INTERMEDIATES

AND
REARRANGEMENTS
IN ORGANIC SYNTHESIS

Bapusaheb S. Jagdale
M.Sc., Ph.D.
Thansing B. Pawar
M.Sc., Ph.D.
Vishnu A. Adole
M.Sc., CSIR-NET (JRF), UGC- SET, GATE

MUMBAI  NEW DELHI  NAGPUR  BENGALURU  HYDERABAD  CHENNAI  PUNE

 LUCKNOW  AHMEDABAD  ERNAKULAM  BHUBANESWAR  KOLKATA
© Authors
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We Dedicate This Book
To Our Students
 Preface
We are very much happy to present this book titled “Intermediates and Rearrangements in
Organic Synthesis” in the hands of students and teachers. The main purpose of writing this book is to
create more interest in the subject of organic chemistry. This book provides the deeper understanding
of organic reaction mechanism. The special thing about this book is it is written by keeping in mind
various competitive exams. The book consists of main topics of organic chemistry which are very
useful for the preparation of different exams based on chemistry. The topics included are intermediates
and rearrangement reactions. Intermediates and rearrangements are very important parts of organic
chemistry without which students cannot get good understanding of organic chemistry. The topics are
explained in simple way which will give clear ideas to the students. Each concept is explained by
giving ample number of examples to help a detailed understanding. The examples from various
competitive exams are also included and thus, this will provide easy platform for the students who are
preparing for different exams. So we hope that this book shall be received by the students and teachers
with great excitement.
Suggestions for next edition will be accepted with warm welcome.

Authors
 ACKNOWLEDGMENT
To write a book not only requires hard work of the authors but also the support of well-wishers.
Our special thanks goes to Hon. Dr. Apoorbhau Prashantdada Hiray who always motivates us for
undertaking challenging academic works.
We would like to extend our thanks to the staff and students of the Department of
Chemistry, Loknete Vyankarao Hiray College, Nashik, who made our work easier. We would
like to thank Prof. Kishore R. Nikam, Department of English, Loknete Vyankarao Hiray
College, Nashik, who helped us in drafting the language.
Mr. V.A. Adole would like to thank the teachers who developed excitement in the subject of
organic chemistry.
We authors would also like to thank all the people who helped directly and indirectly during our
project. Last but not the least, we are very much thankful to our publishers who showed interest in our
work.

Authors
 Contents
Name
Sr. No. Page No.

1 Reaction Intermediates 1 – 32
1.1 Carbocation 2
1.2 Carbanion 9
1.3 Free radicals 16
1.4 Carbenes 22
1.5 Nitrenes 28
1.6 Benzyne 29
2 Molecular Rearrangements 33 – 142
2.1 Introduction 33
2.2 Pinacol-pinacolone rearrangement 36
2.3 Beckmann rearrangement 46
2.4 Baeyer-Villiger rearrangement 51
2.5 Dienone-Phenol rearrangement 58
2.6 Wagner-Meerwein rearrangement 60
2.7 Favorskii rearrangement 65
2.8 Benzil-Benzillic acid rearrangement 71
2.9 Wolff rearrangement 74
2.10 Hofmann rearrangement 78
2.11 Schmidt rearrangement 81
2.12 Curtius rearrangement 85
2.13 Lossen rearrangement 88
2.14 Fries rearrangement 89
2.15 Claisen rearrangement 92
2.16 Cope rearrangement 99
2.17 Sommelet-Hauser rearrangement 102
2.18 Stevens rearrangement 105
2.19 Dakin rearrangement 106
2.20 Lumiketone rearrangement 108
2.21 Di--methane rearrangement 112
2.22 Transannular rearrangements 118
2.23 Eschenmoser-Tanabe fragmentation 122
 2.24 Grob fragmentation 125
2.25 Wharton olefin synthesis 128
2.26 Baker-Venkataraman rearrangement 129
2.27 Benzidine rearrangement 130
2.28 Ciamician-Dennstedt rearrangement 131
2.29 Neber rearrangement 132
2.30 Payne rearrangement 133
2.31 Pummerer rearrangement 134
2.32 Smiles rearrangement 134
2.33 Bamberger rearrangement 135
2.34 Brook rearrangement 136
2.35 Meyer-Schuster rearrangement 137
2.36 Mislow-Evans rearrangement 138
2.37 Carroll rearrangement 138
2.38 Orton rearrangement 139
2.39 Hofmann-Martius rearrangement 140
2.40 Hydroperoxide rearrangement 141
3 Practice Problems 143 – 155
Bibliography 156
 3 Practice Problems
Chapter

A. Explain each of the following observations.

1. Cyclopentadiene is more acidic than cycloheptatriene.
2. 1-Bromotrypticine is inert towards SN1 reaction.
3. Benzene on reaction with neopentyl chloride/AlCl 3 gives following compound as a major
product.

4. Addition of HBr to styrene in presence of H2O2 forms (2-Bromoethyl)benzene.

5. How will you account for given variation in pka value?

6. In the following reaction, compound A is formed and not compound B.

7. The compound given below is less acidic.

8. Cis- and trans-1,2- dimethylcyclohexane-1,2-diol give different products on treatment with

concentrated sulfuric acid.
9. The dehydration of 3,3-dimethylbutan-2-ol gives tetramethylene.
144 Intermediates and Rearrangements in Organic Synthesis

10. In the pinacol rearrangements of PhMeC(OH)-C(OH)PhMe and Ph2C(OH)-C(OH)Me2, a

phenyl group migrates in the former case but a methyl group migrates in the latter.
11. Compound X reacts faster than Y in Pinacol-Pinacolone rearrangement.

12. The reaction given below does not proceed via normal Favorskii rearrangement pathway.

13. Both compound A and B gives same product C when treated with NaOMe/MeOH.

14. Compound given below does not undergo Pinacol-Pinacolone rearrangement.

15. Wolff rearrangement is used to prepare higher homologue of starting acid.

16. Pinacol rearrangement is used to prepare spiroketone.
17. Aldoximes are not suitable substrates for the Beckman rearrangement.
18. Fries rearrangement of Phenyl acetate gives o-hydroxy acetophenone at high temperature and
p-hydroxy acetophenone at low temperature.
19. Ortho tolyl group is having less migratory aptitude than phenyl group in Benzil-Benzillicacid
rearrangement.
20. N-Methyl benzamide does not give N-Methyl aniline when treated with Br2/NaOH whereas
benzamide gives aniline under similar reaction conditions.
21. Beckman rearrangement is used prepare synthetic polymer.
22. In the Claisen rearrangement of β-phenyl allyl ether, the allyl group migrates to the 1 position
and not to the 3 position.
Practice Problems 145

23. The reaction of compound A with conc. H2SO4 forms compound B and C with 57% and 43%
respectively.

24. In the Baeyer-Villiger rearrangement of compound 1 with PhCO3H, compound 2 is obtained

and not compound 3.

25. In Baeyer-Villiger rearrangement, t-butyl group migrates in preference to phenyl group.

B. Provide suitable reaction pathways for following transformations and

justify your answer.

2
146 Intermediates and Rearrangements in Organic Synthesis

H H
Cl O
Ba(OH)2
6
N O N OH
H H
H H

10

11
Practice Problems 147

NaOH
12

Br
COOH

13

14

15

16

17

18
148 Intermediates and Rearrangements in Organic Synthesis

19

20

21

22

23

24

25

26

27
Practice Problems 149

O
H
N
28 1.NH2OH
O
2. PCl5

29

30

31

32

33

34

35
150 Intermediates and Rearrangements in Organic Synthesis

36

37

38

39

40

41

42

43
Practice Problems 151

44

45.

46

47

O
O
CH3CO3H, NaOAc
48 O
AcOH

49

50
152 Intermediates and Rearrangements in Organic Synthesis

C. Predict the products of following.

O CH3
7
AlCl3
?
Low Temperature
Practice Problems 153

10

11

12

13

14

15

16
154 Intermediates and Rearrangements in Organic Synthesis

17

OH
AgNO3
Cl ?
18
H2O
R

19

20

21

22

23

24

25
Practice Problems 155

26

27

28

29

30

31

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