Добавил:
Sekretar
kiopkiopkiop18@yandex.ru
t.me/Prokururor I Вовсе не секретарь, но почту проверяю
Опубликованный материал нарушает ваши авторские права? Сообщите нам.
Вуз:
Предмет:
Файл:Ординатура / Хирургия / Библиотека им академика М.И. Перельмана / Книга_5710_Библиотеки_им_академика_М_И_Перельмана
.pdf
Oxadiazole in Material and Medicinal
Chemistry
Oxadiazole in Material
and Medicinal Chemistry
Priya Ranjan Sahoo
Department of Chemistry
State University of New York at Buffalo
New York, United States
Abhishek Saxena
Department of Chemical Engineering
Hanyang University
Seoul, South Korea
Satish Kumar
Department of Chemistry
St. Stephen’s College, University of Delhi
Delhi, India
A SCIENCE PUBLISHERS BOOK
Cover credit,PDJHXVHGRQWKHFRYHULVSUHSDUHGE\WKH LUVWDXWKRU'U3UL\D5DQMDQ6DKRR
First edition published 202
by CRC Press
2385 NW Executive Center Drive, Suite 320, Boca Raton FL 33431
and by CRC Press
4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 202 Priya Ranjan Sahoo, Abhishek Saxena and Satish Kumar
CRC Press is an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the author and
publisher cannot assume responsibility for the validity of all materials or the consequences of
their use. The authors and publishers have attempted to trace the copyright holders of all material
reproduced in this publication and apologize to copyright holders if permission to publish in this
form has not been obtained. If any copyright material has not been acknowledged please write and
let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information
storage or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, access
www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive,
Danvers, MA 01923, 978-750-8400. For works that are not available on CCC please contact
mpkbookspermissions@tandf.co.uk
Trademark notice: Product or corporate names may be trademarks or registered trademarks and are
used only for identification and explanation without intent to infringe.
Library of Congress Cataloging-in-Publication Data (applied for)
ISBN: 978-1-032-47066-5 (hbk)
ISBN: 978-1-032-47067-2 (pbk)
ISBN: 978-1-003-38444-1 (ebk)
DOI: 10.1201/9781003384441
Typeset in Times New Roman
by Prime Publishing Services
Preface
Oxadiazole, a five-membered heterocyclic molecule affords multifaceted electronic
utility. As a favorable acceptor, its quantum efficiency can be tuned with functional
group engineering. As a result, many of us are using electronic gadgets every day,
either in the form of laptops, smartphones liquid-crystal-display television sets, etc.
It would be interesting to know the basic materials used in such devices during their
assembly and manufacturing. This book explores various ways by which a variety
of oxadiazole derivatives including its isomers could be synthesized. Further, it also
discusses its significance and practical applications in electrochromic materials
including electrochemical reduction, color change, and oxidation status.
Oxadiazole motifs are also widely found in bioactive drugs and medicinal
compounds. It is one of the most treasured scaffolds for drug discovery scientists
and biologists. Its aromatic flat surface facilitates biological target binding
WKURXJK ʌVWDFNLQJ LQWHUDFWLRQV ,Q WKH IROORZLQJ FKDSWHUV UHDGHUV ZLOO HQJDJH
with oxadiazole-based inhibitors, cell imaging probes, and medicinally relevant
molecules. The book is designed to promote small molecule heterocyclic scaffold
in its prodigious applications in the areas of light-emitting diodes, liquid crystals,
and electroluminescent features. It will provide a comprehensive account of various
oxadiazole-based molecules where the reader will find material perspective in the
initial section and the medicinal aspects in the later section. The detailed synthesis
and practice would serve as a combo for the students and researchers practicing both
material and medicinal domains.
https://t.me/med1917
Preface iii
Oxadiazole-Based Heterocyclic Scaffolds
1. Introduction 1
2. Synthesis of 1,2,4-Oxadiazole Derivatives 2
2.1 Coupling Agent Assisted 1,2,4-Oxadiazole Synthesis 2
2.2 Pd Catalyzed Oxadiazole Synthesis 3
2.3 Solid Phase-Based Synthesis of 1,2,4-Oxadiazole Derivative 3
2.4 1,2,4-Oxadiazole Synthesis Using Oxidants 4
2.5 Visible Light Promoted 1,2,4-Oxadiazole Synthesis 5
3. Synthesis of 1,3,4-Oxadiazole Derivatives 6
3.1 POCl
3
-Promoted Oxadiazole Synthesis 6
3.2 Pd Catalyzed Oxadiazole Synthesis 7
3.3 Microwave-Assisted Synthesis 7
3.4 Solid Phase-Based Synthesis of 1,3,4-Oxadiazole Derivative 9
3.5 Iodine-Promoted Synthesis of 1,3,4-Oxadiazole Derivative 9
3.6 1,3,4-Oxadiazole Synthesis Using Oxidants 10
3.7 Visible Light Promoted 1,3,4-Oxadiazole Synthesis 10
3.8 Polymer-Based 1,3,4-Oxadiazole Derivative Synthesis 12
3.9 Other Methods for Synthesis of 1,3,4-Oxadiazole Derivative 13
4. Conclusions 14
References 14
Light-Emitting Diodes
1. Introduction 18
2. Organic Light-Emitting Diodes Based on 1,2,4-Oxadiazole Derivatives 19
3. Organic Light-Emitting Diodes Based on 1,3,4-Oxadiazole Derivatives 20
4. Metal Complex-Based Oxadiazole Systems 36
5. Polymer-Based Oxadiazole Systems 37
6. Conclusions 40
References 40
1. Introduction 44
2. Classification of Liquid Crystals 44
Contents
https://t.me/med1917
3. Classification of Liquid Crystalline Phases 45
4. Oxadiazole as Liquid Crystals 47
5. Mesomorphic Features 47
6. Conclusion 51
References 52
4. Oxadiazole as Electrochromic Materials 56
1. Introduction 56
2. Mechanism of Electrochromism 56
3. Advantages of Oxadiazole as Electrochromic Materials 58
3.1 Oxadiazole in Combination With Polythiophene 58
3.2 Oxadiazole in Combination With TTF Derivatives 65
3.3 Oxadiazole in Combination With Carbazole Derivatives 67
3.4 Oxadiazole in Combination With Organic Amines 71
3.5 Oxadiazole in Combination With Fluorene 74
4. Conclusion 75
References 76
5. Oxadiazole as Nonlinear Optical (NLO) Materials 81
1. Introduction 81
2. Oxadiazole Derivatives With Donor-Acceptor Properties 83
2.1 Polyacetylenes Containing Oxadiazole Pendant Groups 87
2.2 Polyacetylenes Containing Oxadiazole and Thiophene 91
Pendant Groups
2.3 Poly(3,4-Dialkoxythiophene)s-1,3,4-Oxadiazole 94
Derivative Conjugates
2.4 Oxadiazole-Bisphenol Conjugates 99
3. Conclusion 104
References 104
6. Oxadiazole-Based Heterocyclic Compounds as Chemical Probes in 109
Live Cell Imaging
1. Introduction 109
2. Oxadiazole-Based Probes in PET Imaging 110
3. Oxadiazole-Based Probes for SPECT Imaging 113
4. Oxadiazole-Based Probes as Enzyme Markers 114
5. Oxadiazole-Based Probes in Protein Imaging 115
6. Nitric Oxide Imaging 116
7. Oxadiazole-Based Probes for Metal Ion Imaging 116
7.1 Al
3+
Imaging 117
7.2 Ca
2+
Imaging 117
7.3 Fe
2+/3+
Imaging 117
7.4 Zn
2+
Imaging 118
8. Oxadiazole-Based Probes for pH Imaging 120
vi Oxadiazole in Material and Medicinal Chemistry
https://t.me/med1917
9. Oxadiazole-Based Probes in Cell Imaging and Nrf2 Activation 120
10. Conclusions 124
References 125
1. Introduction 128
2. The Derivatized Compound From Oxadiazole: A Potential Inhibitor 129
2.1 Inhibitors as Anti-Methicillin-Resistant Staphylococcus aureus 129
(MRSA) Agents
2.2 Inhibitors Against MRSA as Antibacterial Agents 136
3. Role of Histone Deacetylase (HDAC) Inhibitors in 139
Anticancer Therapy
4. Conclusion 142
References 143
1. Introduction 147
2. Different Types of Conjugates 149
2.1 Oxadiazole-Pyridine Conjugate 149
2.2 Oxadiazole-Benzofuran Conjugates 150
2[DGLD]ROHဨ7KLD]ROH&RQMXJDWHV
3LSHUD]LQH,QFRUSRUDWHGဨ2[DGLD]ROH'HULYDWLYHV
2.5 Oxadiazole-Indole, Pyridine, Benzothiazole, and
153
Benzoimidazole Conjugates
3. Applications 154
3.1 Antitubercular Activity 154
3.2 Antimalarial Activity 155
$QWLဨ,QIODPPDWRU\$FWLYLW\
$QWLဨ+,9$FWLYLW\
3.5 Antimicrobial Activity 158
3.6 Antitumor/Anticancer/Antiproliferative Activities 159
4. Conclusion and Prospects 163
References 163
Index 171
https://t.me/med1917
CHAPTER 1
Diverse Synthetic
Approaches to Design and
Develop Oxadiazole-Based
Heterocyclic Scaffolds
1. Introduction
The heterocyclic oxadiazole motif exists mostly in four different regioisomeric forms
(attachment at different positions) (Figure 1). However, 1,2,4- and 1,3,4-oxadiazole
motifs are most common in biologically active compounds (Boström et al. 2012).
The 1,2,4-oxadiazole exhibits higher lipophilicity (log D) in comparison to
1,3,4-oxadiazole. Therefore, both these regioisomers display distinct difference
in terms of hydrogen bonding potential, dipole moment, metabolic stability, etc.
Tiemann and Krüger, in the year 1884, achieved the first synthesis of 1,2,4-oxadiazole
(Tiemann and Krüger 1884). Since then, several ways have been explored to construct
1,2,4-oxadiazole moiety-based compounds. It can be constructed from nitriles via
a 1,3-dipolar cycloaddition reaction to form nitrile oxide and 1,2,4-oxadiazole
species (Pace and Pierro 2009). Alternatively, nitriles also react with hydroxylamine
and activated carboxylic acid to form a 1,2,4-oxadiazole derivative. Additionally,
O-acylation of amidoxime in the presence of an anhydride or acid chloride and
subsequent cyclization often generate an oxadiazole scaffold. Similarly, substituted
carboxylic acids and their conversion to symmetrical anhydrides in contact with
EDC as a coupling reagent can also generate oxadiazole.
Oxadiazole derivatives possess inherent thermal as well as hydrolytic stability.
The 1,2,4-oxadiazole moiety exists in a variety of medicinal compounds as
pharmacophores, such as dopamine ligands (Carroll et al. 1993), benzodiazepine
receptor agonists (Watjen et al. 2002), muscarinic agonists (Orlek et al. 1991),
serotoninergic antagonists (5-HT
3
) (Swain et al. 1991). Similar to 1,2,4-oxadiazole
regioisomer, 1,3,4-oxadiazole has also been prepared via different routes including
through oxidative cyclization (Gómez-Saiz et al. 2002; Jagadeesh Prathap et al.
2014; Niu et al. 2015), dehydrative cyclization (Yang et al. 2014; Tokumaru and
https://t.me/med1917
O
O
O
O
R
1
N
N N
R
1
R
2
R
1
N
NN
R
2
R
1
R
2
N
N
R
2
1,2,3-oxadiazole
1,2,4-oxadiazole
1,2,5-oxadiazole
1,3,4-oxadiazole
Figure 1. Structures of oxadiazole regioisomers.
O
O
N
COOH
O
N
CDI,
DMF
1.
CDI,
DMF,
30
min
OCH
3
N
NH
2
OH
OCH
3
115
o
C,
6h
H
3
CO
N
1
H
3
CO
OCH
3
2.
NH
2
H
3
CO
Scheme 1. Synthesis of oxadiazole derivative 1.
OH
N
O
X
N
i. EDC
X
NH
2
N
HO
ii.
110
o
C
O
X
=
H
(
2a
),
OMe
(
2b
),
NO
2
(
2c
)
Scheme 2. Synthesis of oxadiazole derivative 2.
2 Oxadiazole in Material and Medicinal Chemistry
Johnston 2017), Huisgen reaction (Mansoori et al. 2012; Wang et al. 2019), etc. Most
routinely used protocols for oxadiazole ring constructions are discussed as follows.
2. Synthesis of 1,2,4-Oxadiazole Derivatives
2.1 Coupling Agent Assisted 1,2,4-Oxadiazole Synthesis
Carbonyldiimidazole (CDI) is an organic reagent useful for synthesizing various
amides, peptides, and other organic scaffolds by activating carboxylic acid groups.
One such application of CDI is to prepare oxadiazole-based heterocyclic compounds
(Nandeesh et al. 2016). Deegan et al. synthesized oxadiazole derivative 1
(Scheme 1) from commercially available 4-methoxybenzoic acid in 97% yield
(Deegan et al. 1999). The reaction of O-acyl benzamidoxime with CDI resulted in
simpler isolation of oxadiazole compounds through liquid-liquid extraction followed
by vacuum filtration.
Employing peptide coupling reagents in the reaction flask containing amidoxime
and substituted carboxylic acid also leads to oxadiazole formation (Shaikh et al.
2023). N-(3-Dimethylaminopropyl)-N’-ethylcarbodiimide (EDC) is a water-soluble
compound popularly known for its role in activating carboxylic acid. Liang et al.
synthesized various 1,2,4-oxadiazole derivatives 2a–c (Scheme 2) using EDC as a
coupling reagent (Liang and Feng 1996).
https://t.me/med1917
Соседние файлы в папке Библиотека им академика М.И. Перельмана