Organic Chemistry / Edition 6

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Overview


In this innovative text, Bruice balances coverage of traditional topics with bioorganic chemistry to show how organic chemistry is related to biological systems and to our daily lives. Functional groups are organized around mechanistic similarities, emphasizing what functional groups do rather than how they are made. Tying together the reactivity of a functional group and the synthesis of compounds resulting from its reactivity prevents students from needing to memorize lists of unrelated reactions. The Sixth Edition has been revised and streamlined throughout to enhance clarity and accessibility, and adds a wealth of new problems and problem-solving strategies.
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Editorial Reviews

Booknews
New edition of an organic chemistry text that encourages students to think about what they have already learned and then apply this knowledge in a new setting. Bruice U. of California has organized the material in a way that discourages rote memorization. Functional groups are organized around mechanistic similarities such as electrophilic and nucleophilic additions; radical, nucleophilic, electrophilic aromatic, and nucleophilic acyl substitutions; and eliminations. The 30 chapters discuss introductory material; hydrocarbons, stereochemistry, and resonance; substitution and elimination reactions; identification of organic compounds; aromatic, carbonyl, and bioorganic compounds; and special topics. Includes some short biographies of scientists, together with a b&w photograph, and color illustrations and diagrams. Annotation c. Book News, Inc., Portland, OR booknews.com
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Product Details

  • ISBN-13: 9780321663139
  • Publisher: Prentice Hall
  • Publication date: 1/18/2010
  • Edition description: Older Edition
  • Edition number: 6
  • Pages: 1440
  • Sales rank: 661,392
  • Product dimensions: 8.66 (w) x 11.12 (h) x 1.84 (d)

Meet the Author

Paula Yurkanis Bruice was raised primarily in Massachusetts, Germany, and Switzerland and was graduated from the Girls' Latin School in Boston. She received an A.B. from Mount Holyoke College and a Ph.D. in chemistry from the University of Virginia. She received an NIH postdoctoral fellowship for study in biochemistry at the University of Virginia Medical School, and she held a postdoctoral appointment in the Department of Pharmacology at Yale Medical School.

She is a member of the faculty at the University of California, Santa Barbara, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, and two Mortar Board Professor of the Year Awards. Her research interests concern the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading mystery/suspense novels and her pets (three dogs, two cats, and a parrot).

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Read an Excerpt

PREFACE:

Preface

TO THE INSTRUCTOR

The guiding principle in writing this book was to create a text for students—a text that presents the material in a way that encourages students to think about what they have already learned and then apply this knowledge in a new setting. I want students to reason their way to a solution rather than memorize a multitude of facts, hoping they don't run out of memory before the course ends. I am convinced that the what of organic chemistry is much easier to grasp and retain if the why is understood.

Comments I have received from both colleagues and students on the second edition indicate the book is working in the way I had hoped. As much as I cherish having faculty tell me that their students are scoring higher than ever before on tests, nothing is more gratifying than hearing from the students themselves—a wonderful advantage of being the author of a textbook during the email age. (Even my dog has received e-mail from students.) Many students have generously accredited their success in organic chemistry to the book—not giving themselves nearly enough credit for how hard they studied to achieve that success. And they always seem surprised that they have come to love "orgo" (on the East Coast) or "o-them" (on the West Coast). I also hear from many pre-meds who say that the book gave them such a permanent understanding of organic chemistry that they found it to be the easiest part of that dreaded test, the MCAT.

As I strove to make this book even more useful to the student, I have relied on constructive critical comments from many of you. For these I am very grateful. Ialso kept a journal of questions students had when they came to my office hours. These questions let me know what sections in the book needed clarifying and what answers in the Study Guide/Solutions Manual needed more in-depth explanations. Most importantly, this analysis showed me where new problems needed to be created so that these same questions had less of a chance of being asked by students using the third edition. Because I teach a class of more than 400 students, I clearly have a vested interest in minimizing their confusion! In this edition, many sections have been rewritten to optimize readability and comprehension, and there are many new in-chapter problems, new end-of-chapter problems, and more solved problems to help students master organic chemistry by solving problems. There are also new interest boxes to show students the applications of organic chemistry, and additional margin notes to remind students of important concepts and principles.

I hope you find the third edition even more appealing to your students than the second. As always, I am eager to hear your comments—positive comments are the most fun, but critical comments are the most useful.

I would also like to draw your attention to the following features of the text:

A Functional Group Approach with a Mechanistic Organization That Ties Together Synthesis and Reactivity

This book is organized to discourage the student from rote memorization. The functional groups have been organized around mechanistic similarities—electrophilic additions, radical substitutions, nucleophilic substitutions, eliminations, electrophilic aromatic substitutions, nucleophilic acyl substitutions, and nucleophilic additions. This organization allows a lot of material to be understood based on unifying principles of reactivity.

In addition, instead of discussing the synthesis of a functional group when its reactivity is discussed—reactions that generally have little to do with each other—I discuss the synthesis of the compounds that are formed as a result of the functional group's reactivity. In the alkene chapter, for example, students learn about the reactions of alkenes but they do not> learn at this point about the synthesis of alkenes. Instead, they learn about the synthesis of alkyl halides, alcohols, ethers, and alkanes—the compounds formed when alkenes react. Because alkenes are synthesized from the reactions of alkyl halides and alcohols, the synthesis of alkenes is covered when the reactions of alkyl halides and alcohols are discussed. Tying together the reactivity of a functional group and the synthesis of compounds resulting from its reactivity prevents the student from having to memorize lists of unrelated reactions. Understanding different ways functional groups can be prepared is useful in designing syntheses, however, so the different reactions that yield a particular functional group are compiled in Appendix IV As students learn how to design syntheses, they appreciate the importance of reactions that change the carbon skeleton of a molecule; these reactions are compiled in Appendix V.

A Detailed Look at the Organization of the Text

The book has been divided into eight sections. Each section starts with a one-page overview so students can understand where they are "going:" Chapter 1 provides a summary of the material that students need to recall from General Chemistry. The sections on acids and bases were rewritten to emphasize the relationship between acidity and stability of the conjugate base. (Acids and bases are covered even more extensively in the Study Guide/Solutions Manual.) In Chapter 2, students learn how to name five classes of organic compounds—those that will be the products of the reactions in the chapters that immediately follow. Chapter 2 also covers topics that are necessary before the study of reactions can begin—structures, conformations, and physical properties of organic compounds. Chapter 3 discusses the reactions of alkenes. In this chapter, students are first introduced to the concept of "curved arrows." (The Study Guide/Solutions Manual contains an extensive exercise on "electron pushing:" I have found this exercise to be very successful in making my students comfortable with a topic that should be easy, but somehow perplexes even the best of them unless they have sufficient practice.) Chapter 3 also contains a discussion of thermodynamics and kinetics. This section was rewritten to make it even easier for students to understand. Rate equations are derived in an appendix for those who wish to give their students a more mathematical treatment, and the Study Guide/Solutions Manual contains a section on calculating kinetic parameters.

I chose to lead off with the reactions of alkenes because of their simplicity. Chapter 3 covers a wide variety of reactions but they all have similar mechanisms—an electrophile adds to the least substituted sp2 carbon and a nucleophile adds to the other sp2 carbon. The many reactions differ only in the nature of the electrophile and the nucleophile. Because organic chemistry is all about the interactions of electrophiles and nucleophiles, starting the study of organic reactions in a way that familiarizes students with a wide variety of electrophiles and nucleophiles makes sense. The reactions in Chapter 3 are discussed without regard to stereochemistry because I have found that students do well as long as only one new concept is introduced at a time. Chapter 4 reviews the isomers introduced in Chapters 2 and 3 (conformers and cis-trans isomers) and then discusses isomers that result from having a chirality center (the most recent IUPAC-approved term for a carbon bonded to four different groups). There is an extensive model-building exercise in the Study Guide/Solutions Manual to help the students get used to building molecular models, and the book's Companion Website gives students the opportunity to manipulate many molecules in three dimensions. Now that the students are comfortable with both isomers and electrophilic addition reactions, the two topics are considered together at the end of Chapter 4, where the stereochemistry of the addition reactions covered in Chapter 3 is presented. Chapter 5 covers alkynes. This chapter should build the students' confidence because of the similarity of the material to what was presented in Chapter 3.

Understanding electron delocalization is vitally important in organic chemistry, so it is covered in its own chapter (Chapter 6). This chapter is a continuation of the introduction to this topic in Chapter 1. Chapter 7 covers the reactions of dimes, allowing students to apply the concept of electron delocalization just studied to the electrophilic addition reactions that were mastered in Chapters 3 and 5. Chapter 8 covers the reactions of alkanes. The lack of a functional group in alkanes further emphasizes the importance of a functional group to chemical reactivity.

The next three chapters deal with substitution and elimination reactions at an sp3 hybridized carbon. Chapter 9 covers substitution reactions of alkyl halides. Chapter 10 covers elimination reactions of alkyl halides and then goes on to consider competition between substitution and elimination. Chapter 11 covers substitution and elimination reactions at an sp3 hybridized carbon when a group other than a halogen is the leaving group—reactions of alcohols, ethers, epoxides, thiols, sulfides, and quaternary ammonium ions.

Next are two spectroscopy chapters (mass spectrometry, IR spectroscopy, and UV/Vis spectroscopy in Chapter 12, followed by NMR spectroscopy in Chapter 13). Each spectral technique is written as a "stand-alone topic" so it can be covered independently at any time during the course. Chapter 12 opens with a table of functional groups for those who want to cover spectroscopy before students have been introduced to all the functional groups.

Chapter 14 covers aromaticity and the reactions of benzene. Chapter 15 discusses the reactions of substituted benzenes. Because not all organic courses cover the same amount of material in a semester, Chapters 12-15 have been strategically placed to come near the end of the first semester. Ending a semester before Chapter 12, Chapter 13, or Chapter 14, or after Chapter 15 won't interfere with the flow of information.

The order of the topics dealing with the chemistry of carbonyl compounds in Chapters 16 and 17, where carboxylic acid derivatives are discussed before aldehydes and ketones, was initially met with skepticism by many considering using the book. However, when the opinions of those who had used the two editions of the book were sought, there was strong agreement that this is a preferred order of treatment. Chapter 16 discusses the reactions of carboxylic acids and their derivatives with oxygen and nitrogen nucleophiles. Thus, the students are introduced to carbonyl chemistry by learning how tetrahedral intermediates partition. Chapter 17 starts by discussing the reactions of aldehydes, ketones, and carboxylic acid derivatives with strong (carbon and hydrogen) nucleophiles. By studying these compounds as a group, students see how the reactions of aldehydes and ketones differ from those of carboxylic acid derivatives. Then when they move on to study the formation and hydrolysis of imines, enamines, and acetals, they can easily understand these mechanisms because they are well versed in how tetrahedral intermediates partition. Over the years I have experimented with my classes and I believe this to be the most effective and easiest way to teach carbonyl chemistry. That being said, these chapters can easily be switched so long as Section 17.6 is skipped and then covered with Chapter 16.

Chapter 18 revisits reduction reactions, and discusses oxidation reactions, which my students tend to find troubling. I have found it helps to cover them all together as a unit. Because the reduction reactions appear in earlier chapters, this is an opportunity for students to extend their knowledge within the framework of what they already know. Chapter 19 deals with reactions at the carbon of a-carbonyl compounds.

One special note about amines. There is no question that amines are exceedingly important in organic chemistry. (In Chapter 30, The Organic Chemistry of Drugs, Table 30.1 lists the names, structures, and uses of the most widely prescribed drugs, and a majority of them are amines.) So then, why is there no separate chapter on amines?

My aim again is to organize organic chemistry in a way that allows students to understand and predict rather than memorize. This book covers the functional groups from the point of how they react rather than what they are called. Amines don't undergo additions, substitutions, or eliminations. Their reactivity lies in how they react with other organic compounds. Thus, all the chemistry that would be found in a typical chapter called Amines is in this book, but it is found when that reactivity with other compounds is discussed (for example, acid/base properties of aliphatic and aromatic amines—Chapters 1, 6, 15, and 27; amines as nucleophiles in substitution reactions—Chapters 9 and 16; amines as nucleophiles in addition reactions—Chapter 17; and elimination reactions of quarternary ammonium ions and amine oxides—Chapter 11). Amine synthesis is covered in those sections where amines are the products of the reactions being discussed (for example, the Gabriel synthesis of amines results from imide hydrolysis; amines are synthesized as the result of SN2 reactions; and anilines are synthesized as a result of electrophilic aromatic substitution followed by reduction or as a result of nucleophilic aromatic substitution).

A Modular Organization in the Last Third of the Book

I anticipate that the first 21 chapters will be covered by most instructors during a year-long course. An instructor can then choose among the remaining chapters depending w his or her preference and the interests of the majority of the students enrolled in the course. Those teaching students whose interests are primarily in the biological and health sciences might be more inclined to cover Chapter 22 (Catalysis), Chapter 23 (The Organic Mechanisms of the Coenzymes. Metabolism), Chapter 24 (Lipids), and Chapter 25 (Nucleosides, Nucleotides, and Nucleic Acids). Those teaching courses designed for chemistry or engineering majors may decide to include Chapter 26 (Synthetic Polymers), Chapter 27 (Heterocyclic Compounds), Chapter 28 (Pericyclic Reactions), and Chapter 29 (More About Multistep Organic Synthesis). The book ends with a chapter on drug discovery and design-a topic that in my experience interests students enough that they will choose to read it on their own, even if it is not covered in the course.

Changes to This Edition—Organization

In response to reviewer comments, electron delocalization and resonance are now introduced in Chapter 1. The number and kinds of Kekulé structures students see at the beginning of their study has been increased. Chapter 2 now covers the conformations of both mono- and disubstituted cyclohexanes. Material on aromaticity that appeared in Chapter 6 of the second edition has been expanded and moved to a new Chapter 14. In Chapter 12, the treatment of mass spectrum fragmentation patterns has been reworked to emphasize the common behavior of a variety of compounds when they fragment. The treatment of IR spectroscopy has been reorganized and expanded and includes many additional FT-IR spectra. Because the NMR spectra in the book are FT-NMR spectra and because FT-NMR spectra are what most students see in their laboratory courses, the discussion of the theory of NMR spectroscopy in Chapter 13 describes Fourier transform spectrometers, a theory easier for students to understand than the traditional description of continuous wave spectrometers. In response to user feedback, more problems that involve interpreting spectra have been added to this edition. To help students analyze these specta, more signals have been enlarged. As in the last edition, most of the H NMR spectra shown are 300 MHz FT NMR spectra, which are more like the NMR spectra students are likely to see in their undergraduate laboratories and after they graduate. More spectroscopy problems have also been added to subsequent chapters to enhance the integration of spectroscopy throughout the course. In Chapter 19, the sections on enolate chemistry have been expanded and clarified.

Organic Chemistry with a Bioorganic Flavor

Bioorganic material is introduced throughout this text to encourage students to recognize that organic chemistry and biochemistry are not separate entities, but two parts of a continuum of knowledge. For example, students learn not just how carboxylic acids are activated for reaction in the laboratory, but also how they are activated for reaction in biological systems and why the mode of activation differs in the two situations. Once students learn how such things as electron delocalization, leaving-group tendency, electrophilicity, and nucleophilicity affect the reactions of simple organic compounds, they can appreciate how these same factors are involved in the reactions of more complicated organic molecules such as enzymes, nucleic acids, and vitamins.

In the first part of the book, the bioorganic material is limited primarily to interest boxes and the last sections of the chapters, so the material is available to the curious student but the instructor is not compelled to introduce bioorganic topics into the course. Later in the book there are several chapters that focus heavily on bioorganic topics, including the mechanisms of coenzymes, the chemistry of drug design, and the chemistry of biological macromolecules. Each instructor may choose which, if any, of these chapters to cover.

The chapters on bioorganic chemistry (Chapters 20-25) emphasize the chemistry associated with the topic. They contain more chemistry than one would expect to find in a biochemistry text. In the lipids chapter, for example, the mechanisms of prostaglandin formation (allowing students to understand how aspirin works), fat breakdown (allowing students to understand the odor associated with rancidity), and terpene biosynthesis are covered. The chapter on coenzymes emphasizes the role of vitamin B1 as an electron delocalizer, vitamin K as a strong base, vitamin B12 as a radical initiator, biotin as a compound that can transfer a carboxyl group, and how the many different reactions of vitamin B6 are controlled by the overlap of p orbitals. The chapter on nucleic acids explains mechanistically such things as the function of ATP, why DNA contains thymine instead of uracil, and how DNA strands are synthesized in the laboratory. The chapter on catalysis explains the various modes of catalysis that occur in organic reactions and then shows that these are identical to the modes of catalysis that occur in enzymatic reactions—all presented in a way that allows students to understand the lightening-fast rates of enzymatic reactions. Thus, these chapters are not a repetition of what will be covered in a biochemistry course, but are designed to serve as a bridge between the two disciplines.

An Early and Consistent Emphasis on Organic Synthesis

Students are introduced to synthetic chemistry and retrosynthetic analysis early in this book (Chapters 3 and 5, respectively), so they can use this technique throughout the course as they design multistep syntheses. In addition, there are six special sections spread throughout the book on synthesis design, each with a different focus. For example, one emphasizes the proper choice of reagents and reaction conditions to maximize the yield of the target molecule (Chapter 10), and another focuses on the synthesis of cyclic compounds (Chapter 17). Moreover, Chapter 29 (More About Multistep Organic Synthesis) discusses such things as protecting groups, control of stereochemistry during synthesis, and retrosynthetic analysis at a more advanced level. The use of combinatorial methods in organic synthesis is described in Chapter 30, which focuses on drug design.

Changes to This Edition—Synthesis

In this edition I have added more synthetic problems, in particular new multistep (road-map) problems. I also added more problems that involve the synthesis of compounds that students will recognize (like ketoprofen, Novocain, and Valium).

Margin Notes and Boxed Material to Engage the Student

Margin notes and biographical sketches appear throughout the text. The margin notes remind students of important principles, and the biographical sketches give students some appreciation of the history of chemistry and the people who contributed to that history. Interest Boxes have been included to bring life to the topic being discussed (e.g., Alkyl Halides as Survival Compounds, Chimney Sweeps and Cancer, Ultravolet Light and Sunscreens, and Penicillin and Drug Resistance) or to give the student extra help (e.g., Calculating Kinetic Parameters, A Few Words About Curved Arrows, and Incipient Primary Carbocations).

Changes to This Edition—Interest Boxes

There are a dozen new boxes in this edition, including one on the pericyclic reaction r that makes fireflies glow and one on how the popular new OTC antidepressant SAMe methylates neurotransmitters. I also extensively updated the boxes that remain from previous editions (for example, I mention the recent synthesis of octanitrocubane in the box on strained carbon compounds in Chapter 1).

My students really liked the margin notes in the second edition, so I added more of these in this edition. These emphasize core points and offer pedagogical advice.

Problems, Solved Problems, and Problem-Solving Strategies

The book contains more than 1500 problems. The problems within each chapter are primarily drill problems. They are designed so students can test themselves on the material just covered before they go on to the next section. Solutions to selected problems are shown to give the student an understanding of how to solve a problem, and short answers are provided in the Appendix for problems marked with a diamond so students can quickly test their understanding. Most chapters also contain at least one Problem-Solving Strategy that teaches students how to approach certain kinds of problems. For example, the Problem-Solving Strategy in Chapter 9 teaches students how to determine whether a reaction will be more apt to take place by an SN1 or an SN2 pathway. Each Problem-Solving Strategy is followed by an exercise that gives the student an opportunity to use the problem-solving skill just learned.

The end-of-chapter problems are of varying difficulty. The initial problems are drill problems that integrate material from the entire chapter. This provides a greater challenge by requiring the student to think about all the material in the chapter rather than individual sections. The end-of-chapter problems are purposefully not labeled to indicate the sections the material comes from. The problems become more challenging as the student proceeds through them, and material from more than one chapter is often integrated into later problems. I suspect the problems will not appear more difficult to the student, however, because as the student works through the problems, his or her ability increases and so does his or her confidence (that is why the more difficult problems are not marked as such). I made a concerted effort to make none of the problems so difficult that the student loses confidence. A few problems contain references to the journal in which the original work was published, enabling the curious student to find out more about the work that led to the conclusion shown in the problem.

Changes to This Edition—Problems

Much of the focus of this revision was on the problems, both in-chapter and end-of-chapter. There are 10% more problems in this edition, and there are more Solved Problems and more Problem-Solving Strategy essays. As mentioned previously, many of the new problems are multistep synthetic problems, designed to help students practice their synthetic reasoning skills.

Rich in Three-Dimensional, Computer-Generated Structures

The second edition was widely praised for its effective and useful art program. This edition continues to present energy-minimized, three-dimensional structures throughout the text to give the students an appreciation of the three-dimensional shapes of organic molecules.

Pedagogical, Efficient Use of Color

Organic chemistry is sufficiently challenging without forcing students to use a road map to understand the use of color in a textbook. Therefore, this book does not have such things as blue incoming groups and green leaving groups. Students will not find themselves asking "Why did the nucleophile change its color?" Color is used to make the book visually more appealing and to make learning easier by highlighting points of focus. An attempt has been made to make the color consistent (mechanism arrows are always red, for example), but there is no need in this text for a student to memorize a color palette.

Changes to This Edition—Art Program

Electrostatic potential maps have been added throughout this edition to allow students to visualize molecules in ways not possible before. With them, students can now see things like electron delocalization, how a formal positive charge is not always on the region in a molecule with the least electron density, the effect of electronegativity on pKa, which atom of a cyclic bromonium ion is most susceptible to nucleophilic attack, the difference in the reactivity of substituted benzenes, the electrophilicity of the methyl group of an alkyl halide, and the nucleophilicity of the methyl group of an organometallic compound. There are hundreds of these new illustrations throughout the book.

INSTRUCTIONAL AIDS

The publisher offers a number of products for students and faculty that are designed to complete this learning package:

FOR THE STUDENT

Study Guide/Solutions Manual (ISBN 0-13-017859-4): The Study Guide/ Solutions Manual contains not just answers to the problems, but complete explanations of how the answers were obtained. The Study Guide/Solutions Manual also contains:

  • a section on acid/base chemistry at a more advanced level than what is covered in the text, with a set of problems
  • an 18-page exercise on "pushing electrons"
  • an exercise on building molecular modelsan exercise on calculating kinetic parameters
  • 21 practice tests

For the sake of making the path to mastery of the subject as smooth as possible, I thought it was important that I also write the Study Guide/Solutions Manual.

Bruice 3/e Companion Website (http://www.prenhall.com/bruice). This Companion Website for students features about 100 additional interactive, computer-graded problems for each chapter, regular updates of articles in the popular and lay scientific press that relate to organic chemistry, and a gallery of organic molecules that students can manipulate in real-time on their computers. And for students who are not familiar with the world wide web, we have:

Organic Media Companion for CW (ISBN 0-13-017863-2). This supplement comes FREE with each new copy of the text and is also available for separate purchase for students who buy used textbooks. It includes the web-enabled Organic Chemestry Student CD that accompanies the text as well as a brief, easy-to-understand book that describes the CD, how to use it, and how to use the Internet, world wide web, and Companion Website (CW) for the text. The CD is populated with multimedia elements and interactive exercises and offers students a one-click link to the Companion Website for the text.

Prentice Hall Molecular Model Kit (ISBN 0-205-508136-3). This best-selling model kit allows students to build space-filling and ball-and-stick models of common organic molecules. It allows accurate depiction of double and triple bonds, including heteroatomic molecules (which some model kits cannot handle well).

Prentice Hall Framework Molecular Model Kit (ISBN 0-13-330076-5). This model kit allows students to build scale models that show the mutual relations of atoms in organic molecules, including precise interatomic distances and bond angles. This is the most accurate model kit available.

Chemistry: Themes of the Times. This mini-newspaper is produced by The New York Times for students of chemistry. It features selected articles related to chemistry from the pages of The New York Times and is available free to adopters of the text.

If you wish, students' copies of the text may be accompanied by one of two molecular modeling tools:

Molecular Modeling Workbook, featuring SpartanView and SpartanBuild software (ISBN 0-13-032026-9). This workbook includes a software tutorial and numerous challenging exercises students can tackle to solve problems involving structure building and analysis using the tools included in the two pieces of Spartan software. Available free when packaged with the text; please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

ChemOffice Ltd software, including ChemDraw LTD and Chem3D LTD. A free workbook is available on the Companion Website that includes a software tutorial and numerous exercises for each chapter of the text. The software is available at a substantial discount if purchased with the textbook; please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

FOR THE INSTRUCTOR

Organic Matter: A Presentational CD-ROM (ISBN 0-13-017861-6). This Instructor CD includes almost all images from the book, hundreds of 3-D images of molecules, animations of selected organic reactions, and videos of selected organic laboratory demonstrations. It also includes an easy-to-use interface that allows instructors to review material from the CD. Finally, it includes prebuilt Microsoft PowerPoint slides for those instructors who prefer to use that software for their presentations. Works with both Windows and Macintosh.

Transparency package (ISBN 0-13-017850-0). This set features 250 full-color images from the text, a 50% increase over the last edition.

Test Item File (ISBN 0-13-031012-3). Written by Gary Hollis of Roanoke College, -this test bank features over 2000 questions. For instructors who prefer to customize 'their own tests, we also feature the complete test item file electronically along with the new, easy-to-use TestManager software. This software also includes tools for course management and offering tests over a local area network. Available for Windows (ISBN 0-13-017865-9) and Macintosh (0-13-017866-7).

BlackBoard and WebCT Course Management. The BlackBoard and WebCT course management systems equip faculty members with easy-to-use tools for creating sophisticated web-based educational programs. Prentice Hall provides robust content that is tailored specifically to the Bruice text. This content includes over 6000 prebuilt test questions, animations, 3-D (Chime) models, web links, and more. Using either of these course management systems, you can enhance an on-campus course or construct an entirely online course for distributed learning. Instructors with little or no technical experience can use a point-and-click navigation system to design their own on-line course components, including setting up course calendars, quizzes, assignments, lectures, and self-paced study help. Prebuilt courses in both BlackBoard and WebCT are available. These courses are available for a nominal fee over the price of the text (this fee includes software license fees). Please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

To The Student

Welcome to organic chemistry. This book has been written for you, one who is encountering the subject for the first time. The first thing you should do is familiarize yourself with the book. The material on the inside of the front and back covers is information that you may want to refer to many times during the course. The Key Terms and Summaries of Reactions at the end of the chapters, and the Glossary at the end of the book, can be useful study aids. Also look at the Appendices to see what kind of information is provided there. The electrostatic potential maps and the molecular models throughout the book are there to give you an appreciation of what molecules look like in three dimensions and how electronic charge is distributed within the molecule. Look at the margin notes as you read a chapter—they emphasize important points.

Be sure to work all the problems within each chapter. These are drill problems that will enable you to check whether or not you have mastered the material. Some of them are solved for you in the text. Others—those marked with a diamond—have short answers provided in the Appendix. You will also find Problem-Solving Strategies sprinkled throughout the text. These features provide detailed suggestions for how best to approach important problem types. Please read these Problem-Solving Strategies carefully, and don't be afraid to refer back to them when you're working the end-of-chapter problems.

Work as many end-of-chapter problems as you can. The more problems you work, the more comfortable you will be with the subject and the more prepared you will be for the material in subsequent chapters. Do not let any problem frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study Guide/Solutions Manual to learn how you should have approached the problem. Later on go back and try to work the problem again without consulting the Study Guide/Solutions Manual.

The most important thing for you to remember in organic chemistry is DO NOT GET BEHIND. Organic chemistry consists of a lot of simple steps, so it is not a difficult subject. But the subject can become overwhelming if you don't keep up.

Before many of the theories and mechanisms were worked out, organic chemistry was a discipline that could be mastered only through memorization. Fortunately, that is no longer true. You will find many common threads that will allow you to use what you have learned in one situation to predict what will happen in other situations. So, as you read the book and study your notes, always try to understand why each thing happens. If the reasons behind the behavior are understood, most reactions can be predicted. If you approach the class with the misconception that you must memorize hundreds of unrelated reactions, it could be your downfall. There is simply too much material to memorize, and if all your knowledge is based on memorization, you won't have the necessary foundation on which to lay subsequent material. From time to time, some memorization will be required. Some fundamental rules have to be memorized, and you will have to memorize the common names of some organic compounds. But the latter should not be a problem. After all, your friends have common names and you've been able to learn them.

Students who take organic chemistry to gain entrance into medical school sometimes wonder why medical schools pay so much attention to how they do in organic chemistry. The importance of organic chemistry is not in the subject matter alone. Mastering organic chemistry requires a thorough understanding of fundamentals and the ability to use these fundamentals to analyze, classify, and predict. This parallels the study of medicine; a physician uses an understanding of fundamentals to analyze, classify, and diagnose.

Good luck in your study. I hope you will enjoy your course in organic chemistry and learn to appreciate the logic of the discipline. If you have any comments about the book or any suggestions about how it can be improved for the students who will follow you, I would love to hear from you. Positive comments are the most fun, but critical comments are the most useful.

Paula Yurkanis Bruice
pybruice@bioorganic.ucsb.edu

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Table of Contents

I AN INTRODUCTION TO THE STUDY OF CHEMISTRY

1 Electronic Structure and Bonding • Acids and Bases
1.1 The Structure of an Atom
1.2 How Electrons in an Atom are Distributed
1.3 Ionic and Covalent Bonds
1.4 How the Structure of a Compound is Represented
1.5 Atomic Orbitals
1.6 An Introduction to Molecular Orbital Theory
1.7 How Single Bonds Are Formed in Organic Compounds
1.8 How a Double Bond is Formed: The Bonds in Ethene
1.9 How a Triple Bond is Formed: The Bonds in Ethyne
1.10 Bonding in the Methyl Cation, the Methyl Radical, and the Methyl Anion
1.11 The Bonds in Water
1.12 The Bonds in Ammonia and in the Ammonium Ion
1.13 The Bond in a Hydrogen Halide
1.14 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles
1.15 The Dipole Moments of Molecules
1.16 An Introduction to Acids and Bases
1.17 pka and pH
1.18 Organic Acids and Bases
1.19 How to Predict the Outcome of an Acid-Base Reaction
1.20 How to Determine the Position of Equilibrium
1.21 How the Structure of an Acid Affects its pka Value
1.22 How Substituents Affect the Strength of an Acid
1.23 An Introduction to Delocalized Electrons
1.24 A Summary of the Factors that Determine Acid Strength
1.25 How pH Affects the Structure of an Organic Compound
1.26 Buffer Solutions
1.27 Lewis Acids and Bases

2 An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure
2.1 How Alkyl Substituents Are Named
2.2 The Nomenclature of Alkanes
2.3 The Nomenclature of Cycloalkanes • Skeletal Structures
2.4 The Nomenclature of Alkyl Halides
2.5 The Nomenclature of Ethers
2.6 The Nomenclature of Alcohols
2.7 The Nomenclature of Amines
2.8 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines
2.9 The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines
2.10 Rotation Occurs About Carbon-Carbon Single Bonds
2.11 Some Cycloalkanes Have Angle Strain
2.12 Conformers of Cyclohexane
2.13 Conformers of Monosubstituted Cyclohexanes
2.14 Conformers of Disubstituted Cyclohexanes
2.15 Fused Cyclohexane Rings

II ELECTROPHILIC ADDITION REACTIONS, STEREOCHEMISTRY, AND ELECTRON DELOCALIZATION

3 Alkenes: Structure, Nomenclature, and an Introduction to Reactivity • Thermodynamics and Kinetics
3.1 Molecular Formulas and the Degree of Unsaturation
3.2 The Nomenclature of Alkenes
3.3 The Structures of Alkenes
3.4 Alkenes Can Have Cis and Trans Isomers
3.5 Naming Alkenes Using the E,Z System
3.6 How Alkenes React • Curved Arrows Show the Flow of Electrons
3.7 Thermodynamics and Kinetics
3.8 The Rate of a Reaction and the Rate Constant for a Reaction
3.9 A Reaction Coordinate Diagram Describes the Energy Changes That Take Place During a Reaction

4 The Reactions of Alkenes
4.1 The Addition of a Hydrogen Halide to an Alkene
4.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon
4.3 What Does the Structure of the Transition State Look Like?
4.4 Electrophilic Addition Reactions Are Regioselective
4.5 The Addition of Water to an Alkene
4.6 The Addition of an Alcohol to an Alkene
4.7 A Carbocation Will Rearrange If It Can Form a More Stable Carbocation
4.8 The Addition of a Halogen to an Alkene
4.9 Oxymercuration-Reduction and Alkoxymercuration-Reduction Are Other Ways to Add Water or an Alcohol to an Alkene
4.10 The Addition of a Peroxyacid to an Alkene
4.11 The Addition of Borane to an Alkene: Hydroboration-Oxidation
4.12 The Addition of Hydrogen to an Alkene
4.13 The Relative Stabilities of Alkenes
4.14 Reactions and Synthesis

5 Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions
5.1 Cis-Trans Isomers Result from Restricted Rotation
5.2 A Chiral Object Has a Nonsuperimposable Mirror Image
5.3 An Asymmetric Center Is a Cause of Chirality in a Molecule
5.4 Isomers with One Asymmetric Center
5.5 Asymmetric Centers and Stereocenters
5.6 How to Draw Enantiomers
5.7 Naming Enantiomers by the R,S System
5.8 Chiral Compounds Are Optically Active
5.9 How Specific Rotation is Measured
5.10 Enantiomeric Excess
5.11 Isomers with More than One Asymmetric Center
5.12 Meso Compounds Have Asymmetric Centers but Are Optically Inactive
5.13 How to Name Isomers with More than One Asymmetric Center
5.14 Reactions of Compounds that Contain an Asymmetric Center
5.15 Using Reactions that Do Not Break Bonds to an Asymmetric Center to Determine Relative Configurations
5.16 How Enantiomers Can Be Separated
5.17 Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers
5.18 Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions
5.19 The Stereochemistry of Electrophilic addition Reactions of Alkenes
5.20 The Stereochemistry of Enzyme-Catalyzed Reactions
5.21 Enantiomers Can Be Distinguished by Biological Molecules

6 The Reactions of Alkynes: An Introduction to Multistep Synthesis
6.1 The Nomenclature of Alkynes
6.2 How to Name a Compound That Has More than One Functional Group
6.3 The Physical Properties of Unsaturated Hydrocarbons
6.4 The Structure of Alkynes
6.5 How Alkynes React
6.6 The Addition of Hydrogen Halides and Addition of Halogens to an Alkyne
6.7 The Addition of Water to an Alkyne
6.8 The Addition of Borane to an Alkyne: Hydroboration-Oxidation
6.9 The Addition if Hydrogen to an Alkyne
6.10 A Hydrogen Bonded to an sp Carbon is “Acidic”
6.11 Synthesis Using Acetylide Ions
6.12 Designing a Synthesis I: An Introduction to Multistep Synthesis

7 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa • More About Molecular Orbital Theory
7.1 Delocalized Electrons Explain Benzene’s Structure
7.2 The Bonding in Benzene
7.3 Resonance Contributors and the Resonance Hybrid
7.4 How to Draw Resonance Contributors
7.5 The Predicted Stabilities of Resonance Contributors
7.6 Delocalized Energy Is the Additional Stability Delocalized Electrons Give to a Compound
7.7 Examples That Show How Delocalized Electrons Affect Stability
7.8 A Molecular Orbital Description of Stability
7.9 How Delocalized Electrons Affect pKa Values
7.10 Delocalized Electrons Can Affect the Product of a Reaction
7.11 Thermodynamic Versus Kinetic Control of Reactions
7.12 The Diels-Adler Reaction Is a 1,4-Addition Reaction

III SUBSTITUTION AND ELIMINATION REACTIONS

8 Substitution Reactions of Alkyl Halides
8.1 The Mechanism For an SN2 Reaction
8.2 Factors That Affect SN2 Reactions
8.3 The Reversibility of an SN2 Reaction Depends on the Basicities of the Leaving Groups in the Forward and Reverse Directions
8.4 The Mechanism for an SN1 Reaction
8.5 Factors That Affect SN1 Reactions
8.6 More About the Stereochemistry of SN2 and SN1Reactions
8.7 Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides
8.8 Competition Between SN2 and SN1Reactions
8.9 The Role of the Solvent in SN2 and SN1 Reactions
8.10 Intermolecular Versus Intramolecular Reactions
8.11 Biological Methylating Reagents Have Good Leaving Groups

9 Elimination Reactions of Alkyl Halides • Competition between Substitution and Elimination
9.1 The E2 Reaction
9.2 An E2 Reaction is Regioselective
9.3 The E1 Reaction
9.4 Competition between E2 and E1 Reactions
9.5 E2 and E1 Reactions are Stereoselective
9.6 Elimination from Substituted Cyclohexanes
9.7 A Kinetic Isotope Effect Can Help Determine a Mechanism
9.8 Competition between Substitution and Elimination
9.9 Substitution and Elimination Reactions in Synthesis
9.10 Designing a Synthesis II: Approaching the Problem

10 Reactions of Alcohols, Ethers, Epoxides, Amine, and Sulfur- Containing Compounds
10.1 Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides
10.2 Other Methods Used to Convert Alcohols into Alkyl Halides
10.3 Converting an Alcohol to a Sulfonate Ester
10.4 Elimination Reactions of Alcohols: Dehydration
10.5 Oxidation of Alcohols
10.6 Nucleophilic Substitution Reactions of Ethers
10.7 Nucleophilic Substitution Reactions of Epoxides
10.8 Amines Do Not Undergo Substitution or Elimination Reactions
10.9 Quaternary Ammonium Hydroxides Undergo Elimination Reactions
10.10 Phase-Transfer Catalysts
10.11 Thiols, Sulfides, and Sulfonium Salts

11 Organometallic Compounds
11.1 Organolithium and Organomagnesium Compounds
11.2 The Reaction Organolithium Compounds and Grighard Reagents with Electrophiles
11.3 Transmetallation
11.4 Coupling Reactions
11.5 Palladium-Catalyzed Coupling Reactions
11.6 Alkene Metathesis

12 Radicals • Reactions of Alkanes
12.1 Alkanes Are Unreactive Compounds
12.2 Chlorination and Bromination of Alkanes
12.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron
12.4 The Distribution of Products Depends on Probability and Reactivity
12.5 The Reactivity-Selectivity Principle
12.6 Formation of Explosive Peroxides
12.7 The Addition of Radicals to an Alkene
12.8 The Stereochemistry of Radical Substitution and Addition Reactions
12.9 Radical Substitution of Benzylic and Allylic Hydrogens
12.10 Designing a Synthesis III: More Practice with Multistep Synthesis
12.11 Radical Reactions Occur in Biological Systems
12.12 Radicals and Stratospheric Ozone

IV IDENTIFICATION OF ORGANIC COMPOUNDS

13 Mass Spectrometry, Infrared Spectroscopy, and Ultraviolet/Visible Spectroscopy
13.1 Mass Spectrometry
13.2 The Mass Spectrum • Fragmentation
13.3 Isotopes in Mass Spectrometry
13.4 High-Resolution Mass Spectrometry Can Reveal Molecular Formulas
13.5 Fragmentation Patterns of Functional Groups
13.6 Other Ionization Methods
13.7 Spectroscopy and the Electromagnetic Spectrum
13.8 Infrared Spectroscopy
13.9 Characteristic Infrared Absorption Bands
13.10 The Intensity of Absorption Bands
13.11 The Position of Absorption Bands
13.12 The Position of an Absorption Band is Affected by Electron Delocalization, Election Donation and Withdrawal, and Hydrogen Bonding
13.13 The Shape of Absorption Bands
13.14 The Absence of Absorption Bands
13.15 Some Vibrations Are Infrared Inactive
13.16 How to Interpret An Infrared Spectrum
13.17 Ultraviolet and Visible Spectroscopy
13.18 The Beer-Lambert Law
13.19 The Effect of Conjugation on λmax
13.20 The Visible Spectrum and Color
13.21 Some Uses of UV/Vis Spectroscopy

14 NMR Spectroscopy
14.1 An Introduction to NMR Spectroscopy
14.2 Fourier Transform NMR
14.3 Shielding Causes Different Hydrogens to Show Signals at Different Frequencies
14.4 The Number of Signals in an 1H NMR Spectrum
14.5 The Chemical Shift Tells How Far the Signal Is from the Reference Signal
14.6 The Relative Positions of 1H NMR Signals
14.7 Characteristic Values of Chemical Shifts
14.8 Dismagnetic Anisotropy
14.9 The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal
14.10 The Splitting of the Signals is Described by the N + 1 Rule
14.11 More Examples of 1H NMR Spectra
14.12 Coupling Constants Identify Coupled Protons
14.13 Splitting Diagrams Explain the Multiplicity of a Signal
14.14 Diastereotopic Hydrogens Are Not Chemically Equivalent
14.15 The Time Dependence of NMR Spectroscopy
14.16 Protons Bonded to Oxygen and Nitrogen
14.17 The Use of Deuterium in 1H NMR Spectroscopy
14.18 The Resolution of 1H NMR Spectra
14.19 13C NMR Spectroscopy
14.20 DEPT 13C NMR Spectra
14.21 Two-Dimensional NMR Spectroscopy
14.22 NMR Used in Medicine is Called Magnetic Resonance Imaging
14.23 X-Ray Crystallography

V. AROMATIC COMPOUNDS

15 Aromaticity • Reactions of Benzene
15.1 Aromatic Compounds Are Unusually Stable
15.2 The Two Criteria for Aromaticity
15.3 Applying the Criteria for Aromaticity
15.4 Aromatic Heterocyclic Compounds
15.5 Some Chemical Consequences of Aromaticity
15.6 Antiaromaticity
15.7 A Molecular Orbital Description of Aromaticity and Antiaromaticity
15.8 The Nomenclature of Monosubstituted Benzenes
15.9 How Benzene Reacts
15.10 The General Mechanism for Electrophilic Aromatic Substitution Reactions
15.11 The Halogenation of Benzene
15.12 The Nitration of Benzene
15.13 The Sulfonation of Benzene
15.14 The Friedel-Crafts Acylation of Benzene
15.15 The Friedel-Crafts Alkylation of Benzene
15.16 The Alkylation of Benzene by Acylation-Reduction
15.17 Using Coupling Reactions to Alkylate Benzene
15.18 It Is Important to Have More Than One Way to Carry Out a Reaction
15.19 Polycyclic Benzold Hydrocarbons
15.20 Arene Oxides

16 Reactions of Substituted Benzenes
16.1 How Some Substituents on a Benzene Ring Can Be Chemically Changed
16.2 The Nomenclature of Disubstituted and Polysubstituted Benzenes
16.3 The Effect of Substituents on Reactivity
16.4 The Effect of Substituents on Orientation
16.5 The Effect of Substituents on pKa
16.6 The Ortho-Para Ratio
16.7 Additional Considerations Regarding Substituent Effects
16.8 Designing a Synthesis IV: Synthesis of Monosubstituted and Disubstituted Benzenes
16.9 The Synthesis of Trisubstituted Benzenes
16.10 The Synthesis of Substituted Benzenes Using Arenediazonium Salts
16.11 The Arenediazonium Ion as an Electrophile
16.12 The Mechanism for the Reaction of Amines with Nitrous Acid
16.13 Nucleophilic Aromatic Substitution: An Addition-Elimination Mechanism
16.14 Nucleophilic Aromatic Substitution: An Elimination-Addition Mechanism That Forms a Benzene

VI. CARBONYL COMPOUNDS

17 Carbonyl Compounds I: Reactions of Carboxylic Acids and Carboxylic Derivatives
17.1 The Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives
17.2 The Structures of Carboxylic Acids and Carboxylic Derivatives
17.3 The Physical Properties of Carbonyl Compounds
17.4 Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives
17.5 How Class I Carbonyl Compounds React
17.6 Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives
17.7 General Mechanism for Nucleophilic Addition-Elimination Reactions
17.8 Reactions of Acyl Halides
17.9 Reactions of Acid Anhydrides
17.10 Reactions of Esters
17.11 Acid-Catalyzed Ester Hydrolysis and Transesterification
17.12 Hydroxide-Ion-Promoted Ester Hydrolysis
17.13 How the Mechanism for Nucleophilic Addition-Elimination was Confirmed
17.14 Soaps, Detergents, and Micelles
17.15 Reactions of Carboxylic Acids
17.16 Reactions of Amides
17.17 The Hydrolysis of Amides Is Catalyzed by Acids
17.18 The Hydrolysis of an Imide: A Way to Synthesize Primary Amines
17.19 The Hydrolysis of Nitriles
17.20 Designing a Synthesis V: The Synthesis of Cyclic Compounds
17.21 How Chemists Activate Carboxylic Acids
17.22 How Cells Activate Carboxylic Acids
17.23 Dicarboxylic Acids and Their Derivatives

18 Carbonyl Compounds II: Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives • Reactions of α, β- Unsaturated Carbonyl Compounds
18.1 The Nomenclature of Aldehydes and Ketones
18.2 The Relative Reactivities of Carbonyl Compounds
18.3 How Aldehydes and Ketones React
18.4 The Reactions of Carbonyl Compounds with Gringard Reagents
18.5 The Reactions of Carbonyl Compounds with Acetylide Ions
18.6 The Reactions of Carbonyl Compounds with Hydride Ion
18.7 The Reactions of Aldehydes and Ketones with Hydrogen Cyanide
18.8 The Reactions of Aldehydes and Ketones with Amines and Amine Derivatives
18.9 The Reactions of Aldehydes and Ketones with Water
18.10 Reactions of Aldehydes and Ketones with Alcohols
18.11 Protecting Groups
18.12 Addition of Sulfur Nucleophiles
18.13 The Wittig Reaction Forms an Alkene
18.14 Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces
18.15 Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents
18.16 Nucleophilic Addition to α, β- Unsaturated Aldehydes and Ketones
18.17 Nucleophilic Addition to α, β- Unsaturated Carboxylic Acid Derivatives
18.18 Enzyme-Catalyzed Additions to α, β- Unsaturated Carbonyl Compounds

19 Carbonyl Compounds III: Reactions at the α- Carbon
19.1 The Acidity of an α- Hydrogen
19.2 Keto-Enol Tautomers
19.3 Keto-Enol Interconversion
19.4 How Enolate Ions and Enols
19.5 Halogenation of the α- Carbon and Aldehydes and Ketones
19.6 Halogenation of the α- Carbon of Carboxylic Acids: The Hell-Volhard-Zelinski Reaction
19.7 α- Halogenated Carbonyl Compounds Are Useful in Synthesis
19.8 Using LDA to Form an Enolate Ion
19.9 Alkylating the α-Carbon of Carbonyl Compounds
19.10 Alkylation and Acylation of the α-Carbon Using an Enamine Intermediate
19.11 Alkylation of the β-Carbon: The Michael Reaction
19.12 An Aldol Addition Forms β-Hydroxaldehydes or β-Hydroxyketones
19.13 Dehydration of Aldol Addition Products Form α, β-Unsaturated Aldehydes and Ketones
19.14 The Crossed Aldol Addition
19.15 A Claisen Condensation Forms a β-Keto Ester
19.16 Other Crossen Condensations
19.17 Intramolecular Condensation and Addition Reactions
19.18 The Robinson Annulation
19.19 Carboxylic Acids with a Carbonyl Group at the 3-Position can be Decarboxylated
19.20 The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid
19.21 The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone
19.22 Designing a Synthesis VII: Making New Carbon-Carbon Bonds
19.23 Reactions at the α-Carbon in Biological Systems

VII MORE ABOUT OXIDATION-REDUCTION REACTIONS AND AMINES

20 More About Oxidation-Reduction Reactions
20.1 Oxidation-Reduction Reactions of Organic Compounds: An Overview
20.2 Reduction Reactions
20.3 Chemoselective Reactions
20.4 Oxidation of Alcohols
20.5 Oxidation of Aldehydes and Ketones
20.6 Designing a Synthesis VIII: Controlling Stereochemistry
20.7 Oxidation of Alkenes to 1,2 Diols
20.8 Oxidative Cleavage of 1,2 Diols
20.9 Oxidative Cleavage of Alkenes
20.10 Designing a Synthesis IX: Functional Group Interconversion

21 More About Amines • Heterocylic Compounds
21.1 More about Amine Nomenclature
21.2 More About the Acid-Base Properties of Amines
21.3 Amines React as Bases and as Nucleophiles
21.4 Synthesis of Amines
21.5 Aromatic Five-Membered-Ring Heterocycles
21.6 Aromatic Six-Membered-Ring Heterocycles
21.7 Amine Heterocycles Have Important Roles in Nature

VIII BIOORGANIC COMPOUNDS

22 The Organic Chemistry of Carbohydrates
22.1 Classification of Carbohydrates
22.2 The D and L Notation
22.3 The Configurations of Aldoses
22.4 The Configurations of Ketoses
22.5 The Reactions of Monosaccharides in Basic Solutions
22.6 The Oxidation-Reduction Reactions of Monosaccharides
22.7 Monosaccharides Form Crystalline Osazones
22.8 Lengthening the Chain: The Kiliani-Fischer Synthesis
22.9 Shortening the Chain: The Wohl Degradation
22.10 The Stereochemistry of Glucose: The Fischer Proof
22.11 Monosaccharides Form Cyclic Hemiacetals
22.12 Glucose is the Most Stable Aldohexose
22.13 Formation of Glycosides
22.14 The Anomeric Effect
22.15 Reducing and Nonreducing Sugars
22.16 Disaccharides
22.17 Polysaccharides
22.18 Some Naturally Occurring Products Derived from Carbohydrates
22.19 Carbohydrates on Cell Surfaces
22.20 Synthetic Sweeteners

23 The Organic Chemistry of Amino Acids, Peptides, and Proteins
23.1 Classification and Nomenclature of Amino Acids
23.2 The Configuration of the Amino Acids
23.3 The Acid-Base Properties of Amino Acids
23.4 The Isoelectric Point
23.5 Separating Amino Acids
23.6 The Synthesis of Amino Acids
23.7 The Resolution of Racemic Mixtures of Amino Acids
23.8 Peptide Bonds and Disulfide Bonds
23.9 Some Interesting Peptides
23.10 The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation
23.11 Automated Peptide Synthesis
23.12 An Introduction to Protein Structure
23.13 How to Determine the Primary Structure of a Polypeptide or Protein
23.14 The Secondary Structure of Proteins
23.15 The Tertiary Structure of Proteins
23.16 The Quaternary Structure of Proteins
23.17 Protein Denaturation

24 Catalysis
24.1 Catalysis in Organic Reactions
24.2 Acid Catalysis
24.3 Base Catalysis
24.4 Nucleophilic Catalysis
24.5 Metal-Ion Catalysis
24.6 Intramolecular Reactions
24.7 Intramolecular Catalysis
24.8 Catalysis in Biological Reactions
24.9 Enzyme-Catalyzed Reactions
24.10 The Organic Mechanisms of the Coenzymes

25 Compounds Derived from Vitamins
25.1 The Vitamin Needed for Many Redox Reactions: Vitamin B3
25.2 Flavin Adenine Dinucleotide and Flavin Mononucleotind: Vitamin B
25.3 Thiamine Pyrophosphate: Vitamin B1
25.4 Biotin: Vitamin H
25.5 Pyridoxal Phosphate: Vitamin B6
25.6 Coenzyme B12: Vitamin B12
25.7 Tetrahydrofolate: Folic Acid
25.8 Vitamin KH2: Vitamin K

26 The Organic Chemistry of Metabolic Pathways
26.1 ATP is Used for Phosphoryl Transfer Reactions
26.2 The Three Mechanisms for Phosphoryl Transfer Reactions
26.3 The “High-Energy” Character of Phosphoanhydride Bonds
26.4 Why ATP is Kinetically Stable in a Cell
26.5 The Four Stages of Catabolism
26.6 The Catabolism of Fats
26.7 The Catabolism of Carbohydrates
26.8 The Fates of Pyruvate
26.9 The Catabolism of Proteins
26.10 The Citric Acid Cycle
26.11 Oxidative Phosphorylation
26.12 Anabolism

27 The Organic Chemistry of Lipids
27.1 Fatty Acids Are Long-Chain Carboxylic Acids
27.2 Waxes are High-Molecular-Weight Esters
27.3 Fats and Oils are Triacylclycerols
27.4 Phospholipids and Sphingolipids Are Components of Membranes
27.5 Prostaglandis Regulate Physiological Responses
27.6 Terpenes Contain Carbon Atoms in Multiples of Five
27.7 How Terpenes Are Biosynthesized
27.8 How Steriods Are Chemical Messengers
27.9 How Nature Synthesizes Cholesterol
27.10 Synthetic Steroids

28 The Chemistry of Nucleic Acids
28.1 Nucleosides and Nucleotides
28.2 Other Important Nucleotides
28.3 Nucleic Acids Are Composed of Nucleotide Subunits
28.4 Why DNA Does Not Have A 2’- OH Group
28.5 The Biosynthesis of DNA is Called Replication
28.6 DNA and Heredity
28.7 The Biosynthesis of RNA is Called Transcription
28.8 There Are Three Kinds of RNA
28.9 The Biosynthesis of Proteins Is Called Translation
28.10 Why DNA Contains Thymine Instead of Uracil
28.11 How the Base Sequence of DNA Is Determined
28.12 The Polymerase Chain Reaction (PCR)
28.13 Genetic Engineering
28.14 The Laboratory Synthesis of DNA Strands

IX SPECIAL TOPICS IN ORGANIC CHEMISTRY

29 Synthetic Polymers
29.1 There Are Two Major Classes of Synthetic Polymers
29.2 Chain-Growth Polymers
29.3 Stereochemistry of Polymerization • Ziegler- Natta Catalysts
29.4 Polymerization of Dienes • The Manufacture of Rubber
29.5 Copolymers
29.6 Step-Growth Polymers
29.7 Classes of Step-Growth Polymers
29.8 Physical Properties of Polymers
29.9 Biodegradable Polymers

30 Pericyclic Reactions
30.1 There Are Three Kinds of Pericyclic Reactions
30.2 Molecular Orbitals and Orbital Symmetry
30.3 Electrocyclic Reactions
30.4 Cycloaddition Reactions
30.5 Sigmatropic Rearrangements
30.6 Pericyclic Reactions in Biological Systems
30.7 Summary of the Selection Rules for Pericyclic Reactions

31 The Organic Chemistry of Drugs: Discovery and Design
31.1 Naming Drugs
31.2 Lead Compounds
31.3 Molecular Modification
31.4 Random Screening
31.5 Serendipity in Drug Development
31.6 Receptors
31.7 Drugs as Enzyme Inhibitors
31.8 Designing a Suicide Substrate
31.9 Quantitative Structure-Activity Relationships (QSAR)
31.10 Molecular Modeling
31.11 Combinatorial Organic Synthesis
31.12 Antiviral Drugs
31.13 Economics of Drugs • Governmental Regulations

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Preface

Preface

TO THE INSTRUCTOR

The guiding principle in writing this book was to create a text for students—a text that presents the material in a way that encourages students to think about what they have already learned and then apply this knowledge in a new setting. I want students to reason their way to a solution rather than memorize a multitude of facts, hoping they don't run out of memory before the course ends. I am convinced that the what of organic chemistry is much easier to grasp and retain if the why is understood.

Comments I have received from both colleagues and students on the second edition indicate the book is working in the way I had hoped. As much as I cherish having faculty tell me that their students are scoring higher than ever before on tests, nothing is more gratifying than hearing from the students themselves—a wonderful advantage of being the author of a textbook during the email age. (Even my dog has received e-mail from students.) Many students have generously accredited their success in organic chemistry to the book—not giving themselves nearly enough credit for how hard they studied to achieve that success. And they always seem surprised that they have come to love "orgo" (on the East Coast) or "o-them" (on the West Coast). I also hear from many pre-meds who say that the book gave them such a permanent understanding of organic chemistry that they found it tobe the easiest part of that dreaded test, the MCAT.

As I strove to make this book even more useful to the student, I have relied on constructive critical comments from many of you. For these I am very grateful. I also kept a journal of questions students had when they came to my office hours. These questions let me know what sections in the book needed clarifying and what answers in the Study Guide/Solutions Manual needed more in-depth explanations. Most importantly, this analysis showed me where new problems needed to be created so that these same questions had less of a chance of being asked by students using the third edition. Because I teach a class of more than 400 students, I clearly have a vested interest in minimizing their confusion! In this edition, many sections have been rewritten to optimize readability and comprehension, and there are many new in-chapter problems, new end-of-chapter problems, and more solved problems to help students master organic chemistry by solving problems. There are also new interest boxes to show students the applications of organic chemistry, and additional margin notes to remind students of important concepts and principles.

I hope you find the third edition even more appealing to your students than the second. As always, I am eager to hear your comments—positive comments are the most fun, but critical comments are the most useful.

I would also like to draw your attention to the following features of the text:

A Functional Group Approach with a Mechanistic Organization That Ties Together Synthesis and Reactivity

This book is organized to discourage the student from rote memorization. The functional groups have been organized around mechanistic similarities—electrophilic additions, radical substitutions, nucleophilic substitutions, eliminations, electrophilic aromatic substitutions, nucleophilic acyl substitutions, and nucleophilic additions. This organization allows a lot of material to be understood based on unifying principles of reactivity.

In addition, instead of discussing the synthesis of a functional group when its reactivity is discussed—reactions that generally have little to do with each other—I discuss the synthesis of the compounds that are formed as a result of the functional group's reactivity. In the alkene chapter, for example, students learn about the reactions of alkenes but they do not> learn at this point about the synthesis of alkenes. Instead, they learn about the synthesis of alkyl halides, alcohols, ethers, and alkanes—the compounds formed when alkenes react. Because alkenes are synthesized from the reactions of alkyl halides and alcohols, the synthesis of alkenes is covered when the reactions of alkyl halides and alcohols are discussed. Tying together the reactivity of a functional group and the synthesis of compounds resulting from its reactivity prevents the student from having to memorize lists of unrelated reactions. Understanding different ways functional groups can be prepared is useful in designing syntheses, however, so the different reactions that yield a particular functional group are compiled in Appendix IV As students learn how to design syntheses, they appreciate the importance of reactions that change the carbon skeleton of a molecule; these reactions are compiled in Appendix V.

A Detailed Look at the Organization of the Text

The book has been divided into eight sections. Each section starts with a one-page overview so students can understand where they are "going:" Chapter 1 provides a summary of the material that students need to recall from General Chemistry. The sections on acids and bases were rewritten to emphasize the relationship between acidity and stability of the conjugate base. (Acids and bases are covered even more extensively in the Study Guide/Solutions Manual.) In Chapter 2, students learn how to name five classes of organic compounds—those that will be the products of the reactions in the chapters that immediately follow. Chapter 2 also covers topics that are necessary before the study of reactions can begin—structures, conformations, and physical properties of organic compounds. Chapter 3 discusses the reactions of alkenes. In this chapter, students are first introduced to the concept of "curved arrows." (The Study Guide/Solutions Manual contains an extensive exercise on "electron pushing:" I have found this exercise to be very successful in making my students comfortable with a topic that should be easy, but somehow perplexes even the best of them unless they have sufficient practice.) Chapter 3 also contains a discussion of thermodynamics and kinetics. This section was rewritten to make it even easier for students to understand. Rate equations are derived in an appendix for those who wish to give their students a more mathematical treatment, and the Study Guide/Solutions Manual contains a section on calculating kinetic parameters.

I chose to lead off with the reactions of alkenes because of their simplicity. Chapter 3 covers a wide variety of reactions but they all have similar mechanisms—an electrophile adds to the least substituted sp2 carbon and a nucleophile adds to the other sp2 carbon. The many reactions differ only in the nature of the electrophile and the nucleophile. Because organic chemistry is all about the interactions of electrophiles and nucleophiles, starting the study of organic reactions in a way that familiarizes students with a wide variety of electrophiles and nucleophiles makes sense. The reactions in Chapter 3 are discussed without regard to stereochemistry because I have found that students do well as long as only one new concept is introduced at a time. Chapter 4 reviews the isomers introduced in Chapters 2 and 3 (conformers and cis-trans isomers) and then discusses isomers that result from having a chirality center (the most recent IUPAC-approved term for a carbon bonded to four different groups). There is an extensive model-building exercise in the Study Guide/Solutions Manual to help the students get used to building molecular models, and the book's Companion Website gives students the opportunity to manipulate many molecules in three dimensions. Now that the students are comfortable with both isomers and electrophilic addition reactions, the two topics are considered together at the end of Chapter 4, where the stereochemistry of the addition reactions covered in Chapter 3 is presented. Chapter 5 covers alkynes. This chapter should build the students' confidence because of the similarity of the material to what was presented in Chapter 3.

Understanding electron delocalization is vitally important in organic chemistry, so it is covered in its own chapter (Chapter 6). This chapter is a continuation of the introduction to this topic in Chapter 1. Chapter 7 covers the reactions of dimes, allowing students to apply the concept of electron delocalization just studied to the electrophilic addition reactions that were mastered in Chapters 3 and 5. Chapter 8 covers the reactions of alkanes. The lack of a functional group in alkanes further emphasizes the importance of a functional group to chemical reactivity.

The next three chapters deal with substitution and elimination reactions at an sp3 hybridized carbon. Chapter 9 covers substitution reactions of alkyl halides. Chapter 10 covers elimination reactions of alkyl halides and then goes on to consider competition between substitution and elimination. Chapter 11 covers substitution and elimination reactions at an sp3 hybridized carbon when a group other than a halogen is the leaving group—reactions of alcohols, ethers, epoxides, thiols, sulfides, and quaternary ammonium ions.

Next are two spectroscopy chapters (mass spectrometry, IR spectroscopy, and UV/Vis spectroscopy in Chapter 12, followed by NMR spectroscopy in Chapter 13). Each spectral technique is written as a "stand-alone topic" so it can be covered independently at any time during the course. Chapter 12 opens with a table of functional groups for those who want to cover spectroscopy before students have been introduced to all the functional groups.

Chapter 14 covers aromaticity and the reactions of benzene. Chapter 15 discusses the reactions of substituted benzenes. Because not all organic courses cover the same amount of material in a semester, Chapters 12-15 have been strategically placed to come near the end of the first semester. Ending a semester before Chapter 12, Chapter 13, or Chapter 14, or after Chapter 15 won't interfere with the flow of information.

The order of the topics dealing with the chemistry of carbonyl compounds in Chapters 16 and 17, where carboxylic acid derivatives are discussed before aldehydes and ketones, was initially met with skepticism by many considering using the book. However, when the opinions of those who had used the two editions of the book were sought, there was strong agreement that this is a preferred order of treatment. Chapter 16 discusses the reactions of carboxylic acids and their derivatives with oxygen and nitrogen nucleophiles. Thus, the students are introduced to carbonyl chemistry by learning how tetrahedral intermediates partition. Chapter 17 starts by discussing the reactions of aldehydes, ketones, and carboxylic acid derivatives with strong (carbon and hydrogen) nucleophiles. By studying these compounds as a group, students see how the reactions of aldehydes and ketones differ from those of carboxylic acid derivatives. Then when they move on to study the formation and hydrolysis of imines, enamines, and acetals, they can easily understand these mechanisms because they are well versed in how tetrahedral intermediates partition. Over the years I have experimented with my classes and I believe this to be the most effective and easiest way to teach carbonyl chemistry. That being said, these chapters can easily be switched so long as Section 17.6 is skipped and then covered with Chapter 16.

Chapter 18 revisits reduction reactions, and discusses oxidation reactions, which my students tend to find troubling. I have found it helps to cover them all together as a unit. Because the reduction reactions appear in earlier chapters, this is an opportunity for students to extend their knowledge within the framework of what they already know. Chapter 19 deals with reactions at the carbon of a-carbonyl compounds.

One special note about amines. There is no question that amines are exceedingly important in organic chemistry. (In Chapter 30, The Organic Chemistry of Drugs, Table 30.1 lists the names, structures, and uses of the most widely prescribed drugs, and a majority of them are amines.) So then, why is there no separate chapter on amines?

My aim again is to organize organic chemistry in a way that allows students to understand and predict rather than memorize. This book covers the functional groups from the point of how they react rather than what they are called. Amines don't undergo additions, substitutions, or eliminations. Their reactivity lies in how they react with other organic compounds. Thus, all the chemistry that would be found in a typical chapter called Amines is in this book, but it is found when that reactivity with other compounds is discussed (for example, acid/base properties of aliphatic and aromatic amines—Chapters 1, 6, 15, and 27; amines as nucleophiles in substitution reactions—Chapters 9 and 16; amines as nucleophiles in addition reactions—Chapter 17; and elimination reactions of quarternary ammonium ions and amine oxides—Chapter 11). Amine synthesis is covered in those sections where amines are the products of the reactions being discussed (for example, the Gabriel synthesis of amines results from imide hydrolysis; amines are synthesized as the result of SN2 reactions; and anilines are synthesized as a result of electrophilic aromatic substitution followed by reduction or as a result of nucleophilic aromatic substitution).

A Modular Organization in the Last Third of the Book

I anticipate that the first 21 chapters will be covered by most instructors during a year-long course. An instructor can then choose among the remaining chapters depending w his or her preference and the interests of the majority of the students enrolled in the course. Those teaching students whose interests are primarily in the biological and health sciences might be more inclined to cover Chapter 22 (Catalysis), Chapter 23 (The Organic Mechanisms of the Coenzymes. Metabolism), Chapter 24 (Lipids), and Chapter 25 (Nucleosides, Nucleotides, and Nucleic Acids). Those teaching courses designed for chemistry or engineering majors may decide to include Chapter 26 (Synthetic Polymers), Chapter 27 (Heterocyclic Compounds), Chapter 28 (Pericyclic Reactions), and Chapter 29 (More About Multistep Organic Synthesis). The book ends with a chapter on drug discovery and design-a topic that in my experience interests students enough that they will choose to read it on their own, even if it is not covered in the course.

Changes to This Edition—Organization

In response to reviewer comments, electron delocalization and resonance are now introduced in Chapter 1. The number and kinds of Kekulé structures students see at the beginning of their study has been increased. Chapter 2 now covers the conformations of both mono- and disubstituted cyclohexanes. Material on aromaticity that appeared in Chapter 6 of the second edition has been expanded and moved to a new Chapter 14. In Chapter 12, the treatment of mass spectrum fragmentation patterns has been reworked to emphasize the common behavior of a variety of compounds when they fragment. The treatment of IR spectroscopy has been reorganized and expanded and includes many additional FT-IR spectra. Because the NMR spectra in the book are FT-NMR spectra and because FT-NMR spectra are what most students see in their laboratory courses, the discussion of the theory of NMR spectroscopy in Chapter 13 describes Fourier transform spectrometers, a theory easier for students to understand than the traditional description of continuous wave spectrometers. In response to user feedback, more problems that involve interpreting spectra have been added to this edition. To help students analyze these specta, more signals have been enlarged. As in the last edition, most of the H NMR spectra shown are 300 MHz FT NMR spectra, which are more like the NMR spectra students are likely to see in their undergraduate laboratories and after they graduate. More spectroscopy problems have also been added to subsequent chapters to enhance the integration of spectroscopy throughout the course. In Chapter 19, the sections on enolate chemistry have been expanded and clarified.

Organic Chemistry with a Bioorganic Flavor

Bioorganic material is introduced throughout this text to encourage students to recognize that organic chemistry and biochemistry are not separate entities, but two parts of a continuum of knowledge. For example, students learn not just how carboxylic acids are activated for reaction in the laboratory, but also how they are activated for reaction in biological systems and why the mode of activation differs in the two situations. Once students learn how such things as electron delocalization, leaving-group tendency, electrophilicity, and nucleophilicity affect the reactions of simple organic compounds, they can appreciate how these same factors are involved in the reactions of more complicated organic molecules such as enzymes, nucleic acids, and vitamins.

In the first part of the book, the bioorganic material is limited primarily to interest boxes and the last sections of the chapters, so the material is available to the curious student but the instructor is not compelled to introduce bioorganic topics into the course. Later in the book there are several chapters that focus heavily on bioorganic topics, including the mechanisms of coenzymes, the chemistry of drug design, and the chemistry of biological macromolecules. Each instructor may choose which, if any, of these chapters to cover.

The chapters on bioorganic chemistry (Chapters 20-25) emphasize the chemistry associated with the topic. They contain more chemistry than one would expect to find in a biochemistry text. In the lipids chapter, for example, the mechanisms of prostaglandin formation (allowing students to understand how aspirin works), fat breakdown (allowing students to understand the odor associated with rancidity), and terpene biosynthesis are covered. The chapter on coenzymes emphasizes the role of vitamin B1 as an electron delocalizer, vitamin K as a strong base, vitamin B12 as a radical initiator, biotin as a compound that can transfer a carboxyl group, and how the many different reactions of vitamin B6 are controlled by the overlap of p orbitals. The chapter on nucleic acids explains mechanistically such things as the function of ATP, why DNA contains thymine instead of uracil, and how DNA strands are synthesized in the laboratory. The chapter on catalysis explains the various modes of catalysis that occur in organic reactions and then shows that these are identical to the modes of catalysis that occur in enzymatic reactions—all presented in a way that allows students to understand the lightening-fast rates of enzymatic reactions. Thus, these chapters are not a repetition of what will be covered in a biochemistry course, but are designed to serve as a bridge between the two disciplines.

An Early and Consistent Emphasis on Organic Synthesis

Students are introduced to synthetic chemistry and retrosynthetic analysis early in this book (Chapters 3 and 5, respectively), so they can use this technique throughout the course as they design multistep syntheses. In addition, there are six special sections spread throughout the book on synthesis design, each with a different focus. For example, one emphasizes the proper choice of reagents and reaction conditions to maximize the yield of the target molecule (Chapter 10), and another focuses on the synthesis of cyclic compounds (Chapter 17). Moreover, Chapter 29 (More About Multistep Organic Synthesis) discusses such things as protecting groups, control of stereochemistry during synthesis, and retrosynthetic analysis at a more advanced level. The use of combinatorial methods in organic synthesis is described in Chapter 30, which focuses on drug design.

Changes to This Edition—Synthesis

In this edition I have added more synthetic problems, in particular new multistep (road-map) problems. I also added more problems that involve the synthesis of compounds that students will recognize (like ketoprofen, Novocain, and Valium).

Margin Notes and Boxed Material to Engage the Student

Margin notes and biographical sketches appear throughout the text. The margin notes remind students of important principles, and the biographical sketches give students some appreciation of the history of chemistry and the people who contributed to that history. Interest Boxes have been included to bring life to the topic being discussed (e.g., Alkyl Halides as Survival Compounds, Chimney Sweeps and Cancer, Ultravolet Light and Sunscreens, and Penicillin and Drug Resistance) or to give the student extra help (e.g., Calculating Kinetic Parameters, A Few Words About Curved Arrows, and Incipient Primary Carbocations).

Changes to This Edition—Interest Boxes

There are a dozen new boxes in this edition, including one on the pericyclic reaction r that makes fireflies glow and one on how the popular new OTC antidepressant SAMe methylates neurotransmitters. I also extensively updated the boxes that remain from previous editions (for example, I mention the recent synthesis of octanitrocubane in the box on strained carbon compounds in Chapter 1).

My students really liked the margin notes in the second edition, so I added more of these in this edition. These emphasize core points and offer pedagogical advice.

Problems, Solved Problems, and Problem-Solving Strategies

The book contains more than 1500 problems. The problems within each chapter are primarily drill problems. They are designed so students can test themselves on the material just covered before they go on to the next section. Solutions to selected problems are shown to give the student an understanding of how to solve a problem, and short answers are provided in the Appendix for problems marked with a diamond so students can quickly test their understanding. Most chapters also contain at least one Problem-Solving Strategy that teaches students how to approach certain kinds of problems. For example, the Problem-Solving Strategy in Chapter 9 teaches students how to determine whether a reaction will be more apt to take place by an SN1 or an SN2 pathway. Each Problem-Solving Strategy is followed by an exercise that gives the student an opportunity to use the problem-solving skill just learned.

The end-of-chapter problems are of varying difficulty. The initial problems are drill problems that integrate material from the entire chapter. This provides a greater challenge by requiring the student to think about all the material in the chapter rather than individual sections. The end-of-chapter problems are purposefully not labeled to indicate the sections the material comes from. The problems become more challenging as the student proceeds through them, and material from more than one chapter is often integrated into later problems. I suspect the problems will not appear more difficult to the student, however, because as the student works through the problems, his or her ability increases and so does his or her confidence (that is why the more difficult problems are not marked as such). I made a concerted effort to make none of the problems so difficult that the student loses confidence. A few problems contain references to the journal in which the original work was published, enabling the curious student to find out more about the work that led to the conclusion shown in the problem.

Changes to This Edition—Problems

Much of the focus of this revision was on the problems, both in-chapter and end-of-chapter. There are 10% more problems in this edition, and there are more Solved Problems and more Problem-Solving Strategy essays. As mentioned previously, many of the new problems are multistep synthetic problems, designed to help students practice their synthetic reasoning skills.

Rich in Three-Dimensional, Computer-Generated Structures

The second edition was widely praised for its effective and useful art program. This edition continues to present energy-minimized, three-dimensional structures throughout the text to give the students an appreciation of the three-dimensional shapes of organic molecules.

Pedagogical, Efficient Use of Color

Organic chemistry is sufficiently challenging without forcing students to use a road map to understand the use of color in a textbook. Therefore, this book does not have such things as blue incoming groups and green leaving groups. Students will not find themselves asking "Why did the nucleophile change its color?" Color is used to make the book visually more appealing and to make learning easier by highlighting points of focus. An attempt has been made to make the color consistent (mechanism arrows are always red, for example), but there is no need in this text for a student to memorize a color palette.

Changes to This Edition—Art Program

Electrostatic potential maps have been added throughout this edition to allow students to visualize molecules in ways not possible before. With them, students can now see things like electron delocalization, how a formal positive charge is not always on the region in a molecule with the least electron density, the effect of electronegativity on pKa, which atom of a cyclic bromonium ion is most susceptible to nucleophilic attack, the difference in the reactivity of substituted benzenes, the electrophilicity of the methyl group of an alkyl halide, and the nucleophilicity of the methyl group of an organometallic compound. There are hundreds of these new illustrations throughout the book.

INSTRUCTIONAL AIDS

The publisher offers a number of products for students and faculty that are designed to complete this learning package:

FOR THE STUDENT

Study Guide/Solutions Manual (ISBN 0-13-017859-4): The Study Guide/ Solutions Manual contains not just answers to the problems, but complete explanations of how the answers were obtained. The Study Guide/Solutions Manual also contains:

  • a section on acid/base chemistry at a more advanced level than what is covered in the text, with a set of problems
  • an 18-page exercise on "pushing electrons"
  • an exercise on building molecular modelsan exercise on calculating kinetic parameters
  • 21 practice tests

For the sake of making the path to mastery of the subject as smooth as possible, I thought it was important that I also write the Study Guide/Solutions Manual.

Bruice 3/e Companion Website (http://www.prenhall.com/bruice). This Companion Website for students features about 100 additional interactive, computer-graded problems for each chapter, regular updates of articles in the popular and lay scientific press that relate to organic chemistry, and a gallery of organic molecules that students can manipulate in real-time on their computers. And for students who are not familiar with the world wide web, we have:

Organic Media Companion for CW (ISBN 0-13-017863-2). This supplement comes FREE with each new copy of the text and is also available for separate purchase for students who buy used textbooks. It includes the web-enabled Organic Chemestry Student CD that accompanies the text as well as a brief, easy-to-understand book that describes the CD, how to use it, and how to use the Internet, world wide web, and Companion Website (CW) for the text. The CD is populated with multimedia elements and interactive exercises and offers students a one-click link to the Companion Website for the text.

Prentice Hall Molecular Model Kit (ISBN 0-205-508136-3). This best-selling model kit allows students to build space-filling and ball-and-stick models of common organic molecules. It allows accurate depiction of double and triple bonds, including heteroatomic molecules (which some model kits cannot handle well).

Prentice Hall Framework Molecular Model Kit (ISBN 0-13-330076-5). This model kit allows students to build scale models that show the mutual relations of atoms in organic molecules, including precise interatomic distances and bond angles. This is the most accurate model kit available.

Chemistry: Themes of the Times. This mini-newspaper is produced by The New York Times for students of chemistry. It features selected articles related to chemistry from the pages of The New York Times and is available free to adopters of the text.

If you wish, students' copies of the text may be accompanied by one of two molecular modeling tools:

Molecular Modeling Workbook, featuring SpartanView and SpartanBuild software (ISBN 0-13-032026-9). This workbook includes a software tutorial and numerous challenging exercises students can tackle to solve problems involving structure building and analysis using the tools included in the two pieces of Spartan software. Available free when packaged with the text; please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

ChemOffice Ltd software, including ChemDraw LTD and Chem3D LTD. A free workbook is available on the Companion Website that includes a software tutorial and numerous exercises for each chapter of the text. The software is available at a substantial discount if purchased with the textbook; please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

FOR THE INSTRUCTOR

Organic Matter: A Presentational CD-ROM (ISBN 0-13-017861-6). This Instructor CD includes almost all images from the book, hundreds of 3-D images of molecules, animations of selected organic reactions, and videos of selected organic laboratory demonstrations. It also includes an easy-to-use interface that allows instructors to review material from the CD. Finally, it includes prebuilt Microsoft PowerPoint slides for those instructors who prefer to use that software for their presentations. Works with both Windows and Macintosh.

Transparency package (ISBN 0-13-017850-0). This set features 250 full-color images from the text, a 50% increase over the last edition.

Test Item File (ISBN 0-13-031012-3). Written by Gary Hollis of Roanoke College, -this test bank features over 2000 questions. For instructors who prefer to customize 'their own tests, we also feature the complete test item file electronically along with the new, easy-to-use TestManager software. This software also includes tools for course management and offering tests over a local area network. Available for Windows (ISBN 0-13-017865-9) and Macintosh (0-13-017866-7).

BlackBoard and WebCT Course Management. The BlackBoard and WebCT course management systems equip faculty members with easy-to-use tools for creating sophisticated web-based educational programs. Prentice Hall provides robust content that is tailored specifically to the Bruice text. This content includes over 6000 prebuilt test questions, animations, 3-D (Chime) models, web links, and more. Using either of these course management systems, you can enhance an on-campus course or construct an entirely online course for distributed learning. Instructors with little or no technical experience can use a point-and-click navigation system to design their own on-line course components, including setting up course calendars, quizzes, assignments, lectures, and self-paced study help. Prebuilt courses in both BlackBoard and WebCT are available. These courses are available for a nominal fee over the price of the text (this fee includes software license fees). Please ask your Prentice Hall representative for details or e-mail chemistryservice@prenhall.com.

To The Student

Welcome to organic chemistry. This book has been written for you, one who is encountering the subject for the first time. The first thing you should do is familiarize yourself with the book. The material on the inside of the front and back covers is information that you may want to refer to many times during the course. The Key Terms and Summaries of Reactions at the end of the chapters, and the Glossary at the end of the book, can be useful study aids. Also look at the Appendices to see what kind of information is provided there. The electrostatic potential maps and the molecular models throughout the book are there to give you an appreciation of what molecules look like in three dimensions and how electronic charge is distributed within the molecule. Look at the margin notes as you read a chapter—they emphasize important points.

Be sure to work all the problems within each chapter. These are drill problems that will enable you to check whether or not you have mastered the material. Some of them are solved for you in the text. Others—those marked with a diamond—have short answers provided in the Appendix. You will also find Problem-Solving Strategies sprinkled throughout the text. These features provide detailed suggestions for how best to approach important problem types. Please read these Problem-Solving Strategies carefully, and don't be afraid to refer back to them when you're working the end-of-chapter problems.

Work as many end-of-chapter problems as you can. The more problems you work, the more comfortable you will be with the subject and the more prepared you will be for the material in subsequent chapters. Do not let any problem frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study Guide/Solutions Manual to learn how you should have approached the problem. Later on go back and try to work the problem again without consulting the Study Guide/Solutions Manual.

The most important thing for you to remember in organic chemistry is DO NOT GET BEHIND. Organic chemistry consists of a lot of simple steps, so it is not a difficult subject. But the subject can become overwhelming if you don't keep up.

Before many of the theories and mechanisms were worked out, organic chemistry was a discipline that could be mastered only through memorization. Fortunately, that is no longer true. You will find many common threads that will allow you to use what you have learned in one situation to predict what will happen in other situations. So, as you read the book and study your notes, always try to understand why each thing happens. If the reasons behind the behavior are understood, most reactions can be predicted. If you approach the class with the misconception that you must memorize hundreds of unrelated reactions, it could be your downfall. There is simply too much material to memorize, and if all your knowledge is based on memorization, you won't have the necessary foundation on which to lay subsequent material. From time to time, some memorization will be required. Some fundamental rules have to be memorized, and you will have to memorize the common names of some organic compounds. But the latter should not be a problem. After all, your friends have common names and you've been able to learn them.

Students who take organic chemistry to gain entrance into medical school sometimes wonder why medical schools pay so much attention to how they do in organic chemistry. The importance of organic chemistry is not in the subject matter alone. Mastering organic chemistry requires a thorough understanding of fundamentals and the ability to use these fundamentals to analyze, classify, and predict. This parallels the study of medicine; a physician uses an understanding of fundamentals to analyze, classify, and diagnose.

Good luck in your study. I hope you will enjoy your course in organic chemistry and learn to appreciate the logic of the discipline. If you have any comments about the book or any suggestions about how it can be improved for the students who will follow you, I would love to hear from you. Positive comments are the most fun, but critical comments are the most useful.

Paula Yurkanis Bruice
pybruice@bioorganic.ucsb.edu

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