Wileys Solomons Fryhle Snyder Organic Chemistry For Jee Main Advanced 3Rd Edition M S Chouhan All Chapter

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Organic Chemistry combines the Solomons, Fryhle and Snyder’s • Additional topics in textual and tabular form provided within the Snyder
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requirements. The book has been reorganized based on the challenges • Three new chapters added based on the important topics of
faced by the students preparing for JEE (Main & Advanced) in terms of carbenes, nitrenes and polymers covered in the syllabus of JEE.
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Solomons|Fryhle|Snyder
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Organic
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chapter. Furthermore, the book • Irrelevant chapters/sections removed to present a concise text.
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ORGANIC
• Concept maps provided for each chapter to summarize the
• Contains well-illustrated reactions with elaborate and stepwise reactions and concepts for last-minute revision.
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Organic Chemistry
For JEE (Main & Advanced)
THIRD EDITION
Organic Chemistry
For JEE (Main & Advanced)
THIRD EDITION
Solomons, Fryhle and Snyder Organic Chemistry for JEE (Main & Advanced)
Third Edition
Copyright © 2019 by Wiley India Pvt. Ltd., 4436/7, Ansari Road, Daryaganj, New Delhi-110002.
All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means, electronic, mechanical, photocopying, recording or scanning without the written permission of the
publisher. This book is an adaptation of Organic Chemistry, 11/e by T. W. Graham Solomons, Craig B. Fryhle and
Scott A. Snyder (ISBN: 978-81-265-5684-7). All rights remain with their respective holders.
Limits of Liability: While the publisher and the author have used their best efforts in preparing this book, Wiley and
the author make no representation or warranties with respect to the accuracy or completeness of the contents of this
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There are no warranties which extend beyond the descriptions contained in this paragraph. No warranty may be
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Disclaimer: The contents of this book have been checked for accuracy. Since deviations cannot be precluded
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Third Edition: 2017

Reprint: 2019
ISBN: 978-81-265-9832-8
ISBN: 978-81-265-8874-9 (ebk)
www.wileyindia.com
Preface to the Original Edition
“IT’S ORGANIC CHEMISTRY!”
That’s what we want students to exclaim after they become acquainted with our subject.
Our lives revolve around organic chemistry, whether we all realize it or not. When we
understand organic chemistry, we see how life itself would be impossible without it,
how the quality of our lives depends upon it, and how examples of organic chemistry
leap out at us from every direction. That’s why we can envision students enthusiastically
exclaiming “It’s organic chemistry!” when, perhaps, they explain to a friend or family
member how one central theme—organic chemistry—pervades our existence. We want
to help students experience the excitement of seeing the world through an organic lens,
and how the unifying and simplifying nature of organic chemistry helps make many
things in nature comprehensible.
Our book makes it possible for students to learn organic chemistry well and to
see the marvelous ways that organic chemistry touches our lives on a daily basis.
Our book helps students develop their skills in critical thinking, problem solving, and
analysis—skills that are so important in today’s world, no matter what career paths
they choose. The richness of organic chemistry lends itself to solutions for our time,
from the fields of health care, to energy, sustainability, and the environment. After all,
it’s organic chemistry!
Guided by these goals, and by wanting to make our book even more accessible to
students than it has ever been before, we have brought many changes to this edition.
NEW TO THIS EDITION

With this edition we bring Scott Snyder on board as a co-author. We’re very excited
to have Scott join our team. Scott brings a rich resource of new perspectives to the
book, particularly in the arena of complex molecule synthesis. Scott has infused new
examples and applications of exciting chemistry that help achieve our goals. In addi-
tion to adding his perspectives to the presentation of core chemistry throughout the
book, Scott’s work is manifest in most of this edition’s chapter openers and in all of
the chapter closers, couched in a new feature called “Why do these topics matter?”.
“Why do these topics matter?” is a new feature that bookends each chapter with
a teaser in the opener and a captivating example of organic chemistry in the closer.
The chapter opener seeks to whet the student’s appetite both for the core chemistry
in that chapter as well as a prize that comes at the end of the chapter in the form of
a “Why do these topics matter?” vignette. These new closers consist of fascinating
nuggets of organic chemistry that stem from research relating to medical, environ-
mental, and other aspects of organic chemistry in the world around us, as well as the
history of the science. They show the rich relevance of what students have learned
to applications that have direct bearing on our lives and wellbeing. For example, in
Chapter 6, the opener talks about the some of the benefits and drawbacks of mak-
ing substitutions in a recipe, and then compares such changes to the nucleophilic
displacement reactions that similarly allow chemists to change molecules and their
properties. The closer then shows how exactly such reactivity has enabled scientists
to convert simple table sugar into the artificial sweetener Splenda which is 600 times
as sweet, but has no calories!
Laying the foundation earlier Certain tools are absolutely key to success in organic
chemistry. Among them is the ability to draw structural formulas quickly and correctly.
v
In this edition, we help students learn these skills even sooner than ever before by
moving coverage of structural formulas and the use curved arrows earlier in the text
(Section 3.5). We have woven together instruction about Lewis structures, covalent
bonds, and dash structural formulas, so that students build their skills in these areas
as a coherent unit, using organic examples that include alkanes, alkenes, alkynes, and
alkyl halides. One could say that it’s a “use organic to teach organic” approach.
Getting to the heart of the matter quicker Acid-base chemistry, and electro-
philes and nucleophiles are at the heart of organic chemistry. Students cannot
master the subject if they do not have a firm and early grasp of these topics. In
this edition, we cut to the chase with these topics earlier in Chapter 3 than ever
before, providing a streamlined and highly efficient route to student mastery of
these critical concepts.
Improving a core area: substitution reactions All organic instructors know how
important it is for their students to have a solid understanding of substitution
reactions. This is one reason our text has proven its lasting value. In this edition we
have even further enhanced the presentation of substitution reactions in several
ways, including a revised introduction of SN1 reactions (Section 6.10) through the
classic hydrolysis experiments of Hughes, and a newly organized presentation of
solvent effects on the rate of substitution reactions.
Striking a strong balance of synthetic methods Students need to learn methods

of organic synthesis that are useful, as environmentally friendly as possible, and that
are placed in the best overall contextual framework. In this edition we incorporate
the Swern oxidation (Section 11.4B), long held as a useful oxidation method and one
that provides a less toxic alternative to chromate oxidations in some cases. We also
restore coverage of the Wolff-Kishner reduction (Section 15.8C) and the Baeyer-Vil-
liger oxidation (Section 15.12), two methods whose importance has been proven
by the test of time. The chemistry of radical reactions has also been refocused and
streamlined by reducing thermochemistry content and by centralizing the coverage
of allylic and benzylic radical substitutions (including NBS reactions) in one chapter
(Sections 9.7 and 9.8), instead of distributing it between two, as before. The addition
of sulfuric acid to alkenes and the Kolbe reaction have been deleted from the text,
since these have little practical use in the laboratory.
Maintaining an eye for clarity With every edition we improve the presentation of
topics, reactions, and diagrams where the opportunity arises. This edition includes
improved mechanism depictions for aromatic sulfonation and thionyl chloride sub-
stitution.
Showing how things work A mechanistic understanding of organic chemistry is key

to student success in organic chemistry. Mechanisms have always been central to the
book, and in this edition the authors have added a mechanistic framework for the
Swern and chromate alcohol oxidations (Section 11.4) by presenting elimination of
the carbinol hydrogen and a leaving group from oxygen as the common theme.
TRADITIONAL PEDAGOGICAL STRENGTHS

Solved Problems Knowing “where to begin” to solve organic chemistry problems
is one of the greatest challenges faced by today’s students. By modeling problem
solving strategies, students begin to understand the patterns inherent in organic
chemistry and learn to apply that knowledge to new situations. In this edition we
have added even more Solved Problems. They are usually paired with a related
Practice Problem.
vi
Practice Problems Students need ample opportunities to practice and apply their
new found strategies for solving organic chemistry problems. We’ve added to our
rich array of in-text Practice Problems to provide students with even more oppor-
tunities to check their progress as they study. If they can work the practice problem,
they should move on. If not, they should review the preceding presentation.
SOLVED PROBLEMS
Solved Problem 11.2 model problem solving strategies.
Which reagents would you use to accomplish the follow- Answer
ing transformations?
(a) To oxidize a primary alcohol to a carboxylic acid,
O use (1) potassium permanganate in aqueous base,
OH (a) OH followed by (2) H3O+, or use chromic acid (H2CrO4).
(b) To reduce a carboxylic acid to a primary alcohol, use
(b) LiAlH4.
(c) To oxidize a primary alcohol to an aldehyde, use
O the Swern oxidation or pyridinium chlorochromate
OH (c) H (PCC).
(d) To reduce an aldehyde to a primary alcohol, use
(d) NaBH4 (preferably) or LiAlH4.
PRACTICE PROBLEMS
Practice Problem 11.3 provides opportunities to
Show how each of the following transformations could be accomplished: check progress.
O O
OH ? H OH ? OH
(a) (b)
End-of-Chapter Problems As athletes and musicians know, practice makes perfect.

The same is true with organic chemistry. The End of Chapter problems, categorized
by topic, provide essential practice for students and help them build mastery of both
concepts and skills presented throughout the chapter. Many of the End of Chapter
problems are cast in a visual format using structures, equations, and schemes.
END-OF-CHAPTER
7.28 Give the IUPAC names for each of the following:
CH3 PROBLEMS are grouped
D
and labeled by topic. Students
(a) (d) H
and instructors can more easily
7.34 Outline a synthesis of phenylethyne from each of the
following: select problems for specific
Br Br
(b) (e) Br purposes.
H (a) (b)
Cl Cl
Br
O
(c) (f)
(c) (d)
7.29 Without consulting tables, arrange the following com-

pounds in order of decreasing acidity:
Pentane 1-Pentene 1-Pentyne 1-Pentanol
Dehydrohalogenation and Dehydration
7.35 Write a three-dimensional representation for the tran-
Synthesis sition state structure leading to formation of 2-methyl-
7.30 Outline a synthesis of propene from each of the following: 2-butene from reaction of 2-bromo-2-methylbutane with
(a) Propyl chloride sodium ethoxide.
(b) Isopropyl chloride 7.36 When trans-2-methylcyclohexanol (see the following
(c) Propyl alcohol reaction) is subjected to acid-catalyzed dehydration, the
(d) Isopropyl alcohol major product is 1-methylcyclohexene:
A Mechanism for the Reaction Understanding mechanisms and the ability to recog-
nize patterns among them is a key component in determining student success in organ-
ic chemistry. We provide A Mechanism for the Reaction boxes that show step-by-step
details about how reactions take place so that students have the tools to understand
rather than memorize organic reactions.
vii
A MECHANISM FOR THE
A MECHANISM FOR THE REACTION Hydrogen Atom Abstraction
REACTION Stepped out
General Reaction
reactions with just the right
amount of detail provides the X + H R X H + R
tools for students to understand Reactive Alkane Alkyl radical

radical intermediate
rather than memorize reaction intermediate (reacts further)
mechanisms Specific Example
Cl + H CH3 Cl H + CH3
Chlorine Methane Methyl radical
atom intermediate
(a radical) (reacts further)
Key Ideas as Bullet Points The amount of content covered in organic chemistry can
be overwhelming to students. To help students focus on the most essential topics, key
ideas are emphasized as bullet points in every section. In preparing bullet points, we
have distilled appropriate concepts into simple declarative statements that convey
core ideas accurately and clearly. No topic is ever presented as a bullet point if its
integrity would be diminished by oversimplification, however.
“How to” Sections Students need to master important skills to support their con-
ceptual learning. “How to” Sections throughout the text give step-by-step instruc-
tions to guide students in performing important tasks, such as using curved arrows,
drawing chair conformations, planning a Grignard synthesis, determining formal
charges and writing Lewis structures.
The Chemistry of . . . . Virtually every instructor has the goal of showing students how
organic chemistry relates to their field of study and to their everyday life experience.
The authors assist their colleagues in this goal by providing boxes titled “The Chemistry
of . . .” that provide interesting and targeted examples that engage the student with
chapter content.
Summary and Review Tools At the end of each chapter, Summary and Review
Tools provide visually oriented roadmaps and frameworks that students can
use to help organize and assimilate concepts as they study and review chapter
content. Intended to accommodate diverse learning styles, these include Synthetic
SUMMARY AND REVIEW TOOLS Visually

oriented study tools accommodate diverse
[S U M M A R Y A N Dand Review
Summary R E Tools
V I E W T O O L S ]
learning styles. Synthetic Connections of Alkynes and Alkenes: II
H X X X
H R2 X R2
HX X2
R1 C C R2 C C C C R1 C C R2
(2nd molar (2nd molar
equivalent) R1 X R1 X equivalent)
H X X X
(If R1 in alkyne is H
then addition is
Markovnikov) X2
HX
(1st molar (1st molar
equivalent) equivalent)
• Hydrohalogenation
• Halogenation
• Hydrogenation C C
R1 R2 (1) KMnO4, HO , heat (2) H3O
• Carbene Addition
or
• Ozonolysis
(1) X2 (1) X2 (1) O3 (2) HOAc
• Potassium Permanganate Cleavage
• Alkyne Synthesis by Double E2 (2) NaNH2 (2) NaNH2
(2 equiv.), (2 equiv.),
heat heat
H2, (1) Na, EtNH2
Lindlar’s or
R1 R2 *(1) O3 R1 R2 P-2 catalyst
(2) NH4Cl R1 H *(1) KMnO4, R1 OH
HO , heat
C O O C C C C C C O O C
(2) Me2S (Z) (E) (2) H3O
H H H H H R2 HO R2
H2, catalyst
(Pt, Pd, Rh, Ni)
CH2I2, Zn(Cu) CH2I2, Zn(Cu)
(or other methods) (or other methods)
H H
R1 C C R2
R1 R2 R1 H
H H H H H R2
*If R1 is H, then alkene ozonolysis generates
formaldehyde and KMnO4 generates CO2.
If the alkene is disubstituted at one end, a ketone
results from cleavage by either ozonolysis or KMnO4.
viii
[C O N C E P T M A P ]
Conformers
(Section 5.8)
are
Molecules that differ only by rotation

about sigma (s s ) bonds
can have
Ring strain
Different potential energies (Section 5.10)
of conformers can among conformers
be represented by is a function of is caused by
and
Conformer potential Torsional strain Angle strain
energy diagrams (Section 5.8) (Section 5.10)
(Section 5.9)
are a plot of is caused by and loss of is caused by
Dihedral angle vs. Repulsive Hyperconjugative Deviation from ideal

potential energy dispersion stabilization bond angles
forces (Section 5.8)
result in involves
E
Steric hindrance Favorable overlap of

0 60 120 240 300 360
Degrees of Rotation u
420
(Section 5.8) occupied with
can be unoccupied of cyclohexane
represented orbitals can be
by represented by
Newman projection
formulas Chair conformational structures Boat
(Section 5.8) or
(Section 5.11)
can be used to show have

Axial positions
Eclipsed Staggered
and
conformations conformations and twist-boat
with substituted
groups (G) can be
and
G G
G
Equatorial positions
Anti or Gauche conformational
G structures
Connections, Concept Maps, Thematic Mechanism Review Summaries, and the

detailed Mechanism for the Reaction boxes already mentioned. We also provide
Helpful Hints and richly annotated illustrations throughout the text.
COVERAGE
Throughout the book, we have streamlined or reduced content to match the modern
practice of organic chemistry, and we have provided new coverage of current reactions,
while maintaining our commitment to an appropriate level and breadth of coverage.
• Chapters on carbonyl chemistry that are organized to emphasize mechanistic themes

of nucleophilic addition, acyl substitution, and reactivity at the a-carbon.
ORGANIZATION—An Emphasis on the Fundamentals

So much of organic chemistry makes sense and can be generalized if students
master and apply a few fundamental concepts. Therein lays the beauty of
organic chemistry. If students learn the essential principles, they will see that
memorization is not needed to succeed.
Most important is for students to have a solid understanding of structure—
of hybridization and geometry, steric hindrance, electronegativity, polarity, formal
charges, and resonance—so that they can make intuitive sense of mechanisms. It is
with these topics that we begin in Chapter 1. In Chapter 2 we introduce the families of
functional groups—so that students have a platform on which to apply these concepts.
We begin our study of mechanisms in the context of acid-base chemistry in
Chapter 3. Acid-base reactions are fundamental to organic reactions, and they
ix
lend themselves to introducing several important topics that students need early
in the course: (1) curved arrow notation for illustrating mechanisms, (2) the
relationship between free-energy changes and equilibrium constants, and (3) the
importance of inductive and resonance effects and of solvent effects.
In Chapter 3 we present the first of many “A Mechanism for the Reaction” boxes,
using an example that embodies both Brønsted-Lowry and Lewis acid-base
principles. All throughout the book, we use boxes like these to show the details of
key reaction mechanisms. All of the Mechanism for the Reaction boxes are listed in
the Table of Contents so that students can easily refer to them when desired.
A central theme of our approach is to emphasize the relationship between
structure and reactivity. This is why we choose an organization that combines the
most useful features of a functional group approach with one based on reaction
mechanisms. Our philosophy is to emphasize mechanisms and fundamental
principles, while giving students the anchor points of functional groups to apply
their mechanistic knowledge and intuition. The structural aspects of our approach
show students what organic chemistry is. Mechanistic aspects of our approach show
students how it works. And wherever an opportunity arises, we show them what it
does in living systems and the physical world around us.
In summary, our writing reflects the commitment we have as teachers to do the
best we can to help students learn organic chemistry and to see how they can apply
their knowledge to improve our world. The enduring features of our book have
proven over the years to help students learn organic chemistry.
Preface to the Adapted Version
This book is dedicated to the lotus feet of Revered Guruji
SHRI KESARAM JI MAHARAJ
It is a matter of great pleasure for me to present the second edition of the book before
engineering aspirants. This book was written because I felt the need for a textbook
that corresponds closely to the course that I teach. Although the book is organized
along tried-and- true functional-group lines, it contains some unique features that
have served me well in both my teaching and understanding of Organic Chemistry.
My four major concerns in both the initial writing and the revision of this text
were readability, presentation, organization, and accuracy. In the current scenario of
stiff competition especially for engineering entrances, one must be clear that almost
all the sincere applicants are well equipped with the facts of subject; yet, the winner
is the one who knows how to use these facts with accuracy and efficiency. As an
experienced teacher, I would like to suggest students three golden rules to score high
in Organic Chemistry:
1. Do not lag behind in schedule.

2. Work out a number of problems of different types.
3. Revise through short notes.
I hope that the present book will cater to the needs of engineering aspirants.
As a matter of fact, they will enjoy the present venture and I would feel rewarded
if this book is helpful for the students and teachers in real terms. All efforts have
been made to make the book error-free; however, a few misprints may inadvertently
creep.
I acknowledge the blessing and support of my mother Smt. Raj Kanwar,
father Shri B.S. Chouhan, brother Dr. V. S. Chouhan, wife Ms. Meena Chouhan and
daughter. They inspired me all the time during the preparation of this book.
The support and valuable suggestions from Mr. V.K. Jaiswal, Mr. N. Avasthi,
Mr. Akshay Chawdhary, Dr. S. Kothari, Mr. Navneet Jethwani, Ms. Neha
Joshi, Mr. Ashish Mishra, Mr. Kumud Ranjan, Mr. Mohit Sayal, Mr. Hanuman
Prasad Sahay, Mr. Vineet Khatri, Mr. Govind Khadelwal, Mr. Manish
Arora, Mr. Rahul Malay, Mr. Rahul Pareek, Mr. Divyesh Tiwari, Mr. Omkar
Kelapure, Mr. Mayank Pareek, Mr. Gurpreet Singh, Mr. Yogesh Jain, Ms.
Anjana Kamal, Mr. Anit Chaudhry, Mr. Shaliwahan Singh Rathore and
Mr. Kishore Kilani, are highly acknowledged. I also pay my sincere thanks to all
the esteemed members of Wiley India and specially Ms. Anjali Chadha, Ms. Seema
Sajwan and Mr. Rakesh Poddar in bringing out this book in such a nice form.
In the end, constructive criticism and valuable suggestions from the readers are
most welcome to make the book more useful.
M.S.Chouhan
(MSC Sir)
Email: mschouhan1278@gmail.com
Mobile: 9828025625
xi
FM_FrontMatter.indd 11 3/20/2017 7:02:40 PM

About the Authors
T. W. GRAHAM SOLOMONS did his undergraduate work at The Citadel and
received his doctorate in organic chemistry in 1959 from Duke University where he
worked with C. K. Bradsher. Following this he was a Sloan Foundation Postdoctoral
Fellow at the University of Rochester where he worked with V. Boekelheide. In 1960
he became a charter member of the faculty of the University of South Florida and
became Professor of Chemistry in 1973. In 1992 he was made Professor Emeritus.
In 1994 he was a visiting professor with the Faculté des Sciences Pharmaceutiques
et Biologiques, Université René Descartes (Paris V). He is a member of Sigma Xi,
Phi Lambda Upsilon, and Sigma Pi Sigma. He has received research grants from
the Research Corporation and the American Chemical Society Petroleum Research
Fund. For several years he was director of an NSF-sponsored Undergraduate
Research Participation Program at USF. His research interests have been in the
areas of heterocyclic chemistry and unusual aromatic compounds. He has published
papers in the Journal of the American Chemical Society, the Journal of Organic
Chemistry, and the Journal of Heterocyclic Chemistry. He has received several
awards for distinguished teaching. His organic chemistry textbooks have been
widely used for 30 years and have been translated into French, Japanese, Chinese,
Korean, Malaysian, Arabic, Portuguese, Spanish, Turkish, and Italian. He and his
wife Judith have a daughter who is a building conservator and a son who is a
research biochemist.
CRAIG BARTON FRYHLE is Chair and Professor of Chemistry at Pacific Lutheran

University. He earned his B.A. degree from Gettysburg College and Ph.D. from
Brown University. His experiences at these institutions shaped his dedication to
mentoring undergraduate students in chemistry and the liberal arts, which is a pas-
sion that burns strongly for him. His research interests have been in areas relating
to the shikimic acid pathway, including molecular modeling and NMR spectrometry
of substrates and analogues, as well as structure and reactivity studies of shikimate
pathway enzymes using isotopic labeling and mass spectrometry. He has mentored
many students in undergraduate research, a number of who have later earned their
Ph.D. degrees and gone on to academic or industrial positions. He has participated
in workshops on fostering undergraduate participation in research, and has been
an invited participant in efforts by the National Science Foundation to enhance
undergraduate research in chemistry. He has received research and instrumentation
grants from the National Science Foundation, the M J. Murdock Charitable Trust,
and other private foundations. His work in chemical education, in addition to text-
book coauthorship, involves incorporation of student-led teaching in the classroom
and technology-based strategies in organic chemistry. He has also developed exper-
iments for undergraduate students in organic laboratory and instrumental analysis
courses. He has been a volunteer with the hands-on science program in Seattle
public schools, and Chair of the Puget Sound Section of the American Chemical
Society. His passion for climbing has led to ascents of high peaks in several parts of
the world. He resides in Seattle with his wife, where both enjoy following the lives
of their two daughters as they unfold in new places.
SCOTT A. SNYDER is Associate Professor of Chemistry at Columbia University. He

grew up in the suburbs of Buffalo NY and was an undergraduate at Williams College,
where he graduated summa cum laude in 1999, before pursuing his doctoral studies at
The Scripps Research Institute under the tutelege of K. C. Nicolaou as an NSF, Pfizer,
xiii
and Bristol-Myers-Squibb predoctoral fellow.While there,he co-authored the graduate
textbook Classics in Total Synthesis II with his doctoral mentor. Scott was then an
NIH postdoctoral fellow in the laboratories of E. J. Corey at Harvard University
before assuming his current position in 2006. His research interests lie in the arena
of natural products total synthesis, especially in the realm of unique polyphenols
and halogenated materials, and to date he has trained more than 60 students at the
high school, undergraduate, graduate, and postdoctoral levels and co-authored more
than 40 research and review articles. Scott has received a number of awards and
honors, including a Camille and Henry Dreyfus New Faculty Award, Amgen New
Faculty and Young Investigator Awards, Eli Lilly New Faculty and Grantee Awards,
a Bristol-Myers Squibb Unrestricted Grant Award, an NSF CAREER Award, an
Alfred P. Sloan Foundation Fellowship, a DuPont Young Professor Award, and
an Arthur C. Cope Scholar Award from the American Chemical Society. He has
also received recognition for his teaching through a Cottrell Scholar Award from
the Research Corporation for Science Advancement and a Columbia Presidential
Teaching Award. He is a member of the international advisory board for The
Chemical Record and the editorial board of Chirality. He lives north of New York
City with his wife Cathy where he enjoys gardening, cooking, and watching movies.
About the Adapting Author
Mahendra Singh Chouhan (MSC Sir) is a renowned name in the realm of Organic
Chemistry. Though a Chemical engineer from Mumbai University, he has great
passion for the subject that led him to impart guidance to engineering aspirants on
a regular basis. His in-depth knowledge and vast teaching experience has helped
innumerable students to achieve their dream of excelling in engineering and other
such tough challenges.
He has launched a website to extend the benefits of his expertise beyond the
geographical barriers to all those who dare to dream and seek—www.winvall.com
and www.shivwin.com. The website provides expert guidance in all areas of the
subject in a most skillful manner. There are quizzes, challenging questions, notes,
e-books, videos, etc. This website is a complete guide in itself for organic chemistry
and has been designed for engineering, keeping in mind CBSE syllabus and various
other syllabi. Highly recommended for high flyers!
xv
To the Student
Contrary to what you may have heard, organic chemistry Organic chemistry is best assimilated through the
does not have to be a difficult course. It will be a rigorous fingertips by writing, and not through the eyes by
course, and it will offer a challenge. But you will learn simply looking, or by highlighting material in the
more in it than in almost any course you will take—and text, or by referring to flash cards. There is a good
what you learn will have a special relevance to life and reason for this. Organic structures, mechanisms,
the world around you. However, because organic chem- and reactions are complex. If you simply examine
istry can be approached in a logical and systematic way, them, you may think you understand them thor-
you will find that with the right study habits, mastering oughly, but that will be a misperception. The reac-
organic chemistry can be a deeply satisfying experience. tion mechanism may make sense to you in a certain
Here, then, are some suggestions about how to study: way, but you need a deeper understanding than
this. You need to know the material so thoroughly
1. Keep up with your work from day to day— that you can explain it to someone else. This level
never let yourself get behind. Organic chemistry of understanding comes to most of us (those of
is a course in which one idea almost always builds on us without photographic memories) through writ-
another that has gone before. It is essential, therefore, ing. Only by writing the reaction mechanisms do
that you keep up with, or better yet, be a little ahead we pay sufficient attention to their details, such
of your instructor. Ideally, you should try to stay one as which atoms are connected to which atoms,
day ahead of your instructor’s lectures in your own which bonds break in a reaction and which bonds
class preparations. The lecture, then, will be much form, and the three-dimensional aspects of the
more helpful because you will already have some structures. When we write reactions and mech-
understanding of the assigned material. Your time anisms, connections are made in our brains that
in class will clarify and expand ideas that are already provide the long-term memory needed for success
familiar ones. in organic chemistry. We virtually guarantee that
2. Study material in small units, and be sure that your grade in the course will be directly propor-
you understand each new section before you go tional to the number of pages of paper that your
on to the next. Again, because of the cumulative fill with your own writing in studying during the
nature of organic chemistry, your studying will be term.
much more effective if you take each new idea as it 5. Learn by teaching and explaining. Study with
comes and try to understand it completely before you your student peers and practice explaining concepts
move on to the next concept. and mechanisms to each other. Use the exercises
3. Work all of the in-chapter and assigned problems. your instructor may assign as vehicles for teaching
One way to check your progress is to work each of and learning interactively with your peers.
the in-chapter problems when you come to it. These 6. Use the answers to the problems in the Study
problems have been written just for this purpose and Guide in the proper way. Refer to the answers
are designed to help you decide whether or not you only in two circumstances: (1) When you have fin-
understand the material that has just been explained. ished a problem, use the Study Guide to check your
You should also carefully study the Solved Problems. answer. (2) When, after making a real effort to solve
If you understand a Solved Problem and can work the problem, you find that you are completely stuck,
the related in-chapter problem, then you should then look at the answer for a clue and go back to
go on; if you cannot, then you should go back and work out the problem on your own. The value of
study the preceding material again. Work all of the a problem is in solving it. If you simply read the
problems assigned by your instructor from the end problem and look up the answer, you will deprive
of the chapter, as well. Do all of your problems in a yourself of an important way to learn.
notebook and bring this book with you when you go
to see your instructor for extra help. 7. Use molecular models when you study. Because
of the three-dimensional nature of most organic
4. Write when you study. Write the reactions, mech- molecules, molecular models can be an invaluable
anisms, structures, and so on, over and over again. aid to your understanding of them.
xvii

Contents
Preface to the Original Edition v 2.11 Summary of Important Families of Organic
Preface to the Adapted Version xi Compounds 58
About the Authors xiii 2.12 Physical Properties and Molecular Structure 59
About the Adapting Authors xv 2.13 Summary of Attractive Electric Forces 66
To the Student xvii
3
1 An Introduction to Organic
The Basics: Bonding and Reactions and Their Mechanisms:
Molecular Structure 1 Acids and Bases 73
1.1 Development of the Science of Organic Chemistry 1 3.1 Reactions and Their Mechanisms 73
1.2 Atomic Structure 2 3.2 Acid–Base Reactions 75
1.3 The Structural Theory of Organic Chemistry 3 3.3 Lewis Acids and Bases 77
1.4 Chemical Bonds: The Octet Rule 5 3.4 Heterolysis of Bonds to Carbon: Carbocations
1.5 Resonance Theory 7 and Carbanions 79
1.6 Hyperconjugation 18 3.5 HOW TO Use Curved Arrows in Illustrating
1.7 The Structure of Methane and Ethane: Reactions 80
sp3 Hybridization 25 3.6 The Strength of Brønsted–Lowry Acids and Bases:
1.8 The Structure of Ethene (Ethylene): sp2 Ka and pKa 85
Hybridization 26 3.7 HOW TO Predict the Outcome of Acid–Base
1.9 The Structure of Ethyne (Acetylene): sp Reactions 88
Hybridization 29 3.8 Relationships between Structure and Acidity 90
1.10 How to Interpret and Write Structural Formulas 31 3.9 Energy Changes 94
3.10 The Relationship between the Equilibrium Constant
and the Standard Free-Energy Change, DG° 95
2 3.11
3.12
The Acidity of Carboxylic Acids versus Alcohols 96
The Effect of the Solvent on Acidity 99
Families of Carbon Compounds: 3.13 Organic Compounds as Bases 100

3.14 Acids and Bases in Nonaqueous Solutions 101
Functional Groups and 3.15 Acid–Base Reactions and the Synthesis of
Intermolecular Forces 43 Deuterium- and Tritium-Labeled Compounds 103
3.16 Reaction of NaHCO3 as a Base 104
2.1 Hydrocarbons: Representative Alkanes, Alkenes,
3.17 Steric Inhibition of Resonance (SIR) Effect 105
Alkynes, and Aromatic Compounds 44
3.18 Ortho and Para Effects 106
2.2 Polar and Nonpolar Molecules 47
2.3 Functional Groups 49
2.4
2.5
Alkyl Halides or Haloalkanes 51
Alcohols 51 4
2.6 Ethers 52
2.7 Amines 53 Stereochemistry: Chiral
2.8 Aldehydes and Ketones 54 Molecules 127
2.9 Carboxylic Acids, Esters, and Amides 55
4.1 Chirality and Stereochemistry 127
2.10 Nitriles 57
xix
4.2 Isomerism: Constitutional Isomers and 5.14 Bicyclic and Polycyclic Alkanes 229
Stereoisomers 129 5.15 Chemical Reactions of Alkanes 230
4.3 Enantiomers and Chiral Molecules 130 5.16 Synthesis of Alkanes and Cycloalkanes 230
4.4 A Single Chirality Center Causes a Molecule 5.17 HOW TO Gain Structural Information from Molecular
to Be Chiral 131 Formulas and the Index of Hydrogen Deficiency 233
4.5 More about the Biological Importance of Chirality 133 5.18 Applications of Basic Principles 234
4.6 HOW TO Test for Chirality: Planes of Symmetry 135
6
4.7 Naming Enantiomers: The R,S-System 142
4.8 Properties of Enantiomers: Optical Activity 146
4.9 The Origin of Optical Activity 150
4.10 The Synthesis of Chiral Molecules 152 Ionic Reactions
4.11 Chiral Drugs 154 Nucleophilic Substitution and Elimination
4.12 Molecules with More than One Chirality Center 155
Reactions of Alkyl Halides 243
4.13 Fischer Projection Formulas 159
4.14 Stereoisomerism of Cyclic Compounds 160 6.1 Alkyl Halides 243
4.15 Relating Configurations through Reactions in which 6.2 Nucleophilic Substitution Reactions 245
no Bonds to the Chirality Center are Broken 163 6.3 Nucleophiles 246
4.16 Separation of Enantiomers: Resolution 166 6.4 Leaving Groups 248
4.17 Compounds with Chirality Centers Other than 6.5 Kinetics of a Nucleophilic S
ubstitution Reaction:
Carbon 169 An SN2 Reaction 248
4.18 Chiral Molecules That Do Not Possess a Chirality 6.6 A Mechanism for the SN2 Reaction 249
Center 169
6.7 Transition State Theory: Free-Energy Diagrams 251
4.19 Biphenyl 170
6.8 The Stereochemistry of SN2 Reactions 253
4.20 Racemization of Biphenyl Compounds 172
6.9 The Reaction of tert-Butyl Chloride with Water:
4.21 Tautomerism 173 An SN1 Reaction 256
4.22 Gero Entropy 176 6.10 A Mechanism for the SN1 Reaction 257
6.11 Carbocations 258
5 6.12 The Stereochemistry of SN1 Reactions 260

6.13 Factors Affecting the Rates of SN1 and SN2
Reactions 263
Nomenclature and Conformations 6.14 Organic Synthesis: Functional Group Transformations
of Alkanes and Cycloalkanes 191 Using SN2 Reactions 274
6.15 Elimination Reactions of Alkyl Halides 276
5.1 Introduction to Alkanes and Cycloalkanes 191 6.16 The E2 Reaction 280
5.2 Shapes of Alkanes 192 6.17 The E1 Reaction 282
5.3 HOW TO Name Alkanes, Alkyl Halides, 6.18 HOW TO Determine Whether S ubstitution
and Alcohols: The IUPAC System 194 or Elimination is Favored 283
5.4 HOW TO Name Cycloalkanes 201 6.19 Overall Summary 286
5.5 HOW TO Name Alkenes and Cycloalkenes 203
5.6 HOW TO Name Alkynes 205
5.7 Physical Properties of Alkanes and Cycloalkanes 206 7
5.8 Sigma Bonds and Bond Rotation 208
5.9 Conformational Analysis of Butane 210 Alkenes and Alkynes I
5.10 The Relative Stabilities of Cycloalkanes: Ring Strain 217 Properties and Synthesis. Elimination
5.11 Conformations of Cyclohexane: The Chair Reactions of Alkyl Halides 295
and the Boat 219
5.12 Substituted Cyclohexanes: Axial and 7.1 Introduction 295
Equatorial Hydrogen Groups 221 7.2 The (E )–(Z ) System for Designating Alkene
5.13 Disubstituted Cycloalkanes: Cis–Trans Isomerism 224 Diastereomers 296
xx
7.3 Relative Stabilities of Alkenes 297 8.20 Dimerization of Alkene 379
7.4 Cycloalkenes 299 8.21 Prins Reaction 379
7.5 Synthesis of Alkenes via Elimination Reactions 300
9
7.6 Dehydrohalogenation of Alkyl Halides 300
7.7 Acid-Catalyzed Dehydration of Alcohols 306
7.8 Carbocation Stability and the Occurrence
of Molecular Rearrangements 311 Radical Reactions 403
7.9 The Acidity of Terminal Alkynes 315
7.10 Synthesis of Alkynes by Elimination Reactions 316 9.1 Introduction: How Radicals Form and
How they React 403
7.11 Terminal Alkynes can be Converted to Nucleophiles
for Carbon–Carbon Bond Formation 318 9.2 Homolytic Bond Dissociation Energies (DH °) 405
7.12 Hydrogenation of Alkenes 320 9.3 Reactions of Alkanes with Halogens 408
7.13 Hydrogenation: The Function of the Catalyst 322 9.4 Chlorination of Methane: Mechanism of Reaction 410
7.14 Hydrogenation of Alkynes 323 9.5 Halogenation of Higher Alkanes 413
7.15 An Introduction to Organic Synthesis 325 9.6 Reactions that Generate Tetrahedral
Chirality Centers 416
9.7 Allylic Substitution and Allylic Radicals 419
8 9.8 Benzylic Substitution and Benzylic Radicals 422

9.9 Radical Addition to Alkenes: The Anti-Markovnikov
Addition of Hydrogen Bromide 425
Alkenes and Alkynes II 9.10 Other Important Radical Reactions 427
Addition Reactions 341
8.1 Addition Reactions of Alkenes 341

8.2 Electrophilic Addition of Hydrogen Halides to
10
Alkenes: Mechanism and Markovnikov’s Rule 343
8.3 Stereochemistry of the Ionic Addition to an Alkene 348
Alcohols and Ethers
8.4 Addition of Water to Alkenes: Acid-Catalyzed Synthesis and Reactions 443
Hydration 348
8.5 Alcohols from Alkenes through Oxymercuration– 10.1 Structure and Nomenclature 443
Demercuration: Markovnikov Addition 351 10.2 Physical Properties of Alcohols and Ethers 446
8.6 Alcohols from Alkenes through Hydroboration– 10.3 Synthesis of Alcohols from Alkenes 446
Oxidation: Anti-Markovnikov Syn Hydration 354 10.4 Reactions of Alcohols 448
8.7 Hydroboration: Synthesis of Alkylboranes 355 10.5 Alcohols as Acids 450
8.8 Oxidation and Hydrolysis of Alkylboranes 357 10.6 Conversion of Alcohols into Alkyl Halides 451
8.9 Summary of Alkene Hydration Methods 360 10.7 Alkyl Halides from the Reaction of Alcohols
8.10 Protonolysis of Alkylboranes 360 with Hydrogen Halides 451
8.11 Electrophilic Addition of Bromine and 10.8 Alkyl Halides from the Reaction of Alcohols
Chlorine to Alkenes 361 with PBr3 or SOCl2 454
8.12 Stereospecific Reactions 363 10.9 Tosylates, Mesylates, and Triflates: Leaving Group
8.13 Halohydrin Formation 365 Derivatives of Alcohols 456
8.14 Oxidation of Alkenes: Syn 1,2-Dihydroxylation 366 10.10 Rearrangements 458
8.15 Oxidative Cleavage of Alkenes 368 10.11 Synthesis of Ethers 461
8.16 Electrophilic Addition of Bromine 10.12 Reactions of Ethers 466
and Chlorine to Alkynes 372 10.13 Epoxides 468
8.17 Addition of Hydrogen Halides to Alkynes 373 10.14 Reactions of Epoxides 469
8.19 HOW TO Plan a Synthesis: Some Approaches 10.15 Anti 1,2-Dihydroxylation of Alkenes via
and Examples 374 Epoxides 472
8.18 Oxidative Cleavage of Alkynes 374 10.16 Crown Ethers 472
xxi
11 14
Alcohols from Carbonyl Reactions of Aromatic
Compounds 491 Compounds 577
11.1 Structure of the Carbonyl Group 491 14.1 Electrophilic Aromatic Substitution Reactions 577
11.2 Oxidation–Reduction Reactions in Organic 14.2 A General Mechanism for Electrophilic
Chemistry 493 Aromatic Substitution 578
11.3 Alcohols by Reduction of Carbonyl Compounds 494 14.3 Halogenation of Benzene 580
11.4 Oxidation of Alcohols 497 14.4 Nitration of Benzene 581
11.5 Organometallic Compounds 502 14.5 Sulfonation of Benzene 582
11.6 Preparation of Organolithium and 14.6 Friedel–Crafts Alkylation 583
Organomagnesium Compounds 502 14.7 Friedel–Crafts Acylation 585
11.7 Reactions of Organolithium and 14.8 Limitations of Friedel–Crafts Reactions 587
Organomagnesium Compounds 504 14.9 Synthetic Applications of Friedel–Crafts A
cylations:
11.8 Alcohols from Grignard Reagents 506 The Clemmensen and Wolff–Kishner Reductions 589
11.9 Lithium Dialkylcuprates: The Corey–Posner, 14.10 Substituents Can Affect Both the Reactivity of the
Whitesides–House Synthesis 519 Ring and the Orientation of the Incoming Group 591
14.11 How Substituents Affect Electrophilic Aromatic
12
Substitution: A Closer Look 596
14.12 Reactions of the Side Chain of Alkylbenzenes 605
14.13 Alkenylbenzenes 607
Conjugated Unsaturated 14.14 Synthetic Applications 609
Systems 535 14.15 Allylic and Benzylic Halides in Nucleophilic
Substitution Reactions 613
12.1 Introduction 535 14.16 Reduction of Aromatic Compounds 614
12.2 Alkadienes and Polyunsaturated Hydrocarbons 536
12.3 1,3-Butadiene: Electron Delocalization
12.4 Electrophilic At tack on Conjugated Dienes:
1,4-Addition 538
537
15
12.5 The Diels–Alder Reaction: A 1,4-Cycloaddition Aldehydes and Ketones I.
Reaction of Dienes 542
Nucleophilic Addition to the
Carbonyl Group 629
13 15.1 Introduction 629
15.2 Nomenclature of Aldehydes
Aromatic Compounds 551 and Ketones 629
15.3 Physical Properties 631
13.1 The Discovery of Benzene 551
15.4 Synthesis of Aldehydes 632
13.2 Nomenclature of Benzene Derivatives 552
15.5 Synthesis of Ketones 637
13.3 Reactions of Benzene 554
15.6 Nucleophilic Addition to the Carbon–Oxygen
13.4 The Kekulé Structure for Benzene 555
Double Bond 639
13.5 The Thermodynamic Stability of Benzene 556
15.7 The Addition of Alcohols: Hemiacetals and
13.6 Modern Theories of the Structure of Benzene 557 Acetals 642
13.7 Hückel’s Rule: The 4n + 2 o Electron Rule 560 15.8 The Addition of Primary and Secondary Amines 650
13.8 Other Aromatic Compounds 565 15.9 The Addition of Hydrogen Cyanide:
13.9 Heterocyclic Aromatic Compounds 567 Cyanohydrins 653
xxii
15.10 The Addition of Ylides: The Wittig Reaction 655 18.2 Physical Properties and Structure of Amines 753
15.11 Oxidation of Aldehydes 658 18.3 Basicity of Amines: Amine Salts 754
15.12 The Baeyer–Villiger Oxidation 658 18.4 Preparation of Amines 757
15.13 Chemical Analyses for Aldehydes and Ketones 663 18.5 Reactions of Amines 765
18.6 Reactions of Amines with Nitrous Acid 767
16 18.7 Replacement Reactions of Arenediazonium Salts 769

18.8 Coupling Reactions of Arenediazonium Salts 772
18.9 Reactions of Amines with Sulfonyl Chlorides 774
Aldehydes and Ketones II. 18.10 Synthesis of Sulfa Drugs 775
Aldol Reactions 677 18.11 Eliminations Involving Ammonium Compounds 776
18.12 The Cope Elimination 777
16.1 The Acidity of the ` Hydrogens 18.13 Summary of Preparations and Reactions of
of Carbonyl Compounds: Enolate Anions 677 Amines 777
16.2 Keto and Enol Tautomers 678
16.3 Reactions via Enols and Enolates 679
16.4 Aldol Reactions: Addition of Enolates and Enols
to Aldehydes and Ketones 685
19
16.5 Crossed Aldol Condensations 690
16.6 Cyclizations via Aldol Condensation 696
Phenols and Aryl Halides 787
16.7 Lithium Enolates 697 19.1 Structure and Nomenclature of Phenols 787
19.2 Naturally Occurring Phenols 788
17 19.3 Physical Properties of Phenols

19.4 Synthesis of Phenols 789
789
19.5 Reactions of Phenols as Acids 791

Carboxylic Acids and Their 19.6 Other Reactions of the O—H Group of Phenols 794
Derivatives 709 19.7 Cleavage of Alkyl Aryl Ethers 795
19.8 Reactions of the Benzene Ring of Phenols 795
17.1 Introduction 709
19.9 The Claisen Rearrangement 797
17.2 Nomenclature and Physical Properties 710
19.10 Quinones 798
17.3 Preparation of Carboxylic Acids 715
19.11 Aryl Halides and Nucleophilic Aromatic Substitution 799
17.4 Acyl Substitution: Nucleophilic Addition–Elimination at
the Acyl Carbon 717
17.5 Acyl Chlorides 719
17.6 Carboxylic Acid Anhydrides 721 20
17.7 Esters 722
17.8 Amides 727 Carbohydrates 811
17.9 Derivatives of Carbonic Acid 733
17.10 Decarboxylation of Carboxylic Acids 735
20.2 Monosaccharides 814
17.11 Chemical Tests for Acyl Compounds 738
20.3 Mutarotation 818
17.12 Summary of the Reactions of Carboxylic Acids
20.4 Glycoside Formation 819
and Their Derivatives 741
20.5 Other Reactions of Monosaccharides 821
20.6 Oxidation Reactions of Monosaccharides 824
18 20.7 Reduction of Monosaccharides: Alditols 829
20.8 Reactions of Monosaccharides with
Amines 751 Phenylhydrazine: Osazones 830
20.9 Synthesis and Degradation of Monosaccharides 831
18.1 Nomenclature 751 20.10 The d Family of Aldoses 832
xxiii

20.11 Fischer’s Proof of the Configuration of d-(+)-
Glucose 832
20.12 Disaccharides 835
23
20.13 Polysaccharides 837 Reactions of Nitrene and
20.14 Other Biologically Important Sugars 842 Electron Deficient Oxygen 897
20.15 Sugars that Contain Nitrogen 842
20.16 Carbohydrate Antibiotics 844 23.1 Migration to Electron Deficient Nitrogen 897
23.2 Nitrene Formation 897
23.3 Hofmann—Curtius—Lossen—Schmidt Group
21 of Rearrangements 898
23.4 Curtius Reaction 899
23.5 Schmidt Reaction 899
Amino Acids and Proteins 851 23.6 Hofmann-Bromamide Reaction or Hofman
Rearrangement 900
23.7 Beckmann Rearrangement 902
21.2 Amino Acids 852
23.8 Stieglitz Rearrangement 904
21.3 Synthesis of `-Amino Acids 858
21.4 Polypeptides and Proteins 860
21.5 Primary Structure of Polypeptides and
Proteins 862 24
21.6 Secondary, Tertiary, and Quaternary Structures
of Proteins 863 Polymers 911
24.1 Some Terms Related to Polymers 911
22 24.2 Classification of Polymers 912

24.3 Types of Polymerization Reactions 915
24.4 Natural Rubber 922
Carbene and 24.5 Synthetic Rubbers 924
Carbenoids 871 24.6 Molecular Mass of Polymers 924
24.7 Biodegradable Polymers 925
22.1 Introduction 871 24.8 Polymers of Commercial Importance 925
22.2 Existence of carbenes 871
22.3 Formation of Carbenes 871 Appendix A A-1
22.4 Types of Carbenes 873 Appendix B B-1
22.5 Reactions of Carbenes 873 JEE Advanced Paper 2018 P-1
22.6 Rearrangement in Carbenes 887 JEE Main Papers 2019 P-27
Glossary G-1
Index I-1
xxiv


Cl H
1 H Cl
The Basics:
C C
C C
Bonding and
Cl H Cl H
cis-1,2-Dichloroethene trans-1,2-Dichloroethene
Molecular Structure Contents

1.1 | D
evelopment of the Science
of Organic Chemistry
1.2 | Atomic Structure
1.3 | The Structural Theory of
Organic Chemistry
1.4 | Chemical Bonds: The Octet
Rule
Organic chemistry is a part of our lives at every moment. Organic
1.5 | Resonance Theory
molecules comprise the tissue of plants as mighty as the redwoods,
1.6 | Hyperconjugation
convey signals from one neuron to the next in animals, store the
1.7 | The Structure of Methane
genetic information of life, and are the food we eat each day. The
and Ethane: sp3
growth of living things from microbes to elephants rests on organic
Hybridization
reactions, and organic reactions provide the energy that drives our
1.8 | The Structure of Ethene
muscles and our thought processes.
(Ethylene): sp2 Hybridization
Our lives depend on organic chemistry in many other ways as
1.9 | The Structure of Ethyne
well. Every article of clothing we wear is a product of organic chem-
(Acetylene): sp Hybridization
istry, whether the fibers are natural or synthetic. Hardly a minute
1.10 | HOW TO Interpret and Write
goes by when we’re not using something made of organic molecules,
Structural Formulas
such as a pen, a computer keyboard, a music player, or a cel-
lular phone. We view display screens made of organic liquid crystal
arrays. Natural organic polymers comprise wood and the paper we
read. Natural and synthetic organic molecules enhance our health.
There is not a single aspect of our lives that is not in some way
dependent on organic chemistry. But what is organic chemistry?
Organic chemistry is the chemistry of compounds that contain
the element carbon.
Clearly, carbon compounds are central to life on this planet.
Carbon as an element, however, has its origin elsewhere.
1.1 | D
EVELOPMENT OF THE SCIENCE OF
ORGANIC CHEMISTRY
The science of organic chemistry began to flower with the demise of
a nineteenth century theory called vitalism. According to vitalism,
organic compounds were only those that came from living organ-
isms, and only living things could synthesize organic compounds
through intervention of a vital force. Inorganic compounds were
considered those compounds that came from nonliving sources.
2 Chapter 1 The Basics: Bonding and Molecular Structure
Friedrich Wöhler, however, discovered in 1828 that an organic compound called urea (a constituent of urine) could
be made by evaporating an aqueous solution of the inorganic compound ammonium cyanate. With this discovery, the
synthesis of an organic compound, began the evolution of organic chemistry as a scientific discipline.
O
heat
NH4 + NCO− C
H2N NH2
Ammonium cyanate Urea
Despite the demise of vitalism in science, the word “organic” is still used today by some people to mean “coming from
living organisms” as in the terms “organic vitamins” and “organic fertilizers.” The commonly used term “organic food”
means that the food was grown without the use of synthetic fertilizers and pesticides. An “organic vitamin” means to
these people that the vitamin was isolated from a natural source and not synthesized
OH by a chemist. While there are sound arguments to be made against using food con-
O taminated with certain pesticides, while there may be environmental benefits to be
O C CH CH2OH
CH obtained from organic farming, and while “natural” vitamins may contain beneficial
C C substances not present in synthetic vitamins, it is impossible to argue that pure “natural”
vitamin C, for example, is healthier than pure “synthetic” vitamin C, since the two
HO OH
substances are identical in all respects. In science today, the study of compounds
Vitamin C from living organisms is called natural products chemistry.
1.2 | ATOMIC STRUCTURE

Before we begin our study of the compounds of carbon we need to Practice some basic but familiar ideas about the
chemical elements and their structure.
• The compounds we encounter in chemistry are made up of elements combined in different proportions.
• Elements are made up of atoms. An atom consists of a dense, positively charged nucleus containing protons and
neutrons and a surrounding cloud of electrons.
Each proton of the nucleus bears one positive charge; electrons bear one negative charge. Neutrons are electrically
neutral; they bear no charge. Protons and neutrons have nearly equal masses (approximately 1 atomic mass unit each)
and are about 1800 times as heavy as electrons. Most of the mass of an atom, therefore, comes from the mass of the
nucleus; the atomic mass contributed by the electrons is negligible. Most of the volume of an atom, however, comes
from the electrons; the volume of an atom occupied by the electrons is about 10,000 times larger than that of the
nucleus.
The elements commonly found in organic molecules are carbon, hydrogen, nitrogen, oxygen, phosphorus, and
sulfur, as well as the halogens: fluorine, chlorine, bromine, and iodine.
Each element is distinguished by its atomic number (Z), a number equal to the number of protons in its nucleus.
Because an atom is electrically neutral, the atomic number also equals the number of electrons surrounding the
nucleus.
1.2A Isotopes
Before we leave the subject of atomic structure and the periodic table, we need to examine one other observation: the
existence of atoms of the same element that have different masses.
For example, the element carbon has six protons in its nucleus giving it an atomic number of 6. Most carbon atoms
also have six neutrons in their nuclei, and because each proton and each neutron contributes one atomic mass unit
(1 amu) to the mass of the atom, carbon atoms of this kind have a mass number of 12 and are written as 12C.
• Although all the nuclei of all atoms of the same element will have the same number of protons, some atoms of the
same element may have different masses because they have different numbers of neutrons. Such atoms are called
isotopes.
1.3 The Structural Theory of Organic Chemistry 3
For example, about 1% of the atoms of elemental carbon have nuclei containing 7 neutrons, and thus have a mass
number of 13. Such atoms are written 13C. A tiny fraction of carbon atoms have 8 neutrons in their nucleus and a mass
number of 14. Unlike atoms of carbon-12 and carbon-13, atoms of carbon-14 are radioactive. The 14C isotope is used in
carbon dating. The three forms of carbon, 12C, 13C, and 14C, are isotopes of one another.
Most atoms of the element hydrogen have one proton in their nucleus and have no neutron. They have a mass
number of 1 and are written 1H. A very small percentage (0.015%) of the hydrogen atoms that occur naturally, how-
ever, have one neutron in their nucleus. These atoms, called deuterium atoms, have a mass number of 2 and are written
2
H. An unstable (and radioactive) isotope of hydrogen, called tritium (3H), has two neutrons in its nucleus.
Practice Problem 1.1

There are two stable isotopes of nitrogen, 14N and 15N. How many protons and neutrons does each isotope have?
1.2B Valence Electrons

We discuss the electron configurations of atoms in more detail in Section 1.10. For the moment we need only to point
out that the electrons that surround the nucleus exist in shells of increasing energy and at increasing distances from
the nucleus. The most important shell, called the valence shell, is the outermost shell because the electrons of this shell
are the ones that an atom uses in making chemical bonds with other atoms to form compounds.
• How do we know how many electrons an atom has in its valence shell? We look at the periodic table. The number
of electrons in the valence shell (called valence electrons) is equal to the group number of the atom. For example,
carbon is in group IVA and carbon has four valence electrons; oxygen is in group VIA and oxygen has six valence
electrons. The halogens of group VIIA all have seven electrons.

How many valence electrons does each of the following atoms have?
(a) Na (b) Cl (c) Si
(d) B (e) Ne (f) N
1.3 | THE STRUCTURAL THEORY OF ORGANIC CHEMISTRY

Between 1858 and 1861, August Kekulé, Archibald Scott Couper, and Alexander M. Butlerov, working independently,
laid the basis for one of the most important theories in chemistry: the structural theory.
Two central premises are fundamental:
1. The atoms in organic compounds can form a fixed number of bonds using their outermost shell (valence) elec-
trons. Carbon is tetravalent; that is, carbon atoms have four valence electrons and can form four bonds. Oxygen is
divalent, and hydrogen and (usually) the halogens are monovalent:
C O H CI
Carbon atoms Oxygen atoms Hydrogen and halogen

are tetravalent are divalent atoms are monovalent
2. A carbon atom can use one or more of its valence electrons to form bonds to other carbon atoms:
Carbon–carbon bonds
C C C C C C
Single bond Double bond Triple bond

In his original publication Couper represented these bonds by lines much in the same way that most of the formulas
in this book are drawn. In his textbook (published in 1861), Kekulé gave the science of organic chemistry its modern
definition: a study of the compounds of carbon.
1.3A Isomers: The Importance of Structural Formulas

The structural theory allowed early organic chemists to begin to solve a fundamental problem that plagued them: the
problem of isomerism. These chemists frequently found examples of different compounds that have the same molecu-
lar formula. Such compounds are called isomers.
Helpful Hint: Terms and concepts that are fundamentally important to your learning organic chemistry
are set in bold blue type. You should learn them as they are introduced. These terms are also defined in the
glossary.
Let us consider an example involving two compounds that have practical uses: acetone, used in nail polish remover
and as a paint solvent, and propylene oxide, used with seaweed extracts to make food-grade thickeners and foam stabi-
lizers for beer (among other applications). Both of these compounds have the molecular formula C3H6O and therefore
the same molecular weight. Yet acetone and propylene oxide have distinctly different boiling points and chemical
reactivity that, as a result, lend themselves to distinctly different practical applications. Their shared molecular formula
simply gives us no basis for understanding the differences between them. We must, therefore, move to a consideration
of their structural formulas.
On examining the structures of acetone and propylene oxide several key aspects are clearly different (Fig. 1.1).
Acetone contains a double bond between the oxygen atom and the central carbon atom. Propylene oxide does not
contain a double bond, but has three atoms joined in a ring. The connectivity of the atoms is clearly different in acetone
and propylene oxide. Their structures have the same molecular formula but a different constitution. We call such com-
pounds constitutional isomers.
Acetone Propylene oxide
H O H H O
H C C C H H C C C H
H H H H H
Figure 1.1 Ball-and-stick models and chemical formulas show the different structures of acetone and propylene
oxide.
1. Constitutional isomers are different compounds that have the same molecular formula but differ in the sequence
in which their atoms are bonded, that is, in their connectivity.
2. Constitutional isomers usually have different physical properties (e.g., melting point, boiling point, and density)
and different chemical properties (reactivity).
1.4 Chemical Bonds: The Octet Rule 5
Solved Problem 1.1

There are two constitutional isomers with the formula H H H H
C2H6O. Write structural formulas for these isomers.
H C O C H H C C O H
Answer
H H H H
If we recall that carbon can form four covalent bonds,
oxygen can form two, and hydrogen only one, we can Dimethyl ether Ethanol
arrive at the following constitutional isomers.
It should be noted that these two isomers are clearly differ-
ent in their physical properties. At room temperature and
1 atm pressure, dimethyl ether is a gas. Ethanol is a liquid.
1.3B The Tetrahedral Shape of Methane

In 1874, the structural formulas originated by Kekulé, Couper, and
H
Butlerov were expanded into three dimensions by the independent
work of J. H. van’t Hoff and J. A. Le Bel. van’t Hoff and Le Bel pro-
posed that the four bonds of the carbon atom in methane, for exam- 109°28´
ple, are arranged in such a way that they would point toward the
C
corners of a regular tetrahedron, the carbon atom being placed at its H
H
center (Fig. 1.2). The necessity for knowing the arrangement of the
atoms in space, taken together with an understanding of the order in H
which they are connected, is central to an understanding of organic
Figure 1.2 The tetrahedral structure of
chemistry, and we shall have much more to say about this later, in
methane.
Chapters 4 and 5.
1.4 | CHEMICAL BONDS: THE OCTET RULE

The first explanations of the nature of chemical bonds were advanced by G. N. Lewis (of the University of California,
Berkeley) and W. Kössel (of the University of Munich) in 1916. Two major types of chemical bonds were proposed:
1. Ionic (or electrovalent) bonds are formed by the transfer of one or more electrons from one atom to another to
create ions.
2. Covalent bonds result when atoms share electrons.
The central idea in their work on bonding is that atoms without the electronic configuration of a noble gas generally
react to produce such a configuration because these configurations are known to be highly stable. For all of the noble
gases except helium, this means achieving an octet of electrons in the valence shell.
• The tendency for an atom to achieve a configuration where its valence shell contains eight electrons is called the
octet rule.
The concepts and explanations that arise from the original propositions of Lewis and Kössel are satisfactory for expla-
nations of many of the problems we deal with in organic chemistry today. For this reason we shall Practice these two
types of bonds in more modern terms.
1.4A Ionic Bonds

Atoms may gain or lose electrons and form charged particles called ions.
• An ionic bond is an attractive force between oppositely charged ions.
One source of such ions is a reaction between atoms of widely differing electronegativities (Table 1.1).
Table 1.1 Electronegativities of Some of the Elements
Increasing electronegativity
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0 Increasing

electronegativity
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Br
0.8 2.8
• Electronegativity is a measure of the ability of an atom to attract electrons.

• Electronegativity increases as we go across a horizontal row of the periodic table from left to right and it increases
as we go up a vertical column (Table 1.1).
Helpful Hint: We will use electronegativity frequently as a tool for understanding the properties and reactivity of
organic molecules.
An example of the formation of an ionic bond is the reaction of lithium and fluorine atoms:
–
+
Li + F Li + F
Lithium, a typical metal, has a very low electronegativity; fluorine, a nonmetal, is the most electronegative element of
all. The loss of an electron (a negatively charged species) by the lithium atom leaves a lithium cation (Li+); the gain of
an electron by the fluorine atom gives a fluoride anion (F-).
• Ions form because atoms can achieve the electronic configuration of a noble gas by gaining or losing electrons.
The lithium cation with two electrons in its valence shell is like an atom of the noble gas helium, and the fluoride anion
with eight electrons in its valence shell is like an atom of the noble gas neon. Moreover, crystalline lithium fluoride
forms from the individual lithium and fluoride ions. In this process negative fluoride ions become surrounded by posi-
tive lithium ions, and positive lithium ions by negative fluoride ions. In this crystalline state, the ions have substantially
lower energies than the atoms from which they have been formed. Lithium and fluorine are thus “stabilized” when
they react to form crystalline lithium fluoride.
We represent the formula for lithium fluoride as LiF, because that is the simplest formula for this ionic
compound.
Ionic substances, because of their strong internal electrostatic forces, are usually very high melting solids, often
having melting points above 1000°C. In polar solvents, such as water, the ions are solvated (see Section 2.13D), and
such solutions usually conduct an electric current.
• Ionic compounds, often called salts, form only when atoms of very different electronegativities transfer electrons
to become ions.
1.5 Resonance Theory 7
1.4B Covalent Bonds and Lewis Structures

When two or more atoms of the same or similar electronegativities react, a complete transfer of electrons does not
occur. In these instances the atoms achieve noble gas configurations by sharing electrons.
• Covalent bonds form by sharing of electrons between atoms of similar electronegativities to achieve the configura-
tion of a noble gas.
• Molecules are composed of atoms joined exclusively or predominantly by covalent bonds.
Molecules may be represented by electron-dot formulas or, more conveniently, by bond formulas where each pair of
electrons shared by two atoms is represented by a line. Some examples are shown here:
1. Hydrogen, being in group IA of the periodic table, has one valence electron. Two hydrogen atoms share electrons
to form a hydrogen molecule, H2.
H2 H + H HH usually written H—H
2. Because chlorine is in group VIIA, its atoms have seven valence electrons. Two chlorine atoms can share electrons
(one electron from each) to form a molecule of Cl2.
Cl2 Cl + Cl Cl Cl usually written Cl —Cl
3. And a carbon atom (group IVA) with four valence electrons can share each of these electrons with four hydrogen
atoms to form a molecule of methane, CH4.
H
H
CH4 C + 4H H C H usually written H C H
H
H
These formulas are often called Lewis structures; in writing them we show only the electrons of the valence shell.
4. Atoms can share two or more pairs of electrons to form multiple covalent bonds. For example, two nitrogen atoms
possessing five valence electrons each (because nitrogen is in group VA) can share electrons to form a triple bond
between them.
N2 N N usually written N N
5. Ions, themselves, may contain covalent bonds. Consider, as an example, the ammonium ion.
H
+
H+
+
NH4 H N H usually written H N H
H
H

Consider the following compounds and decide whether the bond in them would be ionic or covalent.
(a) LiH (b) KCl (c) F2 (d) PH3
1.5 | RESONANCE THEORY

Many times more than one equivalent Lewis structure can be written for a molecule or ion. Consider, for example, the
carbonate ion (CO2-
3 ). We can write three different but equivalent structures, 1–3:
O O − O −
C C C
− O O − − O O O O −
1 2 3
Notice two important features of these structures. First, each atom has the noble gas configuration. Second,
and this is especially important, we can convert one structure into any other by changing only the posi-
tions of the electrons. We do not need to change the relative positions of the atomic nuclei. For example, if we
move the electron pairs in the manner indicated by the curved arrows in structure 1, we change structure 1 into
structure 2:
O O −
C becomes C
− O O − − O O
1 2
In a similar way we can change structure 2 into structure 3:
O − O −
C becomes C
− O O O O −
2 3
Structures 1–3, although not identical on paper, are equivalent. None of them alone, however, fits important data about
the carbonate ion.
Helpful Hint: Curved arrows (Section 3.5) show movement of electron pairs, not atoms. The tail of the arrow begins
at the current position of the electron pair. The head of the arrow points to the location where the electron pair will
be in the next structure. Curved-arrow notation is one of the most important tools that you will use to understand
organic reactions.
X-Ray studies have shown that carbon–oxygen double bonds are shorter than single bonds. The same kind of study
of the carbonate ion shows, however, that all of its carbon–oxygen bonds are of equal length. One is not shorter than
the others as would be expected from representations 1, 2, and 3. Clearly none of the three structures agrees with this
evidence. In each structure, 1–3, one carbon–oxygen bond is a double bond and the other two are single bonds. None
of the structures, therefore, is correct. How, then, should we represent the carbonate ion?
One way is through a theory called resonance theory. This theory states that whenever a molecule or ion can
be represented by two or more Lewis structures that differ only in the positions of the electrons, two things will
be true:
1. None of these structures, which we call resonance structures or resonance contributors, will be a realistic repre-
sentation for the molecule or ion. None will be in complete accord with the physical or chemical properties of the
substance.
2. The actual molecule or ion will be better represented by a hybrid (average) of these structures.
• Resonance structures, then, are not real structures for the actual molecule or ion; they exist only on paper. As such,
they can never be isolated. No single contributor adequately represents the molecule or ion. In resonance theory
we view the carbonate ion, which is, of course, a real entity, as having a structure that is a hybrid of the three hypo-
thetical resonance structures.
What would a hybrid of structures 1–3 be like? Look at the structures and look especially at a particular carbon–
oxygen bond, say, the one at the top. This carbon–oxygen bond is a double bond in one structure (1) and a single bond
in the other two (2 and 3). The actual carbon–oxygen bond, since it is a hybrid, must be something in between a dou-
ble bond and a single bond. Because the carbon–oxygen bond is a single bond in two of the structures and a double
bond in only one, it must be more like a single bond than a double bond. It must be like a one and one-third bond. We
could call it a partial double bond. And, of course, what we have just said about any one carbon–oxygen bond will be
equally true of the other two. Thus all of the carbon–oxygen bonds of the carbonate ion are partial double bonds, and
all are equivalent. All of them should be the same length, and this is exactly what experiments tell us. The bonds are all
1.28 Å long, a distance which is intermediate between that of a carbon–oxygen single bond (1.43 Å) and that of a
carbon–oxygen double bond (1.20 Å). One angstrom equals 1 × 10-10 meter.
• One other important point: By convention, when we draw resonance structures, we connect them by double-
headed arrows (↔) to indicate clearly that they are hypothetical, not real. For the carbonate ion we write them
this way:
− −
O O O
C C C
− O O − − O O O O −
We should not let these arrows, or the word “resonance,” mislead us into thinking that the carbonate ion fluctuates
between one structure and another. These structures individually do not represent reality and exist only on paper;
therefore, the carbonate ion cannot fluctuate among them because it is a hybrid of them.
• It is also important to distinguish between resonance and an equilibrium.
Helpful Hint: Each type of arrow in organic chemistry (e.g., , , and ↔) has a specific meaning. It is important
that you use each type of arrow only for the purpose for which it is defined.
In an equilibrium between two, or more, species, it is quite correct to think of different structures and moving (or
fluctuating) atoms, but not in the case of resonance (as in the carbonate ion). Here the atoms do not move, and the
“structures” exist only on paper. An equilibrium is indicated by  and resonance by ↔.
How can we write the structure of the carbonate ion in a way that will indicate its actual structure? We may do
two things: we may write all of the resonance structures as we have just done and let the reader mentally fashion the
hybrid, or we may write a non-Lewis structure that attempts to represent the hybrid. For the carbonate ion we might
do the following:
− −
Od − O O O
C C C C
d−
O Od − − O O − − O O O O −
The bonds in the structure on the left are indicated by a combination of a solid line and a dashed line. This is to indicate
that the bonds are something in between a single bond and a double bond. As a rule, we use a solid line whenever a
bond appears in all structures, and a dashed line when a bond exists in one or more but not all. We also place a d- (read
partial minus) beside each oxygen to indicate that something less than a full negative charge resides on each oxygen
atom. (In this instance each oxygen atom has two-thirds of a full negative charge.) Calculations from theory show the
equal charge density at each oxygen in the carbonate anion.
1.5A HOW TO Write Resonance Structures

1. Resonance structures exist only on paper. Although they have no real existence of their own, resonance structures
are useful because they allow us to describe molecules and ions for which a single Lewis structure is inadequate.
We write two or more Lewis structures, calling them resonance structures or resonance contributors. We con-
nect these structures by double-headed arrows (↔), and we say that the real molecule or ion is a hybrid of all
of them.
2. We are only allowed to move electrons in writing resonance structures. The positions of the nuclei of the atoms
must remain the same in all of the structures. Structure 3 is not a resonance structure of 1 or 2, for example,
because in order to form it we would have to move a hydrogen atom and this is not permitted:
− + +
CH3 CH CH CH2 CH3 CH CH CH2 CH2 CH2 CH CH2
1 2 3
These are resonance This is not a proper

structures. resonance structure
of 1 or 2 because
a hydrogen atom
has been moved.
Generally speaking, when we move electrons, we move only those of multiple bonds (as in the example above)
and those of nonbonding electron pairs.
3. While drawing the resonance structures, a lone pair can be moved in the same manner as an electron. The carbon
bearing the lone pair and negative charge acts as a donor atom, while the carbon atom of a carbonyl group (C=O)
serves as the acceptor atom. A molecule that bears a negative charge next to the carbonyl group is termed as an
enolate. The resonance involving a lone pair of electrons or a positive charge next to the bond is also exhibited in
many cases
O −
O
C
H3C CH2 C
− H3C CH2
However, the lone pair does not necessarily have to be on an atom that bears a formal negative charge as indi-
cated in the previous point. For example:
O −
O
C
H3C NH2 C
H3C NH2
+
Phosphorous is a third-row element and therefore, it can expand its octet to accomodate 10 valence electrons.
It is the only atom commonly encountered in organic chemistry that routinely expands its octet to accomodate
10 valence electrons. The oxygen atoms can lend a lone pair each to the phosphorus and atom and the following
resonance structures are possible:
−
O O
−
O P O O P O
− O −
O
− −
−
O O
− −
O P O O P O
−
O O
−
The resonance of phosphate ion has important biochemical consequences.

4. All of the structures must be proper Lewis structures. We should not write structures in which carbon has five
bonds, for example:
This is not a proper resonance
structure for methanol because
H carbon has five bonds.
Elements of the
H −
C O+ H first major row of the periodic
table cannot have more than
H
eight electrons in their valence
shell.
5. The energy of the resonance hybrid is lower than the energy of any contributing structure. Resonance stabilizes a
molecule or ion. This is especially true when the resonance structures are equivalent. Chemists call this stabiliza-
tion resonance stabilization.
6. Equivalent resonance structures make equal contributions to the hybrid, and a system described by them has a
large resonance stabilization. The following cation, for example, is more stable than either contributing resonance
structure taken separately:
+ + 1 1
+ +
CH2 CH CH CH2 CH CH2 2 CH2 CH CH2 2
2
4 5
Contributing resonance structures Resonance hybrid
Benzene is highly resonance stabilized because it is a hybrid of the two equivalent forms that follow:
or
Resonance structures Representation

for benzene of hybrid
7. The more stable a structure is (when taken by itself), the greater is its contribution to the hybrid.
How do we decide whether one resonance structure is more stable than another? The following rules will help us:
1. The more covalent bonds a structure has, the more stable it is. This is exactly what we would expect because we
know that forming a covalent bond lowers the energy of atoms. This means that of the following structures for
1,3-butadiene, 6 is by far the most stable and makes by far the largest contribution because it contains one more
bond.
− −
+ +
CH2 CH CH CH2 CH2 CH CH CH2 CH2 CH CH CH2
6 7 8
This structure is the

most stable because it
contains more covalent
bonds.
These structures also illustrate two other considerations:

2. Structures in which all of the atoms have a complete valence shell of electrons (i.e., the noble gas structure) are
especially stable and make large contributions to the hybrid. Again, this is what we would expect from what we
know about bonding. This means, for example, that 10 makes a larger stabilizing contribution to the cation below
than 9 because all of the atoms of 10 have a complete valence shell.
+ +
CH2 O CH3 CH2 O CH3
9 10
Here this carbon Here the carbon atom

atom has only six has eight electrons.
electrons.
3. Charge separation decreases stability. It takes energy to separate opposite charges, and therefore a structure with
separated charges is less stable. Structure B for formaldehyde has separated plus and minus charges; therefore, on
this basis, too, it is the less stable contributor and makes a smaller contribution to the hybrid. Therefore, structures
in which opposite charges are separated have greater energy (lower stability) than those that have no charge
separation. This means that of the following two structures for vinyl chloride, structure 11 makes a larger contribu-
tion because it does not have separated charges. (This does not mean that structure 12 does not contribute to the
hybrid; it just means that the contribution made by 12 is smaller.)
−
CH2 CH Cl CH2 CH Cl +
11 12
4. Resonance contributors with negative charge on highly electronegative atoms are more stable than ones with
negative charge on less or nonelectronegative atoms. Conversely, resonance contributors with positive charge on
highly electronegative atoms are less stable than ones with positive charge on nonelectronegative atoms.
5. To predict the energies of the resonance structures, we consider the energy of resonance hybrid structure.
Resonance hybrid is the weighted average of the resonance contributors. The following structures are considered
relatively stable:
(i) Structures having filled octets for second row elements (C, N, O, F) are stable.
(ii) Structures having minimum number of formal charges and maximum number of bonds.
(iii) Structure in which negative charge is on the most electronegative atom (C < N < O).
(iv) Structure in which there is minimal charge separation while keeping the formal charges closer together.
Solved Problem 1.2
Answer
H2C CH3 H2C + CH3 H2C
+ CH3
N+ N N Structure (A) is most stable as it follows all guidelines as
CH3 CH3 CH3
per points (1) to (4).
Structure (B) is more stable as it violates point (1).
(A) (B) (C) Structure (C) is least stable for violating point (1).
Stability order is A > B > C
Which of the following structures is relatively stable?
Solved Problem 1.3

Predict the relative energies of the following resonating structures.
−
N N N
H3C C H3C C H3C C
O O O
+ +
(A) − (B) (C)
−
N N
H3C C H3C +
O + C
O
(D) (E)
Answer
Structure (A) follows all the guidelines as per points (1) Structure (C) violates points (2) and (3), because it
to (4) above. has two formal charges and carries a negative charge on
Structure (B) violates point (2) because it has two carbon atom, respectively.
formal charges.
Structure (D) violates points (1) and (2), because it Thus, the relative energies of the structures are of
has 6 e– on carbon atom and carries two formal charges, the order A << B < C << D < E and their relative con-
respectively. tribution to resonance hybrid is of the order A > B > C >
Structure (E) violates points (1), (2) and (4) because D > E.
it has 6 e− on carbon atom, carries two formal charges and
more charge separation than (D), respectively.
Solved Problem 1.4

The following is one way of writing the structure of the Since these structures differ from one another only in
nitrate ion: the positions of their electrons, they are resonance struc-
O− tures or resonance contributors. As such, no single struc-
ture taken alone will adequately represent the nitrate
N+ ion. The actual molecule will be best represented by
O O−
a hybrid of these three structures. We might write this
However, considerable physical evidence indicates that all hybrid in the following way to indicate that all of the
three nitrogen–oxygen bonds are equivalent and that they bonds are equivalent and that they are more than sin-
have the same length, a bond distance between that expected gle bonds and less than double bonds. We also indicate
for a nitrogen–oxygen single bond and a nitrogen–oxygen that each oxygen atom bears an equal partial negative
double bond. Explain this in terms of resonance theory. charge. This charge distribution corresponds to what we
find experimentally.
Answer −2
O3
We recognize that if we move the electron pairs in the
Hybrid structure for the
following way, we can write three different but equivalent 2
N+ −2 nitrate ion
− O O3
structures for the nitrate ion: 3
O − O O −
N+ N+ N+
O O− −O O− −O O
1.5B Schematic Energy Level Diagrams of Some Mesomeric Molecules/Ions

Energy diagrams of some resonating structures are given as follows. (Note: The downwards arrow marks the conven-
tional mesomeric energies and indicates energy level).
Example 1: Carboxylate ion
O O−
CH3 C CH3 C
Ο −
O
Energy
Carboxylate ion
Interpretation: The two equivalent resonating structures have the same energy.
Example 2: Carbonate ion

− −
O O O
− −
O C O C O C
− −
O O O
Energy
Carbonate ion
Interpretation: The three equivalent resonating structures have the same energy.
Example 3: Carbon dioxide
+ − − +
O C O O C O
Energy
O C O
Carbon dioxide
Interpretation: Polarized structures have higher energy because separation of opposite charges requires energy.
Example 4: Alkyl cyanate
i
− +
R N C O
+ −
R N C O
Energy
R N C O
Alkyl cyanate
Interpretation: Negative charge on the more electronegative element (oxygen) makes the structure more stable.
Example 5: Vinyl ether
− +
H2C CH O CH3
Energy
H2C CH O CH3
Vinyl ether
Interpretation: Separation of opposite charges requires energy.
Example 6: But-1,3-diene
+ −
H2C CH CH CH2
+ −
H2C CH CH CH2
Energy
H2C CH CH CH2
But-1,3-diene
Interpretation: Unlike charges must be closer to each other for the structure to be more stable.
Example 7: Ethanoic acid
−
CH3
+
O
C
O H (c)
−
O
CH3 C
O H (b)
Energy
CH3 O
C (a)
O H
Ethanoic acid
Interpretation: Structure (c) is unstable due to lesser covalent bonds and incomplete octet, while (b) is less stable than
(a) because of separation of opposite charges.
Solved Problem 1.5
The following Lewis/Kekulé structures (A)–(L) are isomeric (with molecular formula CN2H2).
H
H C N N H C N NH2 H2N C N C N N
H
(A) (B) (C) (D)
N C NH2 H2C N N H N C N H C N NH2

(E) (F) (G) (H)
N N CH2 H C N N H N N CH2 H N N C H
(I) (J) (K) (L)
Which of these structures match the following proper- 1. Which of the structures have no atoms with formal
ties? Indicate with letters (A) to (L). If no structure fits charge?
the property write the letter X. 2. Which of the structures have at least one nitrogen
atom with a (+) formal charge?
3. Which of the structures have at least one nitrogen 6. Which of the structures have electron deficient heavy
atom with a (−) formal charge? atoms (N or C)?
4. Which of the structures have at least one carbon
Answer
atom with a (+) formal charge?
5. Which of the structures have at least one carbon 1. (B,C,G); 2. (A,D,E,F,H,I,J); 3. (A,D,E,K,L);
atom with a (−) formal charge? 4. (K,L); 5. (F,H,I,J); 6. (B,I,K,L).
Solved Problem 1.6
Write the possible resonance structures for the following molecules. Show the direction of the movement of electrons
with the help of arrows.
O
O O
1. 2. − 17. + 18.
−
O O H
19. + O 20.
3. 4. −
+
−
5. 6. O+ 22.
21. +
O
O O +
23. 24.
7.
−
8. −
O +
−
O +
N N 26.
9. 10. − 25. +
− O
O O − O
− O 27. N 28.
11. − 12. N
−
− O O
N H
13. − 14. 29. +
30. +
15. 16. +
Answer
O −
O O −
O
O O O O−
1. 3.
−
−
−
O O
2. −
4. − −
5. 15.
−
+ +
+
6. −
16.
−
−
O +
O
O O
7. 17. +
−
O O
O O O O
−
−
8. 18.
− −
−
O
H +
N − O OH
9. N 19.
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10. O− 20. +
O + +
−
O O −
O O O O O+ O
21. + +
11. − O
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12. N O N O −
N O 22. + +
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Another random document with
no related content on Scribd:
matkalle.» Sydämessään ei hän kuitenkaan tuntenut tarpeeksi
voimaa voidaksensa pysyä kotona; hän halusi jotakin tekosyytä. Hän
olisi mielellään ollut hyvin sairas. Hän käyskeli huoneessaan,
istuutui, otti jonkun kirjan, mutta ei voinut tavuakaan lukea. Sitten
hän meni pianon ääreen, mutta ei jaksanut sitä edes avata. Vihelteli,
katseli pilviä ja tahtoi lukea ikkunansa edessä kasvavat poppelipuut.
Vihdoin hän kääntyi katsomaan kelloa ja huomasi, ettei ollut saanut
vielä kolmeakaan minuuttia kulumaan. »Minä en voi olla häntä
rakastamatta», huusi hän hammasta purren ja jalkaa polkien, »hän
hallitsee minua, ja minä olen hänen orjansa, niinkuin Massigny on
ollut ennen minua! No, tottele siis, kurja mies, koska sinulla ei ole
tarpeeksi rohkeutta murtaaksesi kahleet, joita vihaat!»
Lakkiinsa tarttuen hän läksi suinpäin ulos.
Kun joku intohimo meitä ahdistaa, tunnemme tavallisesti

jonkinlaista itserakasta lohdutusta voidessamme katsella
heikkouttamme ylpeytemme kukkulalta. »Minä olen tosin heikko»,
sanomme me, »mutta jos minä oikein tahtoisin…!»
Verkkaisin askelin hän kulki polkua, joka vei puiston portille, ja jo

kaukaa hän näki valkean olennon, joka kuvastui puiden tummempaa
taustaa vasten. Kädellään liehutti siellä nainen nenäliinaa ikäänkuin
merkiksi. Saint-Clairin sydän löi ankarasti, ja hänen polvensa
vapisivat; hän ei jaksanut puhua ja hän oli käynyt niin araksi, että
pelkäsi kreivittären näkevän jo kasvoista hänen olevan huonolla
tuulella.
Hän tarttui ojennettuun kätöseen, suuteli lemmittyänsä otsalle,

tämä kun oitis heittäysi hänen syliinsä, ja sitten hän seurasi
kreivitärtä asuntoon mykkänä ja tuskin jaksaen pidättää huokauksia,
jotka näyttivät tahtovan hänen rintansa halkaista.
Yksi ainoa kynttilä valaisi kreivittären budoaaria. Molemmat
istuutuivat. Saint-Clair tarkasti ystävättärensä tukkakiehkuraa; yksi
ainoa ruusu vain suortuvissa. Edellisenä iltana oli Auguste tuonut
hänelle kauniin englantilaisen piirroksen: »Portlandin herttuatar,
Leslyn mukaan piirretty» (herttuatar laittoi samalla tapaa hiuksensa),
eikä ollut antaessaan sanonut muuta kuin nämä sanat: »Minua
miellyttää enemmän tämä yksinkertainen ruusu kuin teidän
mutkalliset hiuskiehkuranne.» Hän ei myöskään pitänyt jalokivistä,
vaan ajatteli kuin entinen lordi, joka kömpelösti lausui: »Koristetuista
naisista ja loimella peitetyistä hevosista ei pirukaan ota selvää.»
Leikitellessään viime yönä kreivittären kaulassa riippuvalla
helmivyöllä (puhuessaan piti hänellä näet aina olla jotakin
hypisteltävänä) oli hän sanonut: »Jalokivet eivät kelpaa muuhun kuin
vikoja peittämään. Te olette liian ihana, Matilde, sellaisia
tarvitaksenne.» Tänä iltana oli kreivitär, joka piti muistissaan hänen
joutavimmatkin sanansa, jättänyt pois kaikki sormuksensa,
helmivyönsä, korva- ja rannerenkaansa. — Naisen puvussa hän
huomasi ennen kaikkea jalkineet, ja hänellä niinkuin useilla muillakin
oli tässä suhteessa oma makunsa. Oli satanut vahvasti
auringonlaskun edellä. Ruohikko oli vielä vallan märkä; kreivitär oli
kuitenkin tullut kostean nurmikon poikki silkkisukissa ja
satiinikengissä… Jos hän vielä sairastuu?
— Hän rakastaa minua, mietti Saint-Clair itsekseen.
Ja hän huokasi omalle hulluudelleen, katseli Matildea vastoin

tahtoansa hymyillen ja häilyi huonon tuulensa ja sen nautinnon
välillä, minkä tunnemme nähdessämme ihanan naisen koettavan
miellyttää meitä kaikilla noilla pikku turhuuksilla, joille rakastavaiset
antavat niin suuren arvon.
Kreivittären loistavat kasvot taas ilmaisivat rakkautta ja leikillistä
ilkeyttä, joka teki hänet vain sitä suloisemmaksi. Hän otti jotakin
eräästä vernissatusta japanilaisesta lippaasta ja sanoi, ojentaen
pienen, nyrkiksi puristetun kätösensä, jossa hän piti jotakin esinettä
piilotettuna:
— Toissa iltana minä särin teidän kellonne. Tässä se nyt on

korjattuna.
Hän antoi kellon Augustelle ja katseli häntä samalla hellästi ja

veitikkamaisesti purren alahuultaan ikäänkuin estääksensä itseään
nauramasta. Voi, elävä Jumala, kuinka hänen hampaansa olivat
kauniit ja kuinka ne loistivat valkeina huulten punertavien ruusujen
rinnalla! (Mies, joka kylmästi ottaa vastaan ihanan naisen veikistelyt,
on aina tyhmän näköinen.)
Saint-Clair kiitti häntä, otti kellon käteensä ja yritti pistää sen

taskuunsa.
— Katsokaahan toki ensin, jatkoi kreivitär, aukaiskaa se ja

katsokaa, onko se hyvin korjattu. Te kun olette niin taitava ja olette
polyteknikossakin opiskellut, voitte kai kyllä nähdä sen.
— Oh, en minä paljoa sellaisista ymmärrä, sanoi Saint-Clair.
Hajamielisesti hän avasi kellonkuoren. Kuinka suuri oli hänen

hämmästyksensä, kun hän näki, että rouva de Coursyn pienoiskuva
oli maalattu kuoren pohjaan! Vieläkö hän voi nurista? Hänen otsansa
kirkastuikin, eikä hän enää Massignyta ajatellut; hän ei muistanut
muuta kuin että hän seisoi hurmaavan naisen vieressä ja että tämä
nainen häntä jumaloi.
*****
Leivonen, tuo aamukoin airut, alkoi juuri liverrellä, ja pitkät, vaaleat

valonkielekkeet juovittelivat hattaroita itäisellä taivaanrannalla. Siihen
aikaan vuorokaudesta sanoi Romeo hyvästi Julialle, ja se on se
klassillinen hetki, jolloin kaikkien rakastavien pitää erota.
Saint-Clair seisoi erään uunin edessä puistonavain kädessä ja

tuijotteli tuimasti etruskilaiseen vaasiin, josta jo on ollut puhe.
Sielunsa pohjassa oli hänellä vieläkin jonkinlaista kaunaa sitä
kohtaan. Kuitenkin oli hän hyvällä tuulella, ja se luonnollinen ajatus,
että Thémines valehteli, alkoi syntyä hänen aivoissaan. Sillä aikaa
kuin kreivitär, joka tahtoi saattaa häntä puiston portille asti, kääri
shaalia päänsä ympärille, naputteli hän hiljalleen avaimellansa tuota
vihattua vaasia koventaen vähitellen lyöntejänsä, niin että täytyi
luulla hänen pian aikovan rikkoa sen pirstaleiksi.
— Olkaa jumalan tähden varovampi, tehän rikotte minun kauniin

etruskilaisen vaasini! huudahti Matilde.
Ja hän tempasi Augustelta avaimen pois.
Saint-Clair oli peräti tyytymätön, mutta malttoi sentään mielensä.

Hän käänsi selkänsä koko uunille, ettei houkutus kävisi liian
suureksi, ja avasi kellonsa kuoren katsellakseen äsken saamaansa
kuvaa.
— Kuka tämän maalasi? kysyi hän.
— Herra R… Niin, Massignyhan se esittikin hänet minulle.

(Roomasta palattuaan oli Massigny huomannut itsessään erityisen
taipumuksen kaunotaiteihin ja ruvennut kaikkien nuorten taiteilijain
suojelijaksi.) Mielestäni on tämä kuva todellakin minun näköiseni,
vaikka se onkin hiukan kaunisteltu.
Saint-Clairin teki mieli viskata koko kello seinää vasten, niin että
sen korjaaminen olisi käynyt sangen vaikeaksi.
Hän hillitsi sentään itsensä ja pisti sen taskuunsa; huomatessaan

sitten, että oli jo suuri päivä, suoriusi hän ulos huoneesta, pyysi, ettei
Matilde saattaisi häntä, kiiruhti pitkin askelin puiston läpi ja oli
tuokiossa jo nummella yksinään.
— Massigny! Massigny! huusi hän pidätetyllä raivolla, ainako sinä

siis kierrät eteeni!… Epäilemättä on tuo maalaaja valmistanut toisen
kuvan Massignyta varten!… Mikä tomppeli minä olen ollutkin! Että
olen ensinkään voinut luulla hänen rakastavan minua samalla
rakkaudella kuin minä häntä!… ja ainoastaan sen nojalla, että hän
on somistanut hiuksensa vain yhdellä ruusulla eikä ole käyttänyt
jalokiviä!… hänellähän on niitä lipas täynnä… Massigny, joka ei
huomannut muuta kuin naisten puvut, piti paljon tuollaisista
koristuksista!.. Niin, kyllä hänellä on hyvä sydän, täytyy se myöntää.
Hän tietää mukautua rakastajain mieliaistin mukaan. Saakeli!
näkisinpä mieluummin, että hän olisi kevytmielinen ja rahalla
ostettavissa. Ainakin voisin silloin uskoa, että hän rakastaa minua,
koskapa hän on lemmittyni enkä minä hänelle mitään maksa.
Pian ilmestyi toinen, vielä musertavampi seikka hänen

harkittavaksensa. Muutamien viikkojen kuluttua päättyi kreivittären
suruaika. Saint-Clairin oli aikomus naida hänet heti kun hänen
leskivuotensa oli umpeen kulunut. Hän oli sen luvannut. Luvannut?
Ei… Eihän hän ollut siitä koskaan puhunut. Mutta se oli ollut hänen
aikomuksensa, ja kreivitär oli sen ymmärtänyt. Augustelle se oli
samaa kuin lupaus. Edellisenä iltana hän olisi antanut valtaistuimen
jouduttaakseen hetkeä, jolloin saattoi julkisesti tunnustaa
rakkautensa; nyt hän vapisi jo siitä pelkästä ajatuksesta, että
yhdistäisi kohtalonsa Massignyn lemmityn kanssa.
— Ja kuitenkin, minun täytyy se tehdä, sanoi hän, ja niin tuleekin

tapahtumaan. Tuo naisrukka on epäilemättä luullut minun tuntevan
hänen entiset seikkailunsa. Sanovathan asian olleen julkisen. Eikä
hän silloin vielä tuntenut minua… Hän ei voi käsittää minua. Hän
luulee minun rakastavan häntä niinkuin Massigny.
Sitten hän jatkoi jonkinlaisella ylpeydellä:
— Kolme kuukautta olen hänen kauttansa ollut onnellisin mies

maailmassa. Niiden vuoksi kannattaa kyllä uhrata elämänsäkin.
Hän ei nukkunut, vaan ratsasteli metsikössä koko aamupäivän.

Eräällä Verrières'in puistotiellä hän näki miehen pulskan
englantilaisen ratsun selässä ja kuuli tämän jo kaukaa huutavan
nimeänsä ja puhuttelevan häntä. Se oli Alfons de Thémines.
Sellaisessa mielentilassa kuin Saint-Clair oli, on yksinäisyys
erityisesti rakas: Thémines'in tapaaminen kiihottikin hänen pahan
tuulensa kerrassaan tukahuttavaksi kiukuksi. Thémines ei sitä
huomannut tai nautti se ilkiö siitä, että oli hänelle vastukseksi. Hän
puheli, nauroi, laski leikkiä ollenkaan huomaamatta, ettei saanut
mitään vastausta. Nähdessään erään kapean haaratien Saint-Clair
käännytti ratsunsa heti sinne toivoen, ettei tuo kiusaaja häntä sinne
seuraisi. Mutta tässä hän pettyi; kiusaaja ei niinkään hevillä luovu
saaliistaan. Thémines kääntyi hänkin heti sinne ja joudutti
hevostansa päästäksensä Saint-Clairin rinnalle ja voidaksensa
mukavammin jatkaa puhettaan.
Sanoin jo, että puistotie oli kapea. Vaivoin voivat nuo kaksi ratsua
kulkea rinnakkain; eikä ollut siis kumma, jos Thémines, vaikka olikin
hyvä ratsastaja, hipaisi Saint-Clairiä jalkaan siinä rinnalla
ratsastaessaan. Tämä taas, jonka kiukku jo oli äyräilleen noussut, ei
jaksanut kauempaa hillitä itseään, vaan nousi jalustimilleen ja löi
vinhasti piiskallaan Thémines'in hevosta vasten turpaa.
— Mikä lempo sinua riivaa, Auguste? huusi Thémines. Miksi sinä

lyöt hevostani?
— Miksikä sinä seuraat minua? vastasi Saint-Clair hirveällä

äänellä.
— Oletko sinä suunniltasi, Saint-Clair? Unohdatko kenelle puhut?
— Tiedän kyllä puhuvani tomppelille.
— Saint-Clair!… te olette hullu, luulen minä… Kuulkaa, ellette

huomenna anna minulle hyvitystä, on teidän tehtävä minulle tili
hävyttömyydestänne.
— Huomiseen siis, hyvä herra.
Thémines pysähdytti hevosensa; Saint-Clair joudutti omaansa ja

katosi pian metsikköön.
Nyt hän tunsi itsensä tyynemmäksi. Hän oli kyllin heikko

uskoaksensa aavistuksia. Hän arveli kaatuvansa huomenna
kaksintaistelussa, ja silloin olisi koko hänen pulmansa parhaiten
ratkaistu. Siis vielä yksi päivä jäljellä; huomenna ei ollut enää mitään
levottomuuksia eikä häiriöitä. Kotiin tultuaan hän lähetti palvelijansa
viemään kirjettä eversti Beaujeulle, kirjoitteli muutamia kirjeitä, söi
päivällistä hyvällä ruokahalulla ja oli täsmälleen kello puoli yhdeksän
aikana puiston pikku portin luona. — — —
*****
— Mikä teitä tänään vaivaa, Auguste? kysyi kreivitär. Te olette niin

omituisen iloinen ettekä kuitenkaan kaikilla noilla pilapuheillanne saa
minua nauramaan. Eilen te olitte niin surumielinen ja minä iloinen!
Tänään ovat osat vaihtuneet. — Päätäni kivistää niin armottomasti.
— Myönnän kyllä, kaunis ystävättäreni, olleeni eilen aika

ikävystyttävä. Mutta tänään olen ollut ulkoilmassa, olen ollut liikkeellä
ja voin ihan mainion hyvin.
— Minä taas nousin myöhään, nukuin näet niin pitkään tänä

aamuna ja näin niin väsyttäviä unia.
— Vai niin, vai unia? Uskotteko te unia?
— Mitä hullutuksia!
— Minäpä uskon; lyön vetoa, että näitte unessa jonkun surullisen

tapauksen olevan tulossa.
— Minä en, Jumala paratkoon, muista uniani. Kuitenkin

muistelen… nähneeni Massignyn; huomaatte siis, etteivät ne olleet
mitenkään huvittavia.
— Massignyn! Päinvastoin luulin teidän mielellännekin taas

tahtovan nähdä häntä?
— Massigny raukka!
— Massigny raukkako?
— Auguste, sanokaapa mikä teidän on tänä iltana, minä pyydän.
Teidän hymyilyssänne on jotakin pirullista. Te näytätte siltä, kuin
laskisitte leikkiä itsestännekin.
— Kas, kas, kuinka te kohtelette minua yhtä huonosti kuin

ystävättärenne, nuo vanhat leskirouvat.
— Niin, Auguste, te olette tänään sen näköinen kuin tavallisesti

olette ihmisten kanssa, joista ette pidä.
— Te häijy! Kas niin, antakaa nyt minulle kätenne.
Hän suuteli lemmittyänsä kädelle ivallisesti hymyillen, ja sitten he

katselivat toisiansa minuutin verran. Saint-Clair loi ensiksi silmänsä
maahan ja huudahti:
— Kuinka vaikea tässä maailmassa on elää joutumatta häijyksi! Ei

saisi koskaan puhua muusta kuin ilmasta ja metsästyksestä tai
keskustella teidän vanhojen ystävättärienne kanssa heidän
hyväntekeväisyyskomiteansa kulunkiarvioista.
Hän otti pöydältä erään paperilipun.
— Kas tässä pesijättärenne viimeiset muistiinpanot.

Keskustellaanpa siitä, enkelini, niin ette voine sanoa minua häijyksi.
— Te hämmästytätte minua todellakin, Auguste…
— Tämä oikeinkirjoitus muistuttaa minua eräästä kirjeestä, jonka

tänä aamuna löysin säilöistäni. Täytyy näet sanoakseni, että olen
tänään järjestellyt papereitani, sillä, tietäkääs, minullakin on
järjestysintoni silloin-tällöin. No niin, löysin rakkauskirjeen, jonka sain
eräältä ompelijattarelta ollessani häneen rakastunut
kuusitoistavuotiaana. Hänellä on oma tapansa kirjoittaa sanat aina
mitä mutkallisimmin. Kirjoitustapa on oikeinkirjoituksen veroinen. Ja
kun minä siihen aikaan olin hieman yksinkertainen, pidin sellaista
lemmittyä itselleni arvottomana, joka ei osannut kirjoittaa niinkuin
madame Sévigné. Jätin hänet yhtäkkiä. Lukiessani tänään
uudestaan hänen kirjeensä huomasin, että tuo ompelijatar nähtävästi
oli todenteolla minuun rakastunut.
— Hyvä! siis nainen, jota te ylläpiditte?…
— Sangen pulskasti: viisikymmentä frangia kuussa. Mutta

holhoojani ei antanut minulle kovin suurta eläkettä, sillä — sanoi hän
— nuori mies, jolla on paljon rahaa, vahingoittaa itseänsä ja muita.
— Ja mihin tuo nainen on joutunut?…
— En tiedä?… Luultavasti on hän kuollut jossakin

sairashuoneessa.
— Auguste… jos se olisi totta, niin te ette voisi olla noin huoleton.
— No, jos totuuden sanon, meni hän naimisiin erään kunniallisen

miehen kanssa; ja kun pääsin lailliseen ikään, annoin minä hänelle
pienet myötäjäiset.
— Kuinka hyvä te olette!… Mutta miksi tahdotte näyttäytyä

häijynä?
— Oh, minä olen sangen hyvä… Mitä enemmän häntä ajattelen,

sitä enemmän tulen vakuutetuksi siitä, että tuo nainen minua
todellakin rakasti.. Mutta silloin en vielä voinut erottaa todellista
tunnetta naurettavan muodon alta.
— Teidän olisi pitänyt tuoda minulle tuo kirje. En minä olisi ollut
mustasukkainen… Me naiset olemme hienotunteisempia kuin te, ja
me näemme heti kirjeen kirjoitustavasta, onko kirjoittaja hyvässä
uskossa vai teeskenteleekö hän rakkautta, jota ei tunne.
— Ja kuinka usein te kuitenkin joudutte tyhmänsekaisten ja

yksinkertaisten käsiin!
Näin sanoessaan hän silmäili etruskilaista vaasia, ja hänen

silmissään sekä äänessään oli jotakin synkkää, jota Matilde ei
kumminkaan huomannut.
— No niin! Te miehet, te tahdotte kaikki olla don Juaneja. Te

kuvittelette pettävänne muita, vaikka teillä vastassanne onkin dona
Juana, joka on vielä teitäkin ovelampi.
— Minä käsitän, että te naiset hyvällä ymmärryksellänne vainuatte

tyhmeliinin jo virstan päästä. Enkä minä epäilekään, ettei meidän
ystävämme Massigny, joka oli sekä tyhmä että ikävä, kuollut
koskemattomana ja marttyyrina…
— Massigny? Mutta eihän hän ollut niin kovin typerä; ja onhan

niitä tyhmiä naisiakin. Minunpa pitää kertoa teille eräs juttu
Massignysta… Mutta enköhän liene sitä jo kertonutkin teille vai
miten?
— Ette koskaan, vastasi Saint-Clair vapisevalla äänellä.
— Palattuaan Italiasta rakastui Massigny minuun. Mieheni tunsi

hänet; hän esitti minulle Massignyn älykkäänä ja aistikkaana
miehenä. He olivatkin kuin luodut toisillensa. Massigny kävi alussa
ahkerasti meillä; hän lahjoitteli minulle muka omatekemiänsä
akvarelleja, jotka hän sentään oli ostanut Schrothilta, ja puhui
minulle musiikista ynnä maalaustaiteesta ihan huvittavalla
kaikkitietäväisyydellä. Eräänä päivänä hän lähetti minulle
uskomattoman kirjeen. Muun muassa hän sanoi minua Pariisin
kunniallisimmaksi naiseksi; senvuoksi hän juuri halusi
rakastajakseni. Minä näytin kirjeen serkulleni Julialle. Me olimme
molemmat hupsuja silloin ja päätimme tehdä hänelle kepposet.
Eräänä iltana oli meillä muutamia vieraita, m.m. Massigny. »Minäpä
luen teille erään rakkaudentunnustuksen, jonka tänä aamuna sain»,
virkkoi Julia minulle. Hän ottaakin kirjeen ja lukee sen kaikkien täyttä
kurkkua nauraessa. Massigny raukka!…
Saint-Clair lankesi polvilleen riemusta huudahtaen. Tarttuen

kreivittären käteen hän kostutti sitä suuteloillaan ja kyynelillään.
Matilde oli suuresti hämmästynyt ja luuli ensin hänen voivan pahoin.
Saint-Clair ei voinut sanoa muuta kuin: »Antakaa minulle anteeksi,
antakaa minulle anteeksi!» Vihdoin hän nousi seisoalleen. Hän loisti
ilosta. Tällä hetkellä hän oli onnellisempi kuin sinä päivänä, jolloin
Matilde hänelle ensi kerran kuiskasi: »Minä rakastan teitä.»
— Minä olen hulluin hullu ja syytetyistä syyllisin, huudahti hän:

kaksi päivää olen sinua epäillyt… enkä ole koettanut saada sinulta
selitystä…
— Sinä epäilit minua!… Ja mistä!
— Voi, minä olen kurja raukka!… Kerrottiin sinun rakastaneen

Massignyta ja…
— Massignyta! — ja kreivitär purskahti nauramaan, mutta kävi

pian taas totiseksi. — Auguste, sanoi hän, oletteko todellakin niin
hassu, että epäilette tuollaista, ja niin ulkokullattu, että peitätte sitä
minulta!
Ja kyynel kierteli hänen silmissään.
— Minä rukoilen, anna minulle anteeksi.
— Kuinka en antaisi anteeksi, rakas ystäväni…
Mutta salli minun ensin vannoa…
— Ei, minä uskon sinua, minä uskon sinua, älä sano siitä mitään
enää…
— Mutta mistä taivaan nimessä sinä olet tullut epäilemään

tuollaista mahdottomuutta?
— En mistään, en mistään, ainoastaan kirotut aivoni… ja…

näetkös tuota etruskilaista vaasia, minä tiesin sen olevan
Massignylta…
Kreivitär pani hämmästyneenä kätensä ristiin; sitten hän huudahti

nauraen:
— Minun etruskilainen vaasini! Tuo etruskilainen vaasini!
Saint-Clairin täytyi itsensäkin nauraa, ja suuret kyyneleet vierivät

hänen poskiansa myöten. Hän painoi Matildea rintaansa vasten ja
sanoi:
— Minä en hellitä sinua, ennenkuin olet antanut anteeksi minulle.
— Annanhan minä sinulle hupsulle anteeksi, sanoi tämä häntä

hellästi syleillen; — kas nyt näen sinun ensi kerran itkevän, ja minä
kun jo luulin, ettet sinä osaakaan itkeä.
Irrottautuen sitten Augusten syleilystä hän tarttui etruskilaiseen

vaasiin ja viskasi sen lattiaan tuhansiksi murusiksi. (Se oli
harvinainen ja tavaton esine. Siihen oli kolmella värillä maalattu
Lapithen taistelu Kentauria vastaan.)
Saint-Clair oli muutamia tunteja maailman häpeisin ja onnellisin

mies.
*****
— Kuulkaas, sanoi Roquantin eversti Beaujeulle, jonka hän

eräänä iltana tapasi Tortonin kahvilassa, onko se uutinen
todenperäinen?
— Liiankin tosi, ystäväni, vastasi eversti surullisesti.
— Kertokaapa minulle, kuinka se kävi.
— Oh, sangen hyvin. Saint-Clair sanoi aluksi minulle olevansa

väärässä, mutta tahtovansa mieluummin kestää Thémines'in
taisteluinnon kuin pyytää häneltä anteeksi. Minä en voinut muuta
kuin hyväksyä hänen päätöksensä. Thémines halusi, että
ratkaistaisiin arvalla, kuka ensiksi laukaisee. Saint-Clair taas vaati
Thémines'iä ensimäiseksi. Thémines laukaisi: näin Saint-Clairin
pyörähtävän kerran ympäri ja sitten kaatuvan kuolleena maahan.
Olen usein huomannut luodin lävistämäin sotilasten pyörähtävän
samalla omituisella tavalla, joka aina tietää kuolemaa.
— Sepä on kovin merkillistä, sanoi Roquantin. Ja mitäs teki

Thémines?
— Oh! mitä sellaisessa tapauksessa on tehtävä. Hän heitti
pistoolinsa maahan katuvaisen näköisenä. Ja heitti sen vielä niin
lujasti, että hana särkyi. Se oli englantilainen Manton-pistooli, enkä
tiedä tokko hän Pariisista löytäneekään aseseppää, joka voisi sen
korjata.
*****
Kreivitär ei kolmeen vuoteen ottanut ketään vastaan; kesät ja

talvet hän asui maatalossaan tuskin liikahtaen huoneestaan ja
käyttäen palvelijanaan erästä mulattinaista, joka tunsi hänen
suhteensa Saint-Clairiin ja jonka kanssa hän ei vaihtanut kahta
sanaa päivässä. Kolmen vuoden kuluttua palasi hänen serkkunsa
Julia pitkältä ulkomaanmatkalta; hän mursi oven auki ja tapasi
Matilde raukan niin kalpeana ja laihana, että luuli näkevänsä vain
ruumiin tuosta naisesta, joka viime näkemässä oli ollut niin ihana ja
eloa täynnä. Suurella vaivalla sai Julia hänet pois yksinäisyydestä ja
toi hänet mukanansa Hyères'iin. Kolme tai neljä kuukautta kuihtui
kreivitär siellä ja kuoli sitten rintatautiin, johon syynä olivat
perheelliset huolet, kuten tohtori M———, hänen hoitajansa, lausui.
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Organic Chemistry For Jee ( Main &

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Third Edition: 2017

NEW TO THIS EDITION

Striking a strong balance of synthetic methods Students need to learn methods

Showing how things work A mechanistic understanding of organic chemistry is key

TRADITIONAL PEDAGOGICAL STRENGTHS

End-of-Chapter Problems As athletes and musicians know, practice makes perfect.

7.29 Without consulting tables, arrange the following com-

tools for students to understand Reactive Alkane Alkyl radical

SUMMARY AND REVIEW TOOLS Visually

Molecules that differ only by rotation

Dihedral angle vs. Repulsive Hyperconjugative Deviation from ideal

Steric hindrance Favorable overlap of

can be used to show have

Connections, Concept Maps, Thematic Mechanism Review Summaries, and the

• Chapters on carbonyl chemistry that are organized to emphasize mechanistic themes

ORGANIZATION—An Emphasis on the Fundamentals

1. Do not lag behind in schedule.

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CRAIG BARTON FRYHLE is Chair and Professor of Chemistry at Pacific Lutheran

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Families of Carbon Compounds: 3.13 Organic Compounds as Bases 100

5 6.12 The Stereochemistry of SN1 Reactions 260

7.14 Hydrogenation of Alkynes 323 9.5 Halogenation of Higher Alkanes 413

8 9.8 Benzylic Substitution and Benzylic Radicals 422

8.1 Addition Reactions of Alkenes 341

16 18.7 Replacement Reactions of Arenediazonium Salts 769

17 19.3 Physical Properties of Phenols

19.5 Reactions of Phenols as Acids 791

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22 24.2 Classification of Polymers 912

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Molecular Structure Contents

1.2 | ATOMIC STRUCTURE

Practice Problem 1.1

1.2B Valence Electrons

Practice Problem 1.2

1.3 | THE STRUCTURAL THEORY OF ORGANIC CHEMISTRY

Carbon atoms Oxygen atoms Hydrogen and halogen

Single bond Double bond Triple bond

1.3A Isomers: The Importance of Structural Formulas

Acetone Propylene oxide

Solved Problem 1.1

1.3B The Tetrahedral Shape of Methane

1.4 | CHEMICAL BONDS: THE OCTET RULE

1.4A Ionic Bonds

Table 1.1 Electronegativities of Some of the Elements

1.0 1.5 2.0 2.5 3.0 3.5 4.0 Increasing

0.9 1.2 1.5 1.8 2.1 2.5 3.0

• Chapters on carbonyl chemistry that are organized to emphasize mechanistic themes

5 6.12 The Stereochemistry of SN1 Reactions 260

8.1 Addition Reactions of Alkenes 341

16 18.7 Replacement Reactions of Arenediazonium Salts 769

22 24.2 Classification of Polymers 912