CONTENTS Preface v To the student vi CHAPTER 1 CHEMICAL BONDING 1 CHAPTER 2 ALKANES 25 CHAPTER 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES 46 CHAPTER 4 ALCOHOLS AND ALKYL HALIDES 67 CHAPTER 5 STRUCTURE AND PREPARATION OF ALKENES ELM| NATION REACT○NS90 CHAPTER 6 REACTIONS OF ALKENES ADDITION REACTIONS 124 CHAPTER 7 STEREOCHEMISTRY 156 CHAPTER 8 NUCLEOPHILIC SUBSTITUTION 184 CHAPTER 9 ALKYNES 209 CHAPTER 10 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS 230 CHAPTER 11 ARENES AND AROMATICITY 253 CHAPTER 12 REACTIONS OF ARENES ECTROPHILIC AROMATIC SUBSTITUTION 279 Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website
CONTENTS Preface v To the Student vii CHAPTER 1 CHEMICAL BONDING 1 CHAPTER 2 ALKANES 25 CHAPTER 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES 46 CHAPTER 4 ALCOHOLS AND ALKYL HALIDES 67 CHAPTER 5 STRUCTURE AND PREPARATION OF ALKENES: ELIMINATION REACTIONS 90 CHAPTER 6 REACTIONS OF ALKENES: ADDITION REACTIONS 124 CHAPTER 7 STEREOCHEMISTRY 156 CHAPTER 8 NUCLEOPHILIC SUBSTITUTION 184 CHAPTER 9 ALKYNES 209 CHAPTER 10 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS 230 CHAPTER 11 ARENES AND AROMATICITY 253 CHAPTER 12 REACTIONS OF ARENES: ELECTROPHILIC AROMATIC SUBSTITUTION 279 iii Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website
CONTENTS CHAPTER 13 SPECTROSCOPY 320 CHAPTER 14 ORGANOMETALLIC COMPOUNDS 342 CHAPTER 15 ALCOHOLS DIOLS AND THIOlS 364 CHAPTER 16 ETHERS EPOXIDES. AND SULFIDES 401 CHAPTER 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 426 CHAPTER 18 ENOLS AND ENOLATES 470 CHAPTER 19 CARBOXYLIC ACIDS 502 CHAPTER 20 CARBOXYLIC ACID DERIVATIVES NUCLEOPHILIC ACYL SUBSTITUTION 536 CHAPTER 21 ESTER ENOLATES 576 CHAPTER 22 AMINES 604 CHAPTER 23 ARYL HALIDES 656 CHAPTER 24 PHENols 676 CHAPTER 25 CARBOHYDRATES 701 CHAPTER 26 LIPIDS 731 CHAPTER 27 AMINO ACIDS, PEPTIDES, AND PROTEINS. NUCLEIC ACIDS 752 APPENDIX A ANSWERS TO THE SELF-TESTS 775 APPENDIX B TABLES 821 B-1 Bond Dissociation Energies of Some Representative Compounds 821 B-2 Acid Dissociation Constants 822 B-3 Chemical Shifts of Representative Types of Protons 822 B-4 Chemical Shifts of Representative Carbons 823 B-5 Infrared Absorption Frequencies of Some Common Structural Units 823 Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website
iv CONTENTS CHAPTER 13 SPECTROSCOPY 320 CHAPTER 14 ORGANOMETALLIC COMPOUNDS 342 CHAPTER 15 ALCOHOLS, DIOLS, AND THIOLS 364 CHAPTER 16 ETHERS, EPOXIDES, AND SULFIDES 401 CHAPTER 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 426 CHAPTER 18 ENOLS AND ENOLATES 470 CHAPTER 19 CARBOXYLIC ACIDS 502 CHAPTER 20 CARBOXYLIC ACID DERIVATIVES: NUCLEOPHILIC ACYL SUBSTITUTION 536 CHAPTER 21 ESTER ENOLATES 576 CHAPTER 22 AMINES 604 CHAPTER 23 ARYL HALIDES 656 CHAPTER 24 PHENOLS 676 CHAPTER 25 CARBOHYDRATES 701 CHAPTER 26 LIPIDS 731 CHAPTER 27 AMINO ACIDS, PEPTIDES, AND PROTEINS. NUCLEIC ACIDS 752 APPENDIX A ANSWERS TO THE SELF-TESTS 775 APPENDIX B TABLES 821 B-1 Bond Dissociation Energies of Some Representative Compounds 821 B-2 Acid Dissociation Constants 822 B-3 Chemical Shifts of Representative Types of Protons 822 B-4 Chemical Shifts of Representative Carbons 823 B-5 Infrared Absorption Frequencies of Some Common Structural Units 823 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website
PREFACE t is our hope that in writing this Study Guide and Solutions Manual we will make the study of or- ganic chemistry more meaningful and worthwhile. To be effective, a study guide should be more than just an answer book. What we present here was designed with that larger goal in mind The Study Guide and Solutions Manual contains detailed solutions to all the problems in the text. Learning how to solve a problem is, in our view, more important than merely knowing the correct answer. To that end we have included solutions sufficiently detailed to provide the student with the tery of the material. Both fill-in and multiple-choice questions have been included to truly test the student's understanding. Answers to the self-test questions may be found in Appendix a at the back of the book The completion of this guide was made possible through the time and talents of numerous peo- ple. Our thanks and appreciation also go to the many users of the third edition who provided us with helpful suggestions, comments, and corrections. We also wish to acknowledge the assistance and understanding of Kent Peterson, Terry Stanton, and Peggy Selle of McGraw-Hill. Many thanks also go to Linda Davoli for her skillful copyediting. Last, we thank our wives and families for their un- derstanding of the long hours invested in this work. Francis A. Carey Robert c. atkins Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website
PREFACE I t is our hope that in writing this Study Guide and Solutions Manual we will make the study of organic chemistry more meaningful and worthwhile. To be effective, a study guide should be more than just an answer book. What we present here was designed with that larger goal in mind. The Study Guide and Solutions Manual contains detailed solutions to all the problems in the text. Learning how to solve a problem is, in our view, more important than merely knowing the correct answer. To that end we have included solutions sufficiently detailed to provide the student with the steps leading to the solution of each problem. In addition, the Self-Test at the conclusion of each chapter is designed to test the student’s mastery of the material. Both fill-in and multiple-choice questions have been included to truly test the student’s understanding. Answers to the self-test questions may be found in Appendix A at the back of the book. The completion of this guide was made possible through the time and talents of numerous people. Our thanks and appreciation also go to the many users of the third edition who provided us with helpful suggestions, comments, and corrections. We also wish to acknowledge the assistance and understanding of Kent Peterson, Terry Stanton, and Peggy Selle of McGraw-Hill. Many thanks also go to Linda Davoli for her skillful copyediting. Last, we thank our wives and families for their understanding of the long hours invested in this work. Francis A. Carey Robert C. Atkins v Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website
TO THE STUDENT B efore beginning the study of organic chemistry, a few words about"how to do it"are in order. You've probably heard that organic chemistry is difficult; there's no denying that. It need not be overwhelming, though, when approached with the right frame of mind and with First of all you should realize that organic chemistry tends to"build"on itself. That is, once you have learned a reaction or concept, you will find it being used again and again later on. In this way it is quite different from general chemistry, which tends to be much more compartmentalized. In organic chemistry you will continually find previously learned material cropping up and being used to explain and to help you understand new topics. Often, for example, you will see the preparation of one class of compounds using reactions of other classes of compounds studied earlier in the year. How to keep track of everything? It might be possible to memorize every bit of information presented to you, but you would still lack a fundamental understanding of the subject. It is far better to generalize as much as possible You will find that the early chapters of the text will emphasize concepts of reaction theory. These will be used, as the various classes of organic molecules are presented, to describe mechanisms of organic reactions. A relatively few fundamental mechanisms suffice to describe almost every reac tion you will encounter. Once learned and understood, these mechanisms provide a valuable means of categorizing the reactions of organic molecules. There will be numerous facts to learn in the course of the year, however. For example, chemical eagents necessary to carry out specific reactions must be learned. You might find a study aid known as flash cards helpful. These take many forms, but one idea is to use 3 X 5 index cards. As an example of how the cards might be used, consider the reduction of alkenes(compounds with arbon-carbon double bonds) to alkanes(compounds containing only carbon-carbon single bonds) The front of the card might look like thi Alkenes alkane The reverse of the card would show the reagents necessary for this reaction: H2, Pt or Pd catalyst The card can actually be studied in two ways. You may ask yourself: What reagents will convert alkenes into alkanes? Or, using the back of the card: what chemical reaction is carried out with hydrogen and a platinum or palladium catalyst? This is by no means the only way to use the cards- be creative! Just making up the cards will help you to study Although study aids such as fash cards will prove helpful, there is only one way to truly master the subject matter in organic chemistry-do the problems! The more you work, the more you will learn. Almost certainly the grade you receive will be a reflection of your ability to solve problem Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website
TO THE STUDENT Before beginning the study of organic chemistry, a few words about “how to do it” are in order. You’ve probably heard that organic chemistry is difficult; there’s no denying that. It need not be overwhelming, though, when approached with the right frame of mind and with sustained effort. First of all you should realize that organic chemistry tends to “build” on itself. That is, once you have learned a reaction or concept, you will find it being used again and again later on. In this way it is quite different from general chemistry, which tends to be much more compartmentalized. In organic chemistry you will continually find previously learned material cropping up and being used to explain and to help you understand new topics. Often, for example, you will see the preparation of one class of compounds using reactions of other classes of compounds studied earlier in the year. How to keep track of everything? It might be possible to memorize every bit of information presented to you, but you would still lack a fundamental understanding of the subject. It is far better to generalize as much as possible. You will find that the early chapters of the text will emphasize concepts of reaction theory. These will be used, as the various classes of organic molecules are presented, to describe mechanisms of organic reactions. A relatively few fundamental mechanisms suffice to describe almost every reaction you will encounter. Once learned and understood, these mechanisms provide a valuable means of categorizing the reactions of organic molecules. There will be numerous facts to learn in the course of the year, however. For example, chemical reagents necessary to carry out specific reactions must be learned. You might find a study aid known as flash cards helpful. These take many forms, but one idea is to use 3 5 index cards. As an example of how the cards might be used, consider the reduction of alkenes (compounds with carbon–carbon double bonds) to alkanes (compounds containing only carbon–carbon single bonds). The front of the card might look like this: The reverse of the card would show the reagents necessary for this reaction: The card can actually be studied in two ways. You may ask yourself: What reagents will convert alkenes into alkanes? Or, using the back of the card: What chemical reaction is carried out with hydrogen and a platinum or palladium catalyst? This is by no means the only way to use the cards— be creative! Just making up the cards will help you to study. Although study aids such as flash cards will prove helpful, there is only one way to truly master the subject matter in organic chemistry—do the problems! The more you work, the more you will learn. Almost certainly the grade you receive will be a reflection of your ability to solve problems. H2, Pt or Pd catalyst vii Alkenes ? alkanes Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website
TO THE STUDENT Don't just think over the problems, either; write them out as if you were handing them in to be graded. Also, be careful of how you use the Study Guide. The solutions contained in this book have been intended to provide explanations to help you understand the problem. Be sure to write out your solution to the problem first and only then look it up to see if you have done it correctly Q Students frequently feel that they understand the material but don' t do as well as expected on tests. One way to overcome this is to"test"yourself. Each chapter in the Study Guide has a self-test at the end. Work the problems in these tests without looking up how to solve them in the text. You'll find it is much harder this way, but it is also a closer approximation to what will be expected of you when taking a test in class. Success in organic chemistry depends on skills in analytical reasoning. Many of the problems you will be asked to solve require you to proceed through a series of logical steps to the correct answer. Most of the individual concepts of organic chemistry are fairly simple; stringing them to- gether in a coherent fashion is where the challenge lies. By doing exercises conscientiously you should see a significant increase in your overall reasoning ability. Enhancement of their analytical owers is just one fringe benefit enjoyed by those students who attack the course rather than simpl attend it Gaining a mastery of organic chemistry is hard work. We hope that the hints and suggestions outlined here will be helpful to you and that you will find your efforts rewarded with a knowledge nd understanding of an important area of science. Robert c. atkins Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website
viii TO THE STUDENT Don’t just think over the problems, either; write them out as if you were handing them in to be graded. Also, be careful of how you use the Study Guide. The solutions contained in this book have been intended to provide explanations to help you understand the problem. Be sure to write out your solution to the problem first and only then look it up to see if you have done it correctly. Students frequently feel that they understand the material but don’t do as well as expected on tests. One way to overcome this is to “test” yourself. Each chapter in the Study Guide has a self-test at the end. Work the problems in these tests without looking up how to solve them in the text. You’ll find it is much harder this way, but it is also a closer approximation to what will be expected of you when taking a test in class. Success in organic chemistry depends on skills in analytical reasoning. Many of the problems you will be asked to solve require you to proceed through a series of logical steps to the correct answer. Most of the individual concepts of organic chemistry are fairly simple; stringing them together in a coherent fashion is where the challenge lies. By doing exercises conscientiously you should see a significant increase in your overall reasoning ability. Enhancement of their analytical powers is just one fringe benefit enjoyed by those students who attack the course rather than simply attend it. Gaining a mastery of organic chemistry is hard work. We hope that the hints and suggestions outlined here will be helpful to you and that you will find your efforts rewarded with a knowledge and understanding of an important area of science. Francis A. Carey Robert C. Atkins Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website