Chapter 1 - Shodhganga : a reservoir of Indian theses...
Transcript of Chapter 1 - Shodhganga : a reservoir of Indian theses...
REVIEW OF LITERATURE
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Chapter 1
REVIEW OF LITERATURE
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Perilla is an aromatic herb belongs to fa mily Labiatae. Four to six species of
Perilla are found. Only one species is found in India. Commonly grows in
waste places, crop fields, road sides, occasionally cultivated to 3000m.
Leaves and flower tops of Perilla are used as flavouring. Seeds are edible or
used as condiments. Plant extract and powdered dried part of Perilla are
used for bronchitis and uterine ailments. Paste of Perilla leaf is used in
rheumatic arthritis1.The leaf of P. frutescens Britton (Japanese name shiso) is
one of the most popular garnishes in Japan 2 which is prescribed for cold,
cough and promoting digestion 3.The herb is reported to possess sedative,
antispasmodic and diaphoretic properties and prescribed for cephalic and
uterine troubles.
Seeds of Perilla contain 30-51% of a valuable drying oil known as Perilla
oil. Perilla oil finds extensive use in paints and varnishes, printing inks,
Japanese oil papers, waterproof clothes, artificial leather, cheap lacquers,
enamels and linoleum. In U. S.A., oil is mixed with soyabean oil for
protective coatings. The cake left after the expression of the oil is used in
Japan as a fertilizer for mulberry and rice. The essential oil possesses a
strong antiseptic action and is used as antimildew agent. The oil is used in
Japan chiefly for the preparation of the • -antialdoxime of perillaldehyde
which is 2,000 times as sweet as sugar and 4 to 8 times as sweet as
saccharin. The Japanese Government permits the use of these derivatives as
a substitute for maple sugar or liquorices in the sweetening of tobacco 4.
Spermadictyon is a small genus of shrub found in Indomalayan region and
China. It belongs to family Rubiaceae. One species of Spermadictyon occurs
in India. Spermadictyon suaveolens is a shrub upto 12 ft. high found almost
throughout India ascending upto an altitude of 6,500 ft. The plant is also
cultivated in gardens, flowers are blue or white.
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Plant is used as tribal remedies against snake bites and scorpion stings in
Rajasthan5 and also used as a tribal remedy for diabetes 6. Hypoglycemic
activity of S. suaveolens was also observed7. The plant is used by Mundas of
Ranchi district (Bihar), along with mustard oil as an application for wounds.
The bark is ground and rubbed on the body in puerperal fever. The root is
given in diarrhea. The wood is dark grey and reported to be used for making
gunpowder charcoal8. Leaves are used as a insecticide for the stored grains 9.
Verbascum belongs to the family Scrophulariaceae is erect, pubescent herb.
About 360 species of Verbascum are found, only 6 species occur in India10.
The name ‘mullein’ has two possible derivations: It either comes from
mollis, which means soft in Latin or the Latin word mulandrum, which
comes from melanders and means leprosy - an illness this plant was used to
treat. Verbascum means ‘mullein’ in Latin. It is derived from the word
barbascum, which means ‘with beard’. The species name is thapsus because
mullein resembles the European genus Thapsia, named after an ancient town
in the present day Tunisia.
In Europe by settlers, it was used as medicinal herb as a remedy for cough
and diarrhoea and a respiratory stimulant for the lungs when smoked. A
methanol extract from common mullein has been used as an insecticide for
mosquito larvae. The American Indians dried the leaves, (especially the first
year, or new growth leaves) and smoked them to relieve asthma and other
respiratory problems. The leaf tea is also medicinal and is recognized by
herbalists as a traditional remedy for respiratory congestion and hemorrhage.
The flowers are said to have strong microbial qualities an d are used in oil
infusion for ear infections. The roots have been used for their tonic
properties, astringent to treat urinary incontinence. The seeds were also used
by American Indians as a paralytic fish p oison. The plant contains coumarin
REVIEW OF LITERATURE
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and rotenone, especially in seeds. The leaves are a rubefacient which means
that if you rub them against your skin it will become red and irritated.
Mullein tea provides vitamins B -2, B-5, B-12, and D, choline, hesperidin ,
PABA, sulphur, magnesium, mucilage, saponins and other active
constituents.
People use the tea as beverage, but its best known as one of the safest, most
effective herbal cough remedies. Mullein is an expectorant and a tonic for
lungs, mucus membranes and glands. An infusion is good for colds,
emphysema, asthma, hay fever and whooping cough. Labo ratory tests have
shown that it is anti-inflammatory with antibiotic activity and that it inhibits
the tuberculosis bacillus. The Indians smoked dried mullein and coltsfoot
cigarettes for asthma and bronchitis. The tea is also a n astringent and
demulcent. It is good for diarrhoea and it is been used in compresses for
hemorrhoids since it was recommended b y Dioscorides centuries ago. It i s
also supposed to help other herbs get absorbed through the skin. Pliny of
ancient Rome, Gerard in sixteenth century England the Delaware Indians
and country folk in the south used the heated leaves in poultice for arthritis.
A tincture of the flowers is used for migraine headaches. An oil extract of
the flowers which contains a bactericide is used for ear infections 11.
The seeds are said to intoxicate fish when thrown into the water, and are
used by poachers for that purpose, being slightly narcotic. The seeds of
V. sinuatum, which are used in Greece as a fish poiso n, contain 6 to 13 per
cent of saponin. Traces of the same substance were found in the seeds of
V. phlomoides and V. thapsiforme, common in the south of Europe, which
have been used for the same purpose. V. pulverulentum of Madeira (also
used as a fish poison) and V. phlomoides are employed as taenicides
(expellers of tapeworm)12.
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Great Mullein has been used as an alternative medicine for centuries and in
many countries throughout the world . The value of Great Mullein as a
proven medicinal herb is now backed by scientific evidence. Some valuable
constituents contained in Mullein are coumarin and h esperidin, they exhibit
many healing abilities. Researches indicate that some of the uses analgesic,
antihistaminic, antiinflamatory, anticancer, antioxidant, antiviral, bacteristat,
cardiodepressant, estrogenic, fungicide, hypnotic, sedative and pesticide are
valid. An infusion is taken internally in the treatment of a wide range of
chest complaints and also to treat d iarrhoea and bleeding of the lungs and
bowels. The leaves, roots and the flowers are anodyne, anti -inflammatory,
antiseptic, antispasmodic, astringent, demulcent, diuretic, emollient,
expectorant, nervine and vulnerary.
Mullein oil is very medicinal and va luable destroyer of disease germs. An
infusion of the flowers in olive oil is used as earache drops or as a local
application in the treatment of piles and other mucous membrane
inflammations. This infusion is a str ong antibacterial. The oil is used to treat
gums and mouth ulcers. A decoction of the roots is used to alleviate
toothache and also relieve cramps and convulsions. It is also used in
alternative medicine for the treatment of migraine headaches accompanied
with oppression of the ear. The whole plant possesses slightly sedative and
narcotic properties. The seeds are mostly used as narcotic and also contain
saponins. The dried leaves are sometimes smoked to relieve the irritation of
the respiratory mucus membranes. They can be employed with equal ben efit
when made into cigarettes for asthma and spasmodic coughs in general.
Externally, a medicinal poultice of the leaves is applied to sunburn, ulcers,
tumors and piles. A decoction of the seeds is used to soothe chilblains and
chapped skin.
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It is also used as dye, insecticide, insulation, lighting, tinder and wick. A
yellow dye is made from the flowers by boiling them in water. When used
with dilute sulphuric acid they produce a rather permanent green dye, this
becomes brown with the addition of alkalis. An infusion of the flower is
sometimes used to dye the hair in golden colour. The leaves contain rotenone
which is used as an insecticide. The dried leaves are highly flammable and
can be used to ignite a fire quickly or as wick for candles13.
Isolated compounds and biological activity of Perilla frutescens,
Spermadictyon suaveolens and Verbascum thapsus are listed in Table 1.1,
1.2 and 1.3 respectively.
Rotenone (Fig.1.1) and its derivatives commonly referred to as rotenoids are
insecticidal compounds essentially extracted from seeds, roots and
sometimes leaves and stems of the tropical Leguminosae plants Derris,
Tephrosia and Lonchocarpous. Commercially important plants like Derris
elliptica and D. malaccensis contain 4-5% rotenone while Lonchocarpous
utilis and L. urucu contain 8-10% rotenone in dry roots. Rotenone comprises
of an isoflavone nucleus with an isoprene moiety.
Table 1.1. Isolated compounds/activity of different parts of Perilla species
S. No.
Plant Name
Plant Part
Isolated compounds/Activity
Ref.
1
Perilla nankinensis
Leaves
Apigenin glucuronide
14
Essential oil (leaves)
Shisofuran
15
2
Perilla setoyensis
Essential oil
4 - Terpenol and limonene
16
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3
Perilla sikokiana
Leaves
Anti-inflammatory activity
17
Ethyl linolenate, linolenic acid and • -sitosterol
18
Aerial part
(3S,4R)3-hydroxy-4-(1-methyl-ethenyl 1-cyclohexene-1-carboxaldehyde
19
Perilloside A[ ( - ) perillyl 7 - O - • - D glucopyranoside eugenyl O - • - D - glucopyranoside]
20
Perilloside B [1- • - D -glucopyranosyl (-) perillate], Perilloside C [trans- dihydroperillyl 7 - O - • - D - glucopyranoside], Perilloside D [cis - dihydroperillyl 7 - O - • - D - glucopyranoside], • - sitosteryl O - • -D - glucopyranoside, protocatecheuic aldehyde methyl ferulate
21
7 - O - Diglucuronides of apigenin, luteolin and scutellar in
22
Benzyl • - D - glucopyranoside, ursolic acid, tormetic acid, methyl rosmarinate, Perilloside E [6 -methoxy-2, 3 - methylenedioxy - 5 - allylphenyl • - D - glucopyranoside]
23
Weak antidermatophytic activity
24
Sedative effect
25
Luteolin, rosmarinic acid and caffeic acid
4
Perilla frutescens
Leaves
Luteolin as a anti -inflammatory and antiallergic constituent
26
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Rosmarinic acid
Tannic activity
27
Leaves
Caffeic esters, (Z, E) - 2 - (3, 4 -dihydroxyphenyl) ethenyl ester and (Z, E) - 2 - (3, 5 - dihydroxyphenyl) ethenyl ester of 3 - (3, 4 -dihydroxyphenyl) - 2 - propenoic acid
28
Novel antioxidants [5 - (3, 4 - dihydroxyphenyl mehyl oxazolidine 2, 4 - dione (1)] & [3 - (3, 4 - dihydroxyphenyl lactamide -2)]
29
Roasted seeds
Antioxidant activity
30
Stem
Perriloxin and dehydroperriloxin
31
Apigenin, 2,4,5 -trimethoxy cinnamic acid (TMCA)
Antidepressant effect
32
Cytotoxicity and antitumor activity
33
Antiallergic flavonoids
34
Vinyl caffeate, trans - p - menth - 8 -en - 7 - yl caffeate, 3, 4 -dihydroxybenzaldehyde, methyl caffeate, 3’, 4’, 5, 7 -tetrhydroxyflavone, caffeic acid, 6, 7 - dihydroxycoumarin and rosmarinic acid
35
Post coital antifertility effect
36
Glycoprotein
37
Neuropharmacological activity
38
Perilla frutescens
Whole Plant
Antioxidant vinyl caffeate
39
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Limonene, piperitone, •-caryophyllene and germacrene
40
Essential oil (Aerial part)
Perillaketone, Isoegomaketone, egomaketone and perillene
41
Essential oil (leaves & racemes)
Perillaketone, 1 - (3 - furyl) - 4 -methyl - 2 - pentanone, 1 - (3 - furyl) - 4 - methyl - 2 - penten - 1 - one, 1 -(3 - furyl) - 4 - methyl - 3 - penten -1 - one
42
Essential oil (leaves & racemes)
40-55% Perillaldehyde (4 -isoprenyl-I-cyclohexen-7-al)
43
Essential oil (Green leaves)
Perillaldehyde, limonene, • - caryo - phyllene, • - bergomotene and linalool
44
Essential oil (Roasted seeds)
Luteolin, chrysoeriol and apigenin
45
Phenylpropanoid
46
Limonene, linalool, perillaketone and isoegomaketone
47
Limonene (9%) and small quantity of • - pinene
48
•-Caryophyllene, caryophyllene, thujopsene and • - farnescene
Perillaketone
49
Perilla frutescens
Essential oil
Perillaldehyde, elsholtziaketone, perillaketone, citral, perillene and phenylpropanoid
50
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Table 1.2. Activity of different parts of Spermadictyon species
Table 1.3. Compound isolated/activity of different parts of Verbascum species
S. No.
Name of Plants
Plant Parts
Activity
Ref.
Roots
Hypoglycemic activity
7
1
Spermadictyon
suaveolens
Leaves
Insecticidal activity
9
S. No.
Name of Plants Plant Parts
Compound isolated/Activity Ref.
New sterol sigmasta - 5, 9 (11) - dien - 3β - ol, three new saponins: celsiogenin A [olean - 12, 17 (18) -dien - 3β, 23 - diol ], celsiogenin B [olean - 11, 13 (18) - dien - 3β, 23, 28 - triol ], celsiogenin C [olean - 11, 13 (18) - dien - 3β, 22β, 23, 28 - tetriol ].
51
1
Verbascum
chinensis
Whole plant
Fish poisoning
52
2
Verbascum georgicum
New iridoid 6 - alpha - L -rhamnopyranosyl descinnamoyl globularinin
53
Aerial part
New iridoid glycoside 6 - O - alpha - L (3” - O - n - coumaryl) rhamnopyranosylacubin
3
Verbascum laxum
Bark
Haparoside, 6 - O - alpha - L - (2”- O - 3”- O - acetyl, n - methoxy - trans-cinnamoyl) rhamnopyranosylacubin
54
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Inflorescence
6 - O - p - coumaroylcatalpol
55
Verbascosaponin, luteolin 7 - O -glucoside, verbascoside and foraythoside B
4
Verbascum lychnitis
Antiproliferative effect
56
Aerial part
A new spermine alkaloid: verbascenine (C30H40N4O3)
57
5
Verbascum nigrum
Inflorescence
Verbascosaponin, luteolin 7 - O -glucoside, verbascoside, foraythoside B
58
Five flavones, one flavanone, four flavonols, two iridoids, two steroglycosides, four carbohydrate derivatives, two phenolic substances and one terpene derivative Antiproliferative effect
59
Flowers
A new iridoid ester glycoside acylated with p-coumaric acid, speciocide, caffeic esters, verbascoside, forsythoside B, desrhamnosylverbascosaponin
60
6
Verbascum phlomoids
Flowers (oil contents)
Fatty acids: Myristic, palmitic, stearic, oleic, linoleic, arachic and lignoceric Phenolics, p-hydroxy cinnamic acid, protocatechuic acid, p-hydroxybenzoic acid, p - coumaric acid, vanillic acid and ferulic acid
61
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Aerial part
A new spermine alkaloid: verbascenine (C30H40N4O3)
58
Z isomer [13 - acetyl - 1 (Z) - cinnamoyl - 6 - oxo - 8 - phenyl - 1, 5, 9, 13 - tetraazacycloheptadecane, verballoscenine] of verbascenine and analogous N - 13 on acetyl alkaloids verbacine, verballocine and verballoscenine
62
7
Verbascum phoeniceum
17 - membered macrocyclic sperm ine lactam alkaloids ( -) protoverbine and its N, N’ - methylene - bridged natural analogue (+) - protomethine (-) -verbacine, (-) - verballocine, (+) - verbascenine, (+) - verballoscenine, (+) - verbamethine, (+) - incasine (B) and some of their isosteric analogues
63
Alkaloid verbaskine (C 29H36N4O3), (E) - cinnamamide
64
Lactam alkaloids: ( -) protoverbine and its N, N’ - methylene - bridged natural analogue (+) - protomethine (-) -verbacine, (-) - verballocine, (+) - verbascenine, (+) - verballoscenine, (+) - verbamethine, (+) - incasine (B) and some of their isosteric analogues
63
17 - membered macrocyclic spermine alkaloids (-) - (s) - verbasitrine (-) - (s) -isoverbasitrine, (+) - (s) verbametrine and (+) - (s) - isoverbametrine
65
8
Verbascum pseudonobile
Leaves
Novel 17 - membered lactam alkaloids: verbacine and verballocine containing spermine
66
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9
Verbascum pulverulentum
Root
Two iridoids of 6 - O - alpha - L -rhamnopyranosyl - catalpol type
67
10
Verbascum pycnostachyum
Aerial part
sigmasterol, β-sitosterol and unidentified compound (C29H48O)
68
11
Verbascum saccatum
Aerial part
Aucubin, 6 - alpha - L -rhamnopyranosylcatalpol and new iridoid glycoside 6 - alpha - L - (2”- para - coumarin) rhamnopyranosylcatalpol (C39H38O16)
68
Orobol, orobol 7 - O -beta -D- glucoside, 5, 3’, 4’- trihydroxy-8-methyl isoflavone 7 - O - beta - D - glucoside, 5 - hydroxy, 3’- 4’-dimethoxyflavone 7 - O - alpha - L - rhamnoside and phenyl ethanoid glycoside acetoside
70
Aerial part
7 new saikosaponin homologues called mulleinsaponins having 13, 28 epoxyolean- 11 - ene skeleton isolated together with eight known saikosaponin homologues 3 -O-beta-D-fucopyranosyl saikogenin F, saikosaponin A, songarosaponins C, D, mimengoside A and buddlejasaponins I and IV
71
12
Verbascum sinaiticum
Leaves
Two flavonolignans hydrocarpin and novel sinaiticin and two flavones chrysoeriol and luteolin
72
Aerial part
New iridoid glycoside sacatoside 6 -alpha - L (3” - n - coumaroyl) rhamnopyranosylcatalpol and α - methyl rhamnopyranoside
73
Under- aerial part
New diacyliridoiddiglycoside 6 -O-(2”, 3” di - O -acyl) - α -L -rhamnopyranosyl catalpol
74
13
Verbascum sinuatum
Iridoid and phenylpropanoid glycoside
75
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Aerial part
D-glucopyranosyl - (1 - 3) - beta - D -glucopyranosyl - (1 - 2) - beta - D -fucopyranosyl - 13 beta, 28 - epoxyolea - 11 - ene - 3 beta, 16 beta, 23 - triol
76
Aerial part
Two new triterpenoid saponins: songarosaponin E and F and known buddlejasaponin I
77
14
Verbascum songaricum
Root
Flavonoids: apigenin, quercetin, luteolin, cynaroside and daucosterol
78
15
Verbascum spinosum
Aerial part
A new iridoid glycoside verbaspinoside 6 - O - (2” - O - trans - cinnamoyl) -alpha - L - rhamnopyranosyl catalpol
79
Verbascosaponin, luteolin 7 - O -glucoside, Verbascoside and foraythoside B
Antiproliferative effect.
57
Amanthadine derivatives Flowers
Reduced the infectious and haemaglutination yields of influenza viruses
80
16
Verbascum thapsiforme
Aerial parts
7 new saikosaponin homologues called mulleinsaponins having 13, 28 epoxyolean - 11 - ene skeleton isolated together with eight known saikosaponin homologues 3 - O - beta - D -fucopyranosyl saikogenin F, saikosaponin A, songarosaponins C, D, mimengoside A and buddlejasaponins I and IV
71
Aerial parts
New iridoid glycoside unduloside 6 - O - [(2”- O - trans - feruloyl) - alpha - L -rhamnopyranosyl] aucubin
81
A novel macrocyclic dimer lactone: verbalactone,
17
Verbascum undulatum
Root Antibacterial activity
82
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18
Verbascum fruticulosum
Aerial part
7 new saikosaponin homologues called mulleinsaponins having 13, 28 epoxyolean -11 - ene skeleton isolated together with eight known saikosaponin homologues 3 - O - beta-D - fucopyranosyl saikogenin F, saikosaponin A, songarosaponins C, D, mimengoside A and buddlejasaponins I and IV
71
Acetoside, a polyhydroxylated phenyl propanoid glycoside
19
Verbascum macrurum
Aerial part
Antioxidant activity
83
20
Verbascum wiedemannianum
Aerial part
Four new phenylethanoid glycoside (wiedemanniosides B - E) with wiedemannioside A, verbascoside, martynoside,echinacoside, leucosceptoside B
84
21
Verbascum gypsicola
Whole plant
Antimicrobial activity
85
Five novel iridoid glycosides which are classified into two types - one contain ajugol and others contain 6 - O - L - (alpha-L-rhamnopyranosyl) - catalpol
86
Five new phenylethanoid glycosides and one new lignan glycoside
87
22
Verbascum
thapsus
Whole plant
Verbacoside [Luteolin 5 - O - alpha (1 - 3) - beta - D - glucopyranosyl (1 - 6) - beta - D - glucopyranoside]
88
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Sterones, iridoids and sesqueterpenes
89
Catalpol, harpagide, aucubin and ajugol
75
Mild astringent
90
Antiviral activity
91
Whole plant
In vitro - Antihepatoma activity
92
Leaves and Flowers
7, 4’ - dihydroxyflavone - 4’ -rhamnoside, 6 - hydroxyluteolin - 7 - glucoside - 3’-methylquercetin
93
Irridoid glycosides: La teroside, harpagoside, ajugol and aucubin
Verbascum thapsus
Roots
Phytotoxic
94
The genus Tephrosia, estimated to contain 300 species, is endowed with
insect controlling properties 95-98. Besides rotenone other insecticidal
principles include tephrosin (Fig.1.1), degu lin (Fig. 1.1) and isotephrosin 99.
Among alkaloids, nicotine (Fig. 1.1) is probably the most well known and
widely used insecticide100. Nor-nicotine (Fig.1.1) and anabasine (Fig.1.1) are
other toxic constituents present in crude extractives of Nicotiana species.
Acylated nor-nicotinoids gave 100 % kill of I st instar larvae of tobacco
hornworm, Manduca sexta101. The powder of dried flowers of
Chrysanthemum cinerariaefolium or Tanacetum cinerariaefolium also
referred as pyrethrum is well known for insecticidal properties.
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The pyrethrum powder is usually extracted with hexane / kerosene to obtain
viscous oleoresin concentrate containing about 30% pyrethrins. It contains
six closely related insecticidal esters namely pyrethrins I and I I, cinerins I
and II and jasmolins I and II102-103.
Members of family Zingiberaceae have attracted continuous phytochemical
interest due to their considerable importance as natural species or as
medicinal plants. Curcuma longa and Kaempferia pandurata are, on the
other hand, important medicinal plants of South Asia used as folk medicine
for the treatment of stomach discomfort as expectorants or as antiseptic for
wounds104-107. Taxa of Zingiberaceae have also been studied for insecticidal
activity. Dried and powdered rhizomes of C. longa, e.g. have been reported
to deter storage pest insects such as Tribolium castaneum 108.
In Columbia there is a long tradition of plants being used for their
insecticidal, repellent or antifeedant properties to protect crop fr om insect
attack (Perez Arbelaez, E., 1953). Ageratum conyzoides known to contain
precocene I and precocene II109-110 has been used not only in folk medicine,
as a cure for several diseases but also as an insecticide. n -Hexane fraction of
extract is active against Musca domestica larvae but the precocene
containing fraction is not. Some flavonoids are reported 111 to have toxic
effect on insects.
The essential oil of Artemesia monosperma obtained by steam distillation of
the aerial part of the plant was show n to have insecticidal activity against
housefly, cotton leafworm and rice weevil. The chemical structure of the
active ingredient from the steam distillate was shown to be 3 -methyl,
3-phenyl-1, 4-pentadiyne112 (Fig.1.2).
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28
OO
O
O
O
MeOMe
MeOMe
H
H
H
O
MeO
MeO
O OO
O
OH
OO
O
O
MeOMe
O
N
Me
H
N
H
H
N
H
H
OO
O
O
O
Rotenone Tephrosin
Deguelin Amorpholone
Nicotine Nor-nicotine Anabasine
Fig. 1.1
Fig. 1.1
REVIEW OF LITERATURE
29
C CCC CH H
Me
Fig. 1.2
DIFFERENT CLASSES OF NATURAL COMPOUNDS AS
INSECTICIDES
MONOTERPENES
Monoterpenoids have profound effect on insects. They are widely distr ibuted
in the plant kingdom and are utilized as attractants, defensive and
allelopathic agents. When applied to flies, cockroaches and the western corn
rootworm, limonene, linalool and pulegone exhibited insecticidal and
antifeedant activity113. Monoterpenoids in the essential oils of Ocimum
basilicum have activity as deterrents and toxicants. The major active
constituents in the essential oils of Ocimum basilicum include linalool,
methyl chavicol, eugenol, methyl eugenol, geraniol, geranial and neral 114.
Zanthoxylum bungeanum, has been reported to possess insect repellent and
antifeedant action115. Among the principal constituents 1, 8-cineole, linalool,
4-terpineol, α-terpineol, piperitone, 4-terpinoyl acetate, α-terpene, α-
terpineyl acetate and caryophyllene exhibited the strongest feeding deterrent
activity comparable to commercial repellent N, N-diethyl-m-toluamide
(DEET)116. Piperitone, a major component of some oth er essential oils as
well117 acts as feeding deterrent to white pine weevil, Pissodes strobi.
REVIEW OF LITERATURE
30
Linalool is also repellent towards aphids 118 and mosquitoes. 4-Terpineol is
antifeedant against the locusts and repellent to mosquitoe s119.
SESQUITERPENES AND DITERPENES
Many plant sesquiterpenes and diterpenes exhibit biological activity against
insects ranging from insect feeding deterrence to toxocity 120-122. Several
insecticidal and antifeedant sesquiterpenoids 123-127 and diterpenes128 are
known as major deterrents in insect plant interactions. Floral chemicals,
besides being attractive to pollina tors are known for their ant iherbivore
action against insects. Several feeding deterrents have been isolated from the
inflorescence of cultivated sunflower such as sesquiterpene lactone angelate
argophyllin-A (Fig.1.3) and 3-O-methyl niveusin-A, which are most potent.
Such antifeedants produced symptoms in western corn rootworm 129-130.
A sesquiterpene 4,11-selinadien-3-one, also known as α-cyperone, isolated
from the nutgrass tubers showed insecticidal activity against diamondback
moth, Plutella xylostella131. Drimane group of sesquiterpenes, possess a
broad spectrum of activity including antibacterial, antifungal, antifeedant,
plant growth regulatory, cytotoxic, phytotoxic, piscicidal and molluscicidal
activities. Besides, occurring in plants of green Warburgia, Cinnamosina,
Winterana and Cinnamodendron (Cannellaceae) such compounds also occur
in the marsh pepper Polygonum hydropiper (Polygonaceae). They have also
been reported from some fungi and some molluscs. Polygodial , warburganal
and muzigadial are among some potential drimane sesquiterpenes having
anti-insect and antifungal properties 132.
The powdered bark of Chinese bittersweet, Celestrus angulatus , is
traditionally used in China to protect plants from insect damage. An insect
antifeedant celangulin with two possible structures has been reported from
this plant. It is a non-alkaloidal sesquiterpene polyol ester compound that has
REVIEW OF LITERATURE
31
a dihydroagarofuran skeleton with seven hydroxyl functions, five of which
are acetylated, one benzoylated and one free 133. Insecticidal alkaloids with a
β-dehydroagarofuran skeleton such as wilfordine from Tripterygium
wilfordii134 and wilforine alkaloid from Maytenus rigide as insect
antifeedant135 have also been reported.
ACETYLENES AND THIOPHENES
The oil of the desert plant, Artemisia monosperma has been reported to
contain 3-methyl 3-phenyl-1, 4-pentadiyne which is as active as DDT
against housefly and cotton leafworms, S. littolaris larvae. It is five fold
more active against the rice weevil, Sitophilus oryzae136.
PHENYLPROPENOIDS
Phenylpropenoids have some potential as evident fro m the bioactivity shown
by the essential oil of sweetflag, Acorus calamus. The oil has insecticidal,
ovicidal, antigonadal, antifeedant and insect growth inhibitory activities,
which have been attributed to the presence of asarones, the
phenylpropenoids occurring in very high percentage in plant 137. Asarone also
referred to cis asarone is a major constituent though other isomers such as
trans asarone and isoasarone has also been reported from this plant138
(Fig.1.3).
ACETOGENINS
Acetogenins from Annona sp. are waxy substances consisting of C -32 or
C-34 long chain fatty acids combined with a propan-2-ol unit at C-2 to form
•-lactone. Over 220 annonaceous acetogenins have been reported from 26
species139. Entire group of annonaceous acetogenins was patented as
pesticide in which asimicin was claimed as structurally defined pesticidal
acetogenin140.
REVIEW OF LITERATURE
32
ISOBUTYLAMIDES
A large number of unsaturated isobutyl amides have been isolated from
various species of genus Piper141. These compounds have been isolated
mainly from fruits, stem and leaves of various Piper species such as
P. nigrum, P. longum, P. pedicellosum and P. thomsoni. Some of the active
compounds include piperlonguminine, pip erine (Fig.1.4), guineesine,
retrofractamide, pipericide, dihydropipericide, and pellitorine 142-145. Being
neurotoxic, these amides showed both knockdown and lethal action against
pyrethroid susceptible and resistant insects.
QUASSINOIDS
Quassinoids are well known for their anti-inflammatory, antimalarial,
amoebicidal, antifeedant, insecticidal and herbicidal properties. At least 31
quassinoids reported from Picrasama ailanthoides146-149 are potent
antifeedant and insecticidal compounds against 3 rd instar larvae of
diamondback moth, P. xylostella. Some of the bioactive quassinoids include
bruceantin isobrucein and bruceanol A (Fig.1.4) from Bruceae
antidysenterica and bruceoside A, brucein E, bruceoside B and yadanzioside
A, B, C, F G and L from Brucea javanica150.
LIMONIN AND RELATED COMPOUNDS
Limonoids are a group of chemically related bitter tetranortriterpenes found
predominantly in Rutaceae and Meliaceae. Limonin (Fig.1.4) is one of the
principal bitter components of citrus seeds having anti -insect properties. In
addition to having anti -feedant action against various insects, recently it
has been demonstrated that it induces anti -feedant action against the 5 th
instar larvae of P. xylostella which have developed resistance to
conventional synthetic insecticide150. Different parts of the neem,
Azadirachta indica, particularly the seeds, contain the array of biologically
REVIEW OF LITERATURE
33
active tetranortriterpenoids based on apo -euphol or apotirucallol skeleton 152-
153. Two limonoids have been commercialized, azadi rachtin in many parts of
the world and toosendanin in China. Azadirachtin, the main active
compound was identified as a potent anti -feedant against Schistocerca
gregaria, the desert locust. Its structure has been finally established by Kraus
and it induces toxicological, behavioural and physiological responses in over
four hundred insect species.
MELIACINS
Among the various groups of meliacins, which differ from each other in
basic nuclear structure pattern of oxygenation, C -seco meliacins are most
important such as azadirachtins (A & B) (Fg.1.5), salanin and nimbin.
Toosendanin is the major bioactive material in bark of Melia azedarach and
M. toosendan . It possesses strong anti -feedant properties and also inhibits
insect growth development154.
CARDENOLIDE GLYCOSIDES
Fractionation of the methanol extracts of stem and bark of Anodendron
affine has led to the isolation of three cardenolide glycosides, 4,5 -dehydro-
12-oxo-affinoside E, 12-oxo-affinoside E and 16 •-hydroxy affinoside A155
along with previously known carbenolides, affinoside A, E and M
which inhibit growth of silkworm larvae , Bombyx mori at 1 to 3 ppm.
concentration.
SUGAR ESTERS
Resistance to insect pests in Nicotiana sp., wild tomato, Lycopersicon
birsutum, Solanum sp.156 occurs due to glandular trichomes and the exudates
like sugar esters produced by them. Plant sucrose o r glucose esters composed
of the lower fatty acids (C-2 to C-10) possess very interesting biological
properties. Mixtures of sugar esters cibarian, coronarian and karakin
REVIEW OF LITERATURE
34
(Fig.1.4) reported from the forage legume, Lotus pedunculus exhibit
antifeedant activity against white grass grub, Costelytra zealandica157.
FUROCHROMENES AND COUMARINS
Furochromenes and coumarins have mostly anti -feedant action against
insects. The compounds like visnagin, khellin, from Pimpinella monoica and
khellinol ethyl ether are very active158.
NON-PROTEIN AMINO ACIDS
Among the several non-protein amino/imino acids of botanical origin,
azetidine-2-carboxylic acid, 2,4-diaminobutyric acid, mimosine,
3-hydroxyproline, •-cyanoalanine, pipecolic acid and canavinene are
significant in causing insect growth inhibition 159-161.
MOULTING HORMONES, JUVENILE HORMONE MIMICS AND ANTI
JUVENILE HORMONES
The endocrine system is critical for gr owth and survival of the insects. The
biosynthesis and release of brain, juvenile, moulting, eclosion and diapause
hormones generally govern insect growth and moulting. Of these, juvenile
hormones (JHs) and moulting hormones (MHs) are most significant as t heir
mimics and/ or antagonists are capable of disrupting insect growth and
moulting162. Phytoecdysteroids, the chemicals structurally similar to the
MHs, have been found in many plants especially ferns and yews.
The use of Juvenile Hormones (JHs) in insec t control was first demonstrated
by Wiggles-Worth in 1935. JH mimics which functionally resemble natural
JHs have been isolated from plants and shown to disturb normal
metamorphosis moulting and reproductive process of insects. Some of the
important JH mimics include farnesol from several plant oils, juvabiones
(Fig.1.5) from Abies balsamea and juvocimenes from Ocimum basilicum163.
REVIEW OF LITERATURE
35
The compounds like farnesol, farnesal , sesamin, sesamolin are also JH
mimics164.
O
O
O
O
HO
O
O
O
O
OCH O
O
OCH O
O
OCH
R2
R1
a. Pyrethrin I R 1 =CH3, R 2 =CH=CH2b. Pyrethrin II R 1 =COOCH3, R 2 =CH=CH2
c. Cinerin I R 1 = R2 = CH3d. Cinerin II R 1 =COOCH3, R 2 =CH3e. Jasmolin I R 1 =CH3, R 2 = CH2-CH3f. Jasmolin II R 1 =COOCH3, R 2 =CH2-CH3
Agrophyllin-A
3 3 3
-Asarone Isoasarone
Fig.1.3
-Asarone
β-Asarone α-Asarone Isoasarone
Fig. 1.3
REVIEW OF LITERATURE
36
O
O
N
H
O
O
O
N
O
O
O
O
O
O
O
O
O
O
O
H
HHOH
H
H H
Piperlonguminine Piperine
R1
COOCH3
OR2
Bruceantin R1=OH, R2=COCH=C(CH 3)C(CH3)2
Isobrucein-B R1=H, R2=COCH3
Bruceanol-A R1=H, R2=COC6H5
Limonin
Cibarian R1=R3=COCH2CH2NO2
Coronarian R 1=R2=COCH2CH2NO2
Karakin R1=R2=R3=COCH2CH2NO2
Fig.1.4
CH2-O-R3
OR1
R2O
Fig. 1.4
REVIEW OF LITERATURE
37
O
O
OH
O
O
OH
O
OOO
OHOH
OOH
OH
O
O
OO
OOH
OHO
OH
OH
O
OH
CO2Me
AcOMeO2C
Azadirachtin A
Juvabione Dehydrojuvabione
CO2Me
MeO2C
Azadirachtin B
Fig.1.5
Fig. 1.5
REVIEW OF LITERATURE
38
CHEMICAL CLASSES OF NATURAL COMPOUNDS ISOLATED
The continuous use of plants as biologically important source of chemicals
encouraged chemists and biochemists to isolate various types of natural
products from plants. The important classes of compounds that have been
isolated from the undertaken plant species are:
TERPENOIDS
Terpenoids comprise the largest and most widespread group of natural plant
products and over twenty thousand such structures have been described from
plant sources. They all are derived biogenetically from the 5 -carbon
precursor isoprene and, hence, are known as isoprenoids.They are classified
according to whether they contain two (C 10), three (C15), four (C20), six (C30)
such units. They range from essential oil components, the volatile mono or
sesquiterpene (C10 & C15) through less volatile diterpene (C 20) to involatile
triterpenoids (C30).
ESSENTIAL OILS
Chemically the terpenes of essential oils can be divided into two classes, the
mono and sesquiterpenes, C10 and C15 isoprenoids, which differ in their
boiling point range (monoterpenes b.p. 140 - 180 oC, sesquiterpenes b.p. >
200 oC). In monoterpenes, these substances can be further divided into three
groups depending on whether they are acycli c (e.g. geraniol), monocyclic
(e.g. limonene) or bicyclic (e.g. • - and •-pinene) or irregular (γ-thujaplicin).
1. Monoterpenes
Monoterpenes may be simple unsaturated hydrocarbons (e.g. limonene) or
may have functional groups and be alcohols (e.g. menthol), aldehydes or
ketones (e.g. menthone, carvone). Also included with monoterpenes on
biosynthetic grounds are monoterpene lactones (better known as iridiods)
and tropolones.
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39
A typical monoterpene lactone is nepetalactone, the principal odour
constituent of catmint, Nepeta cataria (Labiatae), a plant which has a
peculiar attraction for the domestic cat because of its odour. Other iridoids
such as loganin are of interest because they are intermediates in the
biosynthesis of the indole alkaloids. A typical tropo lone is •-thujaplicin;
these substances have a restricted distribution in certain fungi 165. The
structures of a range of typical monoterpenoids are collected in Fig.1.14
Simple monoterpenes are widespread and tend to occur as components of the
majority of essential oils. Some compounds are regularly found together in
leaf oils, especially • - and • - pinene, limonene, •3- carene, •-phellandrene
and myrcene. Flower and seed oils tend to have more specialized
monoterpenes.
2. Sesquiterpenes
Like the monoterpenes, the sesquiterpenes fall chemically into groups
according to the basic carbon skeleton; the common ones are either acyclic
(e.g. farnesol), monocyclic (e.g. • -bisabolene) or bicyclic (e.g. • -selinene,
carotol). However, within each group there are ma ny different compounds
known indeed, according to a recent estimate, there are several thousand
sesquiterpenoids with well -defined structures, belonging to some 200
skeletal types. The chemical formulae of the various sesquiterpenes
mentioned above are shown in Fig.1.15.
EXTRACTION
For their isolation from plant tissues, mono -and sesquiterpenes are
nowadays separated by extraction into ether, petroleum or acetone. The
classic procedure for essential oils is separation from fresh tissue by steam
distillation. This step is now often omitted, because of the danger of artifact
formation at the raised temperatures involved. Terpenes may either undergo
REVIEW OF LITERATURE
40
rearrangement (e.g. dehydration in the case of tertiary alcohols) or
polymerization. The volatility of the simpl e terpenes means that they are
ideal subjects for separation by GLC. Many have fragrant odours and indeed
can often be recognized in plant distillates directly, if present as the major
constituent.
The mono- and sesquiterpenes identified as volatile consti tuents in most
common fruits and vegetables have been exhaustively listed by Johnson
et al. (1971)166. The more recent general reviews are those of Charlwood and
Banthorpe (1978)167 and Loomis and Croteau (1980)168.
RECOMMENDED TECHNIQUES FOR MONO- AND SESQUITERPENES
1. Gas liquid chromatography
This is undoubtedly the most important technique for study of essential oils
since it yields in one operation both qualitative and quantitative analysis.
This is particularly important when a similar set of c ompounds occur
throughout a particular plant group, since it is the quantitative variations that
are most significant. Certainly, GLC is an indispensable tool for
chemotaxonomic studies of essential oils in leaf or bark, as in the
gymnosperms.
For the identification of volatile terpenes in any plant material, it is essential
to combine the use of GLC with other procedures, and especially with TLC.
TLC is useful, for example, for monitoring fractions separated by
preparative GLC; on the other hand, if a pre parative GLC apparatus is not
available, large-scale separations can be carried out on TLC, with the TLC
fractions subsequently being monitored by GLC. Some examples of relative
retention times are shown in Table. 1.4. These are given to illustrate the nee d
for using more than one column for purpose of terpene separation and
identification. In the detailed analysis of individual oil constituents of a
REVIEW OF LITERATURE
41
particular plant material, it is normal practice to use a range of GLC columns
for identification purposes.
Table 1.4. Relative retention times of terpenes in gas liquid chromatography
RRTs on column*
Terpene 10% Apiezon N
15% Polyethylene glycol
15% Polyethylene glycol bispropionitrile
•-Pinene
42
29
30
Camphene 50 41 44
•-Pinene 63 55 54
•3-Carene 82 73 67
Myreene 60 82 88
•-Phellandrene 82 82 86
Limonene 100 100 100
β-Phellandrene 97 106 116
p-cymene 100 175 232
* RRTs relative to limonene, from isothermal runs at 65 oC on a 300 cm column169
2. Thin layer chromatography
It is even possible, in the absence of a GLC apparatus to analyse essential
oils using TLC as the only separation technique 170. Even when GLC is
available, TLC is useful at all stages for separation and analysis of these
terpenes. Silica gel is the most widely adsorbent with solvents such as
benzene, chloroform, benzene-chloroform (1:1) and benzene -ethyl acetate
(19:1). For the analysis of oxygen-containing terpenes (e.g. carvone), silica
gel layers should not be activated prior to use since the moisture present aids
REVIEW OF LITERATURE
42
the separation. Terpene alcohols are best separated on paraffin -impregnated
plates in 70% methanol. Activated silica gel plates are first immersed in 5%
paraffin in petroleum for 1 min and then allowed to dry before use; the
chromatographic solvent, 70% methanol must also be saturated with paraffin
oil. Another modification to separate terpenes according to the number of
double bonds involves TLC on silica gel plates spread as a slurry with 2.5%
aqueous AgNO3 instead of with water. The solvent system to employ with
the AgNO3 treated plates is methylene dichloride -chloroform-ethyl acetate-
n-propanol (10:10:1:1).
General methods of detection include spraying with 0.2% aqueous KMnO 4,
5% antimony chloride in chloroform, conc. H 2SO4 or vanillin-H2SO4. The
latter reagent is prepared fresh by adding 8 ml ethanol with cooling to 0.5 g
vanillin in 2 ml conc. H 2SO4. The plates are heated after spraying at
100-105 oC until full development of colours has occurred. More selective
agents are available for de tecting terpenes with double bonds (bromine
vapour) and those with ketonic groupings (2, 4 -dinitrophenyl-hydrazine).
The responses of some of the common terpenes to a range of detection
agents are indicated in Table 1.5. TRITERPENOIDS
Plant triterpenoids have been classified into tetracyclic (Fig.1.6) and
pentacyclic triterpenes according to their skeletal type and are widespread in
nature (Fig.1.7). Squalene is universally present in green plants since it is the
basic precursor of all triterpenoids and tetraterpenoids171.
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43
Table. 1.5. Detection of monoterpenes on thin layer chromatography
plates
Response to test
Terpene UV
Bromine
2,4-DNP
Conc. H2SO4
Limonene
-
+
-
Brown
•-Pinene - + - Brown
Pulegone + + + Yellow
Geraniol - + - Purple
Carvone + + + Pink
p-cymene + - - -
•-Terpineol - + - Green
1,8 Cineoic - - - Green
Key: UV = examine in short UV light; bromine = spray with 0.5% fluorescein in water,
expose plate to bromine vapour, yellow spots on a red background; 2,4 DNP = spray with
0.4g2.4-DNP in 100 ml 2 M HCl, yellow spots on white background, conc. H2SO4 =
spray with conc. H2SO4 and heat plate at 100 oC for 10 min.
REVIEW OF LITERATURE
44
Cucurbitane Drammarane
Euphane Halimone
Lanostane Trucalane
Basic skeleton of naturally occurring tetracyclic triterpenes
Fig. 1.6
REVIEW OF LITERATURE
45
Triterpenic Groups
Tetracyclic Pentacyclic
(A) Cucurbitane (a) Pleanane
(b) Dammarane (b) Ursane
(c) Lanostane (c) Friedelane
(d) Euphane (d) Serratane
(e) Halimone (e) Strictane
(f) Tirucalane (f) Taraxasterane
(g) Lupane
(h) Hopane
(i) Feranane
FATTY OILS OR FIXED OILS
Fatty oils or fixed oils are chemi cally triglyceraldehyde or simply
glyceraldehyde i.e., esters of glycerols with saturated or unsaturated fatty
acids containing minor portion of sterols (free or as esters), vitamins,
pigments, hydrocarbons and other substances. The natural stuff consistin g of
glycerol esters, which is solid at room temperature, is commonly called fat
(saturated) and one that is liquid at room temperature is called oil. The two
terms are purely conventional since the same substance may be a fat in one
climate and oil in another.
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46
EXTRACTION
Fresh leaf tissue is extracted by maceration in 20 vols of cold isopropanol
(this alcohol de-activates hydrolytic enzymes) and this is followed by re -
extraction with chloroform-methanol (2:1). Seed tissue can be extracted
directly with the latter solvent mixture or with petroleum. For tissues in
which the lipids are very tightly bound such as cereals, extraction with
chloroform-ethanol-water (40:19:1) is advisable.
1. Thin layer chromatography
The total lipids of plant tissues can be a nalysed by two-dimensional TLC.
This was obtained from potato tuber 172 but most other plant tissues show a
range of similar components. The solvent in the first direction is chloroform -
methanol-acetic acid-water (170:25:25:4), and that in the second,
chloroform-methanol-7M NH4OH (65:30:4). In order to avoid
decomposition of lipids during TLC, Galliard (1968) recommends adding
BHT (5 mg) to the first solvent and drying the plate after the first run at
50 oC in an atmosphere of nitrogen.
Phospho-and glycolipids can be separated one-dimensionally on silica gel
plates using solvents such as chloroform -methanol-acetic acid-water
(170:30:20:7) and acetone-benzene-water (90:30:8). Phosphatidylglycerol is
better separated from phosphatidylethanolamine by running the second
solvent on plates previously impregnated with 0.15M ammonium
sulphate173.
2. Gas liquid chromatography
The fatty acids obtained after acid hydrolysis are converted to the methyl
esters with ethereal diazomethane and then analysed by GLC. Alte rnatively,
the fatty acid methyl esters can be obtained directly by transmethylation of
REVIEW OF LITERATURE
47
the parent lipids by refluxing them for 90 min with methanol -benzene-
H2SO4 (20:10:1). Some unsaturated acids cannot be identified by GLC
alone. In such cases, it is necessary to carry out argentation TLC in order to
determine the degree of unsaturation.
3. High performance liquid chromatography
Although HPLC has been applied to many lipid separations, there is still the
major difficulty of finding a suitable detection s ystem for a class of
compounds essentially lacking UV absorbance. In the case of the fatty acids
this can be overcome by derivatizing them and separating them as their
phenacyl or p-bromophenacyl esters. In the case of the bound lipids it is
possible to measure their end absorption at about 195 nm or use a refractive
index detector, but in general HPLC has not yet become a routine procedure
in plant lipid studies.
The common fatty acids are either saturated or simple unsaturated
compounds of C16 or C18 chain length (Fig. 1.6). Palmitic acid, a C 16 acid is
the major saturated acid in leaf lipids and also occur in some seed oils.
Stearic acid, C18 is less prominent in leaf lipids but is a major saturated acid
in seed fats in a number of plant families 174.
STEROIDS
Steroids are based on the 1,2-cyclopentenophenanthrene (Fig.1.7 a) skeleton,
and form a group of structurally related compounds, which are widely
distributed in animals and plants. Many natural steroids are unsaturated
(mostly at C-5) and are designed as ‘sterols’. On dehydrogenation with
selenium at 420 oC, all steroids give chrysene as the main product with small
amount of pinene. They all give D iel’s hydrocarbons among other products.
α-Spinasterol, ergosterol, campasterol, stigmasterol and β-sitosterol are
common plant steroids. These steroids are sometimes present in glycosidic
REVIEW OF LITERATURE
48
forms and as acetate derivatives. The aglycones of this group, possessing
spirostane nuclei having rings A B C D E and F were isolated first
(Fig.1.7 b). Some steroidal glycosides have open F rings (Fig.1.7 c) and
known as furostanol glycosides or bisdesmoside 175.
The most common steroid, β-sitosterol has been isolated invariably from
almost all plant species. Due to the different types of pharmacological
activities like antinflamatory, antifungal, antirheumatic etc., the vast majority
of steroids play an important role in field of medicines. They occur
invariably, where life exists and have profound importance in animal
metabolism. They are structurally related to hor mones (oestrogen group and
male sex hormones), co-enzymes, bile acids and provitamin-D.
FLAVONOIDS
The term flavonoid embraces a large group of naturally occurring
compounds such as anthocyanins, leucoanthocyanins, chalcones,
dihydrochalcones and aurones e tc. Flavonoids are benzo-γ-pyrone
derivatives, which resemble coumarine and are ubiquitous in
photosynthesizing cells. Their occurrence is therefore widespread in the
plant kingdom. A wide variety of flavonoids are known for centuries.
Preparations which contain flavonoids as principal physiologically active
constituents have been used by Laymen and Physicians in attempt to treat
human diseases176. Flavonoids occur as aglycones, glycosides and
methylated derivatives176-179. All the flavonoid aglycones consi st of a
benzene ring (A) condensed with a six membered heterocyclic ring (C),
which is either a γ-pyrone (Chromone) or its dehydro derivative (4 -
chromone). 4-Chromanone substituted by an aryl ring (B) at position -2 gives
rise to flavonones and dihydroflavo noids (Fig.1.8). The position of aryl ring
REVIEW OF LITERATURE
49
O
O
OH
H
H
H
H
H
(b)
(c)
Me
2720
(a)
Fig. 1.7
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50
O
O
O
O
O
O
O
O
O
O
OH
O
O
OH
O
O
OH O
O
OH
Chromone 4-Chromanone
Flavone Flavanone
Flavonol Flavanol
Isoflavonol Isoflavanol
Fig. 1.8
REVIEW OF LITERATURE
51
divides the flavonoids class into flavonoids (2-position) and isoflavonoids
(3-position). Flavonoids differ from flavonoids by OH -group in 3-position
and C2-C3 double bond. Flavonoids are often hydroxylated at 3, 5, 7, 3’, 4’
and 5’-positions. Methyl ethers and acetyl ethers of the alcohol groups ar e
known to occur in nature. When glycosides are formed, the glycosidic
linkage is normally located at 3 - or 7-position and the carbohydrate can be
L-rhamnose, D-glucose, glucorhamnose, galactose or arabinose 176.
Structurally flavonoids resemble with nucleo sides, isoalloxazine. and folic
acid and this similarly is the basis of many of the current hypothesis o f their
physiological action180.
EXTRACTION AND ISOLATION OF FLAVONOIDS
Since the last five decades number of techniques were developed and used
for the isolation of flavonoids from the plant material including solvent
extraction181-182.
Flavonoids are found in almost all parts of the plants and methods of
extractuion used basically depend on the type of flvonoids to be isolated. In
general, freshly dried plant material provides the ideal material for a
flavonoid analysis. The flavonoids can be conveniently and sequentially
extracted with the solvents of increasing polarity. This method is used to
separate the less polar and highly methylated flavonoids from the
hydroxylated flavonoids and their glycosides. In general, the solvents used
for the extraction are chosen according to the nature of the compounds to be
studied. Higly methylated flavonoids are soluble in the less polar solvents
such as petroleum ether, dichloromethane and chloroform. Flavonoids
possessing a number of unsubstituted hydroxyl groups or a sugar are soluble
in polar solvents183-184.
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52
The isolation and purification of the flavonoids mixture along with other
constituents can be achieved by chromatographic techniques such as column
chromatography over silica gel, Sephdex -20 and preparative TLC183, 185. The
various methods (GC, MPLC, HPLC, and DCCC) are well established for
the isolation of the flavonoids 186. The choice of isolation techniq ues depends
largely on the solubility and nature of the compounds to be isolated. PC is
particularly useful to isolate the water -soluble constituents185-186.
METHODS OF IDENTIFICATION
1. Chemical Methods
Once the flavonoids are purified, the following steps are used to identify the
pure compounds.
1.1. Hydrolysis
1.1.1. Acidic Hydrolysis
Acidic hydrolysis of flavonoid glycoside is commonly carried out by
dissolving the compound in 2 -5 ml of 2-6% aqueous HCl or H2SO4 and
refluxed for 45 min., on water bath. The cooled solutionis extracted with
diethyl ether or eyhyl acetate to remove the aglycone portion of the
flavonoid glycoside. The aqueous layer contains the sugar moiety and
used for the estimation of sugar. More dilute acid e.g. formic acid in
cyclohexane or 10% acetic acid at lower temperature is used for partial
hydrolysis of di and triglycosides187-188. Acidic hydrolysis can be also be
carried out by using the Kiliani mixture 189.
1.1.2. Enzymatic Hydrolysis
Compound (1 mg) is treated with 2 ml of 0.5 M acetic acid-sodium
acetate buffer (pH = 5.0) in presence of 1mg β-glycosidase. The mixture
was allowed to stand over night at 37 oC, which afforded aglycone and
REVIEW OF LITERATURE
53
sugar moiety190.The sugar(s) thus obtained was identified by paper
chromatography and gas chromatography by comparing with the
authentic samples. The sugars can also be identified by PC, developed by
using the developing solvent systems such as n -butanol-pyridine-water
(6:4:3), n-butanol-acetic acid-water (4:1:5) or ethyl acetate -pyridine-
water (12:5:4)191.
2. Spectroscopic Methods of Identification
2.1. UV-VIS Spectroscopy
Flavonoid contains conjugated aromatic system and thus showed intense
absorption bands in the UV -VIS regions of the spectrum. The substitution
patterns of flavonoid nuleus can be determined by adding shift reagents.
Sodium methoxide, sodium acetate, sodium acetate -boric acid, aluminium
chloride and aluminum chloride -hydrochloric acid are used as shift
reagents192.
UV spectrophotometry of flavonoids dissolved in MeOH or EtOH and with
the addition of the classical shift reagents is a method of choice in structure
determination. Flavonoids exhibit two characteristic UV bands depending
upon the hydroxylation patterns of the aromatic ring. Band I is usually
recorded in the region 300-380 nm for all flavonoes and flavonols and band
II in the region 240-280 nm191.
2.2. IR Spectroscopy
The IR spectrum of flavonoids displayed characteristic absorption in the
region 3200-3450 cm-1 of free hydroxyl and chelated hydroxyl groups, two
bands in the region 1600-1700 for •, •-unsaturated carbonyl function and
the aromatic absorption in the region 1500 -1600 cm-1 193.
REVIEW OF LITERATURE
54
2.3. NMR Spectroscopy
The application of NMR in structure elucidation of flavonoids is well
established. Many methylated and acet ate derivatives of flavonoids are
sufficiently soluble in the commonly used solvent deuterated chloroform
(CDCl3) for direct NMR analysis. However, most naturally occurring
flavonoids including flavonoid glycosides have less or no solubility in
CDCl3. Thus the NMR spectra of highly hydroxylated and flavonoid
glycosides are recorded in CD 3OD, DMSO-d6, or C5D5N and TMS an
internal standard191-192 .
2.4. Mass Spectrometry
The MS is very useful in the characterization and structure elucidation of
6- and 8-C-flavonoid glycosides related to apigenin and luteolin 196.
C-glycosyl flavones show initial fragmentation of the sugar moiety. Electron
impact mass spectrometry (EI-MS) serves as valuable aid in determining the
structure of flavonoids especially when very small quantities are available.
Most aglycones are sufficiently volatile at probe temperature 100 -300 oC to
allow successful MS without derivatization 192, 195.
The fragmentation of flavonoids takes place by Retro-Diels Alder (RDA)
cleavage. The RDA fragmentation leads to the clevage of the flavonoid
molecules by the double bond in ring -C giving fragments derived from ring-
A and B which show the substitution pattern on each ring (Fig.1.9).
Fragment A1 gives information on the substitution pattern of A-ring and
fragment B1 and B2 show the substitution pattern of B -ring196-198.
The initial products of fragmentation of flavonols are the ion A 1 and B1,
while flavones give ions A2 and B2 showing that main cleavage involves the
bonds between oxygen and C-2 and C-3, C-4 (Fig.1.9). Another important
fission product of flavones involves elimination of C -4 carbonyl group with
REVIEW OF LITERATURE
55
the formation of an M-28 ion. Isoflavones give a similar fragmentation
pattern to that for flavones. Flavanones give A 1, A2 and B3 ions while
dihydroflavonols give A2, B3 and B4 and chalcones produce A 3, B3 and B5
ions (Fig.1.9)199-200.
O
O
O
C
O
C
CH
O
O
O
CO
CO
H
O
C
O
C
CH
C
C
O
+
+
R1
R1O
R3
R3
R1O
R1
R1O
R1O
R1O
R1O
+
+
A
A
B+
+
X
H
R
H2+
+
A
R2
R2
A1
A2
B1
B2
A3 B3, X=H or OH
B4 B5
C
Fig.1.9
REVIEW OF LITERATURE
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