Spectroscopic Properties of Natural Flavonoids

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 “6x9” b3314 Spectroscopic Properties of Natural Flavonoids

Dedicated to
Ranjit Chattopadhyay
Malati Chattopadhyay

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 “6x9” b3314 Spectroscopic Properties of Natural Flavonoids

Abbreviations

UV Ultraviolet Spectrocopy
FT-IR Fourier Transform Infrared Spectroscopy
1
H NMR Proton (1H) Nuclear Magnetic Resonance Spectrocopy
13
C NMR Carbon (13C) Nuclear Magnetic Resonance Spectrocopy
COSY Correlated Spectroscopy (2D-NMR)
NOSEY Nuclear Overhauser Effect Spectroscopy
HMQC Heteronuclear Multiple Quantum Coherence Spectroscopy
(2D-NMR)
HMBC Heteronuclear Multiple Bond Coherence Spectroscopy
(2D-NMR)
EI-MS Electron Impact Mass Spectroscopy
CI-MS Chemical Ionization Mass Spectroscopy
HR-MS High Resolution Mass Spectroscopy
TOF-MS Time-Of-Flight Mass Spectroscopy
ESI-MS Electronspray Ionization Mass Spectroscopy
MeOH Methanol
EtOH Ethanol
(CH3)2CO Acetone
CHCl3 Chloroform
CDCl3 Chloroform-d (deuterochloroform)
DMSO-d6 Dimethyl sulfoxide-d6 (Hexadeuterodimethyl sulfoxide)
Api b-Apiofuranosyl
Arb a-L-Arabinopyranosyl

vii

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viii Spectroscopic Properties of Natural Flavonoids

Gal b-Galactopyranosyl
Glc b-D-Glucopyranosyl
Rha α-L-Rhamnopyranosyl
Xyl b-D-Xylopyranosyl

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 “6x9” b3314 Spectroscopic Properties of Natural Flavonoids

Foreword

The birth of ‘Chemistry for Human Health’ started with the discovery that
Mother Nature has provided us with the cure for many diseases in form of
natural products, or the so called secondary metabolites. Plant and micro-
bial world offer a wide diversity of compounds that can serve as exciting
new pharmacophores with novel mechanisms of action for controlling
disease processes. Later on marine natural products added greater diver-
sity to the structural architect. The challenge to understand nature’s magi-
cal chemistry is continuously stimulating much of our intellectual
thoughts, scientific discoveries, and advances in technology. Understanding
the structures of the secondary metabolites is arguably the starting point
to make progress in pharmaceutical research. Until and unless one knows
the structure of a bioactive molecule, further advancement to bring its
activity to a higher level and also to enhance the efficiencies of other phar-
maceutical parameters is not possible. The chemistry of penicillin remains
a classic example. Once the structure was confirmed by X-ray and synthe-
sis, new derivatives could be made with broader activity profile.
It is a pleasure for me to write a foreword on this book on Spectroscopic
Properties of Natural Flavonoids written by Professor Goutam
Brahmachari. Flavonoids have emerged as an important class of second-
ary metabolites possessing wide array of biological activities. Anti-
oxidant, anti-mutagenic, anti-carcinogenic, anti-proliferative and
anti-inflammatory are just to name a few. This class of natural products
has already played an indispensible privileged skeleton for the develop-
ment of new therapeutic agents. Due to their wide range of activities, cor-
relation of structural motifs with the bioactivity has become a subject of
immense interest. So having a book rich with information on physical

ix

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x Spectroscopic Properties of Natural Flavonoids

characteristics and spectral data of 150 selected natural flavonoids will

certainly aid to our research in quest for new natural products of this class.
Mentioning the biological activities wherever reported and NMR spectral
data assignment are added attraction of this book. It reminded me of our
earlier days, when those working on natural product chemistry that
included terpenes, shikimates etc. heavily relied on the famous handbook
by Scott and Devon.
Vital role of flavonoids in a variety of nutraceutical, pharmaceutical,
medicinal and cosmetic applications has stimulated current trends of
research on isolation, identification, characterization and functions of
flavonoids and eventually their beneficial effect on health. I have no doubt
that this book will readily become attractive and helpful to practicing
natural product chemists. I hope that Prof. Brahmachari’s next effort will
be to cover other natural products of similar importance and expand the
present version.
Congratulations and many thanks to Professor Brahmachari for his
outstanding effort to come out with this important handbook.
26th July, 2018 Amit Basak
Indian Institute of Technology, Kharagpur
India

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 “6x9” b3314 Spectroscopic Properties of Natural Flavonoids

Preface

When studying science, the examples are more useful than the rules

— Sir Isaac Newton

Structural elucidation of organic molecules has always been a challenge

in the field of organic chemistry, and it is obvious that the task is more
challenging when one deals with natural products characterized by unex-
pected and unprecedented scaffolds. The scope of such investigations with
natural products is diverse and broad. It may be recalled in this connection
that more than 20,000 and more than 30,000 new marine-derived and
higher plant-derived compounds, respectively, were isolated and structur-
ally investigated in the past 10–12 years, with the help of modern spectro-
scopic techniques. Identification and in-depth understanding of the
chemical structure of a newly isolated compound from any natural source
is the very first and key step prior to advancing into further developments.
Bioactive natural products are a rich source of novel therapeutics, and
are of great interest and promise in the present day research directed
towards drug design and discovery. Many naturally occurring bioactive
compounds and/or their derivatives have become drugs of central impor-
tance, and represent a high percentage of the drugs used today. At present,
plants, microorganisms, and marine invertebrates represent major sources
of natural products for discovering new and novel drugs. Medicinal chem-
istry of such bioactive compounds encompasses a vast area that primarily
includes their isolation from natural sources, followed by their structural
elucidation. Among diverse natural products, flavonoids comprise a group
of phenolic secondary plant metabolites that are widespread in nature.
Major flavonoids that have well categorized structures as well as structure

xi

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xii Spectroscopic Properties of Natural Flavonoids

function-relationships are flavans, flavanones, flavones, isoflavones, fla-

vonols, flavanols, flavanonols, catechins, chalcones, dihydrochalcones,
aurones, anthocyanidins and anthocyanins. Bio-flavonoids are well-
known for their multi-directional pharmacological potentials that include
antioxidant, anticancer, antitumor, cytotoxic, enzyme inhibitory, anti-
inflammatory, antimicrobial, anti-HIV, anti-diabetic, anti-platelet aggre-
gation, and neuroprotective activity. Hence, this group of natural
polyphenols is now-a-days regarded as promising and significantly attrac-
tive natural substances to enrich the current therapy options against a
variety of diseases. Under this purview, researchers from different fields
are actively engaged with natural flavonoids.
Spectroscopic Properties of Natural Flavonoids — Volume 1 offers
detailed physical characteristics and spectral data of 150 selected com-
pounds from this important class of natural products, arranged according
to their chemical structures in various subclasses. Natural source, molecu-
lar formula, chemical structure, IUPAC name, physical characteristics
(state, melting point, molecular weight, and specific rotation) and detailed
spectral data (UV, FT-IR, 1H-NMR, 13C-NMR, 2D-NMR, Mass) along
with their assignments for each compound are documented. Being a first-
time comprehensive reference guide on natural flavonoids, which presents
the actual spectral data rather than just references to the data, this book
will prove to be of great benefit to advanced organic chemistry students,
organic chemists, natural product chemists, medicinal chemists and
pharmacologists.
I would like express my sincere thanks to Professor Amit Basak,
Indian Institute of Technology, Kharagpur, India, for his keen interest in
the manuscript and for writing the foreword to the book.
I would also like to express my deep sense of appreciation to all of the
editorial and publishing staff members associated with World Scientific
Publishing Co. Pte. Ltd., Singapore, for their keen interest in publishing
the work as well as their all-round help so as to ensure that the highest
standards of publication have been maintained in bringing out this book.
My effort will be successful only when it is found helpful to the readers
at large. Every step has been taken to make the manuscript error-free; in
spite of that, some errors might have crept in. Any remaining error is, of

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Preface xiii

course, of my own. Constructive comments on the approach of the book

from the readers will be highly appreciated.
Finally, I should thank my wife and my son for their well understand-
ing and allowing me enough time throughout the entire period of writing;
without their support, this work would not have been successful.
Goutam Brahmachari
Chemistry Department
Visva-Bharati (a Central University)
Santiniketan, India
July 2018

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Contents

Abbreviationsvii
Forewordix
Prefacexi

Acacetin 7-O-(3-acetyl-b-D-glucopyranoside)  1
6′′′-O-Acetyl amurensin 3
(2R,3R)-2′′-Acetyl astilbin [(2R,3R)-5,7,3′,
4′-tetrahydroxyflavanonol 2′′-acetylrhamnoside] 5
Aciculatinone 7
Afzelin A [6,7-(2′′,2′′-dimethylpyrano)-3,5,4′-trihydroxyflavanone] 9
Afzelin C [7,6-(2′′,2′′-dimethylpyrano)-5-hydroxy-3,
4′-(3,3-dimethylallyloxy)flavone] 11
Amyrisin B [5,7-dihydroxy-2-(4-((2-hydroxy-3-methylbut-3-
en-1-yl)oxy)phenyl)-6-methoxy-4H-chromen-4-one] 13
Amyrisin C [5,7-Dihydroxy-6-methoxy-2-(3-methoxy-4-
((3-methylbut-2-en-1-yl)oxy)phenyl)-4H-chromen-4-one] 15
Angepubebisin 17
Apigenin-4′-O-(2′′-O-p-coumaroyl)-b-D-glucopyranoside 19
Apigenin 6-C-[2′′-O-(E)-feruloyl-b-D-glucopyranosyl]-
8-C-b-D-glucopyranoside  22

xv

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xvi Spectroscopic Properties of Natural Flavonoids

Apigenin 8-C-[a-L-rhamnopyranosyl-(1→4)]-a-D-
glucopyranoside 25
Apigenosylide C  28
Aquisiflavoside [4′,5-dihydroxy-3′,7-dimethoxyflavone
5-O-b-D-xylopyranosyl-(1→6)-b-D-glucopyranoside] 30
Artelasticinol  33
Artelastoheterol [5,2′,4′,5′-tetrahydroxy-6,7-(2,2-dimethyl-
6H-pyrano)-8-prenyl-3-(9-hydroxy)prenyl-flavone] 35
Asphodelin A 4′-O-b-D-glucoside 37
Bismurrangatin 39
Brosimacutin K [(2S)-3′,4′-dihydroxy-7,8-
(2,2-dimethyl-3-hydroxy-2,3-dihydro-4H-pyrano)-flavan] 41
Celtiside A [Isoswertisin 8-C-[a-L-rhamnopyranosyl-
(1→6)-b-D-glucopyranoside] 43
Celtiside B [7-Methoxyluteolin 8-C-[a-L-rhamnopyranosyl-
(1→2)-b-D-glucopyranoside] 46
Citrumedin-B 49
Corbulain Ib [2-(4-Hydroxyphenyl)-3,4,9,10-tetrahydro-3,
5-dihydroxy-10-(3,4-dihydroxyphenyl)-(2R,3R,10S)-
2H,8H-benzo[1,2-b:3,4-b′]dipyran-8-one] 51
Cyanidin 3-O-(2′′-(5′′′-(E-p-coumaroyl)-
β-apiofuranosyl)-b-xylopyranoside)-5-O-b-glucopyranoside 53
7-De-O-methylaciculatin [8-C-b-D-digitoxopyranosylapigenin] 55
Delphinidin 3-O-b-galactopyranoside-3′,5′-di-O-b-
glucopyranoside  57
Denticulatain C 59
Denticulatain D 61
Devenyol 63

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Contents xvii

(2R,3S)-6,8-Di-C-methyldihydrokaempferol 65
(3R)-2′,7-Dihydroxy-3′-(3-methylbut-2-enyl)-2′′′,
2′′′-dimethylpyrano[5′′′,6′′′:4′,5′]isoflavan 67
(3R)-5,4′-Dihydroxy-2′-methoxy-3′-(3-methylbut-2-enyl)-
(6′′,6′′-dimethylpyrano)-(7,6:2′′,3′′)-isoflavanone  69
5,2′-Dihydroxy-3,6,7-trimethoxyflavone-5-O-b-D-xylopyranosyl-
(1→4)-O-b-D-glucopyranoside 71
5,4′-Dihydroxy-8-(3′′-methylbut-2′′-enyl)-2′′′-
(4′′′-hydroxy-4′′′-methylethyl)furano-[4′′′,5′′′;6,7]isoflavone 73
5,6-Dihydroxy-7,8,4′-trimethoxyflavone 75
5,7-Dihydroxy-6-(2′′-hydroxy-3′′-methylbut-3′′-enyl)-4′-
methoxylisoflavone 77
5,7-Dihydroxy-6,8,4′-trimethoxyflavone 79
5,7-Dihydroxy-8-(3-methylbut-2-enyl)-4-phenyl-
2H-chromen-2-one 81
5,7-Dihydroxy-8,3′,5′-trimethoxyflavone 83
7,4′-Dihydroxy-6,8-dimethoxy-4-phenylcoumarin 85
7,8-Dihydroxy-3-(3-hydroxy-4-oxo-4H-pyran-2-yl)-
2H-chromen-2-one 87
8,4′′-Dihydroxy-3′′,4′′-dihydrocapnolactone-2′,3′-diol 89
(2R,3R)-2-(2,4-dihydroxyphenyl)-3,5-dihydroxy-8,8-dimethyl-2,
3-dihydropyrano[2,3-f]-chromen-4(8H)-one 91
(2R,3R)-2-(2,4-Dihydroxyphenyl)-3,5,7-trihydroxy-8-
prenyl-chroman-4-one 93
3′,5′-Dimethoxy-[2′′,3′′:7,8]-furanoflavone 95
7,4′-Dimethylapigenin-6-C-b-glucopyranosyl-2′′-O-a-L-
arabinopyranoside 97
Eriodictyol 7-O-(6′′-feruloyl)-b-D-glucopyranoside 99

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xviii Spectroscopic Properties of Natural Flavonoids

Eriodictyol 7-O-sophoroside [Eriodictyol-7-O-b-D-

glucopyranosyl-(1→2)-b-D-glucopyranoside] 102
7-O-Feruloylorientin 105
Flemingichromone 107
Fleminginin 109
3′-Formyl-5,4′-dihydroxy-7-methoxyisoflavone 111
7-O-b-D-Glucopyranosylchamaejasmin 113
Griffinoid A 115
Griffinoid D 117
(+)-Hexanoyllomatin 119
Hildegardiol [(3R)-6,2′-dihydroxy-7-methoxy-4′,5′-
methylenedioxyisoflavan] 121
Hirsutissimiside A [formononetin 7-O-b-D-(6′′-ethylmalonyl)-
glucopyranoside]  123
Hovenin A 125
Hovenin B 127
Hovenin C 129
(2R)-5-Hydroxy-7,8-dimethoxy flavanone-5-O-b-
D-glucopyranoside 131
(2S)-3′-(2-Hydroxy-3-methylbut-3-enyl)licoflavone-
4′-methyl ether 133
2′-Hydroxy-3,4-dimethoxy-[2′′,3′′:4′,3′]-furanochalcone135
2′-Hydroxy-6,4′,6′′,4′′′-tetramethoxy-[7-O-7′′]-bisisoflavone 137
5-Hydroxy-3,7-dimethoxy-4′-prenyloxyflavone 139
5-Hydroxy-6,8-dimethoxy-3′,4′-methylenedioxyflavone 141
5-Hydroxy-7,8,2′,4-tetramethoxyflavone 143

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Contents xix

5-Hydroxy-8,8-dimethyl-4-phenyl-9,10-dihydropyrano
[2,3-f ]chromen-2(8H)-one 145
7-Hydroxy-4′-methoxy-3′-(3-hydroxy-3-methyl-trans-
but-1-enyl)-5′-(3-methylbut-2-enyl) flavanone 147
7-Hydroxy-6,4′-dimethoxy-isoflavonequinone  149
7-Hydroxy-6-methoxy-3,8-bis(3-methyl-2-butenyl)coumarin 151
6-Hydroxyluteolin 7-O-laminaribioside
[6-hydroxyluteolin-7-O-b-D-glucopyranosyl-(1→3)-b-D-
glucopyranoside] 153
Irilone 4′-O-[b-D-glucopyrano-(1→6)-O-b-D-glucopyranoside] 156
Kaempferol 3-O-b-D-apiofuranosyl-(1→6)-b-D-glucopyranoside 158
Khonklonginol A [3,5-Dihydroxy-4′-methoxy-6′′,6′′-
dimethylpyrano(2′′,3′′:7,6)-8-(3′′′,3′′′-dimethylallyl)
flavanone] 160
Khonklonginol E [3,5-Dihydroxy-4′-methoxy-6′′,
6′′-dimethylpyrano(2′′,3′′:7,6)-8-(3′′′,3′′′-dimethyl-2′′′,
3′′′-dihydroxypropyl)flavanone] 162
Khonklonginol F [3,5-Dihydroxy-4′-methoxy-6′′,
6′-dimethylpyrano(2′′,3′′:7,6)-8-(3′′′,
3′′′-dimethylallyl)flavone] 164
Kurzphenol B 166
Lawsochrysin (5-hydroxy-6-n-pentyl-7-n-pentyloxyflavone) 168
Lawsonaringenin [4′,5-dihydroxy-7-(4′′-pentenyloxy)flavanone] 171
Licoflavanone-4′-O-methyl ether 174
Liquiritigeninyl-(I-3,II-3)-naringenin  176
Luteolin 7-O-[6′′-(3′′′-hydroxy-4′′′-methoxy cinnamoyl)]-
b-D-glucopyranoside 178
Lyratin B 180

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xx Spectroscopic Properties of Natural Flavonoids

Malvidin 3-O-[6-O-(3-hydroxy-3-methylglutaryl)-
b-glucopyranoside] 182
3-Methoxy-(3′′,4′′-dihydro-3′′,4′′-diacetoxy)-2′′,
2′′-dimethylpyrano-(7,8:5′′,6′′)-flavone 184
7-Methoxy-2′′-O-(2′′′-methylbutyryl)orientin 187
6-Methoxykaempferol-3-O-b-D-gentiobioside
[6-methoxy-3,5,7,4′-tetrahydroxyflavon 3-O-b-D-
glucopyranosyl(1→6)-O-b-D-glucopyranoside] 189
5-Methoxyl-4,2′-epoxy-3-(4′,5′-dihydroxyphenyl)-
linear pyranocoumarin  192
(2R,3R)-6-Methylaromadendrin 3-O-b-D-glucopyranoside 194
3′,4′-Methylenedioxy-[2′′,3′′:7,8]-furanoflavonol  196
N-(8-Methylquercetin-3-O-[a-L-rhamnopyranosyl-(1→2)-
[a-L-rhamnopyranosyl-(1→6)]-b-D-galactopyranosyl])-3-
hydroxypiperidin-2-one 198
Murrmeranzin 201
Naringenin 5-methyl ether 203
Nervilifordin A [Rhamnocitrin-3-O-b-D-xylopyranosyl-
(1→4)-b-D-glucopyranoside] 205
Nervilifordin E [4′-O-b-D-glucopyranosylrhamnetin-3-O-b-D-
glucopyranosyl-(4→1)-b-D-glucopyranoside] 207
Noidesol A 209
Ormosinol [5,7,2′,4′-tetrahydroxyl-6,8,5′-tri-(g,g-dimethylallyl)
isoflavanone] 212
Ormosinoside [Isoprunetin-7-O-b-D-xylopyranosyl-(1→6)-
b-D-glucopyranoside 214
Oxytropisoflavan A 216
Pavietin 219

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