Mahato
Mahato
Mahato
00/0
Printed in Great Britain. @ 1982 Pergamon Press Ltd.
REVIEW
STEROID SAPONINS
Key Word Index-Steroid saponins; sapogenins; isolation; structure elucidation; natural distribution.
Ah&a&-Steroid saponins isolated from various plants are reviewed. The newer techniques used in their
isolation and strucure elucidation are discussed. A compilation of the saponins isolated up to 1980 along with
their available physical data is included. The basic steroidal saponins isolated after 1972 are also compiled.
959
PHYTO Vol. 21. No. 5-A
960 S.B.MAHATO, A.N. GANGLJLYand N. P. SAW
and triethylamine as the mobile phase. Anthracene saponin consisting of kammogenin and five molecules
was used as an appropriate int. standard for quan- of 2deoxyribose has been reported by Backer et al.
titative analysis. The saponin mixture obtained from [37]. The furostanol bisglycosides so far isolated
Tribulus terrestris (Mahato, S. B. et al., unpublished contain a glucose unit attached to the C-26 hydroxyl.
results) was separated on a column of p-Bondapak In the classical method, the structure of the sugar
Cl8 using methanol as the mobile phase. The very moieties of the saponins is determined by
complex mixtures of saponins which were not identification of the monosaccharides obtained on
amenable to separation previously can now be acid hydrolysis by PC and GLC, quantitative deter-
effectively separated by a combination of silica gel mination of monosaccharides by GLC, partial
CC, gel chromatography on Sephadex LH-20 and hydrolysis followed by isolation and characterization
HPLC on a reversed phase column. of prosapogenins and also, where possible, by charac-
terization of oligosaccharides. The points of attach-
STRUCTUREELUCIDATION ment of different sugar units are revealed by per-
The conventional method of structure elucidation of methylation of the saponins followed by hydrolysis or
steroidal saponins starts with acid hydrolysis which methanolysis and identification of the methylated
yields the aglycone and the sugar moieties which are sugars by PC or GLC. The mode of sugar linkage in
separately investigated. Extensive chemical studies saponins is determined by enzymic hydrolysis with a-
on the aglycones revealed that they are almost and @glycosidases or by the application of Klyne’s
exclusively spirostane derivatives. But furostanol rule [38] on molecular rotation difference. However,
glycosides, which according to Marker and Lopez [29] both of these methods are not always applicable,
are precursors of spirostane glycosides, have also particularly in the case of complex glycosides.
been isolated and characterized. A simple qualitative
test for furostanol glycoside has been developed by Mass spectrometry
Kawasaki et al. [30]. The furostanol glycosides with Until very recently MW determination of saponins
some exceptions [18], show a characteristic red was a difficult task. But newer developments in mass
colour on a TLC plate when sprayed with p- spectrometry have almost solved this problem. Elec-
dimethylaminobenzaldehyde and hydrochloric acid tron impact mass spectrometry (EIMS) has been
(Ehrlich reagent). Moreover, the furostane skeleton shown to be a very useful method [39-42] for
does not exhibit the characteristic IR absorptions of identification, determination of purity and structural
spirostane derivatives [6]. Confirmatory evidence for elucidation of saponins, although volatile derivatives
the furostane structure is obtained by examination of have to be produced. Moreover, saponins containing
the products of Marker’s degradation or Baeyer- more than four sugars do not give molecular ions,
Villiger oxidation followed by hydrolysis. The first even when derivatized.
isolation of a furostanol glucoside, jurubine (l), was Field ionization mass spectrometry (FIMS) has
announced by Schrieber and Ripperger [31] and later been applied to the structural analysis of permethyl-
Tschesche et al. [32, 331 isolated and characterized a ated oligosaccharides r43,441, underivatized
furostanol bisglycoside, sarsaparilloside (2), cor- nucleosides [451, naturally occurring glycosides, e.g.
responding to the spirostanol glycoside, parillin. somalin [46] and cardiac glycosides [47,48].
Moreover, some glycosides have been isolated whose However, mass spectrometry has had limited ap-
aglycones are not spirostanol but a modification. In plication in the field of underivatized oligosaccharides
general, the sugar moieties of steroidal saponins are because it requires volatilization and ionization of the
oligosaccharides which consist of 2-4 kinds of sugar sample. Ionization and volatilization are coupled in
units, e.g. D-glucose, u-galactose, u-xylose and L- one process in field desorption mass spectrometry
rhamnose. DXylose and L-rhamnose generally occur (FDMS) [49,50]. Very little of the energy goes into
at the terminal positions. Arabinose-containing internal excitation and the degree of fragmentation is
steroidal saponins are also known. In a very few relatively small. FDMS of underivatized steroid and
cases, quinovose occurs as the carbohydrate moiety. triterpenoid saponins have been reported 151-551. The
Trillenoside A, a novel ll-norspirostanol glycoside, spectra show the intense ions formed by attachment
contains xylose, rhamnose, arabinose and apiose as of alkali cations to the neutral molecule. The FDMS
the sugar constituents [34-361. Another unusual of the saponins not only gives the MW but also clear
Moreover, it is
observed that the anomeric proton signal of (Y-D-
glucosides, a-D-mannosides,
generally at lower field (8
5.0-6.0) than those of the corresponding
4.5-5.0). This difference
structure.
“C NMR spectroscopy
developed and
20 Yonogenin, 25 R, 28, 3a-OH
very useful tool for the elucidation of the structures
Tokorogenin, 25 R, 18, 28, 3a-OH
32 Diosgenin, 25 R, 3f3-OH
33 Ruscogenin, 25 R, I/3, 3fi-OH
34 Yuccagen in, 25177, 2a, 3/3-OH
35 Kammogenin, 25R, 20, 3/3-OH, 12-w
36 Pennogenin, 2!iR, 38, 17a-OH
37 Prazerigenin A, 25 R, 38, 14a-OH
36 Epidiosgenin, 25R, 3a-OH
39 Epiruscogenin, 25 R, Ig, 3a-OH
40 Yamogenin, 25 S, 38-OH
OH
*--
HO- HO@
OH
41 Cryptogenin 43 Hispigenin
42 17 (201- Dehydrocryptogenin
HO
H
45 Convallaaarogenin
44 Trillenqenin 46 A5- Convallamarogeain
HO”
..
HO
50 Solasodine
Steroid saponins 963
Table 1. Steroidal saponins whose genins and sugars have been fully characterized
xyl
Agave saponin H Agave americana Hecogenin (7). 77,80
rha-‘rha
)Lc-‘glc-‘ga1~3a-0H,:
XYl
dc-W-OW
Agavoside A Agave americana Hecogenin (7). 77,83
gal-Q&OH)
Agavoside B Agave americana Hecogenin (7). 77, 83
glc-‘gal-(3g-OH)
Agavoside C Agaue americana Hecogenin (7). 77,a4
275”, - 55’ (DMP) glc-‘glc-‘gal-(3&OH)
Agavoside G Agave americana Hecogenin (7). 78.81
rha
)&-‘glc-‘gal-(36 - OH);
xyl
glc-(26-OH)
Aginoside All&m gigantenin Agigenin (8). a2
XYl
)&lc-‘gal_(3g-OH)
glc
Allionin Allium karataviense Alliogenin (0, 85
gW3@-OH)
Alliumoside B Album narcissiflorum Diosgenin (32). a6
glc-‘glc-3glc-(3&OH);
glc-@-OH)
Alliumoside C Allium narcissiflorum Diosgenin (32). 86
rha-4rha-4rha-6gal-6Blc-(3B-OH);
glc-(26-OH)
Alliumoside D Allium narcissiflorum Diosgenin (32), 86
rha-‘rha-$&z
>&lc<3&OH);
gl~_(26Xr:)~
Alliumoside E Allium narcissifloncm Diosgenin (32). 86
glc-‘rha-‘rha-6glc
-
)&tlc_(3&OH);
glc
glc-(26-OH)
ASP-IV, 165-167’ Asparagus Sarsasapogenin (27)
- 23” (MeOH) cochinchinensis xyl-‘glc-Q/&OH); glc_(26-OH); (22-OMe) I9
ASP-V, 150-156” (dec), Asparagus Sarsasapogenin (27). 19
- 45.5” (MeOH) cochinchinensis rha-6glc-(3&OH); glc_(26_OH); (22-OMe)
964 S. B. MAHATO,A. N. GANGULYand N. P. SAHU
Table l-continued
Saponins (mp, [&) Source Structure Reference
dc
Asparagoside A Asparagus Sarsasapogenin (27). 87
0fEcinalis gw38-OH)
Asparagoside B Asparagus Sarsasapogenin (27). 87
oficinalis dc-wOH)
Asparagoside D Asparagus Sarsasapogenin (87). 88
oficinalis glc
>kdc-c3/3-oH)
glc
Asparagoside G Asparagus Sarsasapogenin (27). 88
oflicinalis dc
>!c_(38_OH); glc-W-OH)
dc
Asperin, 222-231”. Smilax opera Yamogenin (48). 89
rha-‘rha
- loo” (pyridine) 1.
,&_(38-OH)
rha
Asperoside Smilax aspem Yamogenin (48), 89
rha-%a
>‘kdc_(38_OH); gL(26-OH)
rha
Aspidistrin, Aspidistra elatior Diosgenin (32). 90
265-267”, - 65” ac
>&lo’gal-(3&OH)
XYl
Avenacoside A Avena sativa Nnatigenin (48). 91
rha
)Wc-(3&OH): glc-(26-OH)
glc
Avenacoside B Avena sativa Nuatigenin (48), 92
rha-‘$_(3&OH); glc-(26_OH)
dc-*glc
Balanitiscin A, Balanites Diosgenin (32). 93
274278”, - 39” roxburghii rha
):glc-(38-OH)
glc
Capsicoside, 295”. Capsicum annum Gitogenin (4). 94
glc
- 35’ (CHClr + MeOH) >&k-$aL3glc-(3~-OH); glc-(26OH)
glc
Capsicosin Capsicum annum Gitogenin (4). 94
glc
>&c-4gal-3glc-(3g-OH)
glc
Convallamaronin, Convallaria Convallamarogenin (4fl). 95
215-218’. - 30” (MeOH) majalis rha-(3g-OH); rha-‘qui-(l&OH)
Steroid sapottins 965
Table l-continued
13
,2glc-‘gal_(3&OH)
BlC
Deglucoderhamnoruscin Ruscus aculteatus A5-Convallamarogenin (40, 103
ara-(l&OH)
Deglucodigitonin LXgitalis purpurea Digitogenin (12), 184
xyt
>&lc&al~3g-OH,
gal
Deglucoruscin Ruscus aculeatus A’-Convallamarogenin (46). 103
rha-zara-(l&OH)
Deglucoruscoside Ruscus aculeatus As-Convallamarogenin (40, 105
rha-*ara-(l&OH); glc-(26-OH)
Dehydrocryptogenindi- Trillium kamtschaticum 17(20)-Dehydrocryptogenin (42), 18
glycoside, 265-268” (dec), rha-*glc_(3S-OH); glc-@-OH)
- 80” (pyridine)
Dehydrocryptogenin- Paris tetraphyl~a 17(20)-dehydrocryptogenin (42). 18, 106
tetraglycoside rha-‘rha
)&_(3g_OH); glc_(26-OH)
rha
Deltonin Dtoscorca deltoidea Diosgenin (32). 107
dc
>&lc43&OH)
rha
Dioscorea ddtoidea Diosgenin (32). 108
dc
14
,&-(3g-OH); glc-(26-OH)
rha
Desghtcodesrhamnoparillin. Smilax aristolo- Sarsasapogenin (27) 109
250-265”. - 65.5” (CHCI, + MeOH) chiaefolia glc-“glc-(3S-OH)
Desghrco-lanatigonin, Digtialis lanata Tigogenin (3), 110
246-251”, -47.6” (CHCl3+ MeOH) gal
)$glc-‘gal~3S_OH)
xyl
Desglucoparillin, Smiiax aristolo- Sarsasapogenin (27). 109
250-265”. - 67.5” (EtOH) chiaefolia Blc
):glc_(3S-OH)
rha
Digalonin, 25tX295” LXgitalis purpurea Digalogenin (9) 6, 104
Blc-‘gal
S. B. MAHATO, A. N. GANGULY and N. P. SAHU
Table l-continued
Digitalis lanata
Blc
glc
Filiferine A, 292”. Yucca jihfera Sarsasapogenin (27). 126
- 50.5” (DMSO) xyl-‘gal-(3p-OH)
Filiferine B, Yucca filifera Sarsasapogenin (27), 126
319-321”, - 35” (DMSO) glc-*gaL(3/3-OH)
Floribundasaponin B, Dioscorea Pennogenin (36). 127
251-253” (dec), - 86:5” (pyridine) floribunda rha-‘glc-(3@-OH)
Floribundasaponin C, Dioscorea Diosgenin (32), 128
255-258”. - 93.6” (pyridine) fion’bunda rha-‘rha-‘glc-(3@OH)
Floribundasaponin D, Dioscorea Diosgenin (32). 128
232234”, - 85” (pyridine) floribunda rha-3rha-3rha-3rha-‘glc-(3g-OH)
Floribundasaponin E, Dioscorea Diosgenin (32). 128
226-229” (dec), - 66” (pyridine) floribunda rha-3rha-3rha-3rha-‘glc-(3&OH);
glc_(26-OH); (22a-OMe)
Floribundasaponin F, Dioscorea Diosgenin (32). 128
243-247” (dec), - 74.6’ (pyridine) jloribunda rha-%ha-3rha-3rha-4glc-(3/3-OH);
glc-(ZCOH)
Funkioside B, Funkia ovata Diosgenin (32), 129
258-266”. - 135’ (MeOH) glc-(3g-OH); glc-(26-OH)
Funkioside C Funkia ovata Diosgenin (32), 129-131
glc-‘gal-(38-OH)
Funkioside D Funkia ovata Diosgenin (32). 129-131
glc-*glc-‘gal-(38-OH)
Funkioside E Funkia ovata Diosgenin (32), 129, 130, 132
rha-‘glc-‘glc-‘gal-(3@-OH)
Funkioside F Funkia ovata Diosgenin (32), 129, 130
g)c
)fglc-‘gal-(3g-OH)
XYl
Steroid saponins %7
Table l-continued
gic-(26OH)
Furostanol bisglycoside, Tribulus terrestris, Diosgenin (32). 133-13s
189-193” Trigonella coerulea rha
>&lc-c3@OH); gIc_(26-OH)
rha
Furostanol glycoside, Trigonella Neotigogenin (13).
242-246” joenum-graecum rha
)~c_c3s- OH); glc-(26-oH): (22-OMe)
tdc
Furostanol saponin, Lycopersicon Neotigogenin (13).
217-220” (dec), - 24” esculentum glc-*gl~-~gal-(3~-OH);
(CHCls + MeOH)
Furostanol saponin-1 Asparagus oficinalis
Glucoconvalla-saponin A, Convallaria
213&O (MeOH) keisukei
Glucoconvalla-saponin B, Convallaria
221-222’. - 35” (MeOH) keisukei
Glycoside A (identical Dioscorea prazeri
to Kallstroemin E)
Glycoside B Dioscorea prazeri
Glycoside B Trigonella
foenum-graecum
Glycoside B Allium
narcissif7orum
Glycoside C, Discorea prazeri
272-274”, - 87”
Glycoside D, Dioscorea prazeri
278-280”. - 85”
Glycoside I, 300-303” Methanarthecium
luteo-viride
Glycoside II, Methanarthecium
297-3W, - 84” (pyridine) luteo-viride
968 S. B. MAHATO, A. N. GANGIJLY and N. P. SAHU
Table l-continued
Tribulus rewestris
Hispigenin glycoside Solanum hispidum Hispigenin (4% 145
rha-‘rha_(3&OH)
Hispinin A, Solanum hispidum Solagenin (a), 146
220-224”. - 44” (pyridine) rha_(6a-OH)
Hispinin B, Solanum hispidum Solagenin (18). 146
258-260”. - 68” (pyridine) rha-%ha_(6a-OH)
Hispinin C, Solanum hispidum Neochlorogenin (II), 146
2%288”, - SSP (pyridine) rha-‘rha_(6a-OH)
Kallstroemin A, Kallstmemia Diosgenin (32), 147
235-238”, - 82” (pyridine) pubescens rha-%ha-%a-“glc-(3&OH); gl~-(26-OH)
Kallstroemin B, Kallstmemia Diosgenin (32), 147
232235”, - 79.5” (pyridine) pubescens rha-2rha-%ha-6glc-(3&OH); glc-(26_OH);
(22a-OMe)
Kallstroemin D, Kallsfmemia Diosgenin (32), 147
275-276”. - 94.5” (pyridine) pubescens rha-%ha-%ha-6glc_(3&OH)
Kallstroemin E, Kallstmemia Diosgenin (32). 147
218-219’, - 101” (pyridine) pubescens rha-6glc-(3&OH)
Karatavegenin B, Allium Karatavegenin (5). 148
glucoside. 294-298” karataviense gIc-(36-OH); gIc_(26-OH)
Karatavioside A Allium spp. Yuccagenin (34), 149
XYl
)&&al-(3/3-OH)
glc
Karatavioside C ANium spp. Yuccagenin (34). 150
XYl
>&lc-‘gal_(SB-OH): glc-(26-OH)
glc
Kikuba saponin, Dioscorea septemloba, Diosgenin (32), 113. 134
249-251”. - 77O (MeOH) Tn’bulus rerresMs glc-*glc
>jcsa-OH)
rha
Lanadigalonin Bgitalis lanata Digalogenin (9), 151
glc-‘gal
)&@gal-(3~-OH)
XYl
Lanagitoside Digitalis lanara Gitogenin (4), 110
glc-‘gal
)fgl&al_(3~-OH): glc_(26-OH)
XYl
Lanatigonin I, Digitalis lanato Tigogenin (3), 151
275-285” (de@, + 42’ (pyridine) glc-‘gal
>&Io’BalO@-OH)
XYl
Lanatigoside Digitalis lanata Tigonenin (3). 110
glc-‘gal
>:glc-‘gal-(3fl-OH): glc_(26-OH)
XYl
Metanartheticum Metanatihecium Z&acetyl metagenin (23), 152
prosapogenin luleo- viride 2,3,4-tri-O-acetyl ara_(lla-OH)
Steroid saponins %9
Table l-continued
Sawnins(mp, [eld source Structure Reference
Molluscicidal Comusjkwida Sarsasauogenin (27). 22
saponin-1,24&245’ (dec), - 68.5” gaM3&OH)
Mulluscicidal Comus florid0 Sarsasapogenin (27), 22
saponin-2,286-288O xyl-*gal-(3~-oH)
Molluscicidal Comus firida Sarsasapogenin (27). 22
saponin-3, 320-322” gic-*gaL(3/3-OH)
Neochlorogenin Solanum hispidum Neochlorogenin (18, 145
glycoside rha-‘rha-(3@OH)
Neohecogenin glucoside Tribulus rcnwtris Sisalagenin (19), 153
280-282“(dec), - 41” (pyridine) gW3bOH)
Neotokoronin, Dioscorea tenuipes Neotokorogenin (31). 154
270-274”(dec), - 11”(pfidine) ara-(l&OH)
Ophiopogonin A, Ophiopogon japonicus Ruscogenin (33). 155
183”. - 98” (pyridine) (3-0-acetyl) rha-%co~lfi-OH)
Ophiopogonin B, Ophiopogon japonicus Ruscogenin (X3), 155, 156
269-271”. - 105’ (pyridine) rh&uco-(lfi-OH)
Ophiopogonin D, Ophiopogon japonicus Ruscogenin (33). 155, 157
263-265”, - 108’ (pyridine) rha
>$fuco-(l&OH)
xyl
Ophiopogonin B’, Ophiopogon japonicus Diosgenin (32). 158
245-248”(dec), - 86” (pyridine) (4-0-acetyl) rha
>bW3a-oH)
XYl
Ophiopogonin C’, Ophiopogon japonicus Diosgenin (32). 158
238-W (dec), rha-*glc-(3p-OH)
- 99” (pyridine)
Ophiopogonin D’, Ophiopogon japonicus Diosgenin (32). 158
255-25T, - 41” Wridine) xyl
)&c-(3@-OH)
rha
Paniculonin A, Solanum paniculatum Paniculogenin (15). 159
262-264”. - 61’ (pyridine) xyC’qui_(6u-OH)
Paniculonin B, 237-238”. Solanum panicularum PanicLogenin (is, 160
- 79” (pyridine) rha-‘qui-(6a-OH)
Paniculogenin glycoside, Solanum paniculatum Paniculogenin (15). 160
262-264’. - 61” (pyridine) xyl-‘rha-(6a-OH)
Paniculogenin Solomon hispidum Paniculogenin (U), 145
glycoside rha-‘rha-(3&OH)
glc 109
Parillin, 22&223”, Smilax aristoloch- rhh>:$dc-(3B-OH)
- 64” (EtOH) iaefolia
Table I-continued
Saponins (mp, [alo) Source Structure Reference
>&-(3fl-OH)
rha
Polygonatoside E Polygonatum Diosgenin (32), 164
latijolium glc-3glc-4gal-3glc43~-OH)
Prazerigenin Dioscorea prazeri Prazerigenin A (37). 121
glucoside, 260”. glc-(3&OH)
- 79” (pyridine)
Protodioscin, 1904%” LXoscorea gracillima Diosgenin (32), 165
(dec), - 57.8 (pyridine) rha
> &lc-(3/3-OH); gb(26-OH)
rha
Protogracillin, Doscorea Diosgenin (32), 165
235-238” (dec), septemloba glc
- 57.8” (pyridine)
)&(3p_OH); glc-(ZCOH)
rha
Protometeogenin Metanatihecium Protometagenin (24), 166
glycoside, 265-270” luteo-viride ara-(1 la-OH)
Protopolygonatoside E’ Polygonatum Diosgenin (32), 164
latifolium glc-3glc-4gal-3glc-(3fl-OH); glc-(26-OH)
Prototokorin, Dioscorea tokoro Tokorogenin (21). 167
W-178”, - 3.8” (MeOH) glc-(l~3-OH); glc-(26-OH)
Protoyuccoside C, Yucca filamentosa Sarsasapogenin (27), 168
182WV’, - 30” (MeOH) gal-2glc-4glc-(3~-OH); glc-(26-OH)
Protoyuccoside E Yucca filamentosa Sarsasapogenin (27), 169
gal
>&lc-‘&-(Jg-OH); glc_(26-OH)
gal
Rockoside A Agave americana Rockogenin (lo), 170
gal-(3&OH)
Rockoside B Agave ameticana Rockogenin (lo), 170
glc-‘gal-(3&OH)
Rockoside C Agave americana Rockogenin (lo), 170
xyl-*glc-‘glc-‘gal_(3@OH)
Ruscin Ruscus aculeatus A’-Convallamarogenin (40, 103
glo3rha-*ara-(l@OH)
Ruscoside Ruscus aculeatus A’-Convallamarogenin (46), 105
glc-‘rha-*ara-(l/3-OH); glc (26-OH)
Saponin P-a, Paris polyphylla Diosgenin (32), 116, 161
276-278” - 133” rha
>&Jc-(3p-OH)
(fur)ara
Saponin P-d, Paris polyphylla Diosgenin (32), 116
203-206”, 153 rha-‘rha
Table l-continued
xyl /ha
Trigonelloside C Trigonella Yamogenin 40). 176
joenum-graecum rha
)jglc_(3&OH); gM26-OH)
rha
Trillenoside A, Trillium kamtsch- Trillenogenin (44). 34-36
269-220” (dec), - 142” aticum, Trillium small, apio(fu+‘rha
Trillium eschonoskii
)$ua-(lg-OH)
xyl
Trillin, 260”, Dioscorea saliva, Diosgenin (32). 177, 178
- 89’ (dioxan) Polygonotum lotijolium glc_(3g-OH)
Trillioside A Trillium kamtschot- Diosgenin (32), 179
scense glc-‘rha-*glc-(3~-OH)
Trillioside B Trillium komtschat- Diosgenin (32). 180
scense glc
>&lcd3&OH,
glc
Turoside A Allium turcomanicum Neoagigenin (16). 181
xyl
)&zlc-‘gal_(3g-OH)
glc
Turoside A-6-0- Allium turcomonicum Neoagigenin (16). 182
bcnzoate xyl
13
,,&-‘gal-(3g-OH); 6-0-benxoate
glc
Turoside C Allium turcomanicum Neoagigenin (16). 183
glc-*glc
):glc&l_(3g-OH): glc-(26_OH)
xyl
Yononin, Dioscorea tokoro Yonogenin (28). 184, 185
238-240”. - 14” ara-(Zg-OH)
Yuccagenin glycoside Yucca schottii Yuccagenin (jr), 37
gal_(38-OH)
Yuccoside B Yucca jilamentoso Tigogenin (3) 186
gal-‘glc-(3g-OH)
Yuccoside C, Yucca filamentosa Sarsasapogenin (27). 168. 187-189
282-284”. - 41” gal-*glc-‘glc-(3&OH)
Yuccoside E Yucca jilamentosa Sarsasapogenin (87). 188,190
gal\
,$glc-‘&_0,9_OH)
gal
Abbreviations used: glc, g - D - glucopyranosyl; rha, a - L - rhamnopyranosyl; ara, (I - L - arabinopyranosyl; gal, g - n -
galactopyranosyl; xyl, g - D - xylopyranosyl; ara -fur, n - L - arabinofuranosyl; qui, B - D - quinovopyranosyl; api -fur, g - o -
apiofuranosyl.
972 S. B. MAHATO,A. N. GANGULY and N. P. SAHU
Table 2. Steroidal saponins whose genins and sugars have been identified
Table 3. Basic steroid saponins (characterized and uncharacterized) isolated after 1972
fk’
Khasianine, Solanum khasianum Solasodine (SO), 63
226-228”, - 95” (MeOH) rha-‘glc-(3p-OH)
Solapersine, Solanum persicum Solasodine (50). 207
282-2&W, - 46” (MeOH) gal+glc+xy1
Solaplumbin, Nicotiana Solasodine (SO), 208
lNL181”, -90” plumbaginijolie glc-‘rha’-(3B-OH)
The steroidal saponins isolated and characterized and increase cholinesterase activity in the cytoplasm
up to 1980 are listed in Table 1 along with the mps [216]. The Na+ or K’ activated ATPase in rabbit red
and specific rotations and Table 2 shows the steroidal blood cell membranes is inhibited by low concen-
saponins which have not been fully characterized. As trations of saponin but activated by high concen-
comprehensive reviews [M-171 of basic steroidal trations while ouabain, a cardiac glycoside, inhibits
saponins are available, the characterized and un- the activating effect [217]. The effect of digitonin on
characterized basic steroidal saponins isolated after glucose uptake by isolated fat cells in the presence or
1972 are compiled in Table 3. absence of insulin was studied by Akhtar and Perry
[218] who observed that low concentrations of
BIOLOGICAL ACTIVITY saponin inhibited the stimulation of glucose uptake by
An extensive study of the physical, chemical and insulin without causing severe cell damage suggesting
physiological properties of saponins has been con- digitonin-cholesterol complex formation in the fat
ducted owing to their wide occurrence in nature. cell plasma membrane.
There are several excellent reviews on the properties
of saponins [6-l 1, 141 and on tomatine [15]. Saponins, Action on the cardio-vascular system
in general, are very powerful emulsifiers, toxic, The cardiotonic actions of g-strophanthin (0.15-
haemolytic and able to form complexes with choles- 3.25 mg/kg), a-solanine (2.5-5 mg/kg) and T.T.
terol. Here information on the biological activities of saponin were studied on a comparative basis. g-
various saponins, particularly the steroidal saponins, Strophanthin and T.T. saponin decreased the
reported durjng the period 1972 to 1979 is given. frequency of cardiac contraction whereas a-solanine
had no effect 12191. Cardiotonic activity of some
Action on metabolism glycoalkaloids, when compared with K-strophan-
Saponins (1%) in the diet of rats decreased the thoside by the use of isolated frog heart, is found to
plasma cholesterol level and increased bile acid be directly related to the nature of the aglycone and
production [212]. The depression of growth in vitro the number of sugar units [220]. Saponin isolated
caused by complex formation of saponin with fat- from the seeds of Achyranthes aspera is found to
soluble vitamins has been studied [213]. A change in increase the force of contraction of isolated frog
the thyroid gland in experimental haemolytic anaemia heart, guinea-pig heart and rabbit heart [221]. Two
has been observed [214] when subcutaneous injection new steroidal saponins ruscoside A (ruscogenin + 1
of saponin at doses of 1, 4 and 8 mg/kg once every glc + 1 gal + 2 rha) and ruscoside B (ruscogenin + 1
third day is given to rabbits. The development of gal+ 1 glc +2 rha+ 1 ara) isolated from Ruscus hyr-
proteins, carbohydrate and lipid dystrophy in the liver canus [ 1991 exhibit various biological activities. They
of rabbits is prevented by the oral administration of decrease the cholesterol content of the blood, lipid
Tribulus terrestris saponin at 10-15 mglkglday for 90 deposition in the aorta and liver arterial tension. They
days with the simultaneous administration of choles- also slow down the cardiac rhythm and respiration of
terol (200 mg/kg/day) [2151. Certain steroidal humans and rabbits suffering from arteriosclerosis.
saponins isolated from egg-plant, which contain Ruscoponin and ruscogiponin from R. penticus and
mainly tigogenin and neotigogenin as aglycones, par- R. hypophyllum exhibit fibrinolytic activity in oitro at
tially normalize lipase activity in the mitochondria 0.1 and 0.25% concentration, respectively. Ruscoponin
974 S. B. MAHATO,A. N. GAN~ULY
and N. P. SAHU
31. Schreiber, K. and Ripperger, H. (1966) Tetrahedron and Matwiyoff, N. A. (1976) J. Am. Chem. Sot. 98,
Letters 5997. 5807.
32. Tschesche, R., Ludke, G. and Wulff, G. (1967) Tetra- 63. Mahato, S. B., Sahu, N. P., Ganguly, A. N., Kasai, R.
hedron Letters 2785. and Tanaka, 0. (1980) Phytochemistry 19,2017.
33. Tschesche, R., Ludke, G. and Wulff, G. (1%9) Chem. 64. Seo, S., Tomita, Y., Tori, K. and Yoshimura, Y. (1978)
Ber. 102, 1253. J. Am. Chem. Sot. 100.3331.
34. Nohara, T., Nakano, A., Miyahara, K., Komori, T. and 65. Eggert, H. and Djerassi, C. (1975) Tetrahedron Letters
Kawasaki, T. (1975) Tetrahedron Letters 4381. 3635.
35. Kawasaki, T. Japan Kokai 77,51,011 (Co A 61 K 31/58) 66. Lemieux, R. U. and Koto, S. (1974) Tetrahedron 30,
23 April 1977. [Chem. Abstr. (1977) 87,65 4941. 1933.
36. Nohara, T., Komori, T. and Kawasaki, T. (1980) Chem. 67. Kasai, R., Suzuo, M., Asakawa, J. and Tanaka, 0.
Pharm. Bull. 28, 1437. (1977) Tetrahedron Letters 175.
37. Backer, R. C., Bianchi, E. and Cole, J. R. (1972) J. 68. Tori, K., Seo, S., Yoshimura, Y., Arita, H. and Tomita,
Pharm. Sci. 61, 1665. Y. (1977) Tetrahedron Letters 179.
38. Klyne, W. (1950) B&hem. J. 47, XLI. 69. Kasai, R., Okihara, M., Asakawa, J., Mijutani, K. and
39. Komori, T., Ida, Y., Mutou, Y., Miyahara, K., Nohara, Tanaka, 0. (1979) Tetrahedron 35, 1427.
T. and Kawasaki, T. (1975) Biomed. Muss Spectrom. 2, 70. Mizutani, K., Kasai, R. and Tanaka, 0. (1980) Carbo-
65. hydr. Res. 87, 19.
40. Komori, T., Tanaka, 0. and Nagai, Y. (1974) Org. Mass 71. Itano, K., Yamasaki, K., Kihara, C. and Tanaka, 0.
Spectrom. 9,744. (1980) Carbohydr. Res. 87,27.
41. Higuchi, R., Komori, T. and Kawasaki, T. (1976) Chem. 72. Mahato, S. B., Sahu, N. P. and Ganguly, A. N. (1980)
Pharm. Bull. 24, 2610. Indian .I. Chem. 19, 817.
42. Kasai, R., Matsuura, K., Tanaka, O., Sonada, S. and 73. Weston, R. J., Gottlieb, E., Hagamann, E. W. and
Shoji, J. (1977) Chem. Pharm. Bull. 25, 3277. Wenkert, E. (1977) Aust. J. Chem. 30, 917.
43. Krone, H. and Beckey, H. D. (1%9) Org. Mass Spec- 74. Tori, K., Seo, S., Yoshimura, Y., Nakamura, M.,
trom. 2,427. Tomita, Y. and Ishii, H. (1976) Tetrahedron Letters
44. Krone, H. and Beckey, H. D. (1971) Org. Mass Spec- 4167.
trom. 5, 983. 75. Tori, K., Thang, T. T., Sangare, M. and Lukacs, G.
45. Brown, P., Pettit, G. R. and Robins, R. K. (1%9) Org. (1977) Tetrahedron Letters 717.
Mass Spectrom. 2,521. 76. Bock, K. and Pederson, C. (1975) Acta Chem. Stand.
46. Brunnee, Z. (1967) Z. Noturforsch. Teil B 22. 121. Ser. B 29, 258.
47. Brown, P., Bruschweiler, F. R., Pettit, G. R. and 77. Kintya, P. K. and Bobeiko, V. A. (1975) Tezisy. LIokl.
Reichstein, T. (1970) J. Am. Chem. Sot. 92.4470. Vess. Simpol. Bioorg. Khim 20 [Chem. Abstr. (1976)
48. Brown, P., Bruschweiler, F. R. and Pettit, G. R. (1972) 85, 160 4611.
Helv. Chim. Acta 55, 531. 78. Lazurevskii, G. V., Bobeiko, V. A. and Kintya, P. K.
49. Beckey, H. D. and Schulten, H. R. (1975) Angew. Chem. (1975) Dokl. Acad. Nauk SSSR 2241442.
14,403. 79. Kintya, P. K. and Bobeiko, V. A. (1975) Khim. Prir.
50. Beckey, H. D. (1977) Principles of Field-Zonization and Soedin. 11, 751.
Field-Resorption Mass Spectrometry. Pergamon Press, 80. Kintya, P. K., Wilkomirski, B. and Bobeiko, V. A.
Oxford. (1975) Phytochemistry 14,2657.
51. Schulten, H. R., Komori, T. and Kawasaki, T. (1977) 81. Kintya, P. K., Bobeiko, V. A. and Gulya, A. P. (1976)
Tetrahedron 33,2595. Khim. Prir. Soedin. 486.
52. Schulten, H. R., Komori, T., Nohara, T., Higuchi, R. 82. Keliginbaev, A. N., Gorovits, M. B., Gorovits, T. T.
and Kawasaki, T. (1978) Tetrahedron 34, 1003. and Abubakirov, N. K. (1976) Khim. Prir. Soedin. 480.
53. Schiebel, H. M. and Schulten, H. R. (1979) Tetrahedron 83. Kintya, P. K., Bobeiko, V. A., Krokhmalyuk, V. V. and
35, 1191. Chirva, V. Ya. (1975) Pharmazie 30, 3%.
54. Hinze, R. P., Schiebel, H. M., Lass, H., Heise, K. P., 84. Kintya, P. K., Bobeiko, V. A. and Gulya, A. P. (1975)
Gossauer, A., Inhoffen, H. H., Ernst, L. and Schulten, Khim. Prir. Soedin. 11, 104.
H. R. (1979) Justus Liebigs Ann. Chem. 811. 85. Gorovits, M. B., Khristulas, F. S. and Abubakirov, N.
55. Komori, T., Kawamura, M., Miyahara, K., Kawasaki, K. (1973) Khim. Prir. Soedin. 6,747.
T., Tanaka, O., Yahara, S. and Schulten, H. R. (1979) 86. Lazurevskii, G. V., Krokhmalyuk, V. V. and Kintya, P.
2. Naturforsch. Teil C 314, 1094. K. (1975) Dokl. Akad. Nauk. SSSR 221,744.
56. Macfarlane, R. D. and Torgerson, D. F. (1976) Science 87. Goryanu, G. M., Krokhmalyuk, V. V. and Kintya, P.
191,920. K. (1976) Khim. Prir. Soedin. 400.
57. Kasai, H., Nakanishi, K., Macfarlane, R. D., Torger- 88. Goryanu, G. M. and Kintya, P. K. (1976) Khim. Prir.
son, D. F., Ohashi, Z., McCloskey, 3. A., Gross, H. J. Soedin. 762.
and Nishimura, S. (1976) 1 Am. Chem. Sot. 98, 5044. 89. Tschesche, R., Harz, A. and Petricic, J. (1974) Chem.
58. Anderson, W. R. Jr., Frick, W. and Daves, G. D. Jr. Ber. 107,53.
(1978) J. Am. Gem. Sot. 100, 1974. 90. Mori, Y. and Kawasaki, T. (1973) Chem. Phnrm. Bull.
59. Gorin, P. A. J. and Mazurek, M. (1975) Can. J. Chem. 21, 224.
53, 1212. 91. Tschesche, R., Tauscher, M., Fehlhaber, H. W. and
60. Yahara, S., Kasai, R. and Tanaka, 0. (1977) Chem. Wulff, G. (1%9) Chem. Ber. 102,2072.
Pharm. Bull. 25, 2041. 92. Tschesche, R. and Lauven, P. (1971) Chem. Ber. 104,
61. Stothers, J. B. (1972) Curbon- NMR Spectroscopy 3549.
p. 461. Academic Press, New York. 93. Varshney, I. P., Vyas, P., Srivastava, H. C. and Singh,
62. Walker, T. E., London, R. E., Whaby, T. W., Baker, R. P. P. (1977) Indian J. Phurm. 39, 125.
94. Tschesche, R. and Gutwinski, H. (1975) Chem. Ber. de Vivar, A. and Castillo, M. (1977) Carbohydr. Res.
188,265. 55,113.
95. Tschesche, R., Hermann, K. H., Langlais, R., Tjoa, B. 127. Mahato, S. B., Sahu, N. P. and Ganguly, A. N. (1981)
T. and Wulff, G. (1973) Chem. Ber. 106,301O. Phytochemistry 28, 1943.
96. Kimura, M., Tohma, M., Yoshizawa, I. and Akaiyama, 128. Mahato, S. B., Sahu, N. P. and Pal, B. C. (1978) Indian
H. (1%8) Chem. Pharm. Bull. 16, 25. J. Chem. 16,350.
97. Kimura, M., Tohma, M. and Yoshizawa, I. (1%6) 129. Kintya, P. K., Mashchenko, N. E., Kononova, N. I.
Chem. Phonn. Bull. 14,SS. and Lazurevskii, G. V. (1976) Khim. Prir. Soedin. 267.
98. Yoshizawa, I., Tohma, M. and Kimura, M. (1967) 130. Lazurevskii, G. V., Kintya, P. K. and Mashchenko, N.
Chem. Phann. Bull. 15, 129. E. (1976) Dokl. Akud. Nauk. SSSR 230.476.
99. Kimura, M., Thoma, M. and Yoshizawa, I. (1968) 131. Mashchenko, N. E., Lazurevskii, G. V. and Kintya, P.
Chem. Phann. Bull. 16, 1228. K. (1977) Khim. Prir. Soedin. 123.
100. Kimura, M., Tohma, M., Akaiharu, F. and Yoshizawa, 132. Kintya, P. K., Mashchenko, N. E. and Lazurevskii, G.
I. (1%8) Chem. Pharm. Bull. 16,219l. V. (1977) Khim. Prir. Soedin. 69.
101. Kawasaki, T. and Nashioka, I. (1964) Chem. Pharm. 133. Bogacheva, N. G., Gorokhova, M. M. and Kogan, L.
Bull. 12, 1311. M. (1977) Khim. Prir. Soedin. 421.
102. Kawasaki, T., Nishioka, I., Komori, T., Yamauchi, T. 134. Perepelitsa, E. D. and Kintya, P. K. (1975) Khim. Prir.
and Miyahara, K. (1%5) Tetrahedron 21,299. Soedin. 11, 260.
103. Bombardelli, E., Bonati, A., Gabetta, B. and Mustich, 135. Tomowa, M. and Gjulemotowa, R. (1978) Planta Med,
G. (1971) Fifoteropiu 42, 127. 34, 188.
104. Tschesche. R. and Wulff, G. (1963) Tetrahedron 19, 136. Hardman, R., Kosugi, J. and Per&t, R. R. (1980) Phy-
621. tochemistry 19,698.
105. Bombardelli, E., Bonati, A., Gabetta, B. and Mustich, 137. Sato, H. and Sakamura, S. (1973) Agric. Biol. Chem. 37,
G. (1972) Fitoterapia 43, 3. 225.
106. Nohara, T., Ogata, Y., Miyahara, K., Aritome, M. and 138. Kawano, K., Sato, H. and Sakamura, S. (1977) Agric.
Kawasaki, T. (1975) Chem. Pharm. Bull. 23,925. Biol. Chem. 41, 1.
107. Paseshnichenko, V. A. and Guseva, A. R. (1975) P&Z. 139. Meena, W., Rajaraman, K. and Rangaswami, S. (1977)
Biokhim. Mikrobiol. 11, 94. Indian J. Chem. 15,451.
108. Sviridov, A. F., Paseshnichenko, V. A., Kadentsev, V. 140. Bogacheva, N. G., Sheichenko, V. I. and Kogan, L. M.
I. and Chizhov, 0. S. (1975) Zzu. Akad. Nauk. SSSR. (1977) Khim. From-Zh. 11,65 [Chem. Absrr. (1977) 87.
Ser. Khim. 1, 90. 1806851.
109. Tschesche, R., Kottler, R. and Wulff, G. (1966) hstus 141. Krohmalyuk, V. V. and Kintya, P. K. (1976) Khim.
Liebigs Ann. Chem. 699,212. Prir. Soedin. 55.
110. Tschesche, R., Seidel, L., Sharma, S. C. and Wulff, G. 142. Kitagawa, I., Imkwang, S. and Morii, Y. (1976) Chem.
(1972) Chem. Ber. 105, 3397. Pharm. Bull. 243114.
111. Tsukamoto, T., Kawasaki, T. and Yamauchi, T. (1956) 143. Yosioka, I., Morii, Y. and Kitagawa, I. (1973) Chem.
Chem. Pharm. Bull. 4, 35. Pharm. Bull. 21,2092.
112. Yamauchi, T. (1959) Chem. Phnrm. Bull. 7,343. 144. Madaeva, 0. S., Ryzhkova, V. K. and Panina, V. V.
113. Kawasaki, T., Yamauchi, T. and Yamauchi, R. (1%2) (1%7) Khim. Prir. Soedin. 3, 237.
Chem. Pharm. Bull. 10,698. 145. Chakravorty, A. K., Dhar, T. K. and Pakrashi, S. C.
114. Heitz, S. (1959) C. R. 248, 283. (1978) Tetrahedron Letters 3875.
115. Pal, B. and Marruan, M. S. (1969) Magy. Kern. Foly. 75, 146. Chakravorty, A. K., Saha, C. R. and Pakrashi, S. C.
343. (1979) Phytochemistry 18,902.
116. Nohara, T., Yabuta, H., Suenobu, M., Hida, R., Miya- 147. Mahato, S. B., Sahu, N. P., Pal. B. C. and Chakravarty.
hara, K. and Kawasaki, T. (1973) Chem. Pharm. Bull. R. N. (1977) Indian J. Chem. 15.445.
21, 1240. 148. Khristulas, F. S., Gorovits, M. B. and Abubakirov, N.
117. Nohara, T., Kumanoto, F., Miyahara, K. and Kawas- K. (1974) Khim. Prir. Soedin. 4, 530.
aki, T. (1975) Chem. Pharm. Bull. 23, 1158. 149. Vollermer, Yu. S., Gorovits, M. B., Gorovits, T. T. and
118. Tschesche, R. and Pandey, V. B. (1978) Phytochemistry Abubakirov, N. K. (1978) Khim. Prir. Soedin. 740.
17, 1781. 150. Vollermer, Yu. S., Gorovits, M. B., Gorovits, T. T. and
119. Perepelitsa, E. D. and Kintya, P. K. (1974) Zzu. Akad. Abubakirov, N. K. (1980) Khim. Prir. Soedin. 355.
Nauk Mold. SSR. Ser. Biol. Khim. Nauk. 76. 151. Tschesche, R. and Balle, G. (1963) Tetrahedron 19.
120. Iskenderov, G. B., Manedova, M. N. and Musaey, N. I. 2323.
(1975) Khim. Prir. Soedin. 11, 805. 152. Yosioka, I., Imai, K. and Kitagawa, I. (1971) Tetra-
121. Rajaraman, K., Seshadri, V. and Rangaswami, S. (1976) hedron Letters 1177.
Indian. .Z.Chem. 14,735. 153. Mahato, S. B., Sahu, N. P., Ganguly, A. N., Miyahara,
122. Takahira, M., Kondo, Y., Kusano, G. and Nozoe, S. K. and Kawasaki, T. (1981) Z, Chem. Sot. Perkin Trans. 1,
(1977) Tetrahedron Letters 3647. 2405.
123. Yosioka, I., Mai, K. I., Morii, Y. and Kitagawa, I. 154. Akahori, A., Yasuda, F., Kagawa, K. and Iwao, T.
(1974) Tetrahedron 38, 2283. (1973) Chem. Phann. Bull. 21, 1799.
124. Takahira, M., Kondo, Y., Kusano, G. and Nozoe, S. 155. Kato, H., Sakuma, S., Tada, A., Kawanishi, S. and
(1979) Yukugaku Zusshi 99,528. Shoji, J. (1968) Yokugaku Zasshi 88,710.
125. Chincharadze, D. G., Kelginbaev, A. N., Gorovits, M. 156. Tada, A. and Shoji, J. (1972) Chem. Pharm. Bull. 26,
B., Eristavi, L. I., Gorovits, T. T. and Abubakiiov, N. 1729.
K. (1979) Khim. Prir. Soedin. 509. 157. Tada, A., Kobayashi, M. and Shoji, J. (1973) Chem.
126. Lemieux, R. U., Ratcliffe, R. M., Arreguin, B., Romo Pharm. Bull. 21,308.
Steroid saponins 977
158. Watanabe, Y., Sanada, S., Tada. A. and Shoji, J. (1977) 190. Dragalin, I. P., Gulya, A. P., Krokhmalyuk, V. V. and
Chem. Phawn. Bull. 283049. Kintya, P. K. (1975) Khim. Prir. Soedin. 11,747.
159. Ripperger, H. and Schreiber, K. (1%8) Chem. Ber. 101, 191. Goryanu, G. M., Krokhmalyuk, V. V. and Kintya, P. K.
2450. (1976) Khim. Prir. Soedin. 823.
160. Ripperger, H., Schreiber, K. and Budzikiewicz, H. 192. Varshney, I. P., Vyas, P.. Shrivastava, H. C. and Singh,
(1967) Chem. Ber. 100, 1741. P. P. (1979) Indian Z. Pharm. Sci 41, 122.
161. Seshadri, T. R. and Vydeeswaran, S. (1972) Indian J. 193. Madaeva, 0. S., Ryzhkova, V. K. and Panina, V. V.
Chem. 10,589. (1967) Khim. Prir. Soedin. 3,237.
162. Khana, I., Seshadri, R. and Seshadri, T. R. (1975) 194. Janeczko, Z. and Sendra, J. (1979) Acta Pol. Pharm. 36,
Indian J. Chem. 13, 81. 415.
163. Seshadri, T. R., Vydeeswaran, S., Rao, P. R. and 195. Kinyta, P. K., Perepelitsa, E. D., Chriva, V. Ya. and
Thakur, R. S. (1972) Indian Z. Chem. 10,377. Kretsu, L. G. (1972) Khim. Prir. Soedin. 8,475.
164. Kintya, P. K., Stamova, A. I., Bakinovskii, L. V. and 1%. Gangrade, H. and Kaushal, R. (1979) Indian Drugs 16,
Krokhmalyuk, V. V. (1978) Khim. Prir. Soedin. 350. 149.
165. Kawasaki, T., Komori, T., Miyahara, K., Nohara, T., 197. Varshney, I. P., Jain, D. C., Srivastava, H. C. and
Hosokawa, I. and Mihashi, K. (1974) Chem. Pharm. Singh, P. P. (1977) J. Indian Chem. Sot. 54, 1135.
Bull. 22,2164. 198. Varshney, I. P. and Jain, D. C. (1979) Natl. Acad. Sci.
166. Kitagawa, I., Nakanishi, T., Morii, Y. and Yosioka, I. 2, 331.
(1976) Tetrahedron Letters 1885. 199. Guseinov, D. Ya. and Iskenderov, G. B. (1972) Biol.
167. Tomita, Y. and Uomori, A. (1974) Phyrochemistry 13, Nauki (Moscow) 15,85 [Chem. Abstr. (1972) 77,16542].
729. 200. Brown, J. M. and Kock, W. T. (1959) S. Afr. Znd.
168. Dragalin, I. P. and Kintya, P. K. (1975) Phytochemistry Chemist. 13, 189 [Chem. Abstr. (l%O) 54,9011].
14, 1817. 201. Stabursvik, A. (1959) Nor. Tek. Vitenskapsakad. 2, 89.
169. Kintya, P. K. and Dragalin, I. P. (1975) Khim. Prir. 202. Chakravarti, R. N., Dutt, S. and Mitra, M. N. (1%2)
Soedin. 11, 806. Bull. Calcutta Sch. Trop. Med. 10,123.
170. Kintya, P. K. and Bobeiko, V. A. (1979) Khim. Prir. 203. Pkheidze, T. A. (1979) Zzv. Akad. Nauk. Gruz SSSR.
Soedin. 102. Ser. Khim. $3 11.
171. Pharn, H. N., Kelginbaev, A. N., Gorovits, M. B. and 204. Tomowa, M., Panowa, D. and Wulfson, N. S. (1974)
Abubakirov, N. K. (1980) Khim. Prir. Soedin. 352. Planta Med. 25,231.
172. Sato, H. and Sakamura, S. (1973) Agric. Biol. Chem. 37, 205. Sharma, H. C. and Narula, J. L. (1977) Chem. Era 13,
225. 15.
173. Kawasaki, T. and Yamauchi, T. (1%3) Chem. Pharm. 206. Zacharius, R. M. and Osman, S. F. (1977) Plant Sci
Bull. 11, 1221. Letters 10, 283.
174. Miyahara, K., Isozaki, F. and Kawasaki, T. (1969) 207. Novruzov, E. N., Aslanov, S. M., Ismailov, N. M. and
Chem. Phann. Bull. 17, 1735. Imanova, A. A. (1975) Khim. Prir. Soedin. 11,434.
175. Miyahara, K. and Kawasaki, T. (1%9) Chem. Pharm. 208. Singh, S., Khanna, N. M. and Dhar, M. M. (1974)
Bull. 17, 1369. Phytochemistry 13,202O.
176. Bogacheva, N. G., Kiselev, V. P. and Kogan, L. M. 209. Guevara, M. C. and Martinod, D. P.(1972) Politencica,
(1976) Khim. Prir. Soedin. 268. 2, 107.
177. Huang, W., Chen, Y. and Chu, J. (1956) Hua Hsueh 210. Coune, C. and Denolel, A. (1975) Plant. Med. Phy-
Hsueh Pao 22,409. tother. 9, 14.
178. Kinyta, P. K., Veleva, A. I. and Lazurevskii, G. V. 211. Puri, R. K. and Bhatnagore, J. K. (1975) Phytochemis-
(1976) Khim. Prir. Soedin. 670. try 14,2096.
179. Konyukhov, V. P., Sviridov, A. F., Subbotin, B. S. and 212. Topping, D. L., Hood. R. L., Illman, R. J., Storer, G. B.
Chizhov, 0. S. (1973) Khim. Prir. Soedin. 6,741. and Oakenfull, D. G. (1978) Proc. Nutr. Sot. Aust. 3,
180. Konyukhov, V. P., Sviridov, A. F. and Subbotin, B. S. 68.
(1972) Khim. Sb. 86 [Chem. Abstr. (1975) 82, 121 7281. 213. West, L. G. and Greger, J. L. (1978) J. Food Sci. 43,
181. Pirtskhalava, G. V., Gorovits, M. B., Gorovits, T. T. 1340.
and Abubakirov, N. K. (1978) Khim. Prir. Soedin. 355. 214. Natoi, T. (1973) Showa Zgakkai Zasshi 33, 119.
182. Pirtskhalava, G. V., Gorovits, M. B. and Abubakirov, 215. Umikashvilli, R. S. (1972) Soobshch. Akad. Nauk.
N. K. (1978) Khim. Prir. Soedin. 532. Gruz. SSSR 67,729.
183. Pirtskhalava, G. V., Gorovits, M. B., Gorovits, T. T. 216. Varvashtyan, V. M., Gromova, L. G., Kopytin, B. M.
and Abubakirov, N. K. (1979) Khim. Prir. Soedin. 514. and Kupreeva, S. T. (1975) Deposited Dot. 3763 [ Chem.
184. Kawasaki, T. and Miyahara, K. (1%5) Tetrahedron 21, Abstr. (1978) S&99 0971.
3633. 217. Kang, B. N. and Koh, I. S. (1974) Taehan Saengn’
185. Takeda, K., Okanishi, T. and Shimaoka, A. (1958) Hakhoe Chi 8,67.
Chem. Pharm. Bull. 6,532. 218. Akhtar, R. A. and Perry, M. C. (1975) Biochim. Bio-
186. Kinyta, P. K., Draglin, I. P. and Chirova, V. Ya. (1972) phys. Acta 411, 30.
Khim. Prir. Soedin. 615. 219. Turova, A. D. and Skachkova, N. I. (1974) Vestn.
187. Madaeva, 0. S. (1958) Zh. Obshch. Khim. 28, 1988. Akad. Nauk. Kaz. SSSR. 68.
188. Lazurevskii, G. V., Kinyta, P. K. and Dragalin, I. P. 220. Nishie, K., Fitzpatrick, T. T., Swain, A. P. and Keyl,
(1975) Dokl. Akad. Nauk. SSSR 221,481. A. C. (1976) Res. Commun. Chem. Pathol. Pharmacol.
189. Dragalin, I. P. (1975) Tezisy ZIokl. Soobshch-konf. 15,601.
Molodykh. Uch. Mold 9th (1974) 97 [Chem. Abstr. 221. Gupta, S. S., Bhagwat, A. W. and Ram, A. K. (1972)
(1976) 84, 147 7311. Indian .Z.Med. Res. 60,462.
978 S. B. MAHATO,A. N. GANGULYand N. P. SAHU
222. Kereselidze, E. V., Pkheidze, T. A., Kembertelidze, E. 230. Singh, S., Sanyal, A. K., Bhattacharya, S. K. and
P., Khardziani, S. D., Dzhaparidze, T. N. and Mak- Pandey, V. B. (1972) Indian I. Med. Res. 60, 287.
haradze, Sh. K. (1975) Soobshch. Akad. Nauk. Gruz. 231. Pandey, V. B., Dasgupta, B., Bhattacharya, S. K.,
SSSR 78,485. Debnath, P. K., Singh, S. and Sanyal, A. K. (1972)
223. Assa, Y., Gestetner, B., Chet, I. and Henis, Y. (1972) Indian .Z.Pharm. 34, 116.
Life Sci 11,637. 232. Tewari, P., Chaturvedi, C. and Pandey, V. B. (1973)
224. Vichkanova, S. A., Adgina, V. V., Makarova, L. V. and Indian. .Z.Pharm. 35, 114.
Rubinchick, M. A. (1971) Tr. Vses Nauchi-Jssled Vst. 233. Chou, S. C., Ramanathan, S., Matsui, A., Rogers, J. and
14, 191. Cutting, W. C. (1971) Indian J. Z&p. Biol. 9, 503.
225. Segal, R. and Schloesser, E. (1975) Arch. Mcrobiol. 234. Elferink, J. G. R. (1977) Pharm. Weekbl. 112, 1.
104, 147. 235. Muravev, I. A. and Dzhumaev, M. A. (1973) Vopr.
226. Vasyukova, N. I., Paseshnichenko, V. A., Davydova, Farm Dalnem Vostoke 1,45.
M. A. and Chalenko, G. I. (1977) Prikl. Biokhim. Mik- 236. Capra, C. (1972) Fitoterapia 43,99.
robiol. 13, 172. 237. Mitev, G., Tekerlekov, P., Zhlebinkov, Z. and Shopov,
227. Cioaca, C., Margineanu, C. and Cucu, V. (1978) Phar- I. (1973) Vet. Med. Nauki 10, 55.
mazie 33,609. 238. Strobbe, R., Charlier, G., Devecq, J. and Vanaert, A.
228. Markosyan, L. S., Nalbandyan, A. D., Grigoryan, N. (1976) Arch. Rxp. Veterinaermed. 30, 173.
L., Bagdasaryan, I. B., Muradyan, A. A. and Mus- 239. Kemertelidze, E. P., Pkheidze, T. A., Kachukhashvili,
aelyan, M.S. (1975) Biol. Zh. Arm. 28, 66 [Chem. T. N., Turova, A. D., Sokolova, L. N. and Umikashvili,
Abstr. (1976) 84, 100 1351. R. S. (1977) OtkrytiyaZzobretProm. Obrartsy Touamye
229. Dasgupta, B. and Pandey, V. B. (1970) Experientia 26, Znaki 54, 10 [Chem. Abstr. (1977) 87, 157 1811.
475.