Phymhmisrry. Vol. 31. No. 1. pp. 2199 2249. 1992 Primed I” Grem Bntam.
0031-9422192 ss.oo+o.oo C 1992 Pergamon Pmss Ltd
REVIEW ARTICLE NUMBER 67
TRITERPENOIDS
SHASHI B. MAHATO, ASHOKE K. NANDY and GITA ROY
Indian Institute of Chemical Biology, 4, Raja S. C. Mullick Road, Jadavpur, Calcutta 700032, India
(Received 19 June 1991)
Key Word Index--Triterpenoids; newer skeleton triterpenes; isolation; structure elucidation; natural distribution; chemical modification; synthesis: biological activity.
Abehnct-Ttiterpenoids isolated and characterized from various sources are reviewed. The newer techniques used in their isolation and structure elucidation, the newer skeleton triterpenoids characterized, chemical modifications and synthetic studies reported are discussed. A compilation of the triterpenoids isolated during the period 1982-1989 along with their occurrence. available physical data, spectroscopy and X-ray analysis used for their characterization, is included. The biological activities of the triterpenoids are also described.
INTRODIJfflON
Triterpenoids are the most ubiquitous non-steroidal secondary metabolites in terrestrial and marine flora and fauna. Their presence, even in non-photosynthetic bac- teria, has created interest from both evolutionary and functional aspects. Although medicinal uses of this class of compounds are rather limited, considerable recent work in this regard strongly indicates their great potential as drugs. Moreover, despite the remarkable diversity that is already known to exist among the carbon skeletons of triterpenes, new variants continue to emerge.
The purpose of this review is to present an overview of triterpenoids in relation to their occurrence, the newer methodology used for their isolation and structure elu- cidation and the biological activities of these compounds reported during the period 1982-1989. Our previous review on triterpenoids [I] covered the literature for the period 1977-1981. Earlier comprehensive reviews [24] are available on the subject covering the literature up to 1976. In recent years reviews of specific and general interest have appeared. Besides the continuing general reviews on triterpenoids [7-93, a few specific reviews have been published, e.g. on pentacyclic triterpenoids [IO], on cycloartane compounds detected in 43 species belonging to 34 genera and 32 families [ 111, and on the constituents of Azadirachta indica [ 123. An excellent review on bac- terial triterpenoids giving an account on triterpenoid occurrence as well as function in bacteria has also been published [ 133.
ISOLATION AND PURIFICATION
2199
The general methods of solvent extraction and column chromatography of the extract followed by preparative TLC are effective in most cases for the isolation of the triterpenoids. However, in the cases of complex mixtures of closely related isomeric products special techniques, such as HPLC, GC-MS and capillary CC [ 143, are found
to be helpful. Twenty lupane triterpenoids including five (ZOR.S)-epimeric pairs have been isolated from the chloro- form extractives of the lichen Pseudocyphehria rubella using GC-MS procedures [IS]. Twenty-four oxygenated lanostanoid acids, including eight pairs of stereoisomers and five pairs of positional isomers in Ganoderma lucidum were separated by reversed-phase HPLC [ 163. The capa- city factors obtained in MeOH-H,O and MeCN-H,O solvent systems were useful for the correlation of the molecular polarities due to the presence of multiple oxygenated functional groups in the products. The num- ber and position of functional groups, as well as their stereochemistry, played important roles in governing the polarity of these compounds. The unique stereochemical character and eluting sequences of these lanostanoid acids provided information to generate emperical rules for predicting the role of individual polar functional groups in the chromatographic behaviour during re- versed-phase HPLC. A method for the separation of substituted olean-12-en-28-oic acids from the corres- ponding urs- l2-en-28-oic acid isomers has been reported by Lewis et al. [ 173. The method involves the treatment of the mixture with bromine in acetic acid. Members of the ursene family were inert under the conditions used. Thus, a mixture of ursolic acid and oleanolic acid was dissolved in 90% HOAc-EtOH and treated with bromine in acetic acid to give a mixture of the bromolactone of oleanolic acid and unreacted ursolic acid. This mixture was separ- ated by solvent extraction or chromatography. The au- thors of this work have also suggested that a similar separation is possible with the l2-en-28-01 systems [ 173. Kawanishi et 01. [ 181 have reported the separation of the pentacyclic triterpenes. tylolupenols A and B from Tylophora kerrii, by automatic recycling HPLC.
It is noteworthy that triterpenoids, like many other secondary metabolites. occur in nature either in the free state or as glycosides. In the latter case cleavage of the sugar moiety by acid or enzymic hydrolysis, or by other techniques, is sometimes necessary before isolation and
2200 S. B. MAHATO er 01.
purification of the triterpenoid moiety. The usual method of acid hydrolysis ofglycosides often leads to artifacts and many of the triterpenoids known today are artifacts. For
example, panaxadiol, panaxatriol [ I9 3 careyagenol D [20]. aescigenin [Zl], soyasapogenols C. D. and F [22, 231, saikogenin A and saikogenin C [24]. are acid rearranged triterpenoids formed during acid hydrolysis of the parent glycosides. Alternative newer techniques of
splitting the carbohydrate moiety are sometimes adopted for the isolation of genuine aglycones. A few such tech- niques have been reported previously [l, 25, 261. The newer technique of hydrolysis using alcoholic-alkali metal solution containing a trace of water has proved to be useful for isolation of acid labile aglycones [27. 283.
The USC of n-BuOH -Na-metal at water bath temperature (95%) for 48 hours afforded the genuine triterpenoid anagalligenin B [29] as the major product which, how- ever, could not be isolated by the usual acid hydrolysis.
STRUCTURE ELUCIDATIOY
The application of the newer spectroscopic techniques has tremendously eased the problem of structure elucida- tion of natural products which. in most cases, is now successfully achieved without resorting to the convcn- tional chemical degradative procedures. Although the widespread adoption of these techniques in structure elucidation studies may appear to have created a limita- tion on the generation of new chemical knowledge, these methodologies have nevertheless opened up new vistas and research activities can now move forward into areas which were otherwise inaccessible.
N hI R sprctrosc~op)
The developments in NMR spectroscopy for structure elucidation are very remarkable. “C NMR spectroscopy
is now very frequently employed for the structural ana- lysis of triterpenoids using various methods of signal
assignment, e.g. attached proton test (APT), insensitive nucleus enhancement by polarization transfer (INEPT).
distortionless enhancement by polarization transfer (DEPT), ZD-spectroscopy and single frequency off-reson- ante decoupling. The recent development of ZD-NMR spectroscopy has provided a number of signal assignment techniques which are very useful in the area of natural products chemistry, including triterpenoids. Total assign- ment of 13C and ‘H NMR spectra of three isomerlc
triterpenoids, taraxasterol, pseudotaraxasterol and lupeol by ZD-NMR has been reported by Reynolds et 01. [30]. They have demonstrated that the indirect “C-‘H shift-correlated pulse sequence, XCORFE (X-nucleus
correlation with fixed evolution time) 1313 was very
useful for unambiguously assigning 13C NMR spectra of these products without resorting to the use of shift
reagents as an aid to assignment [32]. These authors have
also pointed out that XCORFE has advantages over Kessler’s COLOC sequence [33]. The ability of XCORFE to distinguish two-and three-bond connectivi- ties was particularly useful in completing the assignment of carbons which show no methyl ‘H cross peaks. The sensitivity of this sequence is particularly impressive. The spectra were obtained for 50 mg of each sample with a total measuring time of two hours using a spectrometer operating at 400 MHz.
The new triterpenoid carbon skeleton of the pouoside
aglycones which parallels that of the C,,-carotenoids was determined by spectroscopic data, especially extensive ‘H and “C NMR data and ZD-NMR experiments [34]. Information gleaned from a COSY plot and dttierence double resonance (DDR) experiments led to the formula- tion of partial structures. Proton carbon correlation experiments, optimized separately for detecting one-and two-/three-bond couplings, confirmed the partial struc-
tures and unambiguously identified thechemical shifts for the three pairs of geminal protons whose shifts could not
be confidently assigned from ‘HNMR data alone be- cause of inadequate dtspersion in the upfield region of the spectrum. The vicinally coupled sequence of protons was also confirmed by COSY and relayed coherence transfer
(RCT) [35] I!D-spectra. The authors have demonstrated the usefulness of a long-range COSY spectrum 1353 for confirming the presence of geminal dimethyl groups on a carbon next to the methine carbon. The utility of a NOESY spectrum for structure elucidation has also been demonstrated. The structure of two triterpenes possessing novel side chains isolated from the fungus Pisolithus tinctoriu, were elucidated by chemical correlation with known compounds coupled with spectroscopic methods involving nuclear Overhauser effect (NOE) difference spectroscopy [36]. The structures of two new nortriter-
penes. glycinocclcpins B and C isolated from the aqueous extracts of roots of Phasc~du.s rdquris [373 have been determined from their 13CNMR spectra taken under completely decoupled and off-resonance conditions, com- bined with INEPT studies and their ‘HNMR spectra. The COSY spectra and extensive decoupling studies. as well as the measurement of the NOE differcncc spectra. were of much help in the determination of the structures.
The structures ofseveral neu Ianastane-type tetracyclic trlterpenes isolated from the surface part of the gills of Gwwdrrmcr lucidurn [M. 3YJ were elucidated by detailed analysts of ‘H and ‘“C NMR spectra using two-dimen- sional ‘H -‘H and ‘H-‘“C shift correlation techniques. For example. ‘H- ‘H shift correlated spectra allowed in
some cases the assignments of most of the proton signals. In particular. the signals due to methyl groups, except the
C-30(4%)-and C-3114/1)-methyl groups. were precisely assigned on the basis of the presence of long range coupling between Cl,-19 and H-12. H,-I8 and H-121 and
H,-21 and H-22. The assignments of the C-30 and C-31 methyl signals were achieved by measurement of the NOE difference spectra. Irradiation of the methyl signal
at (5 I. I2 gave appreciable NOE rncreascs of the H-5 and H-62 signals, while irradiation at ci I .I0 gave a small NOE
increase of the H-6fi signal. The ‘H -“C shift correlation spectra led readily to precise assignments of the “C signals, except for the quaternary carbon signals, which
were assigned by comparison of the “CNMR spectral
patterns of the known compounds.
The molecular skeletons of two of the less common triterpenes. moretenone (hop- 22-ene-3-one) and 3-acetyl-
alcuritolic acid (3/3-acetoxy-taraxer-l4-ene-28-oic acid) were elucidated by ‘H “C shift correlated two dimen- sional spectra obtained for polarization transfer via two- bond and three-bond ‘.‘C ‘H coupling correlation, in conjunction with related experiments [40].
The ‘“CNMR spectra offive pairs of IX/I- and 182-l I- oxo-oleanolic acid derivatives were recorded and the signals were assigned by Wrreciono et al. [4l]. The chemical shafts of C- 12, C- 13, C- 17. C- 18 and C-28 are of diagnostic value for the determination of the D/E-junc-
Triterpenoids 2201
bon stereochemistry. The stereochemistry of D/E-ring fusion of some pentacyclic triterpenoid derivatives was also determined by Grahn et al. [42] from the 13C NMR spectral analyses. It was shown that the analyses of the 13C chemical shifts of variously substituted 18~/18/3- pentacyclic triterpenes could be significantly simplified by the use of a multivariate data-analytical approach. The authors claimed that the present approach minimizes the risk from incorrect assignments or other errors which are associated with large data tables.
The conformation of cycloartenol, a possible mem- brane component, was investigated by Milon et al. [43] by NMR spectroscopy and molecular mechanics. Molecular modelling suggested that two conformations of nearly equal energy coexist, differing mainly at the level of ring C and each having rings A, B in a chair and half chair conformation, respectively, with ring C being 1,3- diplanar in one and in the chair conformation in the other. A complete assignment of the ‘H and “CNMR spectra of the triterpene and the entire coupling network in rings A and B were determined by various NMR techniques. Low temperature NMR experiments showed a fast equilibrium between the two conformations. It was concluded that the cyclopropane ring produces a flexibil- ity at the level of ring C which may be important for the membrane properties of the triterpene.
CD spectroscopy
The circular dicroism spectra of C-8 and C-14 substitu- ted onocerane-3,21-diones was interpreted [44] by assuming ring A (and ring D) of the compounds in equilibrium between chair and twist forms with variable ratios. This equilibrium was affected by minor structural changes at remote positions and by the polarity of the solvent. An increase of the steric bulkiness of the 8p- substituent increases the proportion of the twist form. The A-ring conformation of compounds which carry an oxygenated function at 8/l was greatly affected by changes of the solvent polarity. The conformation of the com- pounds without an 8fi-oxygenated substituent was al- most solvent independent. These conclusions were sup- ported by measurements of solvent shift in the ‘H NMR spectra of the compounds. The authors proposed the presence of a new kind of steric effect which they called the ‘8/I-substituent effect’. Klinot et al. 1453 reported that the A-ring of 3-oxotriterpenoids allobetulone and 3-0x0- lupane-28-nitrile exists 40% in the boat form from com- parison of their dipole moments to those of 2x-methyl derivatives (chair model) and 2b-methyl compounds (boat model). The same result was obtained from the CD spectra of these two compounds and of other 3-oxotriter- penoids and from isomerization of 2a- and 2fl-substituted ketones.
NEW SKELETONS OF TRITERPENOIDS
During the period covered by this review a number of triterpenoids possessing novel carbon frameworks have been isolated from various sources. The structures of these triterpenoids are of much interest from the point of view of their formation biogenetically.
Sipholane
The sipholane skeleton (21) consists of a cis-octa- hydroazulene linked via an ethylene bridge to a trans-
decahydrobenzoxepine. The structure of the sipholane skeleton was established by an X-ray diffraction analysis of one of the natural compound derivatives [46]. Eight new triterpenes possessing this skeleton have been isol- ated from the Red Sea sponge Siphonochulina siphonella [47]. The X-ray derived structure of the major triterpene, sipholenol-A made possible the NMR and mass spectral interpretations and the structure elucidation of the addi- tional seven new compounds. Of special interest is the suggested biogenesis of the sipholanes starting from 2,3:6, 7: 18, 19-triepoxysqualene. In contrast to the single cyclization process that takes place in the biogenesis of tetra- and pentacyclic triterpenes, the suggested route leading to the sipholanes involves two consecutive cycliz- ations.
Siphonellane
Siphonellinol, a triterpene, possessing the new car- bocyclic skeleton, siphonellane (22) was also isolated from the marine sponge Siphonochulina siphonella by Carmely er 01. [48]. The proposed biogenesis of this triterpene shows a close relationship to that of the squalene-derived sipholanes and differs only in cycliz- ation of one half of the molecule.
Polypodane
A new oily triterpene hydrocarbon having a novel bicyclic carbon skeleton, polypodane (26) and named a-polypodatetraene was isolated from the fresh leaves of Polypodium jauriei and Lemmaphyllum microphyllum [49]. A related new triterpene, y-polypodatetraene, was isolated from leaves of Polysrichum ouato-poleaceum and P. polyblephatum [49]. A bicyclic diol possessing this polypodane skeleton has also been isolated by Boar er al. [SO] from gum mastic, the abundantly available resin obtained from the Mediterranean shrub Pistacia lentis-
cus. The structure and absolute stereochemistry of the bicyclic diol are fully consistent with its formation by interception of the bicyclic carbocation postulated as an intermediate in the cyclization of the chair-chair-boat conformation of (3Sksqualene-2,3-epoxide. This bicyclic triterpenoid retains all of the regio- and stereochemical features necessary for continued cyclization. The isola- tion of these bicyclic triterpenoids supports the postul- ation of van Tamelen and his co-workers [Sl], that the cyclization of squalene proceeds via a series of discrete conformationally rigid carbocationic intermediates.
Spirosupinane
The structure of spirosupinanonediol, a new triter- penoid isolated from Euphorbia supina has been estab- lished by spectral and X-ray analyses as 7(8+9)abeo-9S-
D:C-friedo-B’:A’-neogammaceran-8-one-3S,7S-diol with a novel skeletal system for which the name spirosu- pinane (27) has been proposed [52]. This is the first example of a triterpene possessing a Spiro-skeleton. The probable biogenesis of spirosupinanonediol involving an 8,9-dihydroxyfernane derivative has been rationalized c521.
Radermasinin
Radermasinin, a novel cytotoxic triterpene lactone isolated from Radermachia sinica was shown to have
2202 S. B. MAnAT er al.
23 24 Olcanonc ( I)
Urosonc (2) 30
23 24 Toroxastonc (3)
Frrcdelone (4)
23 24
Gornmocerone (5)
structure 31 by spectral data and single-crystal X-ray analysis of its monohydrate. It possesses a yem-dimethyl- vinyl group at C-18 in addition to a spiro y-hydroxy-y- lactone moiety at C-17 and its possible biogenetic path- way involving 21-hydroxy-l8z-olean-28-oic acid derivat- ive as precursor has been suggested [S3].
23 24 Serratone (6)
30-&g
Lupone (7)
23 24 Hopone (8)
23 24
Fernone (9)
. 22
Y2g 30
26 29
Dammorone (IO)
Baccharane
The structure of hosenkol-A. the first example of the natural baccharane (23) triterpenoid of the missing inter- mediate shionane (25) and lupane (7). has been deter- mined [54] by spectroscopic methods as well as by X-ray crystallographic analysis. The isolation of hosenkol-A
28 2e Lanortone (II) (30) (31)
26
27
Cucurbitonc (12)
_ 2i) is 23 24
Euphonc (13) Toroxeronc (I@)
21
Tirucollnc (14)
26
27
Protortonc (IS)
which has a unique Spiro-ring strongly supports the postulated biogenesis of lupane and shionane via baccharane.
Rearranged lanostanes
17,13-friedolanostane (36) and 8 (14+13R)abeo-17,13- friedolanostane (37), have been isolated from seeds of Abies mariesii [SS, 563, A.jrma [56] and A. sibirica [S-I]. The new rearranged lanostane skeletons (35-37) have been considered to be biosynthesized from the lanostane skeleton by enzymic dehydrogenation of H-17 or dehy- droxylation of OH-17 followed by successive l.tshifts of Some new rearranged lanostanoids having novel
carbon skeletons, such as 17.14-friedolanostane (35), methyl group(s) and a ring bond.
Triterpenoids 2203
. Apotlrucollone (b)
Glutonc (I71
26 27 Moloborlcone (19)
23 24 Onocerone (20)
S. B. MAHATO er al.
Slpholone (21) Polypodone (26)
3 2 Spiroruplnonc (27)
2Fi is Bocchorane (23)
Swcrtanc (261
Lcmmophyllane (24) Pfoffone (29)
Stuonone (251 Corotenold - IIke skeleton (30)
A few triterpenoids possessing the novel 14(13-+12)- ubeo lanostane skeleton (34) have been isolated from Kadsura longipedunculata [.58] and K. hereroclita [59].
Degraded and teurrawed lanosranes
Glycinoeclepin A, a natural hatching stimulus for soybean cyst nematode, has been isolated from the aque- ous extract of roots of kidney bean (Phuseoiur oulgaris). Its novel structure (41) was elucidated by spectroscopic and X-ray crystallographic analyses [6oJ. The structure 41 is characterized by migration of two methyl groups
involved in the C and D rings and oxidative cleavage of the B-ring with loss of one carbon atom, compared with those of cycloartanes (9&19-cyclolanostane), and is re- garded as a pentanortriterpene. Two other new nortriter- penes. glycinoeclepins B (42) and C (43) possessing a similar ring system to that of glycinoeclep~n A. but with a non-degraded side chain. have also been isolated from the same source [37].
Javeroic acid (44) and phellinic acid (45) having a novel degraded and rearranged Ianostane skeleton were isol- ated from Pheffinus pomaceus [61] and their structures were determined by a combination of chemical and
Trtterpcnotds 2205
AcO-
Radtrmor~n~n (31) Rearranged bnortanr (36)
26
27
” 24 Sorghumot (32) Rearranged Ianostone (St)
Rcarraflgcd fcrnanr (33)
Rearranged Ianostane (34)
27
Rearranged Ianostanr (35)
26
27
l-4 :, 4-hgwmonol (30)
f - Ir~gcrmanal (39)
Y (CH2)2CH=CM~(CH2)2CH-CM~CH~H(OHJCH-CM~2
HO
spectral analyses. The new carbon skeleton of these two
triterpenes was confirmed by X.ray crystallographtc ana. and monocychc carbon skeletons. have btcn isolated
lysib of the dimethyl ester of Jareroic acid. from rhizome5 of Iris yermanica [62]. The compounds are closely related to ambrcinc.
Carotenoid-like triterpenes
Ksebati and his co-workers [34] have isolated five new
triterpene galactosides named pouosides A-E from
Asteropus sp.. d Pacific marine ,ponge. The carbon
skeleton 30 of the pouoside aglycones is new and parallels
that ofthe C,,-carotenoids, with it\ terminal cyclohexane rings linked by a symmetrical. acyclic chain.
Swertane
New tkeleton monocyc lit. and bit v( lit triterpenoidc
Three new triterpenoids. a-irigermanal (38). ;-irigerma-
nal (39) and iridogermanal (40). possessing novel bicyclic
The structure and stereochemistry of swertanone, a triterpene ketone with a novel skeleton. swertane (28) isolated from Swertia c&rata [63]. have been established
from spectroscopic data and X-ray crystallographic ana-
lysis. A plausible biogenetrc pathway for the formation of the swertane skeleton has been envisaged involving cychzation of squalcnc-2.3-cpoxide in the usual manner leading to the nonclassical carbocation followed by a l.3-hydride shift from C.17 to C-21. a series of 1.2~shifts and elimination of a proton from C-7.
Mr
2206 S. B. MAHATO er al.
Glyctnocctcpin A (41)
Glyctnoccleptn 3 (42)
Glyclnoecleptn C (43)
H02C
Joverolc acid (44)
Phellmc ocld (45)
Extended hopone (48)
Pfaffanes
Pfaffic acid [64], a novel hexacyclic nortriterpene possessing the pfaffane skeleton (29) was isolated from Pfaf/;a panicdata and its structure was established by X-ray crystallographic analysis of its methyl ester. Sub- sequently, four new pfatfane-type nortriterpenes were isolated from P. puherulenra [65] together with pfaffic acid and its fi-D-glucuronopyranosidc.
CHEMICAL MODIFICATION AND SYNTHESIS
The structure elucidation of a natural product is no longer, or only rarely, an end in itself. While much of our
basic knowledge was in the past derived from degradative studies its extension today rests primarily on the synthesis of natural products and their analogues and their chem- ical modifications for a variety of purposes.
Skeletal rearrangemenrs
There have been considerable activities during the years on the studies of skeletal rearrangements of triter- penoids which have made valuable contributions to our knowledge of triterpcnoid chemistry. A detailed discus- sion on this aspect is beyond the scope of this review. However. some interesting transformations are described briefly.
Triterpenoids 2207
Edwards and Paryzek [66] first successfully intro- duced the Westphalen rearrangement for the trans- formation of lanostane to cucurbitane. 3/l-Acetoxy-9a- hydroxy-lanosta-1 l-one (I) derived from lanosterol yielded two 19(10+9/?)abeo lanostanoids, II and III when subjected to the rearrangement conditions.
Borontrifluoride etherate (BF,-Et,O)-catalysed re- arrangement [67, 683 of the ketoepoxide IV in acetic anhydride resulted in the formation of two 19(10+9&obeo compounds V and VI in addition to the unexpected 18( 13 -. 12fi)abeo compound VII as the major product.
Transformation of 3,7,9,1 I-tetraoxygenated lanostane derivatives, e.g. VIII (R = H, AC) into 3,7,1 I-trioxygenated cucurbit-l(lO)-enes such as IX (R’=H, R2 =H, AC; R’ = AC, R2 = H, AC) and cucurbit-5( IO)-enes such as X was achieved [69]. The steric and electronic factors influ- encing the course of dehydration under Westphalen conditions of 9a-hydroxylanostane derivatives were dis- cussed. Unusual autooxidation and dehydrogenation
AcO
AcO
AcO
AcO
promoted by RhCI, and Fe(CO), were also described. Wagner-Meerwein rearrangements in the taraxastane
type of triterpenoid derivatives were studied by Anjaneyulu et al. [70]. Taraxasterol (XI, R=H) and pseudotaraxasterol (XII, R = H) on heating with PCI, in hexane gave the corresponding ring A-nor-3,4-dichloro derivatives XIII, whereas with POCI, in pyridine gave the same rearranged product XIV without ring contraction. Solvolysis of XI (R =p-MeC,H,SO,) and XII (R=p- MeC,H,SO,) gave the same ring contraction product XV. The Wagner-Meerwein rearrangement of these two compounds (XI. XII) was rationalized mechanistically.
Acid catalysed rearrangement [7l] of trevoagenins A (XVI, R = z-Me) and B (XVI, R =/?-Me), two dammarane triterpenoids isolated from Treuoa rrineruis, in refluxing ethanol containing HCI for five hours gave lactones XVII (40%). XVIII (13%) and cyclodammaranone XIX (2%). The formation of XVII and XVIII was explained by a heterolytic fragmentation mechanism.
3B,28-Diacetoxy-l8~,19B-epoxylupane (XX) on treat-
XI XII
S. B. MAHATO er al.
I? 4 o --f0l-l
@
0
HO Cl+OH
,’
XVI
Me2CH -CO- CHZ- CH2
7f
Me
XVIII
ment with non-aqueous HF in anhydrous chloroform gave a novel skeletally rearranged triterpenoid (XXI). possessing the baccharane skeleton as the major product (53%) along with lupadiene (XXII. 13%) [72].
A novel skeletal rearrangement of marsformoxide-A (XXIII), an 1 Ir, 12z-epoxide prepared from z-amyrin, was observed 1731 when the epoxide was treated with HBr in acetic acid to give rearranged products XXIV-XXVI.
A new method [74] for opening the cyclopropane ring of cycloartane derivatives was described. Cycloartanone (XXVII) (prepared from cycloartenol) was converted to XXVIII, which rearranged in ethanolic H,SO, to give XXIX. This experiment was an attempt to establish the biogenetic origin of the 9/j-hydroxymethyl in cucurbita- tins.
An intramolecular carbonyl-mediated electrochemical oxidation was shown to occur during the anodic oxida- tion [75] of methyl 30acetylglycyrrhetate (XXX) to provide the skeletally rearranged triterpene (XxX1). This rearrangement is also applicable to glycosides as the sugars remain unchanged during the oxidation.
Partid synthesis
Although the structure elucidation ofa natural product using modern instrumentation has become a routine affair. the partial syntheses of novel triterpenoids from easily available compounds are sometimes adopted as a
xv
Me CH2-CH2-CO - CHMe2
-K . H
% L (0 0
XVII
-.
.o:F
-_ f
OH
OO
XIX
confirmative step for establishment of the structure. Thus the structure of marformosanone (XxX11). isolated from Diospyros peregrina [76]. was confirmed by its partial synthesis from z-amyrin.
Starting from 3/?.7/?,18-trihydroxylanastane. the agly- cone (XxX111, R = H) of bivittoside C. was synthesized in a six step sequence in 6Yb overall yield [77]. A key step was the treatment of hydroxylactone (XXXIV) with
EtO,CN-SO,NEt, to give unsaturated lactone (XxX111. R = AC).
Lansiolic acid (XXXV) was prepared [78] from a.;‘- onoceradiene dione (XXXVI) via regioselective reduction with NaBH, in isopropanol. conversion to oxime by NH,OH, Beckmann rearrangement and hydrolysis by KOH in ethanol.
The structures of zeylasterol (XXXVII. R=H. R’ = CHO. R2 = Me) and desmethylzeylastcronc (XXXVII. R = R’ = H. R’ = CO,H) isolated from E;okoo~~ :er/uri- ica were confirmed [79] by chemical correlation with trimethylzeylasterone (XXXVII. R = R2 = Me. RI =CO,Me). synthetically prepared in four steps from pristimerin (XXXVIII).
The partial synthesis of isomultiflorenol (XxX1X. R = H) from alnus-5( IO-en-3P-yl-acetate (XL) was described [80]. The acetate (XL) on epoxidation with MCPBA gave the epoxide (XL]). which underwent back- bone rearrangement in the presence of borontrifluride etherate to gave multiflora-5,8-diene-3/j-yl-acetate (XLII). The latter compound on hydrogenation then gave the
Tritcrpcnoids 2209
AcO
Br /
I & \
AcO , ,
XXIV
AcO 0
XXVI XXVII
monoacetate (XXXIX, R=Ac), hydrolysis of which fi- nally yielded isomultiflorenol.
The dihydro derivative (XLIII) of the novel triterpen- oid thysanolactone (XLIV) was synthesized [Sl] from the readily available pentacyclic triterpenoid, hydroxy- hopanone (XLV).
Some 29-norlanostane derivatives, e.g. 29-norlanostan- 24one and -23-one, 29-norlanost-9( 1 l)-en-24-one, -23- one and 3-one, 29-norlanost-7-en-3-one, and 29-nor- lanostan-3-one, were synthesized from commercial lanosterol containing dihydrolanosterol for their use in the identification of 29-norlanostane derivatives isolated from a plant fossil [82].
Approaches to total synthesis
Total synthesis of a triterpene molecule is a formidable task and elegant synthetic methods in this direction are yet to be established. However, there are reports on the synthesis of triterpenoid precursors which may conveni- ently be used as intermediates for the synthesis of target compounds.
A model for tetracyclic triterpene side chain synthesis has been reported [83] which has also been further developed by Reusch et al. [84]. Although many methods
2\ / 0
@ , x XVIII XXIX
have been developed for the side chain construction starting from l7-keto steroids [85, 861, very few of them have been applied to equivalent l4-methyl analogues. Bycylononanone (XLVI) was used as a model for the sparingly available 17-0~0 triterpenoid derivatives to explore the synthesis since this bicyclic ketone (XLVI) incorporated both of the angular methyl groups found at the C/D-ring juncture in triterpenes of the lanostane, euphane and cucurbitane families. Wittig olefination of the ketone (XLVI) gave the alkene (XLVII), which (XLVII, R= Me) on diborane reduction, followed by oxidation with PCC (pyridinium chlorochromate), yielded the ketone (XLVIII). This on further Wittig reaction with appropriate alkylidenephosphorane (e.g. Me,CHCH,CH,CN=PPh,) afforded a mixture of the potential triterpene synthons (XLIX) epimeric at C-20. The authors have further developed [84] the synthesis by introduction of an oxygen function at C-8 of XLVI (C-16 of triterpene) concurrently with the side chain elabor- ation. It is of interest to note here that many naturally occurring triterpenoids possess hydroxyl or carbonyl functions at this position. Since these functions were shown to be easily removed or transformed, their pre- sence enhanced the scope and flexibility of procedures that made use of their directional influence to achieve
S. B. MAHATO CI d.
XXX(R=Horsugor) XXX1 (R=H or sugar)
CO H I *
XXXVI XXXVII XXXVIII
selective configurational control at C-20. Two alternative methods were described for stereoselective preparation of intermediate enones (L, E and Z). Finally the synthesis of LI was accomplished by a facial selective conjugate addition of lithum bis-4-methyl-3-pentenyl-cuprate to Z-L, whereas the E-isomer gave only an unresolved mixture.
A stereoselective synthesis of the A, B, C-ring system of pollinastanol (LII). a triterpene bearing 9fl,lO/?- cyclopropane ring with a cis B/C-ring fusion was described by Kametani er al. [87]. The key intermediate, the /?.y-unsaturated ketone (LIII), was prepared from benzocyclobutene carbonitrite (LIV) by a series of reac- tions of which stereoselective thermal cycloaddition of the benzocyclobutene derivative (LV) was an important step to control the stereochemistry of B,/C-ring juncture. The /l,T-enone (LIII) was then subjected to intra- molecular y-alkylation to give the cyclopropane derivat- ive (LVI), which on reduction with NaBH, afforded the desired product (LVII).
Most of the triterpenes are hydrophobic m nature but the sugar moieties of the triterpene glycosides render them hydrophilic, leading to their easy absorption in the body tissues. Moreover. because the receptors for differ- cnt sugars arc present in various body organs. the syn- thetic glycosides might be expected to be more effective as therapeutic agents. Attempts have been made by some workers to synthesize triterpene glycosides of potential therapeutic interest. Thus, glycosylation of triterpenes of the dammarane series was described by Atopkina et al. [8X-90]. Glycosidation of 3-epiocotillol (LVIII, R’ = R’ = RJ = H) and betulafolienetriol oxide (LVIII, R’ = R’ = H: R’ = OAc) by acetobromoglucose catalysed by Ag- zeolite or Hg(CN), in various solvents gave the mixture containing the 3-O-. 25O-mono- and diglucosides. The yield of the products was found to be dependent on the nature of the solvents. Kocnigs-Knorr glycosidation of betulafolienetriol (LIX) gave 3-. 12-. 20-mono- and 3.12-.
AcO
Triterpenoids
XLlll R= CHMc2
XLIV R- C<$
XLVI XLVII XLVIII
2211
AcO
l-4
XLIX
Me6
LI
3,2@di-0-/?-D-glucopyranosides. However, glycosidation by the Hellerich reaction was accompanied by a dehydra- tion in the side chain which led to the corresponding 20- dehydroxy derivatives.
Miscellaneous
A general method for functionalization of the C-4 methyl group in triterpenes, leading finally to 4ararboxyl or 4x-hydroxymethyl derivatives of triterpenes was de- scribed by Dev et al. [913. The method was illustrated by conversion of cyclolaudanone (LX) into methyl 3-0x0- cyclolaudan-29-oate (LXI). The latter was transformed into a known nortriterpene, cycloeucalanone (LXII) by a simple sequence of reactions. The key step was the selective oxygenation of4a-methyl group by photolysis of
LII
LXIII in cyclohexane containing iodine and Pb(OAc), followed by oxidation with CrO, and aq. H,SO, to give lactone (LXIV).
A method for side chain degradation of euphol. a tetracyclic triterpene, has been reported [92]. Euphol (LXV, R=H) was converted into androsterone (LXVI, R=Me). The key step was the photochemical degrada- tion of ketones LXVII (R = Me; R’ =CHMe, or Ph) to yield pregnadiene LXVIII (R = Me).
The transformation of a triterpenoid ring A into a steroidal enone by a new short route was studied [93]. Exhaustive Baeyer-Villiger oxidation of 4,4-dimethyl- cholestan-3-one gave the lactone (LXIX), which on methylation by MeLi gave hemiacetal (LXX). Oxidation of this hemiacetal by pyridinium dichromate or pyridin- ium chlorochromate yielded the secocholestanedione
2212 S. B. MAHATO er al
LXIl,R’-H, f?‘.Me L
-Y -. \
l-i
-A e H _b,-# ; 0 *.
\
HOW2 \ O-4 0 RO {fi
, r’
LXlll LXIV LXV LXVI
LXVII LXVlll
(LXXI), which could be cyclized by known methods to cholest-4~ene-3-one (LXXII).
Oxidative transformations of some 12-oleanenes and 12-ursenes were studied by Majumder and Bagchi [943. For example, 38-acetoxy-olean-l2-en-28-oic acid (LXXIII) on treatment with H,O, in boiling AcOH gave the corresponding 1 la,l2a-epoxy 28+ 13glactone (LXXIV) and 12a-hydroxy 28+ 13/&lactone (LXXV). Ac- cording to the authors the CO,H-28 group was first converted into C(O)O,H, which epoxidized the A”- double bond. H,O,-Se02 in Me,C-OH was found to be a good reagent for the preparation of I la,l2a- oxidotriterpenoids with the oleanane and ursane skeletons [95].
Anodic oxidation as the key reaction converted olean- 12-ene sapogenols into olean- I 1 -en-28.13/I-olide,
LXIX LXX
1 la, 12z-epoxyoleanan-28,13/I-olide and 13/3,28_epoxy- olean-11-ene derivatives in high yields [96]. Since protection of hydroxyl groups in the starting compounds was not required, this conversion was directly applied to hederagenin oligoglycosides to obtain oligoglycosides of olean-1 l-ene sapogenols. The phase transfer catalysed sodium periodate oxidation of olean-12-en-28-01 derivat- ives gave expected 13/?,28-epoxyolean- 11 -ene derivatives c971.
Epimerization ofsome pentacyclic triterpene acid agly- cones during acid hydrolysis of their glycosides has also been reported [98]. For example, arjunglucoside-1 (LXXVI) and its aglycone, arjungenin (LXXVII) on boiling with 5% methanolic hydrochloric acid afforded tomentosic acid (LXXVIII). the 19b-isomer of arjun- genin. The mechanism of this transformation involving
Tritcqxnoids 2213
L-XI 0
LXX1
oJx~co&2H@j LXXII
,’
LXXIV
LXXVII ,R = R’=H, R’= OH LXXX, R’=OH, R’= H
LXXVIII, R l R’ =H,R’-OH
formation of the 28+ 19jNactone has been rationalized. The epimerization of the 16j-hydroxyl group of cochalic acid (LXXIX) to its 16~~isomer (LXXX) has also been described by this lactonization and declactonization mechanism.
BlOLOGlCAL ACTIVITY
The wide occurrence and the structural diversity of triterpenoids have always attracted attention for evalu- ation of their biological activities. Although applications of these secondary metabolites as successful therapeutical agents is very limited, extensive exploratory activities in this area have been underway during recent years. Some interesting results are mentioned below.
Anritumour and anticancer activity
The relation between chemical structure and anti- cancer activity of some pentacyclic and tetracyclic tri- terpenoids was studied by Ling et a/. [99]. The anticancer effects were tested against human cancer cell lines ME- 180, u-87MG, SK-HEP-1, CAL&l, CAMA-1, SK-OV-3 and HEC-1-A. Among the pentacyclic triterpenoids, epi- manidiol (3/?,16a-dihydroxy-olean- 12-ene) was found to be cytotoxic at 100 pgml- l against HEC-l-A, CAMA-1, ME-180, u-87MG, CALAU-1 and SK-OV-3. The re- quired concentration producing 50% inhibition against HEC-1-A was approximately 10 pgml- ‘. Maniladiol, the 16/?-epimer, exhibited cytotoxicity against ME-180 and CAM A-l at 100 pg ml- I, whereas sophoradiol (3/?,22fi- dihydroxyolean-12-ene) was cytotoxic only against ME- 180 at IOO~gml~‘. This result suggested that the pre- sence of a 16a-hydroxy group is important for the
appearance of cytotoxicity of 12-oleanenes. Glycyrrhe- tinic acid (3/?-hydroxy-1 I-oxo-olean-12cn-30-oic acid) and 1 I-oxo-/?-amyrin, both with a free 3/3-hydroxyl group, were active at 100 pgml- ’ against SK-OV-3 and CAMA-1, respectively, while disodium glycyrrhetinic acid succinate, with the esterified 3/?-hydroxyl group, was found to be inactive. Among the tetracyclic triterpenoids, (f )-I I-oxotrinortirucall-8-enoic acid was cytotoxic against SK-OV-3 at 100 pgml- ‘. ( f )-7,11-Dioxotri- nortirucall-&enoic acid and ( k )-3fl,7-dihydroxy- ll- oxotrinortirucall-8-enoic acid were inactive. Several oleanane-type triterpenoids which were chemically de- rived from oleanolic acid and hederagenin were tested [lOO] in virro and in viuo against the tumour promotor 12-0-tetradecanoyl-phorbol 13-acetate (TPA). The in vitro experiment was monitored by TPA-induced stimu- lation of 32Pi-incorporation into phospholipids. The in vivo test on skin tumour formation in mice was initiated with 7,12-dimethyl-benz[a]anthracene DMBA and promoted with TPA, 18fl-olean-12-ene-3j3, 1 (’ 8diol eryth- rodiol), 18~-olean-l2tne-3~,23,28-triol, 18a-olean-12- enc-3fl-28-diol and 18a-olean-12-ene-3/?,23,28-trio& showed remarkable suppressive effects. In particular, 18~ oleanane derivatives having a -CH20H group at C-17 were found to be lOO-fold more effective than glycyrrhetic acid, an usual suppressor both in vitro and in vivo. Bioassay-directed fractionation of the cytotoxic antileuk- emit extracts of Prunella vulgaris, Psychotria serpens and Hyptis capitata led to the isolation of ursolic acid as one of the active principles [loll. Ursolic acid showed signi- ficant cytotoxicity in the lymphocytic leukemia cells P- 388 and L-1210 as well as the human lung carcinoma cell A-549. It also demonstrated marginal cytotoxicity in the KB and human colon (HCT-8) and mammary (MCF-7)
2214 S. B. MAHATO cr al.
tumour cells. Esterification of the hydroxyl group at C-3 and -COOH group at C-17 led to compounds with decreased cytotoxicity in human tumour cell lines. but with equivalent or slightly increased activity against the growth of L-1210 and P-388 leukemic cells. Further investigation [IO21 on the cytotoxic polar triterpene fraction of the plant Hypris capirara led to isolation of two new triterpenoids. hyptatic acids A and B as well as three known triterpenoids, Za-hydroxyursolic acid, tormentic acid and maslinic acid. Hyptatic acid A and 2x-hydrox- yursolic acid demonstrated significant in cirro cytoto- xicity in human colon HCT-8 tumour cells. The effects of glycyrrhizin and its aglycone. glycyrrhetinic acid on the growth and differentiation of mouse melanoma (B-16) cells in culture were studied) [103]. Glycyrrhetinic acid inhibited the growth of B-16 melanoma cells, caused morphol alteration and stimulated melanogenesis. Gly- cyrrhizin also resulted in the same change but only when the concentration was 20 times more than that needed for its aglycone. When glycyrrhetinic acid was removed after 84 hours of treatment, the growth rate recovered slightly but the doubling time was about twice that of control. Cytofluometric analysis showed that the growth inhibi- tion of glycyrrhetinic acid is the result of inhibition of transfer from G, to S phase. Olean-I 1.13( l8)-diene-3b,30- diol and its derivatives were found [104] to inhibit tumour-promoting agents such as TPA. These com- pounds have greater inhibiting activities on tumours than glycyrrhetinic acid and have less side effects. Thus, the increases in phospholipid synthesis in various tumours by TPA were inhibited in vifro by the title compound and five of its analogues. Plumeric acid, a nortriterpene acid and its methyl ester isolated from the leaves of Plumeru~ acutifolia showed antitumour activity [ IOS]. The free acid at a concentration 25 lcgml _ ’ was 100% effective in inhibi- ting Yoshida sarcoma cells in vitro. An injection formula- tion containing 10 mg of plumeric acid and 5 mg of glucose was prepared. The anticancer activity of anwu- weizonic acid, a new lanostane. triterpene, and manwu- weizic acid, a new ring-A-srco-lanostane triterpene isol- ated from Schisandra propinqua [ 1061. was tested. Man- wuweizic acid showed significant inhibitory activity against Lewis lung cancer, brain tumour-22 and solid hepatoma in mice but exhibited no cytotoxic action in virro. Isoiridogermanal. zeorin and missourin, a new hopane-type triterpene isolated from Iris missouriensis [107], were studied for their anticancer action. They demonstrated cytotoxic activity towards cultured P-388 cells (ED,,=O.l, 1.1 and 8.5 pgrnl- ‘, respectively). Wilfortrine isolated from Tripferyyium wiljordii inhibited leukemia cell growth in mice at a dose 4 mg kg ’ [ 1083. Radermasinin, possessing a new carbocyclic skeleton isolated from Radermachia sinica and its acetate derivat- ive showed significant cytotoxicity (ED,o = 3.3 pg ml _ ’ and 3.5 pg ml _ ‘, respectively) in the KB cell culture in vitro [53]. 7P-Hydroxymaptounic acid, a new ursane- type triterpene from Maprounea a/ricana [ 1091 exhibited in viva P-388 activity. Betulinic acid, a common triterpene was shown to be an inhibitor for growth of the leukemia cell line P-388 [I IO]. Oral administration of 18/%olean- l2-ene-3&23,28-trio1 tri-0-hemiphthalate sodium and olean-ll,l3(18)-dien-3/I-ol-30-oic acid-3-O-/Y-D-glucuro- nopyranosyl-(l+2)-/?-D-glucuronopyranoside sodium suppressed [l 1 I] carcinogenesis in mouse skin induced by DMBA and TPA. This is the first report of an effective oral administration of triterpenoid compounds supp-
ressing skin tumour promotion in mice. Arjunolic acid, an oleanene triterpene (2cc,3/?,23-trihydroxy-olean-l2-en-28- oic acid) isolated from the rhizome of Cochlospermum tincrorium and its derivatives (triacetate and methyl ester triacetate) were tested using the short-term in uirro assay [ 1123. Their inhibitory effects on skin tumour promoter were found to be greater than those of previously studied natural products. Pfaffic acid. a new hexacyclic nortriter- pene isolated from PjobFa peniculara also showed high inhibitory effects on the growth of cultured tumour cells, such as melanova (B-16). Hela (S-3) and Lewis lung carcinoma cells at 4-6 pg ml- ’ [64]. The antitumour and antibacterial activities of 1 I triterpene quinones isolated from Maytenus horrida and Rzedowskia rolantonguensis
were studied in cultures of Hela cells and several bacteria, respectively [I 133. Among the tested compounds, netza- hualcoyone was found to be most active antitumour agent.
Action on metabolism
The mechanism of mineralocorticoid action of car- benoxolone ( I I -oxo-olean-I 2-en-30-oic acid 3/?-succin- ate) was studied by Armanini et al. [ 1143. In cirro and in cit:o studies showed that carbenoxolone has demon- strable affinity for rat renal mineralocorticoid receptors, intrinsic mineralocorticoid activity in the adrenalectom- izcd rats at doses consistent with its receptor affinity and a powerful amplifying action on the urinary response to near-maximal doses of aldosterone administered to ad- renalectomized rats. The influence of oral carbenoxolone on prostaglandin E2 release mto gastric juice was exam- ined [ 1151 in peptic ulcer patients during modified sham feeding and following bolus stimulation of acid secretion by pentagastrin (6 pg kg I). Carbenoxolone increased the overall mean of prostaglandin E, concentrations in gastric juice following modified sham feeding by 329; and decreased the acidity slightly but significantly. Changes in lipid metabolism indexes under the influence of gly- cyrrhetinic acid in experimental hyperlipemia were studied [ 1161. The acid decreased the blood cholesterol, ,%lipoprotein. /?-lipoprotein cholesterol and triglyceride levels in rats with hyperlipemia (Tween-80 or vitamin D, and cholesterol) and rabbits with experimental atheros- clerosis (cholesterol). Cholesterol and /?-lipoprotein levels were decreased in the aorta and the former was decreased in liver tissue. Glycyrrhetinic acid has hypolipemic and antiatherosclerotic activity greater than the established antiatherosclerotic polysponin. Administration of IR- dehydroglycyrrhetic acid orally (50 mg kg- ’ day _ ’ for six days) to rats with experimental gastric ulcers stimu- lated catabolism of fatty acid in hepatic mitochondria and increased ATP production necessary for repair processes in mucora [ 1173. 3,7-Dioxo-lanost-8-ene and 7/?-hydroxy-3-oxo-lanost-8-ene were found to be anti- cholesteremics [ 1181. In I;irro experiments with rat liver homogenates indicated that both the compounds inhib- ited the formation of cholesterol by the liver. The inhibi- tion rates were 98% for the former and 47% for the latter compound. A pharmacological study on the antihepatitis effect of cucurbitacins B and E has been reported [ 1193. In rats with experimental fatty liver (Ccl,-induced), the serum glutamate-pyruvate transaminase and hepatic col- lagen levels were significantly decreased, whereas the serum /I-lipoprotein level was increased by administra- tion of cucurbitacin B. The hepatic damages, including
Trircrpenoids 2215
fibrosis and cirrhosis, were also markedly reduced by this triterpene. The serum CAMP to cGMP ratio was in- creased following intravenous injection of cucurbitacin B or cucurbitacin E, suggesting that the changes in cyclic nucleotide balance might be refated to the therapeutic mechanism of action of cucurbitacins in hepatitis. Gano- deric acid and its derivatives isolated from Ganoderma lucidurn were shown to be inhibitors of cholesterol bio- synthesis [ 1203. These compounds were tested for their effect on cholesterol biosynthesis from 24,25-dihydro- lanosterol by rat hepatic subcellular IOOOOy supernatant fraction. The lanosterol (4OpM) with 7-0~0 and 15a- hydroxy groups potently inhibited the biosynthesis of cholesterol. In a similar study [ 121),27-nor-24-dihydro- lanosterol was found to be markedly active in depressing cholesterol biosynthesis from lanosterol.
The anti-inflammatory activity of some triterpenoid derivatives of the oleanane series were examined on arachidonic acid (AA)-induced ear edema in mice [122]. Of the compounds examined, dihemiphthalate derivat- ives of 18&olean- 12-ene-3~,30-dial, 18/j’-olean-9( II), 12- diene-3/?,30-diol and olean- I 1,13( 18)-diene-3/3,30-diol showed a strong inhibition of ear edema on both topical (ID,, = I .9, 2.8 and 1.7 mg per ear, resp.) and oral (ID,, =90,130 and 88 mg kg- *, resp.) administration. Topical ID,, values were approximately the same as nordihy- droguaiaretic acid (ID,, = 2.1 mg per ear). Given topically these compounds were also capable of inhibiting PGE, and LTC, formation at an early stage of AA-induced ear edema. The most effective time for the topical administra- tion of the compounds against ear edema was found to be O-30 minutes before AA application. This is different from dexamethasone which requires a time lag for reac- tion. Glycyrrhetinic acid and deoxoglycyrrhetol, the parent compounds of the derivatives, showed no detect- able inhibition on edema at I mg per ear (topical) or 200 mg kg‘ ’ (oral). The same result was also obtained from the similar study on TPA-induced mouse ear edema [ 1231. 1 I-Oxooleanolic acid and 1 I-oxohederagenin in- hibited corticoid S/?-reductase [ 1241 and the inhibitory effect of the former was found to be higher than the latter. To study the corticoid-like activities, 1 l-keto-triterpen- oids were prepared and their anti-inflammatory activities were tested in ~rrag~nin-induced hind paw edema in rats [ 125). Corticoid-5/?-reductase inhibition was also evaluated. All the 1 l-oxo-triterpenes tested inhibited corticoid-5fi-reductase and 11.19-diketo-18,19-seco- ursolic acid was found to have the highest inhibitory potency. Gly~yrrhetinic acid inhibited carragenin-in- duced edema in the rat paw and inhibited leukocyte migration in the pleural space induced by dextran injec- tions [126]. The acid did not prevent prostaglandin release by phag~ytosing leukocytes or slowing the con- traction of isolated ileum strips induced by PGE*. The mechanism of the anti-inflammatory action of papyriog- enins A and C. two triterpenoids isolated from Tena- panax papyri$erum was studied by Sugishita ef al. [ 1271. The cotton-pellet granuloma test in normal and ad- renalectomized rats, the blockade by antiglucocorticoids of vascular permeability caused by serotonin, and the competition on S/&reduction of steroidal compounds were followed for the investigation. Papyriogenin A was found to be more potent than papy~ogenin C as an
infl~mation inhibitor of carrag~nin-induced paw edema in mice. Pretreatment with progesterone (SO, 100 and 200 mg kg- ’ ) completely blocked the anti-inflam- matory effects of papyriogenin A or C (10 and 50 mg kg _ ’ ) against ~rotonin-indu~d paw edema. Ac- tinomycin D (1 and 2 mgkg- ‘) or cycloheximide (6 mg kg- ‘), given twice during the latent period, com- pletely blocked the anti-inflammatory effects of both papyriogenins. The effects of papyriogenin A or C, 30 mg kg- I, orally, on the cotton-pellet granuloma test in adrenaiectomized rats were similar to those of normal rats. On the other hand, the competitive effects of papyr- iogenin A and C on S/&reduction of testosterone and cortisol were recognized to be significant. These activities of papyriogenin A and C were explained by their steroidal actions in the target cell and their competitive effects in endogenous corticoid metabolism in the liver. Pyracrenic acid, isolated from the bark of Pyracantha crenukza and characterized as 3~-3’,~-dihydroxycinnamoyloxylup- 20(29)-en-28-oic acid was tested for its anti-inflam- matory activity by the cotton method and was shown to be a potential inhibitor of the formation of granulation tissue [ 1281. The fruit juice of Ecballium elaterium, known to be used in Turkey for the treatment of sinusitis was investigated for its anti-inflammatory activity in mice [129]. Various fractions obtained from this juice were also tested for their effects on increased vascular per- meability, as induced by intra peritoneal injection of acetic acid. The active principle thus isolated was charac- terized as cucurbitacin B. This is the first report that cucurbitacin B has a significant anti-inflammatory activ- ity. Triptotriterpenic acid A, a new oleanane triterpene isolated from the roots of Trjpferyg~um wi~ford~j was found to be an effective anti-inflammatory agent [130]. Stearyl glycyrrhetinate and glycyrrhetinyl stearate, two glycyrrhetinic acid derivatives were shown to possess significant anti-inflammatory properties as detected by the rat foot test and the cotton-pellet test [131]. An ointment containing glycyrrhetinic acid was also found to be effective in the treatment of carrageenin-induced edema in rats and UV light-induced erythema in guinea- pigs in a dose-related manner. In patch tests in human subjects, dipotassium glycyrrhizinate or disodium gly- cyrrhetinylsuccinate added to the lotion of a cold hair- waving preparation, reduced the skin irritation induced by the lotion. Olean-12-ene-3/?,30-diol showed anti-ulcer, anti-inflammatory and anti-allergeic activities in rats without undesirable side effects as those observed in the case of glycyrrhetinic acid [132]. The activities were manifested by the administration of the diol at 320, 200 (orally) and 200 mg kg‘ ’ (intraperitoneally), respectively. The aglycone part of the glycoside fraction isolated from Maesa chisia var. angustifolia also showed anti-inflam- matory, analgesic and anti-pyretic activities in various pharmacological test in experimental animals [133]. It was shown that the activities were due to the presence of two 12-oleanene derivatives.
Miscellaneous
Oleanolic acid was effective in the prevention of experi- mental liver injury induced by injection of Ccl, in rats [ 1343. The results suggested that oleanolic acid possesses a potent protective action on C&-induced liver injury. Carbenoxolone was shown to provide a protective effect to ex~rimentaily-indu~d lower urinary tract infections
2216 S. B. MAHATO et 01.
Table 1. Tritcrpenoids isolated from the plant kingdom and other sources
Source
Triterpenotd
mp. [alo spectra: X-ray analysis reported
Basic
skeleton
Structure
Groups Refs
1 2 3 4 5
Abies /inna (Pinaccae)
A. mariesii
A. sibirica
Firmanoic acid; Me ester,
110-I 1 I’. + 23’. UV. IR, ‘H,
“C NMR. HRMS
lsofirmanoic acid; Me ester.
163-164”. +24”. IR. ‘H.
“C NMR. MS
Firmanolide 193-195’ -
IR ‘H “CNMR. HdMS*” , .
23-Epifirmanohdc, 193-195”, +24”. IR. ‘H, 13C NMR. MS
23-Oxomariesiic actd. A.
UV, IR. ‘H, “C NMR
23-Oxomanesiic actd. B.
UV. IR. ‘H. “CNMR
Mariesiic acid A. UV. IR,
‘H. “C NMR. X-ray analysis.
Manesitc acid B. UV. IR.
‘H. “C NMR
Mariesiic actd C; MC ester,
- 33.6’. UV, IR. ‘H. “C NMR, HRMS
Isomariesiic aad C: Me ester, - 154”. UV. IR. ‘H. “CNMR.
HRMS
Abtesolidoic acid, X-ray
analysis
Abiesonic actd. X-ray analysis
Tnterpene acid. IR. NMR. MS
Triterpene acid. IR. NMR. MS
Triterpenoid
Triterpenoid
Triferpenoid
Triterpenoid
Triterpenoid
Triterpenoid
Abrotanella forsterioides
(Compositac)
Abrus canroniensis
(Lcguminosae)
Seco-dammaradiene, IR.
‘H NMR. MS
Abrisapogenol B, 278 -280’.
+26.1”. “C NMR
Abrisapogenol D. 29&291’. + 76.7”
11
II
II
11
35
36
35
36
37
31
11
37
II
II
I1
I1
11
35
35
35
IO
1
I
3,23-0x0; 26COrH;
(24E)A’,‘.; 961-H
3 23-0x0; 26C0,H: A’=‘*“;
9;1-H
3-0x0: A’.‘.; 17.23-epoxy:
26-+23-lactone; 98-H; 17% 23s
3-0x0: A’.2’; 17.23-epoxy;
26-23-lactonc; Y/?-H; 17s; 23R
3a-OH; 23-0x0; 26COrH; A7.1.2.: 9,3H
3x-OH; 23-0x0; 26-CO,H; A’.!z.z.: 98-H
3x,23/LOH: 26-CO,H; A-.1..>.; 90H
3s,238-OH; 26-CO,H; AT.1l.r.. 91-H
3.23-0x0; 26C0,H; A,.i.(,O,.~.. 98-H
3.23-0~0; 26-CO>H; A7.1..>.: 9fi_H
3.4~&co: 26-23-lactonc; A’.irs1: 3_CO,H
3.4Sew 23-0~0; 3,26CO,H: A.,~1(1.:.,.,~~,.r.
3.23-0x0; 26-CO,H;
(24E)A’,‘.
3.23-0~0; 26-CO,H; (24Z)A’.r.
3-0x0; 26-23~lactone; (222) A’.z’.2.; 9jl-H
3-0x0; 26--23~lactone; (22z)A”.>‘.‘.
3a-OMe; 26-23~lactone; A’
3z-OMe; 23-0x0; 26-COaMe; A~.‘..‘.
3,4-Seco; 23-0x0; 3,26CO,Me; A.,~s,&s,,.,.s.
3.4~Seco; 3-CO,Me;
26-+23-lactonc; A.,‘“,.6.8”“.“.‘.
3 4-Seco. 3-OAc; A..z. * *
38,228,24.29-OH; A’*
3&22fi.3O-OH; A”
Cl451
[1451
[1451
r1451
[561
[561
[551
[561
1561
1561
[1461
r1471
[14*1
[14*1
[1491
r1491
c15tJ
[571
c571
c571
[1511
[1521
v521
Triterpenoids
Table I. (Continued)
2217
1 2 3 4 5
A. precarorius
Acanthopanax trijoliatus
(Araliaceac)
Actinidia erianrha
Aesculus hippocasranum Hippocaesculin 254-256”, (Hippocastanaceac) + 25”, IR. ‘H, “C NMR, MS
Aglaia roxburghiana Roxburghiadiol A
Agrimonia pilosa (Rosaceae)
Ailanthus malabarica (Simarubaceae)
Akebia quinara
(Lardizabalaceae)
Alisma plantago-aquatica
(Alismataceae)
Alnasterfruticosus
Abrisapogenol E. 249-252”. +67.7”. MS
1 3&22/l.24.3O-OH; A’*
Abrisapogenol F, 66-67”, + 15.4”, IR, “CNMR
Abrisapogenol G. 231-233”. -5.3”. ‘H, “C NMR, X-ray analysis
1 3jl-OH; 22-0x0; A”
1 38.228-OH; A”“a’
Abrusgenic acid, X-ray analysis
Abruslactone A
Triterpenoid acid, 2 15-2 18”, -27.2’ ‘H “CNMR, MS , , Eriantic acid A, IR. ‘H. “C NMR, MS
Eriantic acid B, IR, *H, “C NMR, MS
2
2
1
11
Roxburghiadiol B 11
Triterpenoid 11
Triterpenoid 11
Triterpcnoid acid; Me ester, +32.2”, IR. ‘H, “CNMR, MS
Triterpenoid acid; Me ester, + 30.0”. IR. ‘H. “C NMR, MS
Ailanthol, +165”. -28”. UV. IR. ‘H NMR, ‘%NMR MS
Akebonic acid; Me ester, 152-155”. + 127.7”. IR, ‘H, “CNMR, MS
3-Epiakebonic acid; Me ester, 200-202”. + 118.1”, IR, ‘H, “C NMR, MS
Triterpene acid; Me ester, +21.2”, IR, ‘H NMR, MS
Quinatic acid, 269-272”, +66 6” ‘H “C NMR, MS . . ,
16/?-Hydroxyalisol B; 23-monoacetate, 196.>198”, +llo” IR ‘H “CNMR ., . .
16/I-Methoxyalisol B; 23-monoacetate, 164-166”, +89.4”, IR, ‘H. ‘sCNMR
Alisol D
2
2
10
1
1
1
1
15
IS
15
a-Alnincanol, 202-203” 10
b-Alnincanol, 228-229” IO
Miricolone 18
3/3,22a-OH; 29-CO,H; Ai2
3/3-OH; 29+22x-lactone; A”
3x.1 la-OH; 23-CHO; 28-CO,H; AZ01291
2a,3a-OH; 24-OAc; 28C0,H; A”
2/I,3(9,23-OH; 28C0,H; A”
3~,15~16x,28-OH; A’*; 2 I /?/22a-angcloyloxy; 222/21/?-tigloyloxy
3fi,7a-OH; 9j?,19cyclo; 24+CH,k 28.29~nor
3/3,6x-OH; 9/7,19cyclo; 24-(=CH,); 28,29-nor
3b-OH; 9/?.19cycl0; 24.2kpoxy; 29-nor
3/?,25-OH; 9/7,19-cycle; A*‘; 29-nor
1/?.2a,3/?,19a-OH; 28-CO,H; A”
I/?,2/?,3/?,19a-OH; 28-CO,H; Al2
3a.7a-OH; 13uJO-cyclo; A”; 21,23-J4.25diepoxy; 17/?-H
3fl-OH; 28C0,H; A’z~‘o”9’; 3O-nor
3a-OH; 28-CO,H; A12.2q19i; 30-nor
38-OH; 28-CO,H; A”; 29/3OCHO
3a,24-OH; 28-COsH; A12.10(19); Bnor
3.0~0; 1 ljI,l6fi-OH; 23-OAc; 24.25-epoxy; AlJo”
3-0x0; 1 l&OH; 168.OMe; 23-OAc; 24,25qoxy; A”‘t”
3-0x0; I lb-OH; 23-OAc; 13/?,17jI-. 24.25diepoxy
3a-OH; 20,24-epoxy
3/I-OH; 2424-epoxy
~1521
~1521
[I521
Cl531
Cl531
Cl541
[lSS, 1561
Cl561
Cl571
Cl581
Cl581
11591
Cl591
116tY
WtJl
Cl611
C1621
C1621
C1621
Cl631
WI
cw
Cl651
Cl661
11661
3-0x0; 28-CHxOH Cl673
2218 S. B. MAHATO er al.
Table 1. (Continued)
1 2 3 4 5
Alnus japonica (Betulaoeae)
4. maximowiczii
A. pendula
Amaracus dicromnus (Labiatac)
Amphyretygium adsrrinyens
Amsonia grandij7ora
(Apocynaceae)
Andrachne cordijolia
(Euphorbiaceae)
Androsace saxifbgijolia
(Primulaceae)
Anlidesma pentandrum
(Euphorbiaceae)
Aphanamixis polystachya
(Meliaceae)
Apocynum venerum
Aschersonia aleyrodis
Asteropus sp
Astraeus hygromerricus
(Gasteromycetes)
Astragalus glycyphyllos
(Leguminosae)
A. taschkendicus
Seco-triterpene acid, + 61.2”.
UV IR ‘H 13CNMR, MS 3 , * Seco-triterpene acid,
1685169.5”, +44.0’. UV.
IR ‘H “CNMR. MS 7 * Sew-triterpene acid, IR. ‘H,
“C NMR. MS
Seco-triterpene acid; Me ester,
+ 30.2. IR. ‘H, “C NMR. MS
Seco-triterpene acid. IR. ‘H.
“C NMR. MS
Seco-triterpene acid, IR, ‘H.
“C NMR. MS
fi-Alnincanol
Monogynol A
12-Deoxyalnustic acid, + 36.7‘. IR. ‘H. “C NMR. MS
Zla-Hydroxyursolic acid; Me
ester, 214” + 24”. ‘H. “CNMR.
MS
Cuachalahc acid
Lupeol octadecanoate, + 22.98a. IR, ‘H NMR. MS
Triterpenoid, 265-268”, IR.
‘H NMR. MS
Tr’terpenoid. 25&254’. IR,
‘H NMR. MS Androsacenol, 262-264”, + 23’. IR ‘H “CNMR, MS . . Lupeolactone. NMR. MS.
X-ray analysis
Aphananin, 151-152”. IR. ‘H,
“C NMR. MS
Triterpenoid
Triterpenoid, >305”, IR. ‘H, “C NMR. MS
Pouoside A; aglycone, IR, ‘H.
“CNMR
Pouoside B; aglycone. IR. ‘H.
“C NMR
Pouos’de C; aglycone, IR. ‘H. “C NMR
Astrahygrol, 186187”. + 18.0’.
IR ‘H “CNMR, HRMS 3 , 3-EpiastrahygroI, 193-194”.
+ 101.0’. IR. ‘H. “CNMR.
HRMS
Astrahygrone. 168-169”.
+ 58 0’. IR. ‘H. “C NMR. HRMS
Sapogcnin
Cycloasgenin C
IO
10
10
10
10
10
10
7
IO
2
14
7
17
17
1
7
14
7
8
30
30
30
11
11
II
I
II
3.4~Sew; (24E)A4’z8’~‘0~“;
3C0,Me; 26-CO,H
3.4~Seco; (24E)A”‘s’ “.“;
3.26~CO,H
[I681
11681
3.4~Seco; 20@),24(S)-OH; A*11s’.s5; 3_CO,H
3,CSeco; Zo(S),ZS-OH; (23E)A”zB’~z’; 3-CO,H
3.4~Seco; 2O(S),25,26-OH; (23E)A4”s’? 3-CO,H
3.4.Seco; 12/?.2O(S).ZS-OH:
(23E)A4”1’~‘3; 3-CO,H
3/I-OH; 20.24-epoxy
3.0~0; 20-OH
3.4~Seco: ZO(StOH: Alt2s’; 24-(=CH,): 3C0,H
3&21x-OH; 28-CO,H; A’*
11681
[1681
[I681
[I681
[I691
L1691
11701
[I711
3a-OH; 26-CO H. A’.zz.2’ 2 * 3/I-octadecanoyloxy. A’(‘iz9’
IfI-OH; A’c’O’
3-0x0; A”“”
38,16a-OH; 22/I-OAc;
3tKHO; 13fi.28-epoxy
24+3/&lactone; AzO””
3/I-OAc; 218.24.25-OH: A’;
21.23(Skpoxy
3/I-arachidoyloxy; A*o’29’
3fi.l5%22-OH
2-0x0; 8,11,22a-OAc; 19/I-OH:
(9E.13E)A4.9.‘3
2-0x0; 8, 222-OAc; 11,19/Y-OH;
(9E.13E)A4,‘.‘s
2-0x0; 11.22a-OAc; 19/I-OH;
(9E.13E)A’~“~”
3fi-OH. 26-22~lactone; As
3x-OH; 26-22.lactone; A*
~721
[I731
[I741
11751
I1761
[I771
[I783
[I791
I1801
[341
[341
[WI
ll811
[I811
3-0x0; 26-22~lactone; A* Cl811
3/?,22/?,24-OH; 19-0x0; A” [I821
Cl831
Triterpenoids
Table I. (Continued)
2219
I 2 3 4 5
Atroxima afieliana Atroxigenic acid 1
Aucoumea klaineana (Burseraceae)
Austropleuckia populnea
Azadirachta indica (Meliaceae)
Bawingtonia speciosa (Barringtoniaceae)
Betula exilis (Betulaceae) 3-Epiisofouquierol
B. maximowicriana Triterpenoid, IR, ‘H, “CNMR
B. nana
B. pendula
Boehmeria excelsa (Urticaceae)
Boswellia cartmii (Burseraceae)
B. freerana
Botryococcus braunii var. showa (Chlorophyceae)
Calendulo ojicinalis (Compositae)
Calotropis procera (Axlepiadaceae)
Atroxigenic acid lactone
Preatroxigenin; dimethyl ester
Triterpenoid, 250”, IR, ‘H NMR, MS
Flindissone, 127-130”. IR,
‘H NMR, MS
Flindissol lactone, 229-234”, -50” IR ‘H ‘%NMR. MS . . .
Flindissone lactone, 193-195”. -68, IR, ‘H NMR, MS
Triterpenoid, 186192”. + 37”, UV IR ‘H ‘%NMR, MS * * . Triterpene acid, UV, IR, ‘H, ‘sC NMR, MS
Azadirachtol
Nimbocinone, 7678”. + IO”, ‘H, i3C NMR, HRMS
Nimolinone
Anhydrobartogenic acid; dimethyl ester, 276272”,
UV. IR, ‘H NMR, MS
l9-Epibartogenic acid; dimethyl ester, 252-254”. + 100”. UV, IR, ‘H NMR, MS
Bartogenic acid
3-0-MalonylbetulaIolientriol oxide, 1688172”, - l.o”, IR, ‘H, ‘3C NMR, FABMS
Triterpenoid
Triterpenoid
Triterpenoid
Boehmerone, 176-178”. + 12.3”, IR ‘H ‘+ZNMR, MS 3 . Boehmerol,215-217’, +47”, IR, ‘H, ‘“C NMR, MS, X-ray analysis
4(23bDihydroroburic acid
Triterpene, 183-185”. + 25”, IR, ‘H NMR, MS
Tetramethylsqualene, +6”, ‘H, ‘% NMR, HRMS
Triterpene MS, of its triacetate
Calotropenyl acetate, 198”. +8.9”, IR, ‘H, ‘sCNMR, MS
1
1
14
2~,3/I,22/I-OH; 23,28-CO,H; A’s’i4’; 27-nor
28,3/&228-OH; 23-CO,H; 28+ 138~lactone; 27-nor
2/?.3/3,22/?,27-OH; 23,28CO,Me; Ai2
3-0x0; 21-CO,H; A’*14
14
14
3-0x0; 215-OH; A’.24; 215,23kpox~
3x-OH; A’.‘.; 21+23(-lactone
14 3-0x0; A’***; 21+23<-lactone
14 3.23-0x0; 22C-OH; A’.r’
4 2-0x0; 3-OH; As; 29-CO,H
16
13114
13
1
3-0x0; I Ia,2Ia-OH; ‘la-OAc; 21.23-epoxy; A’~‘4~20’*2)
3-0~0: 24.26OH; A7.zo; 21,23-epoxy
3-0x0; 21-+23-lactone; A’.‘*
2a,3fi-OH; 24.28~CO,H; A”*is
1 2&3/I,19b-OH; 24,28_CO,H; A’2
1
10
7
10
2~3/?,19z-OH; 24,2&CO,H; Al2
3%20(S)-OH; AZ3
3j?-tram-3’.4’-Dihydroxy- cinnamoyloxy; 2028-08
3a-malonyloxy; 12&25-OH; 20.24epoxy
10
10
10
33
33
3-0x0; 12/3,2O(Q25-OH; A 23 Cl971
3z,l2~,17a,2U(S),24(R)-OH; A2’ Cl971
3~12/?,17~2a(S),24(S)-OH; A2’ Cl973 3-0~0; A”“s’ Cl981
3/$OH; A”(i”) Cl981
2
10
Squalene
7
2
3,CSeco; 3C0,H; A’ 2
3/l-OAc; 16/7,20(R)-OH; A2*
3,7,18,22-Me
3/.?.16/?,28-OH; A2’tz9)
3g-OAc; A19(r9)
Cl841
Cl841
[If351
Cl863
Cl871
CWI
Cl871
ClUl
CW
Cl891
119W
P9~1
[l92, 1933
[I92 1931
Cl931
Cl941
11951
Cl961
Cl991
C2W
C2W
c2021
PO31
2220
1 2
S. B. MAHATO et al.
Table I. (Continued)
3 4 5
Caltha palustris
(Ranunculaceae)
Camellia japonica (Theaceae)
Canarium album (Burseraceae)
Cassine halae
Chionochloa bromoides
Cigarrilla Mexicana
(Rubiaceae)
Cimic@ga acerina
(Ranunculaceae)
Cirrhopetalum elatum
(Orchidaceae)
Cissus quadrangularis
(Vltaceae)
Cistrus libanotis (Rutaceae)
Cieome brachycarpa
(Capparidaceae)
Cnidosculos elasticus
(Euphorbiaceae)
Cocculus hirsutus
(Menispermaceae)
Combretum elaeagnoides
(Combretaceae)
C. imberbe
Commiphora dalzielii
(Burseraceae)
Palustrolide. 310” (dec.). IR, MS
Camelienodiol, 215-216.5‘. + 30”. IR, ‘H NMR
Camelledionol. 232-233”.
+ 49”, IR, ‘H NMR, MS
Maragenin, 228-228.5”, + 41c,
UV IR *H “CNMR, MS , > 3 Triterpenoid, 127-128’. +43”,
‘H, ‘sC NMR, HRMS
Triterpenoid, 29&292”, + 5 I”, ‘H, 13C NMR, HRMS
Baknol, 139-140”, UV, IR, ‘H, ‘sC NMR
Balaenonol, 2OS-208’, UV, IR,
‘H, ‘)C NMR
19aH-Lupeol; methyl ether,
X-ray analysis
Triterpenoid, 283-287”, UV, IR,
‘H NMR, MS
O-Methylcimiacerol; 235-236”.
+ 20.0”, IR, ‘H, “C NMR, MS,
X-ray analysis
Triterpenoid. 255”. + 28.3”,
UV IR ‘%NMR, MS . . Triterpenoid, 20&202”, IR,
‘H NMR. MS
Triterpenoid, 233-234”. IR,
‘H NMR, MS
Triterpenoid
Triterpenoid
Deacetoxybrachycarpene,
185-186”, +47”, UV, IR, ‘H,
‘)C NMR, MS
Lupeol; p-phenylpropionate,
211’. IR, ‘HNMR, MS, X-ray
analysis
Hirsudiol, 238”. -25”. UV, IR,
‘H, 13CNMR. MS
Jessie acid, 196202’, + 55.5”.
UV IR ‘H “CNMR 2 9 1 Methyl jessate, 22&223”, + 60.4’. UV. IR, ‘H. “C NMR. MS
Methyl jessate, I a, I la-oxide
Imberbic acid, 286288”.
+ 70.0”, ‘H, “C NMR. MS
Isofouquierone, + 34’. IR, ‘H,
13C NMR, MS
Cabraliadiol-3-acetate, 155”.
+ lo”, IR, ‘H NMR, MS
1
1
1
1
2
1
4
4
I
2
41
11
20
20
10
10
10
7
1
11
11
11
1
10
10
38,23-OH; 28 + 13-lactone
3fi,18/GOH; 16-0x0; A’*;
28-nor
3.16-0x0; 18/3-OH; A12; 28-nor
3/?-OH; 16-0x0; A”.“; 28-nor
3a,16/.?-OH; A’2
3a,l6/3-OH; AL2
3,21/3-OH; 2-0x0; IS-Me; As*s.7.1w’).‘4; 24,26,29_nor
3,21/?-OH; 2,22-0x0; 1 S-Me; A355.7.‘o(‘1.‘4; 24,26,29_nor
3/l-OMe; A 2”(29’; 19z_H
38,23-OH; 28-CO,H; A”
3/?-p-Coumaryloxy:
9/?,19-cyclo; 2q=CH,)
3a,ZI,%OH; A’
3/.?,21z-OH; A’
3-0x0; 248-OAc;
20(%25epoxy
3-0x0; 24j5OH; Zo(S),ZS<poxy
3.4-Seco; 3-w&, 24-+20(R)-
dilactone; 25.26.27~nor
3/3-3’-phenylpropionyloxy; ~151 A’0’29’
2zx,3a-OH; A’3c’s’
la.3/?-OH; 23-0x0; 28-COIH;
24-(=CH,); 9/?,19_cyclo
Ia.3@-OH; 23-0x0; 28-CO,Me;
24-(=CH,); 9/3,19-cycle
3p-OH; 23-0x0; 28-CO,Me;
24-(=CH,); 9/?,19-cycle;
la.1 lz-epoxy
lz,3/?-OH; 29-CO,H; A’*
3-0x0; 20.25-OH; A=
3a-OAc; ZS-OH; 20.24-epoxy
w41
~2051
PO51
PO51
w41
PW
~2071
~2071
WI
PO91
PlOl
c2111
P121
WI
~2131
~2131
~2141
C2161
P-181
~91
c.w
WOI
Triterpenoids
Table 1. (Continued)
2221
1 2 3 4 5
C. incisa Triterpenoid, ‘H NMR, MS
Corchorus capsularis (Tiliaceae)
Cordia alliodora
(Boraginaceae)
Coriandrum sativum
(Umbelliferae)
Corttulaca monacantha
(Chenopodiaceae)
Cornus capitata (Cornaceae)
Corynebacterium XG
Cunila lythrifolia (Labiatae)
Dammar resin
Desfontainia spinosa
(Loganiaceae)
Douglas fir sapwood
Enkianthus cernuus (Ericaceae)
Enterolobium contorstisiliquum
(Leguminosae)
Nortriterpenoid. +38.2”, IR, ‘H, ‘%NMR, MS
Capsugenin, 23&232”, - 7.65”.
IR ‘H 13CNMR, MS 3 3 Triterpene acid, 21 l-212”. ‘H,
‘% NMR, MS
Triterpene acid, 209”. ‘H,
‘% NMR, MS
Triterpene acid, 223”. ‘H,
‘“CNMR, MS
Triterpene acid, 205-207”, ‘H, %NMR, MS
Triterpcne acid, 219”, ‘H,
‘%NMR, MS, X-ray analysis
Triterpene acid, ‘H, 13C NMR, MS
Coriandrinonediol, 285-290”,
+ 38.3”, UV, IR, MS
Cornulacic acid, IR. NMR, MS
Monacanthic acid, IR, NMR, MS
Triterpenoid, 188”, -24’. IR,
‘H, 13C NMR, MS
Triterpenoid, 176’. - 6”. IR, ‘H NMR, MS
Triterpenoid
Triterpenoid, IR, ‘H NMR, MS
Triterpenoid, 184-186”. +0.64”,
IR ‘H ‘%NMR, MS 3 3 2-Epitormentic acid; Me ester,
+ 16.3”, IR, ‘H NMR, MS
Hydroxyoleanonic lactone,
304-306’. +60.4”. IR, ‘H. “CNMR, MS
1 I-Deoxocucurbitacin I,
212-213”. UV, IR, ‘H,
“CNMR. MS
2CHydroxytormentic acid, IR, ‘H, ‘%NMR, MS
7a-Hydroxytormentic acid, IR,
‘H, “C NMR, MS
7a.23-Dihydroxytormentic acid, IR ‘H “CNMR, MS 3 9 (24R)Cycloeucalanol; acetate,
107.5-108”. +70.9’, IR,
‘H NMR, MS
6/l-Hydroxyursolic acid,
230-235”. IR, ‘H NMR. MS
21/?-E-Cinnamoyloxyoleanolic acid, 270”. IR, ‘H, “CNMR.
MS
11
11
10
1
1
1
1
1
1
5
1
1
14
14 38-OAc; A7s2*; 21.23-epoxy
I
7
8
3/?-OAc; 23/24-CHO, A20’29’
2/?-OH; 3a-OAc;
28+ 13-lactone
2-Me; 22-OH
2
1
2B,3/?,19a-OH; 28-CO,H; A’*
3-0x0; 12u-OH;
28+ 138-lactone
12
11
2
1
la-OAc; 3j&OH; Az4;
s/3,19-cycle
lz,2a,3j?-OH; A8v2*; 29-nor
3j?,l2/3,25,30-OH;
2o(sx24vkpoxY
3a-OH; 27-CO,H; Al2
3-0x0; 27_CO,H; Al1
3.29-0x0; 27-CO,H; Al2
3a-OH; 29-CHO, 27-CO,H;
A’I
3a, 29-OH; 27-CO,H; d”
~K-OH; 27,29_CO,H, Al2
1-0x0; 1 l&ZlC-OH
3p-OH; 27-CO,H; 612; 18&H
3/I-OH; 28-CO,H; A12;
15s 27-cycle; 18&H
3-0x0; A7*24; 21.23-epoxy
WI
WI
c=21
cu31
c2231
I?31
~2231
~2231
12231
~2241
c2251
c2251
CW
CW
cwl
I2281
c2293
cw
Cl391
2,16s20.25-OH; 3,22-0x0; A1.3.23
~2311
2s3/3,19a,24-OH; 28-CO,H; A’2
2u,3/?,7a,l9u-OH; 28-CO,H; AL2
2~,3/?,7a,l9a,23-OH; 28-CO,H; A’2
3/l-OH; 9/?,19cyclo; 24(R)-Me;
29-nor
c2321
c2321
c2321
12331
3/?,6/?-OH; 28-CO,H; A” cw
3/?-OH; 21/?-E-cinnamoyloxy; 28-CO,H; Al2
12351
2222 S. B. MAHATO et al.
Table I. (Continued)
1 2 3 4 5
Euphorhia antiquorum
(Euphorbiaceae)
E. hroteri
E. caudicifolia
E. maculara
E. niculia
E. supina
E. rirwalli
Euonymus revolulus
(Celastraceae) Triterpene acid, 298-300^. IR, ‘H, “C NMR, MS
Triterpene acid. 258-260’. IR,
‘H NMR, MS
Tritcrpene acid, 288-290). IR,
‘H NMR
Triterpene acid, 288.-290”. IR,
‘H NMR, MS
Tr’terpene acid, 3OC-302’, IR,
‘H KMR. MS
Triterpenoid. 268- 269’. + 23.5’.
IR. ‘H NMR, MS
Triterpznoid, 238-240”. + 27.5”
IR, ‘H NMR
Tritcrpenoid, 31 l-312’. 62.8’.
IR. ‘H NMR
Triterpenoid, +28.5, IR. ‘H.
‘“C NMR, MS
Tr’terpenoid; acetate, 98-lOO-,
+ 50.3-. IR. ‘H, “C NMR, MS
Triterpenoid, ‘H, “CNMR, MS
3-Epicyclolaudenol. 140’.
- IO’. IR, ‘H NMR, MS
Triterpenoid, 190- 191.5 ‘,
+ 76.8’. IR, ‘H. “C NMR, MS
Triterpenoid, 150-151.5”. +362.6’, I:V, IR. ‘H NMR, MS
Triterpenoid, 85-, +23’, IR,
‘H NMR, MS
Spirosupinanonediol, 248-250’. -3.8.‘. IR, ‘H. “C NMR, MS,
X-ray analysis
&Amyrinformate, 254-256’. + 15.2., IR, ‘H, “C NMR. MS
Tr’terpenoid, 193 - 196.5’. IR. ‘H NMR. MS
I la,l2a-Oxidotaraxerol,
286.-288’) - 38.9’, IR, ‘H.
“CNMR. MS
Triterpeno’d, 242-244”. - I I’, IR ‘H “CNMR, MS . .
Esp’nendiol A, 194-196’,
+90.7’, IR, ‘H, “CNMR, MS,
X-ray analysis
Espinendiol B, 1922193.5’.
- 17.1”. IR, ‘H, “CNMR. MS
Espinenoxide, 215-218“,
+ 7.8’., ‘H, 13C NMR, MS,
X-ray analysis
Trisnor’soesp’nenoxide,
209213’. -2.9’,, ‘H.
“C NMR, MS
Cycloeuphordenol, 105-106”.
7
4
4
4
1
4
4
4
11
11
18
I1
17
2
11
21
1 3P-formyloxy: A’3”s’
9 3,&OH; A’.“(’ ”
18 3,&OH: A’? 11% I Zz-epoxy
9
9
9
9
11 3/&OH: 9/I. 19-cycle: A”‘; C2471
2z.3z-OH; 2%CO,H; Arotr9’
22-OH; 3-0x0; 28-CO,H
2-0x0; 32-OH; 28-CO,H
3-0x0; 29-OH: 2%CO,H
2z,3z-OH; 28-CO,H; A”
3fl,30-OAc
3&OH; 30-OAc
3/I-OAc; 30-OH
3/GOH; 9~,19-cyclo;
24.25~epoxy
3p-OH; 98.19~cycle; 24-(0Me),;
25,26,27-nor
3.4-Srco: 3C0,Mc; A4’2J’.‘4
3~OH; 24-Me; A”; 9/J,19-cycle
3/I-OAc; A”
3P_OH; AS,“,.‘1
3/j-OH; Az5; 9/?,19-cycle
32,7x-OH; 8-0~0
3P.9r.l lz-OH; A”
3,4-Seco; 2%nor; l&-H; 9/I-Me;
3.5~OH; A”“’
3,4-Seco; 25-nor; IOa-H; 9/i-Me;
3,5/GOH; A4””
3,4-Srco; 25-nor; l&x-H; 9/?-Me;
3,5/kpoxy; A“‘=
3.4~Seco; 9fi-Me; 4,23,24.25-nor;
A”““; 3.5-epoxy
12361
[237]
I2371
CW
[238]
[239]
[2391
L2391
L2401
Pa
c2403
~2411
~2421
~2421
WI
~521
P441
w41
L2441
[245]
[2461
[2461
[2461
C2461
Tritevoids 2223
Table 1. (Continued)
1 2 3 4 5
+39”, UV, IR, ‘H, “C NMR,
MS
Cyclotirucanenol, ‘H,
13C NMR
Euphorginol, 168- 170”,
+22.35”, IR. ‘H, ‘“C NMR, MS
Fe&a link, (Umbelliferae) Triterpenoid, 223-226”. + 315”. UV IR ‘H =CNMR, MS 9 9 7 Triterpenoid, 224-229”, IR,
‘H NMR, MS
G. luclhm
Gaderma applanatum (Polyporaceae)
Ganoderenic acid F, + 93”. UV,
IR ‘H 13CNMR, MS . I
Ganoderenic acid G, + 189”, UV, IR, ‘H, “C NMR, HRMS
Ganoderenic acid H; Me ester,
+61’, UV, IR, ‘HNMR, MS
Ganoderenic acid I; Me ester,
+96”, UV, IR, ‘H, ‘)CNMR,
MS
Furanoganoderic acid, + 70’.
UV, IR, ‘H, 13CNMR, MS
Ganoderic acid AP, Me ester,
+71”, UV, IR, ‘H, “CNMR,
MS
Ganoderic acid A, + 153.8”. IR,
‘H, ‘“C NMR, MS
Ganoderic acid B, IR, ‘H,
‘“C NMR
Ganoderic acid C, 184.5-185.5”.
+ 184.9”. UV, IR, ‘H, “CNMR,
MS
Lucidenic acid A, 194-195”.
+ 173.3”, UV, IR, ‘H,
“CNMR, MS
Lucidenic acid B. 179-181”.
+ 168.9”, UV, IR, ‘H,
13CNMR, MS
Lucidenic acid C, 199-200”,
+ 140”, UV, IR, ‘H NMR, MS
Lucidenic acid D, Me ester,
+ 136”. UV, IR, ‘H, 13C NMR,
MS
Lucidenic acid E; Me ester,
l40-144’=, +86”, UV, IR, ‘H,
13CNMR, MS
Lucidenic acid F, Me ester,
208-211”. +195”, UV. IR, ‘H, “C NMR
Ganoderic acid D; Me ester, 199-200”. +98”, UV,
IR, ‘H NMR, MS
Ganoderic acid E, Me ester,
206-208”, + 167”,
‘H, ‘“CNMR
11
18
1
1
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
24/3-Me; 29-nor
3B-OH; 9/?,19cyclo; A”‘;
248-Me
&OH; A”
3/?-OAc; 6p-OH; Aw111.12
cw
CW
c2501
cw
3,7,11,15,23-0x0; 26-CO,H;
(20E)AB.2q22’
3,7,11,23-0x0; 15,sOH; 26-CO,H; (20E)A**20’22’
3/?-OH; 7,11,15,23-0x0;
26-CO& (20E)A8*20’22’
3,?,15wOH; 7,11,23-0x0;
26-CO,H; (20E)A’.2q22’
12511
WI
c2511
WI
3,7,11-0x0; 15a-OH; 26-CO,H; A8.20s22; 21,23cpoxy
3,7,11,23-0x0; 12/?,15a&OH;
2fX0,H; A8
c2511
c2511
3,11,23-0x0; 78,15a-OH;
26_CO,H; Aa
3a.7jI-OH; 11,15,23-0x0;
26-CO,H; A’
3,11,15,23-0x0; 7j-OH;
2K0,H; A”
c2521
c2521
C2531
3,11,15-0x0; 7/I-OH; 24-CO,H;
AO; 25,26,27-nor C2531
3,11,15-0x0; 7/?,12-08;
24-CO,H; A’; 25,26,27-nor C2531
3j,7j.I,12-OH; 1 l,ls-0x0;
24-CO,H; A*; 25,26,27-nor
3,7,11,15-0x0; 128-OAc;
26C0,H; As; 25,26,27-nor
C2531
cw
3/3-OH; 12/?-OAc; 7,11,15-0x0;
24-CO,H; A*; 25,26,27-nor WI
3,7,11,15-0x0; 24-CO,H;
A8; 25,26,27-nor C2541
3/?,78,15a-OH; 11.23-0x0;
26C0,H; A* C2541
3,7,11,15,23-0x0; ZCCO,H; A’ cw
2224 S. B. MAHATO et ol.
Table I. (Continued)
I 2 3 4 5
Ganoderic ac’d F; Me ester.
III’. UV. ‘H. “C NMR. MS
Ganoderic ac’d H; Me ester. 155-156”. +55’, UV. IR, ‘H,
“C NMR, MS
Ganoderic acid G; Me ester.
134-135”. +64’. UV. IR. ‘H.
“C NMR. MS
Ganoderic acid I; Me ester,
279-281”. + 132’. UV, IR, ‘H.
“CNMR
Ganolucidic acid A; Me ester, 192-194’. + 188”. UV. IR. ‘H.
“CNMR. MS
Ganolucidic acid B, Me ester.
167-169”. + 114’. UV. IR. ‘H,
“CNMR, MS
Ganoderic acid C. UV, IR. ‘H,
“C NMR, MS. X-ray analysis
Ganoderemc acid A. + 127.8’,
UV. IR. ‘H NMR, MS
Ganoderenic acid B, 21 I-214’.
+ 102.9‘. UV, IR. ‘H NMR. MS
Ganoderenic acid C, +66.2”,
UV. IR, ‘H NMR. MS
Ganoderenic acid D. 214-216”.
+ 163.4”. UV. IR, ‘H NMR. MS
Ganoderal A. 127- 128”. + 27”.
UV. ‘H NMR. MS
Ganoderol A. 99-IOI”, + 33”.
UV, ‘H NMR. MS
Ganoderol B, 171-173”. +61’.
UV. ‘H NMR. MS
Ganodenc acid S. 168-169”.
UV. ‘H NMR. MS
Ganoderic acid K. +48”, UV.
‘H NMR. MS
Ganodermatriol; triacetate.
98-100”. 59.91’. UV. ‘H,
“C NMR. MS
Ganodenc acid R. 201-202’. + 8.7’. UV. IR, ‘H. “C NMR
Ganoderic acid T. 200-202’, +23‘. UV. IR. ‘H. “CNMR
Ganoderic acid Ma. - 16.. UV. IR ‘H 13CNMR. MS 8 * Ganoderic acid Mb. -4.0’. UV.
IR ‘H “CNMR, MS . . Ganoderic acid MC, - 23”, UV.
IR ‘H 13CNMR. MS . . Ganoderic acid Md, 180-182”, -20’. UV. IR, ‘H. “CNMR.
MS
Ganoderic acid Me. + 53”. UV.
IR ‘H “CNMR, MS , 3
11
II
11
II
11
11
11
11
11
11
11
I1
11
11
11
II
11
11
II
11
11
11
II
11
3.7.11.15.23-0x0: IZfl-OAc;
26.CO,H: As
3fi-OH; 12jLOAc; 7. I I, 15.23-0x0; 26-CO,H; A*
3fi,7~,12j?-OH; 11.15.23-0x0;
26-CO,H; As
3/?.7~,2O_OH; 11.15.23-0x0:
26-CO,H: A”
3.11.23-0x0; I 52-OH: 26-CO,H; As
3/?.15a-OH; I1.23-0x0;
26-CO,H: A”
3fLOH; IZfi-OAc; 7.1 1.15.23-0x0; 26-CO,H; As
3.11.23-0x0; 7/1’.15+OH;
26-CO,H: (20E)A.8~‘0””
3j?,7/3-OH; 1 I .I 5.23-0x0;
26sCO,H; (20E)As~zo’2z’
3/?.7/?.15s-OH; 11.23-0x0; 26-CO,H: (20E)A8~z0”*’
3.11.15.23-0x0; 7fl-OH; 26-CO,H: (2OE)A”.*““”
3-0x0: 26-CHO; (24~)A,.*#’ 11.21
3-0x0; 26-OH; (24E)A7~9”“.z’
38.26-OH; (24E)A7~Y”“~z’
3-0x0: 26-CO,H; (24~)A~.Wl’hu
3/L7fi-OH; 12B-OAc;
11.15.23-0x0; 26-CO,H;A*
3&26,27-OH: A7.“““.z4
3a,22(S)-OAc; 26-CO,H; (24~)~T.g” ‘1.24
32.152.22JS)-OAc; 26X0,H; (24~)~‘.%1 ‘j.24
32.7sOAc; 15a-OH; 26-CO,H:
(24E) A*.”
3%. ISz.22-OAc; 7a-OH;
26-CO,H: (24E) A”.”
3a.7z.22-OAc: I5s-OH;
26.CO,H; (24E)A”.l’
3a.22-OAc; 7sOMe; 26-CO,H; (24E)AB,*‘
3a.15~OAc; 26-CO,H; (24~)~:.%‘11.24
WI
[2541
L2551
W51
WI
WI
C2561
12571
[2571
[2571
[2571
[Ial
[14(Jl
L 1401
[14w
[]@I
[2581
[2591
[2591
[2601
c26w
[2Wl
C2@1
[2@1
Triterpenoids 2225
Table 1. (Continued)
1 2 3 4 5
Ganoderic acid Mf. +42’, UV,
IR ‘H ‘“CNMR, MS , 3 Ganoderiol A, 232-234”, + 20”. UV IR ‘H ‘“CNMR, MS 9 . 7 Ganoderiol B, UV,
‘H, 13C NMR, MS
Ganodermanondiol, 182- 183”.
+45.8”, UV. IR, ‘H, ‘%NMR,
MS
Ganodermanontriol, 161-162”,
+ 35.7”, UV, IR, ‘H, 13C NMR,
MS
Ganoderic acid K; Me ester,
166-167”, +156”, UV, IR, ‘H,
13C NMR, MS
Compound B8; Me ester,
158-163”, + 128”. UV, IR, ‘H,
13C NMR, MS
Compound B9, UV. IR, ‘H,
13C NMR, MS
Compound C5’, 118.5-121.5”,
+ 101”. UV, IR, ‘H, “CNMR,
MS
Compound C6, 14&148”, UV,
IR ‘H “CNMR, MS , 3 Methyl ganoderate M,
206-210”, UV, IR, ‘H, MS, CD
Methyl ganoderate N,
164167”, + 153”, UV, IR, ‘H,
13C NMR, MS, CD
Methyl ganoderate 0,
168-171”, UV, IR, ‘HNMR,
MS. CD
Triterpene eater, 227-229”. UV,
IR, ‘H NMR, MS, CD
Methyl lucidenate H, 190- 192”.
+ 136”. UV, IR, ‘H, 13CNMR,
MS, CD
Methyl lucidenate I, + 118”.
UV, IR, ‘H, 13CNMR, MS, CD
Methyl lucidenate J, + 78”. UV,
IR, ‘H NMR, MS, CD
Methyl lucidenate K, UV, IR,
‘H NMR, MS, CD
Methyl lucidenate L, UV, IR,
‘H NMR, MS, CD
Methyl lucidenate M, UV,
‘H NMR, MS
Epoxyganoderiol A, +65’, IR,
‘H, 13CNMR, MS, CD
Epoxyganoderiol B, + 35”, UV,
IR, ‘H, “CNMR, MS, CD
Epoxyganoderiol C, +43”, UV, IR ‘H 9 9 13CNMR MS CD 9 * Ganoderal B, +94”, UV, IR,
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
3a-OAc; 15a-OH;
26CO,H; (24E)A7*9*‘11’2*
3/?,24.25,26-OH A’.9’111
3-0x0; 15x,26,27-OH; AT.%1 1,.2.
3-0x0; 24(s). 25-OH; A7.90 ‘)
c2w
WI
WI
CW
3-0x0; 24(5),25,26_OH; A’.9011 CW
3/?,15a-OH; 7,11,23-0x0;
26C0,H; A” C381
7a,lSa-OH;3.11,23-0x0;
26CO,H; A* C381
3/?,7a,15a-OH; 11,23-0x0;
26C0,H; A8
3.1 I.1 5.23-0x0; 78,12/?-OH;
26CO2 Me; Aa
C381
c391
3/3,12/?-OH; 7,11,15,23-0x0;
26C0,Me; A8
3,11,15,23-0x0; 7/?,12a-OH;
26CO,Me; A8
3,11,15,23-0x0; 7B,20<-OH;
26COrMe; A8
c391
C2631
C2633
3,7,11,15,23-0x0; 20C-OH;
26CO,Me; Aa C2631
3.11,15,23-0x0; 7,!f,12/I-OH; 26
CO,Me; (20E)A8~‘M22’
38,7/J,28-OH; I 1,15-0x0;
24CO,Me; As; 25.26.27~nor
C2631
12631
3/?,28-OH; 7,11,15-0x0;
24CO,Me; A’; 25.26.27~nor
3/?,12/$28-OH; 7,11,15-0x0;
24COrMe; A’; 25,26.27-nor
3.7, I 1.15-0x0; 12a-OH;
24CO,Me; A’; 25,26,27-nor
3jI,12/LOH; 7,11,15-0x0;
24CO,Me; A”; 25,26,27-nor
3/?,7a,lSa-OH; 11-0~0; 24C0,Me; Aa; 25,26,27-nor
3-0x0; 7x,26-OH;
A*; 24(s),2Ys)epoxy
3-0x0; 26-OH; A’.9’1 ‘I;
2YSL2Ys)ePoxY
3&26-OH; A’*9”“;
24(s).2Ys)epoxY
3-0x0; 7a-OH; 26CHO;
C2631
C2631
C2631
C2631
C2631
c2641
P541
cw
c2641
2226 S. B. MAHATO er (11.
Table 1. (Continued)
1 2 3 4 5
‘H NMR, MS
Ganodertnic acid Ja UV, ‘H,
l’C NMR, MS
Ganodermic acid Jb, 2OO--202”.
UV ‘H 13CNMR, MS . >
Ganodermic acid Pl, UV, ‘H, “C NMR. MS
Ganodermlc acid P2. UV, ‘H,
“CNMR, MS
Ganodermic acid R, 126- 129’. UV IR ‘H “CNMR. MS . . .
Ganoderrmc acid S, 123- 124.‘.
UV IR ‘H 13CNMR. MS 9 9 * Triterpene acid, UV, ‘H,
“CNMR, MS
Triterpene acid. UV, ‘H.
“C NMR, MS
Triterpene acid, UV, ‘H.
“C NMR, MS
Triterpene acid, 198-199”, UV.
‘H, 13C NMR, MS
Triterpene acid lJV, ‘H.
“C NMR, MS
Ganodermic acid T-N,
145-146‘. UV, ‘H, “CNMR,
MS
Ganodermtc ac’d T-O,
16&162’.. UV. ‘H. 13CNMR,
MS
Ganodermic acid T-Q, UV. ‘H,
“CNMR, MS
Ganoderiol C, IR, ‘H,
13C NMR, HRMS of its 24, 26-
diacetate
Ganoderiol D, “CNMR
Ganoderiol E; triacetate, + 18’.
UV IR ‘H “CNMR, MS . . .
Ganoderiol F, 116- 120”, + 42”.
UV, IR, ‘H, “CNMR, MS
Ganoderiol G, + 34.. IR. ‘H NMR, MS
Ganoderiol H, 2Ot-201.5’.
+ 22’. UV, IR, ‘HNMR, “C NMR. HRMS
Ganoderiol 1, + 53”. IR,
‘H NMR, HRMS
Ganolucidic acid E, + 154-, UV,
IR, ‘H NMR, HRMS
Triterpene acid. UV. ‘H.
“C NMR, MS
Triterpene ac’d, 178-180”. UV,
‘H, “C NMR, MS
Triterpene acid, UV. ‘H, “C NMR. MS
11
II
II
II
I1
II
II
11
II
II
II
II
11
II
I1
11
11
II
I1
II
II
II
11
11
II
(24.k-)A8~“’
3a.l %-OH; 26_CO H. AT.911 ‘I.24
2 7
38.1 %-OH; 26-CO,H; A7.%“,.Z4
3a,22/1-OAc; 1 Sa-OH; 26_CO,H; A7.%1’).24
3/?-OH; 15a,22p-OAc; 26_CO,H; A7.91”).2*
32,1511-OAc; 26-CO,H; A-.rc’1).24
36.1 Sa-OAc; 26-CO,H; AT.%’ ’ b.21
3sOH; 1 Sz-OAc; 23-0x0; 26_CO,H; A7.‘%“L?.*
3sOAc; 1 Sa-OH; 23-0x0; 26_CO H. A7.%“).2*
2 .
3a. 1 Sa-OAc; 23-0x0; 26_CO,H; AT.911 ‘,.2*
3a-OAc; 15a,22(Sj-OH; ‘,6_CO H. AT.‘%“,.?.1
2 . 3/LlSz,22(S)-OH; 26-CO,H; AT.%“).24
3/1-OH; 1 Sa-OAc; 26C0,H; AT.91 1 ’ 1.24
3/?-OAc; 15a-OH; 26_C01H; A7.‘%“l.24
3-0x0; 15sOH; 26_CO,H. A’.Yl”J.24
3-0x0; 7a-OEt; 24,25,26OH; AR
3.7-0~0; 24.25.26OH; As
3/?.26,27-OH; 7-0x0; AR.24
3-0x0; 26,27-OH; A’.9’1 “.‘*
3-0x0; 7z-OMe;
24.25,26-OH; A’
3/?,24,25.26-OH; 7-0x0; A*
3-0x0; 15,26,27-OH; 7sOMe; A*.‘*
3.11-0x0; 15x-OH; 26-CO,H; (24E)A”.”
32,15q22z-OH; 26_CO,H; A’.9(“).24
3fi,l5~.22/3-OH; 26_CO,H. A7.9,1 Lb.24
3cr.I Sz-OAc; 22a-OH; 26_CO,H. A7.%’ ‘j.2.
C2651
I2651
I2651
P651
WI
12661
W71
P71
W71
W71
C2’571
CW
W81
W81
W91
C2691
W91
W91
P91
I391
C2691
V91
12701
c2701
~2701
Triterpenoids 2227
Table 1. (Continued)
1 2 3 4 5
Gardenia jasminoides
(Rubiaceae)
Gentiana jlavo-maculata (Gentianaceae)
Glycyrrhiza uralensis
(Leguminosae)
Guaiacum oficinale Triterpene acid, 290”. +66.66’, (Zygophyllaaae) UV, IR, MS
Gynocardia odorata
(Flacourtiaceae)
Odolactone, 304-305”. 47.06
IR, ‘H NMR, “C NMR, MS
Odollactone, 303-304‘, IR,
‘H NMR, MS
Acetylodollactone, 302-303”. - 19”. IR, ‘H NMR, MS
Gyrinops walla (Thymelaeaceae)
Hedyolis lawsoniae (Rubiaceae)
Heteropanax jiiagraus
Hoya lacunosa (Asclepiadaceae)
Humata pectinata
(Davalliaceae)
Hyptis capitata (Labiatae)
H. mutabilis
Triterpene acid, UV. ‘H,
“C NMR, MS
Triterpene acid, UV, ‘H,
“C NMR, MS
Triterpene acid, UV, ‘H, “CNMR. MS
Triterpene acid, UV, ‘H,
“CNMR, MS
Gardenolic acid. 212-214”.
+ 38.3”. UV, IR. ‘H, ‘% NMR,
MS
Triterpenoid
24-Hydroxy glabrolide
Uralenolide, 302-303”
Glyuranolide
Wallenone, 194-196”. -71.6’.
IR, ‘H. 13CNMR, MS, X-ray
analysis
Triterpene acid; Me ester,
180-181.5”. +64.1’, IR,
‘H NMR, MS
Triterpene acid; Me ester,
l80-182”, +50.8”, IR,
‘H NMR, MS
Triterpene acid; Me ester, 51”.
IR, ‘H NMR, MS
Triterpene acid
Dihydronyctanthic acid; methyl
ester, MS
Seco-triterpenoid, MS
Triterpenoid, 236-238’. + 37.4’.
IR, ‘H NMR, MS
Triterpenoid, 324-326”. + 26.7”.
IR, ‘H NMR, MS
Hyptatic acid A, 298-304”,
+ 57”, IR, ‘H NMR, MS, X-ray
analysis
Hyptatic acid B, 225-228”.
+28’, IR, ‘HNMR, MS
Triterpene acid IR, ‘HNMR,
MS
11
11
11
11
11
2 3/?-Palmityloxy; 28-OH; A”
1
1
4
4
4
14
2
2
2
7 38,23-OH; 27,28-CO,H; A2o’29)
1 3,4-Seco; 3-CO&e; A’*
18 3,4-Seco; 3-CO,Me; A”
8 3/?-OH
8 3/?-OAc
1 Z&38,24-OH; 2&CO,H; Al2
2
2
3B,lSa-OAc; 222-OH; 26_CO,H; AT.‘%’ lb.24
3u,lSu-OH; 22fl-OAc; 26_CO,H; A7.%‘1).24
3/?,1 Sa-OH; 22/l-OAc; 26x0 H. A7.%“).24
2 7 3B.l Sa-OAc,
26-CO,H; A”.24
3/LOH; 23-0x0; 28-CO,H;
A’*; 9~,19-cyclo
38,24-OH; 1 I-0x0; A’*;
30-+22/Llactone
3/j24_OH; A’lJ3f”“;
30+22/?-lactone
3/l-O@ 1 I-0x0; 27-CO,Me;
A’l; 29+22a-lactone
38. 24-OH; 28,29-CO,H; Al2
Cl411
~2721
C2731
I2741
3-0x0; 26+ l2g-lactone
3a-OH; 26-t 12b-lactone
3a-OAc; 26+ 12/l-lactone
3-0x0; 24-(=CH,); 25-Me; A’
C2751
C2761
C2761
C27’51
c2773
3&23-OH; 28-CO,H; A” C2781
3/J,24_OH; 28-CO,H; A’* C2781
h,3fl,24-OH; 28-CO,H; A” C2781
C2791
W’l
WOI
WI
WI
WI
2~,3/?,19s24-OH; 28C0,H;
AL2
3a,l9a-OH; 28_CO,H; A”
cw
L-21
2228 S. B. MAHATO et al.
Table I. (Conrinued)
1 2 3 4 5
Triterpenoid lactone, 292-294‘.
+ 18.8”. IR. ‘H. ‘sC NMR, MS
H. suaveolens
flex rorunda (Aquifoliaceae)
Impariens balsamina (Balsaminaceae)
Inonotus obliquus
Triterpene acid, 307-308”.
+31‘, IR, ‘HNMR, MS
Rotungenic acid, 295-298’.
+ 16”. UV, IR, “C NMR, MS
Rotundioic acid, 295-298”.
+ 50”. UV, IR, ‘-‘C NMR, MS
Hosenkol-A. 225-227’. + 78.9”.
UV IR ‘H > . . “CNMR MS . . X-ray analysis
Triterpenoid, 145-146”. IR. ‘H,
“C NMR, MS
Inuh britannica (Compositae)
Triterpenoid
Triterpenoid. IR, “C NMR.
MS
Triterpenoid, IR, “C NMR, MS
Triterpenoid. IR, ‘H, 13CNMR,
MS
Triterpenoid, IR, ‘H NMR, MS
Triterpenoid, MS
I. missouriensis
Jaspis siellifera
Iris germmica (Iridaceae) z-lrtgermanal, +36”, UV, IR.
‘H, 13C NMR, MS
y-lrigermanal, 74-75’. + IO”,
UV IR ‘H I . 9 13CNMR MS 9 , X-ray analysis
Iridogermanal, +41”, UV, IR,
‘H, “CNMR, MS
Missourin
Missouriensin, 213-216’. IR,
‘H, “C NMR, MS
Triterpene I; Me ester, +22.8”.
UV IR ‘H “CNMR, MS , 3 .
Kadsura coccinea (Schisandraceae)
K. heteroclita
K. longipedunculata
Triterpene II; Me ester, - 154”,
UV IR ‘H “CNMR. MS 9 3 3
Triterpene III, -32.7”, UV, IR,
‘H, 13C NMR, MS
Triterpene IV, -66.7”, UV, IR,
‘H, ‘%NMR, MS
Coccinic acid
Triterpene acid, 95-97”.
+ 69.95”. 13C NMR, MS
Neokadsuranic acid A, -35.0”.
UV ‘H 13CNMR, MS . 1 Neokadsuranic acid B, + 37.4”,
‘H, 13C NMR. MS, CD
Neokadsuranic acid C. +42.0”,
‘H, 13C NMR, MS, CD
11
11
34
34
34
1
7
2
2
23
11
ll
I1
11
11
7
7
38
39
48 _-
8 &-OH; 30-CO,H; Azzfz9’
8 6a-OAc; 21/l-OH; A22’29’
19 3fi-OH; 12-0x0; 28-CO,H;
(13Z.l5E,17E,22E) 413.13.*7,2lw2.2*
3fi-OAc; 12-0~0; 28-CO,H;
(13Z,15&17E,22E) A’&‘% ‘12eL22.21
3&28-OAc; 22-OH; 12-0x0;
(13Z,15E,17E)A”~“~‘7’~0’~2’
38-OH; 12-0x0;
(13Z,lSE,17E,22E) A13.15.17~20~.21.21
3-0x0; 2W0,H; A9”“.s*
19
19
19
3/?-OAc; 28 -+ 13/l-lactone
3/l-OH; 27-CO,H; Azo’29’
3j?,l9a,24-OH; 2%CO,H; Al2
38,19n-OH; 23,28-CO,H; A”
3/?.17@,26,28-OH:
21,24wePOXY
3/?-OH; 21-CHO; As.‘*
3~,22_OH; A’.q(* “.2*
3fl.21-OH; As.“’
3P.22,25-OH; A8.z3
3g,22-OH; 7-0x0: Asz4
3fLPalmityloxy; 16/l-OH; Aro,z%
3/LMyristyloxy; 16/8-OH; Ar0,29’
_
3-0x0; 26C0,H; (242)Ae.s’
3-0x0; 26-COzH; (24Z)As” I’.’ 3118Ltd
3-0x0; 26C0,H;
(24Z)A 8.13,18,.2.
3-0x0; I38-OH; 26CO,H;
(24Z)Asz4
C28-7
C2831
12841
L-41
[543
C2851
PW
I?871
~2871
C-2881
I2893
US91
C6.21
C621
CQI
cwl
c2901
~2911
~2911
~2911
c2911
~2921
c591
c591
C581
C581
2230 S. B. MAHATO el al.
Table 1. (Continued)
1 2 3 4 5
kwsonia iwrmis (Lythraceae)
Triterpenoid, 287-289”, + 62”, UV, IR, ‘H NMR, MS
Hennadiol, ‘H NMR, MS
Triterpenoid, ‘H NMR, MS
Lemmaphyllwn microphyllum (Polypodiaceae)
Triterpene. 103- 104”. +46.6”,
‘H NMR, MS
Triterpene, -39.8”. ‘H NMR,
MS
Triterpene, 93-94”. + 16.1’.
‘H NMR, MS
Triterpene, + 57.1’. IR,
‘H NMR, MS
Triterpene, -24.8”. ‘H NMR,
MS
a-Polypodatetraene, +27.4”,
IR ‘H ‘%NMR, MS . 3 Triterpene, 155-156”. +3.1”,
‘H, “C NMR. MS
Triterpene, + 87.8”. ‘H,
“CNMR, MS
Triterpene, 83-85”. + 15.6”. ‘H,
"CNMR,MS
Triterpene, 174 175”. + 94.8”,
‘H, ‘% NMR, MS
13/IH-Malabaricatriene, + 16.3’. IR. ‘H. ‘-‘CNMR, MS
13aH-Malabaricatriene, - 23.3’. IR, ‘H NMR, MS
Liartris microcephalo
(Eopatotiaceae)
Lindheimera texana (Compositae)
Nortriterpeno’d. 228-233”, IR,
‘H NMR, MS
Triterpenoid. ‘H, ‘%Z NMR,
MS
Triterpenoid, 160-162.5”. IR,
‘H, ‘sC NMR, MS, CD
Triterpenoid, 214-217”. IR, ‘H,
“C NMR, MS, X-ray analysis
Triterpenoid, ‘H, ‘% NMR
Triterpenoid. ‘H, ‘%Z NMR
Triterpenoid, 228-23 1’. IR, 1 H, “C NMR, MS, CD
Triterpenoid, 185-187”, IR, ‘H, “C NMR, MS, CD
Triterpenoid, 225-228” (dec.) ‘H. “CNMR
Lufla amara (Cucurbitaceae) Amarinin
Lygodium Jexuosum (Polypodiaceae)
Macaranga peltara
(Euphorbiaoeae)
Triterpenoid
Cyclopeltenyl acetate, IR,
‘H NMR, MS
I
1
7
23
24
25
10
14
26
20
20
20
20
19
19
11
11
12
8
11
3/I-4’-Hydroxycinnamoyloxy;
28-OH; Al2
3/?,30-OH; A2”‘s9’
38,30-OH; 20s
A12.21
AY.2.
A3.21
A*&‘*
AT.24
AT.14
A7.13
A&14(“’
(17~ 24~)Al*~‘s),‘7l20l.2*.
138-H
(17~ 24~)A’*“s’.l7’ZO).2*.
13a-H
3/I-OAc; A”; 30-nor
3-0x0; 9B,19-cycle; A24;
l6B.2YS)epox~
3-0x0; 9/?,19cyclo; As*;
16&23(R)-epoxy
3-0x0; 9/3,19-cycle; 168,23-,
23.25-diepoxy; 23R
3/?-OH; 9jI,19cyclo; 6”;
168,23(S)-epoxy
38-OH; 9/?,19cyclo; A=;
l6B>2YR)-epoxy
3-0x0; 9/?,19_cyclo;
22+ 16/7-lactone;
23,24,25,26,2%nor
3-0x0; 16@-OH; s/I,1 9-cycle; 23.24-epoxy
3-0x0; 16p,23&24&25-OH;
98.19~cycle
3,11,22-0x0; I6a,20-OH;
25-OAc; A=’
29-pCoumaryloxy
3&OAc; 24-Me; A”; 9/?,19-cyclo; 21-nor
[3041
c3051
c3051
c3w
c3w
c3w
c3w
c3w
[491
c3071
c3071
c3071
[3071
C3W
C3081
c3091
C3lOl
C3lOl
C3lOl
C3lOl
C3lOl
[3lOl
[3lOl
C3lOl
El431
C3lll
~3121
Triterpenoids 2231
Table 1. (Continued)
1 2 3 4 5
Madhuca butyracea (Sapotaceae)
Manggera indica (Anacardiaceae)
Butyracic acid
Triterpenoid, 116-118”. +30.6’,
IR, ‘H NMR
Triterpenoid, 109-l 1 l”, +64.9”
IR, ‘H NMR, MS
Triterpenoid, 154-155”. +51’,
IR, ‘H NMR, MS
Maprounea africano (Euphorbiaceae)
Triterpenoid, 19t- 192”,
+ 18.8”. IR, ‘H NMR, MS
Triterpcnoid, 154-156”. +O”,
IR, ‘H NMR
Triterpenoid, 16% 163”,
+42.5”, IR, ‘H NMR, MS
Triterpenoid, 218-220”, + 27.5”.
UV IR ‘H 13CNMR, MS 3 9 7 Triterpenoid, IR, ‘H, iJC NMR,
MS
Triterpenoid, IR, ‘H, 13C NMR, MS
Triterpenoid, 205-207”, +21.5”,
UV IR ‘H ‘“CNMR, MS . 3 7 Triterpenoid, 253-255”. IR, MS
Maprounic acid 305-307”.
+ 12.8”. IR, MS
Maprounic acid 3-p-hydroxy-
bcnroate, 308-31 l”, + 32.5’.
UV, IR, MS
7B-Hydroxymaprounic acid
3-ghydroxybenzoate, + 8.0”.
UV, IR, MS
Triterpenoid, UV, IR, MS
Maytenus con&rtiJora
(Celastraceae)
M. diwrsifolio
Confertiflorol
Maytenfolic acid, 281-282”.
+34.2”. IR, ‘H, i3CNMR, MS,
X-ray analysis
M. horrida
Maytenfoliol, 290-291”. - 12.8”. IR, ‘H, 13C NMR, MS,
X-ray analysis
Maytensifolin A, 234-236”,
-29.5”. IR. ‘H, ‘sCNMR, MS,
X-ray analysis
Maytensifolin B, 280-282”.
-21.8” IR “CNMR, MS . .
Triterpenoid, ‘H NMR. MS
M. octogona
M. orbiculata
Melia toosendan (Meliaceae)
Triterpenoid
Triterpenoid
Lipomelianol, 5455”, - 3”, IR,
‘H, 13C NMR, MS
21-0-Acetyltoosendantriol,
‘)CNMR, X-ray analysis
1
10
10
11
11
3-0x0; 2qSbOH; 260Ac;
(24E)A”
3&26-OH; 9/?,19_cyclo;
(24E)A”
3/?,24(,27-OH; 9/?,19<ycl0; A*’
11 3&24<,25-OH; 9~,19cyclo
11
11
11
11
11
8
2
3/?,24{-OAc; 25-OH; 98,19-cycle
3x,22{-OH; 26C0,H;
9/?,19-cycle; (24E)A”
3j?,22C-OH; 26-CO,H;
9/?,19-cycle; (24E)A*’
3/?,23(-OH; 26-CO,H; 9~,19cyclo; (24E)A*’
3x,27-OH; 26CO,H;
9/?,19-cycle; (24E)A*’
1/?,3/7,22-OH
3j3-OH; 29C0,H; A’*
2 3/?-O-(p-hydroxybenzoyl); 29C0,H; Ai*
2
4 3-0x0; 28,30-OH c317l
4 3-0x0; I7-OOH; 28-nor C3181
4
1
4
7
14
16
2)9,38,23-OH; 28-CO& A’r
3-0x0; 20(S),26_OH; (24E)A**
38-O-(phydroxybenzoyl~
7fi-OH; 29-CO,H; A”
2q3p-(p-hydroxybenzoyl),; 29C0,H; A’*
3-0x0; 28,29-OH
3f?,22a-OH; 29-CO,H; Ai*
16-0X0
1~,3/?.1 la-OH; A’*
3-0x0; 28-CO,Me
38.29-08; A20t29)
3fi-OCO(CH,),Me; 21<-OH,
21,23-, 24,25diepoxy; A’ where n= 10,12,14,16
3a,7a-OH; 21-OAc; A”;
2123-24.25diepoxy
C3I31
c3141
c3141
c3141
13141
c3141
c3141
c3151
c3151
c3151
c3151
c3151
ClW
CW
ClW
CW
C3161
c3171
C3I91
13201
~3211
~3223
C3231
C3241
2232 S. B. MAHATO et al.
Table I. (Conrinued)
1 2 3 4 5
Methylosinus tricosporiwn
Monechma debile (Acanthaceae)
Musa paradisiaca (Musaceae)
Muscari comosum (Lihaceae)
Myrianthus arboreus Myrianthinic actd; Me ester,
(Cecropiaceae) 145 -147”. IR, ‘H NMR, MS
Myrica rubra (Myricaceae)
Nardia scalaris
(Marchantiopsida)
Neochamaelea pulwrulenta
(Cneoraceae)
Nepeta, hindosrana (Labiatae)
Nerium oleander (Apocynaceae)
Triterpenoid
Monechmol, 292-294”. + 28’.
IR, ‘H NMR, MS
Triterpenoid, IR, ‘H NMR, MS
Triterpenoid, 135’. + 72’. IR.
MS
Nortriterpcnoid. 194-195’.
+67.2”, ‘H, “CNMR, MS
Nortriterpenoid. 196-l 98’. ’ H.
“C NMR, MS
Nortriterpcnoid, I84- 186”. ’ H,
“C NMR. MS
Nortriterpenoid, 234-236’.
‘H NMR, MS
Nortriterpenoid, 195-197”,
-22‘ ‘H “CNMR. MS . 1 Nortriterpenoid. 18 I- 183”. UV,
IR ‘H ‘-‘CNMR, MS > 7
Nortriterpenoid. 221.-224’. UV,
IR, ‘H NMR. MS
Arboreic actd: Me ester,
239-230’. IR, ‘H NMR. MS
Myriabortc acid: dimethyl ester,
2%260’, IR. ‘H, 13CNMR.
MS
Triterpenoid. 225-227’, -0.2’,
IR ‘H ‘%INMR, MS 3 3
Triterpcnoid, 213-215”. +81’,
IR, NMR, MS
Protolimonoid I, 229”. - 66.3’. IR ‘H “CNMR, MS > I Protolimonoid II, 187-189”. -89‘. MS
Nepetidone 300” (dec.),
-28.13’. UV, IR, ‘H.
r3C NMR, MS
Nepedinol, 282”. (dec.),
- 18.67”, UV, IR, ‘H,
13CNMR, MS
Triterpene acid; Me ester,
210-212”. IR, ‘H, “CNMR,
MS
Kaneric acid. 122”. + 16.66”.
UV IR ‘H 13CNMR. MS . 7 .
Ncriucoumaric acid
Oleanderen, ’ H NM R,
‘%NMR,
Oleanderol, 206.-208‘. + 6.15”. UV IR ‘H “CNMR, MS . 1 .
Kamerin, 280-28 1’. + 14.28”,
UV, IR, ‘H NMR, MS
46
5
11
11
II
11
11
11
II
I1
II
1
1
2
18 3-0x0; 2X-CO,H; A“’ [336]
6 3-0x0: 21x-OMe; A”
14
14
7
3-0x0; 23x.25OH; 21-24lactone; A’
3-0x0; 245, 25-OH;
21+23-Iactone; A’
1/7,3&l Ix-OH: 30-nor; 20-0x0
c3371
[3381
C3381
c3391
7 1/7,3/I,lla, 30-OH; A20’29’
2 2j,3a, 23-OH; 28-CO,H; At*
31,32,33,34-OH; 35-NH,
38-OH; A”
3-0x0; 98.19~cycle; A”‘; 29-nor
3/I-OH; 24-Me; A”.“; 29-nor
3.15-0x0; 24(S).29-OH; 17x,23(S)-epoxy; AH; 27-nor
3/I.29-OH: 1 S,24Oxo;
17x23( RFepoxy: A’; 27-nor
3.15.24-0x0; 29-OH;
17x,23( R )-epoxy; A’; 27-nor
3/?,24(S),29-OH; 15-0x0;
17z,23(S)-epoxy; A”; 27-nor
3/?,29-OH; 24-0x0;
17x.23(S)-epoxy: A’: 27-nor
3,15,24-0x0; 29-OH;
17x,23(S)-epoxy; A’.‘; 27-nor
3/I,29-OH; 15,24-0x0;
17x,23(S)-epoxy; A’.““‘; 27-nor
3/%6P-OH. 29-CO,H; A”
2&3/1,24-OH; 28-CO,H; A”
3/1,19x-OH; 24.28-CO,H; A”
l/I,3/I-OH; 28-CO,H; A”
3fi-OH; 2x-cis-p-coumaryloxy;
28-CO,H; A”
A’2
3/1,27,28-OH; A’z~20’29)
3/?,5a-OH; 28-CO,H; 24-nor; A4,23,.te
~3251
13261
C3271
(I3281
C3291
[3301
c3301
c3311
[3311
[3321
[3321
[3331
c3341
[3351
II3391
c3401
c3411
c3421
c3431
[3441
c3451
Triterpcnoids 2233
Table 1. (Continued)
1 2 3 4 5
Neroilia purpwea (Orchidaceae)
Nothohzena candida (Pteridaceae)
Orthopterygium huancuy (Julianaceae)
Orthosphenia mexicana (Celastraceae)
Pachysandra terminalis, (Buxaceae)
Parmelia tinctorwn (Parmeliaceae)
Parsonslo laevigata
(bowa==)
Partheniumfruticosum (Compositate)
P. lozanianwn
Perenniporia ochrokuca (Polyporaceae)
Dihydroursolic acid, 150-l 52”. +6.0”. UV, IR, ‘H NMR, MS
Kanerocin; acetate, 184-185”, + 52.63”. UV, IR, ‘H NMR, MS
Oleanderolic acid, 262-264”, + 50.0”. UV, IR, ‘H NMR, MS
Kanerodione, 178-180”, -36.36”, UV, IR, ‘H NMR, MS
Cyclonervilol, 166- 169”. + 37.9”, ‘H NMR, MS
Cyclohomonervilol, 166-167”. 40.5”, IR, ‘H NMR, MS
24(R/a)-Dihydrocycloeucalenol, 141-142”. ‘H NMR, MS
24(S/&Dihydrocycloucalenol, 152-153”, ‘HNMR, MS
Dihydrocyclonervilol, l54-156”, ‘H NMR, MS
Triterpenoid, 234-236”. IR, ‘H, 13CNMR, MS
Triterpenoid, 204-205”, - 7”. IR ‘H “CNMR, MS 7 , Orthosphenic acid, 298-300 and 330” (double), IR, ‘H, HRMS, X-ray analysis
Netzahualcoyone, 210-212”, UV, IR, ‘H, HRMS, X-ray analysis
Trikrpenoid, IR, ‘H NMR, MS
Pachysandienol A, 21 l-213”. + 153.1”. IR, MS
Pachysandienol B, 236-241”, +89.5”. UV, IR, ‘H NMR, MS
Triterpenoid, 246-247”, + 77.0”, UV, IR, ‘H NMR, HRMS
Triterpenoid, + 52.0”. IR, ‘H NMR, HRMS
Triterpenoid
Triterpenoid, 320”, IR, HRMS 18 3/&24-OH; Al4
Fruticin A, 217-218”, +75”, IR, ‘HNMR, MS
Fruticin B, 235-236”, +12.9”, IR, ‘H NMR, MS, X-ray analysis
Desoxyprefruticin B, IR, ‘H NMR, MS
Desoxyisofruticin B, IR, ‘H NMR, MS
Perenniporiol, 186187”, + loo”, UV, IR, ‘H, I’ CNMR, MS
7
11
11
11
11
11
8
1
4
4
1
4
4
4
4
8
11
11
11
11
11
3/LOH; 28-CO,H
3a-OH; 28-CO,H; A1*.“’
3B-pHydroxylphenoxy; 1 lx-OMe; 12a-OH; 28-CO,H; AZ0
3.7-0x0; 28-OH; A20’29)
J/?-OH; 24-Et; 9/?,19cyclo; A”; 29-nor
3fi-OH; 24t-isopropenyl; 9/?,19-cycle; 29-nor
3B-OH; 24 (R)-Me; 9/?,19cyclo; 29-nor
3/J-OH; 24(!+Me; 9fi,l9_cyclo; 29-nor
3/?-OH; 24(R )-Et; 9/$19-cycle; 29-nor
6a-OAc; 16j?,22-OH; 24-CO,H
3-0x0; 6/?-OH; 28-CO, Me; A’*
2a,3a-OH; 29-CO,H; 38,24-~x~
3,2lj?-OH; 2,22-0x0; 29-CO, Me; 24.26nor; A3.%7.‘0(‘).‘*; 15_Me
3-0x0; 28,29-OH; A’*
3/?-OH, 16-Me; A’6*21; 28-nor
3fi_OH; 16_Me; A1s.1’(22);
28-nor
3!-OH; lCCH,OH; A’6*21; 28-nor
3/?-OH; 16-CH,OH; A16; 28-nor
3/J-OAc, 12/7,22-OH
3-0x0; 168,240.OH; 20,25-epoxy, A”
3-0x0; 16/l,24a-OH; 20,25cpoxy; 9~,19_cyclo
3-0x0; 98, 19cyclo; 24.25-epoxy
3-0x0; 25-OH; 9/.3,19-cycle; 16.24-epoxy
3826-OH; 1 Sa-OAc; 2226-epoxy; A7.9(11).2*; 22s; 26s
13451
c3461
13473
P-473
C3481
C3481
C3481
C3481
WI
c3491
c3501
c3511
C3521
c3531
c3541
c3541
c3551
c3551
C3561
c3571
C3581
C3581
c3591
c3591
c3fw
2234
1 2
S. 0. MAHAT~ er al.
Table 1. (Continued)
3 4 5
Triterpenoid. 197-200,‘. + 102”, IR ‘H “CNMR, MS , 3
Periandra d&is (Leguminosae) Triterpenoid, 290-296’.
+ 123.68”, IR, ‘H NMR. MS
Triterpenold, 283-292’,
+ 1.52”. IR, ‘H NMR, MS
Triterpenoid. 260-263”.
+ 183.36’. IR, MS
Pfajia panicuiata Pfaffic acid, 285-286”.
(Amaranthaceae) + 109.2”. IR, ‘H, ‘% NMR,
MS, X-ray analysis
P. puluerulenta Nortriterpenoid
Nortriterpenoid
Nortrrterpenoid
Nortriterpenoid
Triterpenoid, 188-189”. + 138”.
UV IR ‘H “CNMR, MS 9 . 1
Triterpenoid, 208-209”. + 174”. UV IR ‘H . 7 9 “CNMR MS . 3 X-ray analysis
Triterpenoid, 208-210”. + 117’. UV IR ‘H 13CNMR, MS 3 , 1
Triterpenoid. I70- 171 .I, + 68’.
IR ‘H ‘-‘CNMR, MS , . Triterpenold, 187- 188”. + 43”.
IR ‘H ‘+ZNMR, MS 3 I 12/&Acetoxyperenniporiol, 217-218”. -2.6”. UV. IR, ‘H,
“C NMR, MS
Phase&s vulgaris,
(Leguminosae)
Phellinus pomaceus
Phellodendron chinense (Rutaceae)
Pholidota chinensis
Glycinoeclepin A, ‘H,
“C NMR, MS, X-ray analysis
Glycinoeclepin B, ‘H,
“C NMR, FDMS
Glycinoeclepin C, ‘H,
“C NMR, FDMS
Javeroic acid; dimethyl ester,
125-126”. +lOl”, IR, ‘HNMR,
MS, X-ray analysis
Phellinic acid, 218-220”. UV,
IR, ‘H NMR, HRMS
Niloticin, 147’, -62”, IR, ‘H.
“C NMR, MS
Niloticin acetate, 157”. -75”.
IR, ‘H NMR. HRMS
Dihydroniloticin, 174‘, -47”.
IR ‘H “CNMR, MS , .
Cyclopholidonol
Cyclopholidone
II
II
11
11
I
I
1
29
29
29
29
29
41
42
43
44
45
13/14
13114
13/14
11
11
3/?-OH; I Sa-OAc; 26-OMe; 22.26-epoxy; A7,9” I’.‘*;
22S;26S
38.1 Sa-OAc; 26-OMe; 22.26-epoxy; A’~9”“.2*; 22S;26S
38.1 Sa-OAc; 26-OH; 22,26-epoxy; A’.9f”J~24;
22s;26S
3fi-OH; 2GOMe; 22,26epoxy; A”; 22x26s
3fI.26-OH; 22,26-epoxy; A’;
22x26s
3/?,26-OH; 128.1 Sa-OAc; 22.26epoxy; A’.“’ “.‘*; 22S;26S
3/Y,]%-OAc; 26-OH; 22,2t%epoxy; A8.11; 22S;26S
3-0x0; 25-CHO; 29-CO,H; At2
3-0x0; 25-CHO; 29-CO,H; A”
3-0x0; 25-OH; 30-CO,H; A”
3@-OH; 28-CO,H; A”
3/LOH; I I-0x0; 28-CO,H; A”
3-0x0; 28-CO,H; Al2
3,lI-0x0; 28-CO,H; AL2
3.11-0x0; 72-OH; 28-CO,H;
A’2
-
_
3-0x0; 23&OH; 24(,25epoxy; A’
3-0x0; 23(-OAc 2%. 25cpoxy;
A’
3/?,23<-OH: 24(,25_epoxy; A’
38-OH; 9/3,19-cycle; 24, 24Me; A”; 29-nor
3-0x0; 9/?,19-cycle; 24,24-Me;
A”; 29-nor
[3W
c3m1
c36(Y
C3Wl
C3@1
C3611
C3611
C3621
[3621
C3631
WI
C651
C651
C651
[653
WI
c371
c371
C611
C611
c3641
c3641
c3641
C3651
C3651
2236 S. B. MAHATO et al.
Table 1. (Conrmued)
I 2 3 4 5
Pisolithus rinctorius
(Sclerodennataceae)
P’sracia lentiscus Triterpenoid, ‘H NMR,
(Anacardiaceae) “CNMR
PIectranthus rugosus (Labiatae) Plectranthoic acid, 296”. + 42”,
IR, ‘H NMR, MS
Acetylplectranthoic acid, 258”.
+ 58’. IR, ‘H NMR, MS
Plectranthadiol, 220”. + 26” IR,
‘H NMR, MS
Polygala chomaebuxus Triterpenoid
(Polygalaceae)
Polypodium jauriei Triterp-ene, - 14.4”. ‘H NMR,
(Polypodiaceae) MS
a-Polypodatetraene, + 27.4”.
IR ‘H “CNMR, MS 9 .
P. .formosanum (24R)Cyclolaudenyl acetate
127-128’. + 53.5”. IR, ‘H NMR, MS
(24R)Cyclomargenyl acetate
144-145”. 50.5‘. IR, ‘HNMR,
MS
Pittosporum breuicalyx
(Pittosporaceae)
P. phillyraeoides
Pinus monf icola (Pinaceae)
“C NMR, MS
Picfeltarraegenin VI, UV, IR.
‘H, ‘% NMR, MS
Pittobrevigenin
27-Desoxyphillyrigenin, 294-297”, IR, ‘H NMR, MS
23-Hydroxyphillyrigenin, 330-332’. + 19,“. IR, MS
Triterpenoid, IR, ‘H. “C NMR,
MS
Triterpenoid, IR, ‘H, “CNMR,
MS
Triterpenoid, IR,‘H, “CNMR,
MS
Pisolactone, 279-280’, + 60”,
IR, ‘H, “CNMR, MS, X-ray
analysis
Triterpenoid, IR. ‘H NMR
Triterpenoid, IR, ‘H NMR
3-Oxopisolactone, 248-250”.
+79”, IR, ‘H NMR, MS
Triterpenoid, 161- 165”, + 29”,
IR ‘H ‘%NMR, MS . .
Triterpenoid. 190-192”. + 6”.
IR, ‘H NMR, MS, X-ray
analysis
Triterpenoid, 187-190‘. IR,
‘H NMR, MS
(24R)Cyclolaudenol. 123-124”.
+ 36.5’, IR, ‘H NMR, MS
(24R)-Cyclomargenol,
12
1
3
epoxy; As.”
2/?&,16a-OH; 11,22-0x0;
2424-epoxy; A=’
3/&l 5a. 16a,28-OH; 22a-OAc,
21j%angelyloxy; A’*
3/?-OH; 28+20/I-lactone
3 3/?,23,27-OH; 28+20,3-lactone
6 3@-OMe; 2Ia,30-OH; Al4
6 3/I-OMe; 21a.29-OH; A’*
6 3/I-OMe; 21@,30-OH; Al4
11
11
11
11
11
11
11
26
2
2
2
1
10
26
11
11
11
11
3/I-OH; A”; 24-CO-O-22
3,!7,235-OH; 22<-OAc;
24-(=CH,); A*
3&23<-OH; 22C OAc; 24-(=CHMe); A*
3-0x0; A”; 24-C0-O-22
3/l,22(S)-OH; 24-(=CH’); As
32,22(R)-OAc; 25-OH; A*=
3x,25-OH; 22 (R)-OAc; A“=
38,8z-OH; A13.‘7.2’
3a-OH; 29-CO,H; A”; 18a-H;
19s
3x-OAc; 29-CO’H; A”; 182-H;
19s
3a,29-OH. A”. 18a-H; 19s 3 9
38,23,27,29-OH; 28-CO,H; A”
A’% 17b.2.; 20R
3/3-OAc; 24(R)-Me; 9/?,19-cyclo;
A’s
3/I-OAc; 24(R)-Et; 9/?,19cyclo;
A=s
3/I-OH; 24 (R)-Me; 9/?, 19cyclo;
Al5
3/?-OH; 24(R)-Et; 9~.19cyclo; C3841
c3751
CW
13771
c3771
13781
[3781
WI
c3791
C361
C361
C3801
C3801
C3801
C3801
c5w
C38Il
C38Il
C38Il
C3821
[3831
c491
C3841
[3841
C3841
Triterpenoids 2239
Table 1. (Continued)
1 2 3 4 5
S. nicolsoniana
S. pinnata
S. przewalskii
Santolina oblongi$Aia (Compositae)
Sapium sebjr- (Euphorbiaceae)
Schaefferia cunejrolia (Celastraceae)
Triterpenoid, 2-264”. + 69”. IR ‘H ‘sCNMR. MS * ,
Triterpene acid, > 300”. IR. ‘H NMR, MS
Triterpene acid, > 300”. IR, ‘H NMR, MS
Triterpenoid, 185”. IR, ‘H NMR, MS
Przewanoic acid A, 269-270”. + 125”. UV, IR, ‘H, ‘% NMR, MS
Przewanoic acid B, 258-259”. + 103”. UV, IR, ‘H, ‘sCNMR, MS
Triterpenoid, 136137”, +48.8”, IR ‘H ‘sCNMR, MS , .
Triterpenoid, 161-162”. + 58.6”, IR ‘H ‘%NMR, MS 9 , Triterpenoid, 181-182’, +48.4”. IR ‘H “CNMR, MS . ,
Sebiferenic acid, 325” (de-c.), IR, ‘H, i3C NMR, MS
Triterpenoid, 237-238”, + 8.5”, IR ‘H ‘sCNMR, MS 3 3 Triterpenoid, 230-232”. + 6.35”. IR ‘H ‘+ZNMR, MS ? * Triterpenoid; acetate, 208-210”. +31.5”, IR, ‘H, ‘%NMR, MS
Scheflera octophylla (Araliaceae)
Triterpenoid; acetate, 210-212”. +37”, IR, ‘H NMR, MS
Triterpene acid, 213-214”. -2.0’ IR MS ’
‘H “CNMR. 3 3
Schisandra propinqua Anwuweixonic acid
Manwuweizic acid
Schizandra species
Schizandra grandijlora (Schixandraceae)
Scilla scilloides (Liliaceae)
Schisanlactone B, 205-207”, + 80.2”, UV, IR, ‘H, “C NMR, HRMS, X-ray analysis
Schixandraflorin, NMR, MS
Nortriteqxnoid
Nortriterpenoid, 235-239”, -36.7”, IR, ‘H. “CNMR, HRMS, X-ray analysis
Nortriterpenoid, 214216”, -47.4”. IR, ‘H, ‘%NMR, HRMS
Scutelloria riuularis (Labiatae)
Siphonochalina siphonella
Scutellaric acid, 275-277”. +35.5”, IR, ‘H NMR, MS
Sipholenol A, 169-171”, -60”. IR, ‘H, “CNMR, HRMS. X-ray analysis
PWm 3117-O
7
1
1
1
18
18
10
10
10
18
1
1
1
1
7
11
11
11
11
11
11
11
1
21
l/I,1 la&OH; 3-0~0
3a, 24-OH; 28-CO,H; A”
301.24OH; 28, 3OC0,H; A’*
2a3B.l la-OH; A”““’
&3a-OH; 28-CO,H; A14; 12a.27~cycle
2a,3r-OH; 28-CO,H; 12z,27cyclo; 24-nor; A4’23’.‘4
3B-OAc; l’la-OH; A”‘.”
38,25-OH; Azo**’
3/7,25-OH; Ax’
2a,3p-OH; 28-CO,H; Al4
3rI?.16/?-OH; A’s
3/I.l6/.7-OAc; A’s
3-0x0; 168-OH; A’s
3-0x0; 16a-OH; A’s
301.1 la-OH; 23,28-COzH; AZOW%
3-0x0; 26CO,H; Air.”
3.4Seco; 3.26CO,H; AWs’. 8.x.
3,4-Seco; 9~,19-cyclo; 3+4-, 26-+22dilactone; A’, ”
3.24-0~0; 9/?,19cyclo; AZ0
3fl,29-OH; 240x0; 17a.23-epoxy; As; 27-nor
31,22/?,29-OH; 24-0x0; 17a.23-epoxy; A’; 27-nor
3.24-0x0; 29-OH; 17a.23-epoxy; Aa; 27-nor
3a,24-OH; 28-CO,H; A’*
4a,lOj?,l9~-OH; A”
c4101
c4111
c4111
~4121
[4131
c4131
c4141
14141
c4141
c4151
C4161
C4161
C4161
C4161
c417l
CIW
ClW
C4181
c4191
~4201
~4211
~4211
~4221
c46.471
2240 S. B. MAHATO et al.
Table 1. (Continued)
1 2 3 4 5
Skimmia japonica (Rutaceae)
Sorghum bicolor (Gramineae)
Stauntonia hexaphylla
Stellet ta species
Stirophyllum riparium
(Bignoniaceae)
Swertia chirata
(Gentianaceae)
Terminalia alata
(Combretaczae)
T. bellerica
Treooa trinercis (Rhamnaceae)
Sipholenone A, 187-188”,
-29”, IR, ‘H, “CNMR, MS
Sipholenone B, + SC, IR. ‘H,
13C NMR, MS
Sipholenone C, + 1’. IR,
13C NMR, MS
Sipholenol B. -37’, IR, ‘H.
13CNMR, HRMS
Sipholenol C, -28-, IR. ‘H,
13C NMR, HRMS
Sipholenol D, - 3 1 _. IR,
‘HNMR
Sipholenol E, IR, ‘H,
“CNMR. HRMS
Siphonellinol, 109-I 11”. - 52”.
IR ‘H “CNMR, HRMS . > Skimmiarepin A,
164.S-165.5-, -22.7”. IR, ‘H,
“CNMR. MS
Skimmiarepin B, 1688169”,
-39.8”. UV, IR, ‘H, “CNMR
Sorghumol, 277-282”.
‘H NMR. MS
32 _
3_Epimesembryanthe-
moidigenic acid, ‘H NMR, MS
3-0-Acetyl-3-cp’-
mesembryanthemoidigenic acid. + 106.7’. IR, ‘H,
‘“C NMR. MS
3z,29-OH; 28-CO,H; A”
3z-OAc: 29-OH; 28-CO,H: A”
t4231
t4241
[424]
3-O-Acetylmesembryanthemoi- digenic acid
3fi-OAc; 29-OH; 2X-C&H: A”
3-0-Acetylserratagenic acid,
> 290‘. ‘H, “C NMR. MS
3fi-OAc; 28.29~CO,H; Al2
3-0-Acetyl-3-epi-serratagenic
acid, ‘H. “CNMR, MS
Triterpeno’d. 258.-260’. + 87”,
UV, ‘H. “CNMR. MS, X-ray analysis
32-OAc; 2X,29-CO’H; A”
19 3.12-0x0: 26-22~lactone; A’J.‘%‘W”,.ZZ.L4; 8x_Me(30,
L4241
t4241
t4241
t4251
Triterpenoid, 200 202 ‘, + 28.2”.
UV IR ‘H “CNMR. MS . . >
Triterpenoid, 178-180‘. + 33.3”.
UV IR ‘H ‘%NMR, MS . , . Tr’terpenoid, 195-197’. + 1.58”.
UV, IR, ‘H, 13C’ NMR, MS
Swertanone. 270-272‘.
-98.12’. IR, ‘H, “CNMR,
MS, X-ray analysis
3-Acetylmaslinic acid,
192 195’. ~32’. IR, ‘H NMR
Belleric acid > 300’. + 77”. IR,
‘H. 13C NMR, MS
Trevoagenin A, 297-300”.
-49”, IR, ‘H NMR, MS, X-ray analysis
2
2
2
28
38-OH; 24rrans-fcrulyloxy;
28-CO,H; A’*
3/I-OH; 24-cis-ferulyloxy:
28-CO,H; Al2
3/J,l9-OH; 24-rrans-ferulyloxy:
28-CO,H: A”
3-0x0: A’
t4261
t4261
L4261
t631
I
I
10
2%~OH; 3/I-OAc: 28-C&H. A”
2a,3j,23,24-OH: 28-CO’H: A’2
3jI,25,30-OH; 16-0x0;
2O(R),24(R)-epoxy
t4271
t4281
[429]
Trevoagenm B. 243-246”. - 31 II, 10 3/?.25,30-OH; 16-0x0: t4291
21
21
21
21
21
21
21
22
10
10
40x0; lOfl,19,!?-OH; A”
40x0; 10/3,19/?-OH;
152,l &-epoxy
4.16-0x0; 10/?,19/?-OH; A’%%%
& 10-s 19B-OH; A” 3 3
4a,lO/3,19/&OH;
( 13E,‘Z)A13
42.10/3,19~-OH; 16-0x0;
Al4
4z,lO/LI6~,19~-OH; A’*
4a,lO~,16~-OH: A“‘.‘*
3a-Isovaleryloxy; 7z,21{-OH; 21,23-, 24.25-diepoxy; 30,13a-
cycle
3a-Decan-2’,4’,6’-trienoyloxy:
7x,21(-OH; 21,23-.24,25-
diepoxy; 30,132~cycio
t46 471
t471
t471
t471
t471
t471
t471
[4Rl
~1421
~1421
2242 S. B. MAHATO er al.
Table 1. (Continued)
I 2 3
Wjzrhia mollis (Compositae)
Zanha golunyensis
Triterpenoid, 21 l-212“. IR. ‘H, II
lJCNMR, MS
Triterpenoid, 168.5-171’, UV, II
IR, ‘H NMR, HRMS
Zanhic acid I
Zanhic acid-a,,-lactone I
%ymomono mobilis Triterpenoid 46
4 5
3-0x0; 23/3-OMe; 98.19~cycle; [444]
16/3,23-. 24,2S-diepoxy
3-0~0; A’.““‘; 22.25epoxy c4W
28.3/?.16z-OH; 23,28XO,H;
A’2
2~.3~,16+OH: 23-CO,H;
28+ 13/I-lactone
32-0x0; 33,34,35-OH
C4461
C4461
c4471
in the rabbit model [ 1353. It was suggested that this was effected through an increase in the mucopolysaccharide layer in the bladder. Alisol B and its monacetate isolated from Al&ma orientale were found to be inhibitors of experimentally-induced contractions in isolated rat ileum [I 361. Alisol B at a concentration of 10. ’ M inhibited contractions in isolated rat ileum induced by bradykinin, acetylcholine and S-isoleucine-angiotensin by 63, 50 and 65%, respectively, whereas the monoacetate inhibited by 56, 42 and 33%, respectively. Glycyrrhizin (20 mg kg- ‘, intravenous or 50 mg kg- ‘, intraperitoneal) and its agly- cone, glycyrrhetinic acid (5 mg kg- ‘, intravenous) in- duced interferon (IFN) activity in the blood serum ofmice [137]. Glycyrrhizin was found to be more effective than glycyrrhetinic acid. The antitussive and expectorant ac- tivities of glycyrrhetinic acid choline were evaluated in experimental animals including guinea-pigs and mice [I 381. Subcutaneous injection of glycyrrhetinic acid choline at a dosage of 5..10 mg kg- ’ suppressed coughing in guinea-pigs exposed to citric acid fumes. The antitus- sive effect of this compound was slightly less than that of codeine at a dosage of 3 mg kg- ‘. Intraperitoneal injec- tion of the compound (5-10 mg kg- ‘) also suppressed coughing in mice exposed to ammonia vapour and the antitussive effect was comparable to that of codeine at 1 mg kg I. lntraperitoneal administered glycyrrhetinic acid choline (5-20 mg kg- ‘) markedly stimulated the respiratory tract expectorant activity in mice. Glycyrrhe- tinic acid choline did not suppress the histamine- or acetylcholine-induced contraction of isolated tracheal smooth muscle of guinea-pigs but suppressed the acetyl- choline-induced contraction of isolated colonic smooth muscle of guinea-pigs. The LD,, value of the compound was found to be 584.5 mg kg-’ (orally). Apparently, glycyrrhetinic acid choline is an effective antitussive agent.
The antiviral activity of some dammar resin triterpen- oids was investigated by Poehland et al. [139]. Nine triterpenoids isolated from dammar resin showed anti- viral activity against Herpes simplex virus type I and II in vitro. Each compound caused a significant reduction in viral cytopathic effect when Vero cells exposed continu- ously to l--l0 pg ml- ’ of compound for 48 hours after viral challenge. Mariesiic acid A and other triterpenoid acids having normal and rearranged lanostane skeletons isolated from Abies mariesii and A.firma exhibited anti- microbial activity [SS, 561 against Gram-positive bac- teria and actinomycetes. The results suggested that not
only the carboxylic group, but also the hydrophobic moiety, played an important role in revealing the inhibit- ory activity. The inhibitory effects of 10 lanostane triter- penes (including five new) isolated from Ganoderma lucidurn on angiotensin-converting enzyme (ACE) activity were determined [I401 and expressed in terms of IC,,. The term IC,, was defined as the amount of the sample needed to inhibit 50% of ACE activity. Eight compounds were found to be inhibitory. Ganoderic acid F had the highest effect (IC,, =4.7 x 1O--6 M) whereas, the IC,, values of the other compounds were in the order of lo-’ M. Gentiatriculin, a new triterpene ester isolated from the herbs of Gentianajaco-maculata protected mice against Ccl,-induced hepatotoxicity, as detected by its reduction in pentoberbital-induced sleeping time and SGOTiSGPT blood enzyme levels [141]. Skimmiarepins A and B, two new triterpenoids isolated from the leaves and fruits of Skimmia japonica [ 1421 exhibited an insect growth inhibitory activity against the silk worm, Bomhyx mori. Amarinin (2-deoxycucurbitacin B) isolated from the seeds of f&u amara inhibited the growth of the second leaf sheath of rice both in the presence and absence of GA, [143]. The circulatory effects of oleanolic acid sodium hydrogen succinate (OSS), an analogue of the antiulcer drug carbenoxolone, were investigated by Fil- czewski et al. [ 1443. Carbenoxolone (433 mg kg- ‘, orally) and OSS (666 mg kg ‘, orally) were given to rats twice daily for four weeks. The systolic blood pressure was elevated after the first week of treatment. The hyperten- sion was found to be accompanied by bradycardia and increased with the time of treatment. In the blood an increase in the creatinine level, a decrease in the urea level and a slight elevation in sodium concentration were found after the treatment, while the potassium concentra- tion during the whole period (four weeks) of treatment remained unchanged. Although the principal aldosteron- e-like effects of carbenoxolone were attributed to the presence of the I I -0x0 group in the glycyrrhetinic moiety, the absence of an oxo-function at that position did not cause the loss of the adverse circulatory effect.
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Triterpenoids 2243
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