Study Guide And Solutions Manual To Accompany

Transcription

Study Guide and Solutions Manual to AccompanyT.W. Graham Solomons / Craig B. Fryhle / Scott A. Snyder / Jon Antilla

STUDY GUIDE AND SOLUTIONS MANUALTO ACCOMPANYORGANIC CHEMISTRYELEVENTH EDITION

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STUDY GUIDEANDSOLUTIONS MANUALTO ACCOMPANYORGANICCHEMISTRYELEVENTH EDITIONT. W. GRAHAM SOLOMONSUniversity of South FloridaCRAIG B. FRYHLEPacific Lutheran UniversitySCOTT A. SNYDERColumbia UniversityROBERT G. JOHNSONXavier UniversityJON ANTILLAUniversity of South Florida

Project EditorJennifer YeeSenior Production EditorElizabeth SwainCover Image Gerhard Schulz/Age Fotostock America, Inc.This book was set in 10/12 Times Roman by Aptara Delhi and printed and bound byBind-Rite. The cover was printed by Bind-Rite.Copyright 2014, 2011, 2008 John Wiley & Sons, Inc. All rights reserved. No part ofthis publication may be reproduced, stored in a retrieval system or transmitted in any formor 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, Inc., 222 RosewoodDrive, Danvers, MA 01923, website at www.copyright.com. Requests to the Publisher forpermission should be addressed to the Permissions Department, John Wiley & Sons, Inc.,111 River Street, Hoboken, NJ 07030-5774, (201) 748-6011, fax (201) 748-6008, ion copies are provided to qualified academics and professionals for review puposesonly, for use in their courses during the next academic year. These copies are licensed andmay not be sold or transferred to a third party. Upon completion of the review period, pleasereturn the evaluation copy to Wiley. Return instructions and a free of charge return shippinglabel are available at www.wiley.com/go/returnlabel. Outside of the United States, pleasecontact your local representative.ISBN 978-1-118-14790-0Binder-Ready version ISBN 978-1-118-63649-7Printed in the United States of America10 9 8 7 6 5 4321

ACKNOWLEDGMENTSWe are grateful to those people who have made many helpful suggestions for various editionsof this study guide. These individuals include: George R. Jurch, George R. Wenzinger, and J.E. Fernandez at the University of South Florida; Darell Berlin, Oklahoma State University;John Mangravite, West Chester State College; J. G. Traynham, Louisiana State University;Desmond M. S. Wheeler, University of Nebraska; Chris Callam, The Ohio State University;Sean Hickey, University of New Orleans; and Neal Tonks, College of Charleston.We are especially grateful to R.G. (Bob) Johnson for his friendship, dedication, andmany contributions to this Study Guide and the main text over many years.T. W. Graham SolomonsCraig B. FryhleScott A. SnyderJon Antillav

CONTENTSTo the StudentINTRODUCTION“Solving the Puzzle” or “Structure Is Everything (Almost)”CHAPTER 1THE BASICS: BONDING AND MOLECULAR STRUCTURESolutions to ProblemsQuizCHAPTER 2FAMILIES OF CARBON COMPOUNDS: FUNCTIONALGROUPS, INTERMOLECULAR FORCES, AND INFRARED (IR)SPECTROSCOPYSolutions to ProblemsQuizCHAPTER 3ACIDS AND BASES: AN INTRODUCTION TO ORGANICREACTIONS AND THEIR MECHANISMSSolutions to ProblemsQuizCHAPTER 4NOMENCLATURE AND CONFORMATIONS OFALKANES AND CYCLOALKANESSolutions to ProblemsQuizCHAPTER 5STEREOCHEMISTRY: CHIRAL MOLECULESSolutions to ProblemsQuizvixixiii1115181830343444464662656582

CONTENTSCHAPTER 6IONIC REACTIONS–NUCLEOPHILIC SUBSTITUTION ANDELIMINATION REACTIONS OF ALKYL HALIDESSolutions to ProblemsQuizCHAPTER 7ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS.ELIMINATION REACTIONS OF ALKYL HALIDESSolutions to ProblemsQuizCHAPTER 8ALKENES AND ALKYNES II: ADDITION REACTIONSSolutions to ProblemsQuizCHAPTER 9NUCLEAR MAGNETIC RESONANCE AND MASSSPECTROMETRY: TOOLS FOR STRUCTUREDETERMINATIONSolutions to ProblemsQuizCHAPTER 10RADICAL REACTIONSSolutions to ProblemsQuizCHAPTER 11ALCOHOLS AND ETHERSSolutions to 82182200203203225

viiiCONTENTSCHAPTER 12ALCOHOLS FROM CARBONYL COMPOUNDS: OXIDATIONREDUCTION AND ORGANOMETALLIC COMPOUNDSSolutions to ProblemsQuiz227227257ANSWERS TO FIRST REVIEW PROBLEM SET259(First Review Problem Set is available only in WileyPlus,www.wileyplus.com)CHAPTER 13CONJUGATED UNSATURATED SYSTEMSSolutions to ProblemsQuiz278278299SUMMARY OF REACTIONS BY TYPE, CHAPTERS 1–13301METHODS FOR FUNCTIONAL GROUP PREPARATION,CHAPTERS 1–13305CHAPTER 14AROMATIC COMPOUNDSSolutions to ProblemsQuizCHAPTER 15REACTIONS OF AROMATIC COMPOUNDSSolutions to ProblemsQuizCHAPTER 16ALDEHYDES AND KETONES. NUCLEOPHILIC ADDITION TOTHE CARBONYL GROUPSolutions to ProblemsQuiz308308323325325355357357386

CONTENTSCHAPTER 17CARBOXYLIC ACIDS AND THEIR DERIVATIVES:NUCLEOPHILIC ADDITION-ELIMINATION ATTHE ACYL CARBONSolutions to ProblemsQuizCHAPTER 18REACTIONS AT THE α CARBON OF CARBONYLCOMPOUNDS: ENOLS AND ENOLATESSolutions to ProblemsQuizCHAPTER 19CONDENSATION AND CONJUGATE ADDITION REACTIONSOF CARBONYL COMPOUNDS: MORE CHEMISTRY OFENOLATESSolutions to ProblemsQuizCHAPTER 20AMINESSolutions to ProblemsQuizCHAPTER 21PHENOLS AND ARYL HALIDES: NUCLEOPHILIC 88488526Solutions to ProblemsQuiz530530547ANSWERS TO SECOND REVIEW PROBLEM SET550(Second Review Problem Set is available only in WileyPlus,www.wileyplus.com)CHAPTER 22CARBOHYDRATESSolutions to ProblemsQuiz566567592

xCONTENTSCHAPTER 23LIPIDSSolutions to ProblemsQuizCHAPTER 24AMINO ACIDS AND PROTEINSSolutions to ProblemsQuizCHAPTER 25NUCLEIC ACIDS AND PROTEIN SYNTHESISSolutions to Problems596596607610610625626626Special Topics A–F and H are available only in WileyPlus,www.wileyplus.com. Solutions to problems in the Special Topicsare found on the following pages:Special Topic A13C NMR Spectroscopy634Special Topic BChain-Growth Polymers636Special Topic CStep-Growth Polymers637Special Topic DThiols, Sulfur Ylides, and Disulfides643Special Topic EThiol Esters and Lipid Biosynthesis645Special Topic FAlkaloids646Special Topic GCarbon Carbon Bond-Forming andOther Reactions of Transition MetalOrganometallic Compounds651Electrocyclic and Cycloaddition Reactions654Special Topic HProblemsAdditional ProblemsSolutions to Problems of Appendix A659661662663APPENDIX BANSWERS TO QUIZZES667APPENDIX CMOLECULAR MODEL SET EXERCISES682APPENDIX AEMPIRICAL AND MOLECULAR FORMULAS

To the StudentContrary to what you may have heard, organicchemisty does not have to be a difficult course. Itwill be a rigorous course, and it will offer a challenge. But you will learn more in it than in almostany course you will take—and what you learn willhave a special relevance to life and the world aroundyou. However, because organic chemistry can be approached in a logical and systematic way, you willfind that with the right study habits, mastering organic chemistry can be a deeply satisfying experience. Here, then, are some suggestions about how tostudy:1. Keep up with your work from day to day-neverlet yourself get behind. Organic chemistry is acourse in which one idea almost always builds onanother that has gone before. It is essential, therefore, that you keep up with, or better yet, be a littleahead of your instructor. Ideally, you should tryto stay one day ahead of your instructor’s lecturesin your own class preparations. The lecture, then,will be much more helpful because you will already have some understanding of the assignedmaterial. Your time in class will clarify and expand ideas that are already familiar ones.2. Study material in small units, and be sure thatyou understand each new section before you goon to the next. Again, because of the cumulativenature of organic chemistry, your studying willbe much more effective if you take each new ideaas it comes and try to understand it completelybefore you move on to the next concept.3. Work all of the in-chapter and assigned problems. One way to check your progress is to workeach of the in-chapter problems when you cometo it. These problems have been written just forthis purpose and are designed to help you decidewhether or not you understand the material thathas just been explained. You should also carefully study the Solved Problems. If you understand a Solved Problem and can work the relatedin-chapter problem, then you should go on; if youcannot, then you should go back and study thepreceding material again. Work all of the problems assigned by your instructor from the end ofthe chapter, as well. Do all of your problems in anotebook and bring this book with you when yougo to see your instructor for extra help.4. Write when you study. Write the reactions,mechanisms, structures, and so on, over andover again. Organic chemistry is best assimilatedthrough the fingertips by writing, and not throughthe eyes by simply looking, or by highlightingmaterial in the text, or by referring to flash cards.There is a good reason for this. Organic structures, mechanisms, and reactions are complex. Ifyou simply examine them, you may think you understand them thoroughly, but that will be a misperception. The reaction mechanism may makesense to you in a certain way, but you need adeeper understanding than this. You need to knowthe material so thoroughly that you can explainit to someone else. This level of understandingcomes to most of us (those of us without photographic memories) through writing. Only by writing the reaction mechanisms do we pay sufficientattention to their details, such as which atoms areconnected to which atoms, which bonds break ina reaction and which bonds form, and the threedimensional aspects of the structures. When wewrite reactions and mechanisms, connections aremade in our brains that provide the long-termmemory needed for success in organic chemistry. We virtually guarantee that your grade in thecourse will be directly proportional to the numberof pages of paper that you fill with your ownwriting in studying during the term.5. Learn by teaching and explaining. Study withyour student peers and practice explaining concepts and mechanisms to each other. Use theLearning Group Problems and other exercisesyour instructor may assign as vehicles for teachingand learning interactively with your peers.xi

xiiTO THE STUDENT6. Use the answers to the problems in the StudyGuide in the proper way. Refer to the answersonly in two circumstances: (1) When you havefinished a problem, use the Study Guide to checkyour answer. (2) When, after making a real effortto solve the problem, you find that you are completely stuck, then look at the answer for a clueand go back to work out the problem on your own.The value of a problem is in solving it. If you simply read the problem and look up the answer, youwill deprive yourself of an important way to learn.7. Use molecular models when you study. Becauseof the three-dimensional nature of most organicmolecules, molecular models can be an invaluableaid to your understanding of them. When you needto see the three-dimensional aspect of a particulartopic, use the Molecular VisionsTM model set thatmay have been packaged with your textbook, orbuy a set of models separately. An appendix to theStudy Guide that accompanies this text providesa set of highly useful molecular model exercises.8. Make use of the rich online teaching resourcesin WileyPLUS (www.wileyplus.com) and do anyonline exercises that may be assigned by your instructor.

INTRODUCTION“Solving the Puzzle”or“Structure Is Everything (Almost)”As you begin your study of organic chemistry it may seem like a puzzling subject. In fact,in many ways organic chemistry is like a puzzle—a jigsaw puzzle. But it is a jigsaw puzzlewith useful pieces, and a puzzle with fewer pieces than perhaps you first thought. In order toput a jigsaw puzzle together you must consider the shape of the pieces and how one piece fitstogether with another. In other words, solving a jigsaw puzzle is about structure. In organicchemistry, molecules are the pieces of the puzzle. Much of organic chemistry, indeed lifeitself, depends upon the fit of one molecular puzzle piece with another. For example, whenan antibody of our immune system acts upon a foreign substance, it is the puzzle-piece-likefit of the antibody with the invading molecule that allows “capture” of the foreign substance.When we smell the sweet scent of a rose, some of the neural impulses are initiated by thefit of a molecule called geraniol in an olfactory receptor site in our nose. When an adhesivebinds two surfaces together, it does so by billions of interactions between the molecules ofthe two materials. Chemistry is truly a captivating subject.As you make the transition from your study of general to organic chemistry, it is importantthat you solidify those concepts that will help you understand the structure of organicmolecules. A number of concepts are discussed below using several examples. We alsosuggest that you consider the examples and the explanations given, and refer to informationfrom your general chemistry studies when you need more elaborate information. There arealso occasional references below to sections in your text, Solomons, Fryhle, and SnyderOrganic Chemistry, because some of what follows foreshadows what you will learn in thecourse.SOME FUNDAMENTAL PRINCIPLES WE NEED TO CONSIDERWhat do we need to know to understand the structure of organic molecules? First, we needto know where electrons are located around a given atom. To understand this we need to recall from general chemistry the ideas of electron configuration and valence shell electronorbitals, especially in the case of atoms such as carbon, hydrogen, oxygen, and nitrogen. Wealso need to use Lewis valence shell electron structures. These concepts are useful becausethe shape of a molecule is defined by its constituent atoms, and the placement of t

CHAPTER 20 AMINES 488 Solutions to Problems 488 Quiz 526 CHAPTER 21 PHENOLS AND ARYL HALIDES: NUCLEOPHILIC AROMATIC SUBSTITUTION 530 Solutions to Problems 530 Quiz 547 ANSWERS TO SECOND REVIEW PROBLEM SET 550 (Second Review Problem Set is available only in WileyPlus, www.wileyplus.com) CHAPTER 22 CARBOHYDRATES 566 Solutions to Problems 567