Reaction Mechanism

in
Organic Chemistry
 REACTION MECHANISM
IN
ORGANIC CHEMISTRY
(Revised Edition)

S.M. MUKHERJI ǭ S.P. SINGH

Revised by: S.P. Singh ǭ Om Prakash

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REACTION MECHANISM IN ORGANIC CHEMISTRY

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 This book is dedicated
to
Our grand children
Poorva, Uday, Adi, and Veer
ˆS.P. Singh
Khushi, Avi, Aadya, and Aarna
ˆOm Prakash
 Contents
Preface to the Revised Edition ZK
Preface to the Previous Edition xKKK
Chapter 1: Nature of Bonding in Organic Molecules 1
1.1 Localized Chemical Bonding 2
1.2 Delocalized Chemical Bonding 12
1.3 Bonding Weaker Than Covalent 42
Problems and Review Questions 54
Solutions 58
Chapter 2: Stereochemistry-I 62
2.1 Stereoisomerism 63
2.2 Molecular Representation of Stereoisomers 65
2.3 Chirality 70
2.4 Geometrical Isomerism 100
2.5 Conformational Isomerism 104
Problems and Review Questions 110
Solutions 115
Chapter 3: Stereochemistry-II 118
3.1 Prostereoisomerism 119
3.2 Stereoselective and Stereospecific Reactions 127
3.3 Asymmetric Synthesis 129
3.4 Optical Activity in the Absence of a Chiral Carbon 142
3.5 Chirality Due to Helical Shape 151
3.6 Stereochemistry of the Compounds Containing Nitrogen,
Phosphorus and Sulphur 153
3.7 Conformations of Cyclohexanes and Decalins 159
3.8 Effect of Conformation on Reactivity 177
3.9 Conformational Analysis of Monosaccharides 185
Problems and Review Questions 189
Solutions 194
Chapter 4: Organic Reactions, Reagents and Reaction Intermediate 199
4.1 Types of Organic Reactions 201
4.2 Types of Reagents 204
4.3 Organic Acids and Bases 207
4.4 Reaction Intermediates 207
Problems and Review Questions 242
Solutions 245
viii REACTION MECHANISM

Chapter 5: General Principles and Methods of Determination of Reaction

Mechanism 247
5.1 Energy Considerations 248
5.2 Methods of Determination of Reaction Mechanisms 265
Problems and Review Questions 277
Solutions 279
Chapter 6: Aliphatic Nucleophilic Substitution 280
6.1 Direct Displacement Process: SN2 Reactions 281
6.3 Stereochemistry of Substitution Reactions 285
6.4 Neighbouring Group Participation 289
6.5 SNi and SET Mechanisms 308
6.6 Factors Affecting Reactivity in Substitution Reactions 311
6.7 Ambident Nucleophiles 317
Problems and Review Questions 319
Solutions 324
Chapter 7: Addition to Carbon-Carbon Multiple Bond 328
7.1 Electrophilic Additions 329
7.2 Nucleophilic Additions 355
Problems and Review Questions 357
Solutions 360
Chapter 8: Elimination Reactions 365
8.1 C-Elimination 366
8.2 B-Elimination: Carbenes 384
Problems and Review Questions 392
Solutions 395
Chapter 9: Reactions of the Carbonyl Group 397
9.1 Reactions of Aldehydes and Ketones 398
9.2 Reactions of Carboxylic Acid Derivatives 432
Problems and Review Questions 447
Solutions 452
Chapter 10: Aromatic Electrophilic Substitution 456
10.1 Electrophilic Substitution Reactions of Benzene 462
10.2 Reactivity and Orientation 472
10.3 Quantitative Treatment 484
10.4 Some Synthetically Useful Aromatic Electrophilic Substitution
Reactions 486
Problems and Review Questions 491
Solutions 495
 CONTENTS ix

Chapter 11: Aromatic Nucleophilic Substitution 498

11.1 Mechanisms 499
11.2 Aromatic Nucleophilic Rearrangements 507
Problems and Review Questions 512
Solutions 515
Chapter 12: Molecular Rearrangements 518
12.1 Molecular Rearrangements Involving Electron-Deficient Species 519
12.2 Further Molecular Rearrangements 541
Problems and Review Questions 556
Solutions 560
Chapter 13: Free Radicals 564
13.1 Short-Lived Radicals 565
13.2 Some Synthetically Useful Reactions 593
13.3 Stable Free Radicals 596
13.4 Biradicals 600
Problems and Review Questions 601
Solutions 604
Chapter 14: Organic Photochemistry 607
14.1 Principles of Photochemistry 608
14.2 Photochemistry of Carbonyl Compounds 617
14.3 Photochemistry of Olefins 628
14.4 Photochemistry of Aromatic Compounds 634
14.5 Photorearrangement of Cyclohexadienones 637
Problems and Review Questions 641
Solutions 644
Chapter 15: Pericyclic Reactions 646
15.1 Conservation of Molecular Orbital Symmetry 647
15.2 Electrocyclic Reactions 652
15.3 Cycloaddition Reactions 661
15.4 Sigmatropic Rearrangements 674
15.5 Applications of PMO Method to Pericyclic Reactions 680
Problems and Review Questions 685
Solutions 688
Index 695
 Preface to the Revised Edition
Understanding the mechanisms of reactions constitutes the core of the study of organic chemistry.
We made an effort to meet this objective by writing a book in 1976 which was the first book on
this topic published from India. It is gratifying to know that the book was used by hundreds of
thousands students and researchers in the last four decades hopefully to their benefit.
However, it was felt that the book written in 1970s on such a vibrant and dynamic topic
needs to be thoroughly reworked, updated and enlarged to reflect new facts and advances in
different areas. This became particularly relevant when the UGC Committee on Curriculum
Development in Chemistry-with one of the authors (SPS) being the Convener- recommended
a thorough revision of this topic in particular. Hence we have undertaken the exercise of the
complete rewriting of the book with lot of addition and deletion taking into account the new
developments. Some of the key features of the revised edition are:
We have incorporated two chapters on stereochemistry. While the first chapter deals with
the basic concepts of chirality, the second chapter describes stereoheterotopic ligands and faces,
stereoselective and stereospecific reactions, asymmetric synthesis, effect of conformation on
reactivity and finally conformational analysis of monosaccharides. The objective is to understand
reaction mechanisms with particular focus on spatial relationship among the reacting atoms
which is one of the important factors in determining how fast a reaction goes and what product
it yields.
As the concept of the carbocation has served to relate reactions of many different kinds,
chemistry of this important reactive intermediate has received special attention. Neighbouring
group participation of a lone pair, a double bond and a phenyl group along with a discussion
of sigma bond participation and nonclassical cations have been introduced. Topics such as
photochemistry of aromatic compounds, cheletropic reactions, hydrogenation of unsaturated
systems, ambident nucleophiles, Hammette and Taft equations are incorporated in appropriate
chapters. A large number of energy profile diagrams have been sketched in many chapters to
illustrate different processes, and many synthetically important reactions and rearrangements
have been added in chapters dealing with aromatic electrophilic and nucleophilic substitutions.
Units for expressing energies are given in IUPAC mandated joules as well as in calories which
are still being used by many organic chemists.
We feel confident that this reorganization and revision along with a large number of
problems will assist the students to develop a knowledge and appreciation of structure and
mechanisms of reactions in organic chemistry. Besides helping a large number of post-graduate
students (Chemistry and pharmacy), this revised edition will cater to the needs of those students
who are preparing for NET and other competitive examinations.
[ii REACTION MECHANISM

We will appreciate all those who read and use this revised edition to contact us directly with
their comments, and point out errors for rectification in the next reprint. Our email addresses
are: [email protected]; [email protected]
We thank Ms. Loveena Arora, who had worked as Technical Assistant in the project, for
her assistance in the preparation of the manuscript. Without her support, this work would
not have been completed in time. We thank our former students, Prof. Devinder Kumar (GJU,
Hisar) and Dr. Vinod Kumar (MMU, Mullana) for their help in revising the chapter on Pericyclic
Reactions. We take this opportunity to acknowledge the contributions of all our former students
and colleagues who had helped us in the development of this text. We especially thank Prof.
Ranjana Aggarwal, Prof. Pawan K. Sharma, Prof. Neera Raghav and Dr. Rashmi Pundeer of
our Department and Dr. Ravi Kumar of D. S. College, Karnal for their help at one stage or the
other.
Finally, the authors gratefully acknowledge that the book was revised under a project
catalyzed and supported by the Department of Science and Technology, Govt. of India under
its Utilization of Scientific Expertise of Retired Scientists (USERS) Scheme.
Kurukshetra,
June, 2014
S.P. SINGH
OM PRAKASH
 Preface to the Previous Edition
In the course of teaching post-graduate classes, we have constantly been feeling the need of a
concise volume that gives outlines of most of the important organic reactions, together with a
critical examination of the evidence leading to the accepted mechanisms. The students have
often expressed their difficulty caused by the absence of such a book. Our present effort is to
meet this long-felt need and is designed primarily for the students who had a basic course in
organic chemistry at the undergraduate level. It is an attempt to bridge the gap between an
elementary treatment and the more masterly treatises on the subject.
The book opens with a chapter on the Chemical Bond which apart from describing the
different types of chemical bonds, highlights the importance of the concepts of the electronegativity
and effect of the state of hybridization of the bonding orbitals on the physical properties of the
molecules. In addition to Hückel’s treatment of aromaticity, a new outlook for determining
aromaticity and resonance energy has been introduced based on the Perturbational Molecular
Orbital (PMO) method developed by M. J. S. Dewar. This chapter coupled with the second and
third chapters- which deal with the reaction intermediates, reagents, energies, stereochemical
terms and methods for determining reaction mechanisms- form the background materials for
the subsequent chapters.
In dealing with the conventional topics such as substitution reactions, addition and
elimination reactions, reactions of carbonyl group, free radicals, etc., we have tried to project
current developments, wherever possible. The purpose of giving specific examples in these
chapters is to illustrate principles rather than giving a review-type coverage. We had to be
selective rather than comprehensive because of our anxiety to limit the book to a reasonable
size and price.
The last two chapters, namely, Organic Photochemistry and Pericyclic Reactions, have
been included due to our conviction that these topics should form an integral part of the course
on reaction mechanism in recognition of their growing importance. These topics should also be
helpful to those research students whose training in these fascinating areas of organic chemistry
was not up to the current standard. In addition to Woodward Hoffmann’s orbital correlation
method based on the principles of molecular orbital symmetry, and the frontier orbital method,
we have discussed in reasonable detail the PMO method for the analysis of pericyclic reactions.
This latter method should be particularly welcome to the readers as it offers simple mnemonics
of selection rules for prediction of the stereochemical courses of this class of reactions.
An effort to guide the readers to relevant review articles and books has also been made
for further consultation. It is hoped that this book would be useful and effective in helping the
students of chemistry develop an insight into the mechanistic aspects of organic chemistry as
 Reaction Mechanism In Organic
Chemistry (Revised Edition)

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Author : S. M. Mukherji, S.
Publisher : Laxmi Publications ISBN : 9789351381785
P. Singh

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