and Predicting Products.................. 327 Part VI:The part of Tens337 Chapter 19:Ten Surefire Ways to Fail Organic Chemistry ll. 339 Chapter 20:More than Ten Ways to Increase Your Score on an Organic Chemistry Exam.. .343 Appendix:Named Reactions37 Index.... ,349
Part V: Pulling It All Together .................................. 309 Chapter 17: Overview of Synthesis Strategies ...........................................................311 Chapter 18: Roadmaps and Predicting Products .......................................................327 Part VI: The Part of Tens .......................................... 337 Chapter 19: Ten Surefi re Ways to Fail Organic Chemistry II ....................................339 Chapter 20: More than Ten Ways to Increase Your Score on an Organic Chemistry Exam ......................................................................343 Appendix: Named Reactions ..................................... 347 Index ...................................................................... 349 02_178157-ftoc.indd x 5/28/10 9:44 AM
Table of Contents ●●●●●●●●●●●0●0●●●●●●●●●●●●●●●●●●0●●●●●●●●●●●●0e● About This Book Conventions Used in This Book. What You're Not to Read... 2 Foolish Assumptions.. 2 How This Book Is Organized. 3 Part I:Brushing Up on Important Organic Chemistry I Concepts......3 Part Il:Discovering Aromatic (And Not So Aromatic) Compounds. 3 Part II Carbonyls:Good Alcohols Gone Bad Part IV:Advanced Topics (Every Student's Nightmare) Part Vl Pulling It All Together.… Tens.. ere to Go n here 5 Part 1:Brushing Up on Important Organic Chemistry I Concepts...7 Chapter 1:Organic Chemistry ll:Here We Go Again! 9 Recapping Organic Chemistry I 10 Intermolecular forces. .10 Functional groups. 11 Reactions.. …11 Spectroscopy.. Isomerism and optical activity. Looking Ahead to Organic Chemistry lI .14 Chapter 2:Remembering How We Do It:Mechanisms 17 Duck-Here Come the Arrows. 17 Coming Around to Curved Arrows... .19 Getting Ready for Some Basic Moves .20 Bond lone pair........ 21 Bond->bond.... .2 Lone pair→bond. Combining the Basic Moves. Intermediates eys to st stitution and eli nation mechanisms Revisiting Free-Ra lical Mechanisms
Table of Contents Introduction ................................................................. 1 About This Book ..............................................................................................1 Conventions Used in This Book .....................................................................2 What You’re Not to Read ................................................................................2 Foolish Assumptions .......................................................................................2 How This Book Is Organized ..........................................................................3 Part I: Brushing Up on Important Organic Chemistry I Concepts ...... 3 Part II: Discovering Aromatic (And Not So Aromatic) Compounds .........................................................................................3 Part III: Carbonyls: Good Alcohols Gone Bad .....................................3 Part IV: Advanced Topics (Every Student’s Nightmare)...................4 Part V: Pulling It All Together ...............................................................4 Part VI: The Part of Tens .......................................................................4 Icons Used in This Book .................................................................................4 Where to Go from Here ...................................................................................5 Part I: Brushing Up on Important Organic Chemistry I Concepts ........................................ 7 Chapter 1: Organic Chemistry II: Here We Go Again! . . . . . . . . . . . . . . .9 Recapping Organic Chemistry I ...................................................................10 Intermolecular forces ..........................................................................10 Functional groups ................................................................................11 Reactions ..............................................................................................11 Spectroscopy ........................................................................................11 Isomerism and optical activity ...........................................................12 Looking Ahead to Organic Chemistry II ......................................................14 Chapter 2: Remembering How We Do It: Mechanisms . . . . . . . . . . . . .17 Duck — Here Come the Arrows ...................................................................17 Coming Around to Curved Arrows ..............................................................19 Getting Ready for Some Basic Moves .........................................................20 Bond → lone pair .................................................................................21 Bond → bond ........................................................................................21 Lone pair → bond ................................................................................22 Combining the Basic Moves .........................................................................22 Intermediates .......................................................................................24 Keys to substitution and elimination mechanisms .........................25 Revisiting Free-Radical Mechanisms ...........................................................27 02_178157-ftoc.indd xi 5/28/10 9:44 AM
xii Organic Chemistry ll For Dummies Chapter 3:Alcohols and Ethers:Not Just for Drinking and Sleeping......................................3 Getting Acquainted with Alcohols. 21 Structure and nomenclature of alcohols. Physical properties of alcohols Making moonshine Synthesis of alcohols 34 What will they do besides burn?Reactions of alcohols. 40 Introducing Ether (Not the Ether Bunny).... .46 Structure and nomenclature of ethers...... .......... Sleepy time:Physical properties of ethers.. ..…46 Synthesis of ethers... 4 Reactions of ethers. 49 Summarizing the Spectra of Alcohols and Ethers.. .51 Chapter 4:Conjugated Unsaturated Systems. .53 When You Don't Have Enough:Unsaturated Systems.. 53 Conjugated systems. 53 The allylic radical...... ,54 Butadiene.. ..55 Delocalization and Resonance. Resonance rules. ted systems........ ons oconugated Unsarsustitution reactions React onjugat eisecondt tring: than a tree:Die els-Alder reaction with Diels-Adler Questions 65 ldentifying the reactants.. 66 Chapter 5:"Seeing"Molecules:Spectroscopy Revisited..........67 mical Fingerprints:Infrared Spectroscopy.. co and N-H stretches C-H stretche Suntans and Beve nd:Ultraviolet and Visible Spectroscopy. 70 Not Weight Watchers,Mass Watchers:Mass Spectroscopy 79 The molecular ion 72 Fragmentation. 73 No Glowing Here:NMR Spectroscopy. 73 Proton.. .74 Carbon-13
xii Organic Chemistry II For Dummies Chapter 3: Alcohols and Ethers: Not Just for Drinking and Sleeping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31 Getting Acquainted with Alcohols ...............................................................31 Structure and nomenclature of alcohols ..........................................32 Physical properties of alcohols .........................................................33 Making moonshine: Synthesis of alcohols ........................................34 What will they do besides burn? Reactions of alcohols .................40 Introducing Ether (Not the Ether Bunny) ...................................................46 Structure and nomenclature of ethers ..............................................46 Sleepy time: Physical properties of ethers .......................................46 Synthesis of ethers ..............................................................................47 Reactions of ethers ..............................................................................49 Summarizing the Spectra of Alcohols and Ethers .....................................51 Chapter 4: Conjugated Unsaturated Systems . . . . . . . . . . . . . . . . . . . . .53 When You Don’t Have Enough: Unsaturated Systems ..............................53 Conjugated systems ............................................................................53 The allylic radical ................................................................................54 Butadiene ..............................................................................................55 Delocalization and Resonance .....................................................................56 Resonance rules ...................................................................................56 Stability of conjugated unsaturated systems ...................................57 Reactions of Conjugated Unsaturated Systems .........................................57 Put in the second string: Substitution reactions .............................57 Electrophilic addition ..........................................................................59 More than a tree: Diels-Alder reactions ............................................62 Passing an Exam with Diels-Adler Questions .............................................65 Indentifying the product .....................................................................65 Identifying the reactants .....................................................................66 Chapter 5: “Seeing” Molecules: Spectroscopy Revisited . . . . . . . . . .67 Chemical Fingerprints: Infrared Spectroscopy ..........................................68 Double bonds .......................................................................................68 Triple bonds .........................................................................................69 O-H and N-H stretches .........................................................................69 C-H stretches ........................................................................................69 Suntans and Beyond: Ultraviolet and Visible Spectroscopy ....................70 Not Weight Watchers, Mass Watchers: Mass Spectroscopy ...................72 The molecular ion ................................................................................72 Fragmentation ......................................................................................73 No Glowing Here: NMR Spectroscopy .........................................................73 Proton ....................................................................................................74 Carbon-13 ..............................................................................................77 02_178157-ftoc.indd xii 5/28/10 9:44 AM
Table of Contents xiii Part I1:Discovering Aromatic (And Not So Aromatic)Compoundsg Chapter 6:Introducing Aromatics...............................81 Benzene:Where It All Starts.. ..81 Figuring out benzene's structure... 81 Understanding benzene's resonance 83 The stability of benzene.................. 84 Physical properties of benzene. .85 Organic math-Huckel's Rule . .85 8 of the aromatic family.... erivative of be ne. anch oups He vclic Aromatic Compounds "90 Aromatic ox and sulfur pounds. 0 R 91 UV-vis. 91 NMR 91 Mass spec. 92 Chapter 7:Aromatic Substitution Part I Attack of the Electrophiles.....................................93 Basics of Electrophilic Substitution Reactions. Reac on of benzene zene 97 00 Acvlation 100 Why Do an Alkylation?. 101 Changing Things:Modifying the Reactivity of an Aromatic... .101 Lights,camera,action:Directing.. .102 Turning it on,turning it off:Activating and deactivating. .107 Steric hindrance.. ..109 Limitations of Electrophilic Substitution Reactions.... .109
Table of Contents xiii Part II: Discovering Aromatic (And Not So Aromatic) Compounds ............................................ 79 Chapter 6: Introducing Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .81 Benzene: Where It All Starts .........................................................................81 Figuring out benzene’s structure .......................................................81 Understanding benzene’s resonance ................................................83 The stability of benzene ......................................................................84 Physical properties of benzene ..........................................................85 Organic math — Hückel’s Rule ..........................................................85 Other aromatics ...................................................................................87 Smelly Relatives: The Aromatic Family ......................................................87 Nomenclature of the aromatic family................................................87 Derivatives of benzene ........................................................................88 Branches of aromatic groups .............................................................89 Black Sheep of the Family: Heterocyclic Aromatic Compounds .............89 Aromatic nitrogen compounds ..........................................................90 Aromatic oxygen and sulfur compounds ..........................................90 Spectroscopy of Aromatic Compounds ......................................................90 IR ............................................................................................................91 UV-vis.....................................................................................................91 NMR .......................................................................................................91 Mass spec..............................................................................................92 Chapter 7: Aromatic Substitution Part I: Attack of the Electrophiles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .93 Basics of Electrophilic Substitution Reactions ..........................................94 Reactions of Benzene ....................................................................................95 Halogenation of benzene.....................................................................95 Nitration of benzene ............................................................................96 Sulfonation of benzene ........................................................................97 Friedel-Crafts Reactions ................................................................................99 Alkylation ..............................................................................................99 Acylation .............................................................................................100 Why Do an Alkylation? ................................................................................101 Changing Things: Modifying the Reactivity of an Aromatic ...................101 Lights, camera, action: Directing .....................................................102 Turning it on, turning it off: Activating and deactivating .............107 Steric hindrance .................................................................................109 Limitations of Electrophilic Substitution Reactions ...............................109 02_178157-ftoc.indd xiii 5/28/10 9:44 AM