The manner of teaching Organic Chemistry has changed somewhat since my
days as a student in the early 1970s. Most
notably, organic chemistry textbooks offer more and better descriptions of
topics in related fields such as Biochemistry and Materials Science, the
internet allows one to search for information about specific topics, and
computer software is readily available for modeling chemical structures and
reactions. The overall level of
sophistication has also risen for the presentation of traditional themes such
as stereochemistry, bonding, reaction mechanisms, spectroscopy, and synthesis.
In spite of these changes, however, the mastery of Organic Chemistry as
a course of study still requires a sound knowledge of the principles of
molecular structure and chemical reactivity, which are topics introduced in
most General Chemistry courses. With
such a back-ground, a student studying organic chemistry begins to focus on a
more limited set of atomic building blocks, particularly of carbon and its
elemental neighbors. And while
the study of a smaller portion of the periodic table might be expected to be
easily manageable, understanding organic chemistry can still seem overwhelming
because of the diverse ways that this handful of elements can combine and
interact. To learn
organic chemistry, one must grasp the recurring patterns that correlate the
Toward that end, this
textbook organizes and discusses the patterns of chemical reactivity—which
constitutes the majority of the subject matter—by combining information
about the structures of functional groups (the reactive portions of a
molecule) with the reaction mechanisms (pathways of chemical reactions) that
these functional groups undergo. This approach differs from the one presented in many other
texts, which describe every type of
reaction that can occur for a given functional group; each approach has its
advantages and disadvantages. The
one I have utilized here evolved from my objective to integrate discussions
about biochemical processes with the types of reactions that are carried out
in chemistry laboratories. With
the use of two points of reference—structures and
mechanisms—the similarities that associate biochemical and synthetic
reactions can be appreciated more easily.
ORGANIZATION OF THE TEXT
sound knowledge of structures, bonding, and stereochemistry—the three
dimensional arrangements and shapes of molecules—is required in order to
understand the patterns of chemical reactivity.
For that reason, this book begins in Chapters 1-4 with a detailed
treatment of molecular structures. After
Chapter 5, which describes some general aspects of chemical reactions,
specific transformations are presented in the next several chapters.
Spectroscopic methods are
then covered in Chapters 13 and 14 (and used in subsequent chapters), with the
emphasis in the first of these two chapters on nuclear magnetic resonance
spectroscopy. Chapter 14 introduces other analytical methods and integrates
a number of techniques for the elucidation of molecular structures.
The topic of chemical
synthesis constitutes a sizable portion of Chapters 15 and 16, with the latter
focusing on enantioselective reactions. As
with the spectroscopic methods presented in the previous two chapters,
synthetic methods are used throughout the remainder of the text.
Chapter 17 summarizes the
structures and reactions of aromatic compounds, and then the next several
chapters present information about the reactions associated with the
carbon-oxygen double bond, a structural feature of organic molecules that is
pervasive in biochemical systems. Chapters
18-24 pay particular attention to chemical reactions that occur in nature.
The final four chapters
cover specific topics that make use of the basic structures and reactions that
have already been presented. The
closing two chapters describe the chemistry of amino and nucleic acids, which
establish the background for subsequent studies in Biology, Biochemistry, and
Rodger Griffin, Jr., who taught me organic chemistry, was fond of
saying that organic chemistry was best learned by solving problems and not by
reading chapter-by-chapter as one would do for a history or philosophy course.
This text has many exercises incorporated within the text as well as at
the end of each chapter. Furthermore,
this second edition has included many more examples (solved exercises) within
the chapters so that students can see successful approaches to problem
solving. The accompanying Solutions to Exercises book has the answer to every exercise; in
most instances, the approach needed to work toward the answer is included
along with the factual solution.
Chemistry” at most colleges and universities carries the unfortunate status
of being among the more difficult and demanding courses offered.
With its position in the curriculum as the prerequisite for many upper
level chemistry, biology, and pharmacy courses, its negative repute is
unrivaled. No wonder many
students refer to this two-semester sequence as the “premed weed-out
experience does not have to be that way, however.
Below are listed several suggestions I make at the beginning of each
semester aimed at maximizing my students’ success in this subject.
to class and participate.
have written as clearly about organic chemistry as I can, but let’s be
honest—if you could learn this stuff on your own by reading the book and
working exercises then you’re a whiz kid and going to class probably won’t
matter. If you’re a typical
student, however, verbal explanations will
help, and that’s one thing that class is about.
It’s also about seeing how problems are solved and how others look at
them. Students who genuinely participate usually learn a lot.
They also impress their professors, which can’t hurt.
the sections in the book that will be covered in class on a given day and
think about how the material fits with what you know or have covered recently.
Much of the material that you will learn in your organic chemistry
courses is conceptually new—Organic Chemistry is NOT
a repeat of General Chemistry. If
you have an idea beforehand about the key points of the topics being
discussed, you will learn the material faster.
On the other hand, don’t spend hours and hours reading and taking
notes—Organic Chemistry is not an English or History course.
(even a little) every day.
said than done: I had many
teachers tell me this when I was a student, and I myself have said the same
thing to countless students. Does
anyone listen? Maybe for about a
week at the beginning of the semester. Then
the pressures of life and your other courses get in the way, and you’re back
to cramming the night before an exam. I
learned this lesson by experience: if
you want to do well, studying one hour each day of a week is at least twice as
good as studying seven hours once each week.
the assigned exercises.
organic chemistry is about seeing and learning the recurring patterns that correlate the many facts being presented.
Those who see and learn these patterns—among structures, among
chemical reactions, among molecular properties—usually do well.
Those who don’t (or can’t) learn these patterns will struggle.
Your brain may be wired in ways that make it difficult for you to see
the underlying design of organic chemistry.
There’s not much that can be done about this, but it doesn’t mean
you will fail—it just means that you may have to work harder than others in
order to succeed. The best way to
learn these patterns is to work problems.
And then work more problems. And
then work even more problems.
answers to many of the study exercises may not be obvious when you first read
the problem. Do not give up
quickly and do not consult the Solutions
to Exercises book without making a determined effort to solve the
exercise on your own. Many people
can read an answer and understand it. Don’t
be fooled into thinking that you can solve problems because you understand the
answers when you see them. Write
the solution to each exercise on paper. Even
if the answer seems obvious, writing it will help you remember and learn.
Also, do several problems before you look at their answers.
If you look up the solution as you do each exercise, you may catch a
glimpse of the answer to the next problem.
The result is that you are not really working the next one.
addition to doing the study exercises, some students find it useful to make
“flash cards,” especially to learn the many chemical reactions that you
will have to commit to memory. A
set of cards with important information makes it easy to review the course
material while you’re waiting for a movie to begin, sitting between classes,
riding the bus, or any time during the day when you may have 5 or 10 minutes
to study. Organic chemistry is a
cumulative subject. At the end of the semester, you will need to know material
presented on the first day of the course just as much as you will need to know
it for the first exam. A set of
cards will be invaluable for review. NOTE
WELL: using flash cards prepared
by someone else has limited benefit. Much
of their advantage comes from having to think about structures and chemical
reactions enough to prepare the cards.
an exam, get a good night of sleep.
of you will be expected to solve problems on exams that you have not seen
before. If you have studied
regularly, then being alert and relaxed is more important than last minute
cramming. If you haven't studied
regularly, you’re probably in trouble whether you’re rested or not.
So you might as well be rested.
sooner you realize that you’re in trouble, the better.
Go talk to your professor, a teaching assistant, or a tutor. Or form a study group. Some
students find that other students can help them sort out confusing facts as
well as anyone, and an added benefit is a measure of accountability to your
I am always interested to hear from students about what works and what
doesn’t. If you find factual errors or discussions that are confusing,
please let me know (firstname.lastname@example.org).
Such comments are important to keep this text evolving so that it is as
useful as possible to its readers—you, the students. Sometimes
the most innocent remark can make me understand where a student has lost the
thread of thought that winds through the presentation of a particular topic,
and it is that type of input that teaches me and helps me to teach others
As noted in the Preface to the first edition
of this book, I became dissatisfied with many organic chemistry texts when I
started teaching Biochemistry. The
same students who had done well in Organic Chemistry could not seem to
remember even simple reactions related to the ones being covered in the
biochemistry course. Yet I
remembered, for example, covering the structures and reactions of
carbohydrates, amino acids, and nucleic acids in the previous courses.
I concluded that the text we were using had failed to associate
the material shared by the two disciplines because the topics related to
biochemistry were segregated within their own chapters and students had
compartmentalized the material they had learned, mentally labeling the
information as “organic chemistry” or “biochemistry.”
In writing this textbook, and especially this second edition, my goal
has been to integrate the information about many of the fundamental
biochemical reactions with the corresponding transformations that are carried
out in organic chemistry laboratories. Many
who teach the biochemistry courses will give scant attention to the details of
the chemical reactions that constitute metabolic processes (which I think is
useful information to be learned by the students who hope to pursue a career
in the health professions and who constitute the majority of those taking
Organic Chemistry), so the organic chemistry courses provide the best (and
perhaps only) forum to make students aware of such details. I believe that this awareness can be facilitated by
illustrating the parallels between biochemical processes and the simpler
chemical reactions that are being discussed.
Even if students cannot remember specific facts later, they will likely
recall that such associations exist; and they will be more likely later to dig
out their organic chemistry texts to review these topics when they want to
understand a particular biochemical process at the molecular level.
As most organic chemistry instructors know, the key for understanding
chemical reactions resides in comprehending their mechanisms.
Therefore, reaction mechanisms comprise the major organizational theme
of this text, and their details are presented in order to illustrate and
underscore the similarities between synthetic and biochemical processes.
To develop these connections about chemical reactions, however, one
cannot gloss over the facts about molecular structures, stereochemistry, and
thermodynamics. Therefore, these
topics are developed in the first five chapters of this book, and I trust they
are presented with sufficient depth that students who intend to become organic
chemists will not be shortchanged. Toward
that same end of serving the future chemists in the organic chemistry classes,
I have also included presentations of synthetic reactions that appear
frequently in the current literature—the Misunobu, Swern, and Suzuki
reactions, for example—as well as topics such an enantioselective synthesis
and molecular recognition.
NEW TO THIS EDITION
Based on the feedback given to me by hundreds of students as well as
from the critiques of the dedicated reviewers listed in the Acknowledgements,
several of whom taught their courses using the first edition of this text, I
have made changes that are meant to make the material better organized and
easier to understand. I estimate that one-quarter to one-third of the text has been
completely rewritten. A
substantial change in the content comprises the inclusion of more examples
As is often true of second editions, a number of the more specialized
topics (and chemical reactions) that appeared in the first edition have been
left out. Most notably absent is
the first chapter of the previous edition, which provided a historical
perspective of organic chemistry. The
current first chapter—on basic structures and nomenclature—still stands as
the organizational pillar of structural chemistry for the book, but it has
been modified by incorporating the strategies for naming compounds (which was
Appendix A in the first edition) and eliminating the discussions of some types
of groups that are better saved until later in the book (esters, in
The first chapter that concerns a specific type of chemical reaction—nucleophilic
substitution—has been expanded and divided into two chapters in this edition
(Chapters 6 and 7). In this way,
alkyl halides and alcohol substitution reactions are treated separately, and
some sulfur-containing molecules are now included in the chapter on alcohols.
The oxidation reactions of alcohols have been removed from the chapter
on elimination reactions (1st Edition), and a separate chapter on
reduction and oxidation reactions has been created here (Chapter 11).
The information in this chapter also includes discussions about the
reduction and oxidation reactions of alkenes, which were covered previously in
a chapter about alkene addition reactions.
Also, the chemistry of dienes, including the Diels-Alder reaction, have
been collected in a chapter separate from the one devoted to the addition
reactions of simple alkenes.
The order of topics in the chapters that present spectroscopic
methods has been reversed from that in the previous edition, so nuclear
magnetic resonance spectroscopy is now covered first. The subsequent spectroscopy chapter integrates the use of
several techniques, including elemental analysis, for the elucidation of
The chapter that introduces
synthetic methods has been largely preserved from the first edition, but it is
followed directly by the chapter on enantioselective synthesis (previously,
these two chapters were separated by the spectroscopy chapters).
The discussion of enantioselective reactions has been completely
rewritten, and its emphasis has been changed to encourage students to think
about designing enantioselective syntheses without having to memorize a lot of
details about specific reagents and conditions.
The topic of aromatic
compounds— benzene and its derivatives—has been moved (from Chapter 12 in
the first edition to Chapter 17 in the second) with the material on polycyclic
arenes combined with an abbreviated discussion of heterocycles in Chapter 24.
The presentations about diazonium compounds and nucleophilic aromatic
substitution reactions, which were in the chapter on nitrogen-containing
compounds (Chapter 23, first edition), have been incorporated into Chapter 17
The chapters describing
carbonyl compounds have been kept largely intact.
The most significant change is the division of Chapter 17 (1st Edition)
about aldehydes, ketones, and carbohydrates into two chapters in the current
edition. The division has been
made according to the reaction mechanisms involved (nucleophilic addition
versus nucleophilic addition—elimination), not according to the functional
groups that are undergoing the reactions.
The chapter on
nitrogen-containing compounds (Chapter 23 in the first edition) has been
parceled in this edition among several chapters, as appropriate.
In contrast, the discussions of polymer chemistry, which were
interspersed throughout the book in the first edition, have been collected to
form Chapter 26 in this edition. Some
basic presentations of polymerization processes have been left in the earlier
chapters to show the mechanistic similarities to other fundamental reactions,
but many of the details are developed in this later chapter.
The final two chapters on
amino and nucleic acids, including the topic of molecular recognition, are
similar in style and content to those in the first edition.
For its creation, a good textbook requires participation by many people
besides the author, and I am profoundly grateful to the following individuals
for the work they did to make this second edition a reality.
With their comments and questions while using the first edition of this
text, the students that I have taught during the past several years
contributed invaluably to the development and writing of this second edition.
My daughter Courtney, who is now a graduate student in Chemistry at
Georgia Tech, was especially helpful during the early and middle stages of the
writing process as she helped with the typing, both of the text and Solutions
to Exercises. Her work at
Synthematix, a local startup company, gave her the experience to offer
suggestions that helped organize several topics better.
My professional peers offered much in the way of their technical
comments, corrections, and support. At
the University of North Carolina at Chapel Hill, my colleagues Maurice
Brookhart, Joseph DeSimone, Richard Hiskey, Paul Kropp, and Gary Pielak shared their valuable expertise on specific topics that appeared in both
editions. Paul Kropp suggested
some especially constructive changes for this edition as a result of using the
book in the Honors courses at UNC. At
other institutions, the following persons read all or parts of the manuscripts
and provided detailed critiques and suggestions that helped make the text more
readable, more accurate, and more pedagogical.
Texas A&M University
René Boeré University of Lethbridge
Andrew Bororvik University of Kansas
David Bundle University of Alberta
Marjorie Caserio UC, San Diego
Chuck Doubleday Columbia University
Andrew French Albion College
Warren Giering Boston University
John Hubbard Marshall University
Steven Kass University of Minnesota
Susan King UC, Irvine
Michael Zagorski Case Western Reserve University
Neil Marsh University of Michigan
William le Noble SUNY Stonybrook
Jennifer Radkiewicz Old Dominion University
Christian Rojas Barnard College
Dalibor Sames Columbia University
Martin Semmelhack Princeton University
J. William Suggs Brown University
Marcus Thomsen Franklin & Marshall College
F. Dean Toste UC, Berkeley
Nick Turro Columbia University
Nanine Van Draanen California Polytechnic State University
Tom Bond UC, San Diego
Kansas State University
UC, San Francisco
St. Olaf College
F. Chris Pigge
University of Missouri at St.
University of Nevada
Ohio State University
K. Barry Sharpless
University of Connecticut
Carol Dempster Long Island Research Institute
During and after the writing process, a large amount of work is required
to produce a finished book from hundreds of files containing the text and
figures. As a publisher, Bruce
Armbruster is among the best at orchestrating this transformation, and along
with Kathy Armbruster and Jane Ellis, this team at University Science Books did
their usual excellent job. Mary
Castellion, herself an author, was an especially effective collaborator during
the writing of this edition in helping me to edit the previous text and to
present more succinctly and accurately some of the difficult concepts.
Stiefel did a masterful job with the copy edit, while Ann Knight coordinated the
I sincerely thank all of you for the efforts and support you have
contributed to this creative process.
Chapel Hill, 2005