Phymhmisrry. Vol. 31. No. 1. pp. 2199 2249. 1992 Primed I Grem Bntam.

0031-9422192 ss.oo+o.oo C 1992 PergamonPmss 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.

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. Abehnct-Ttiterpenoids

INTRODIJfflON

Triterpenoids are the most ubiquitous non-steroidal secondary metabolites in terrestrial and marine flora and fauna. Their presence, even in non-photosynthetic bacteria, 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 elucidation 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 bacterial triterpenoids giving an account on triterpenoid occurrence as well as function in bacteria has also been published [ 133.
ISOLATION AND PURIFICATION

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 chloroform 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 capacity 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 number 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 reversed-phase HPLC. A method for the separation of substituted olean-12-en-28-oic acids from the corresponding 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 separated by solvent extraction or chromatography. The authors 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

2199

2200

S. B. MAHATO er 01. 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 formulation of partial structures. Proton carbon correlation experiments, optimized separately for detecting one-and two-/three-bond couplings, confirmed the partial structures and unambiguously identified thechemical shifts for the three pairs of geminal protons whose shifts could not be confidently assigned from HNMR data alone because 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 nortriterpenes. 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, combined 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-dimensional 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-acetylalcuritolic acid (3/3-acetoxy-taraxer-l4-ene-28-oic acid) were elucidated by H C shift correlated two dimensional spectra obtained for polarization transfer via twobond and three-bond .C H coupling correlation, in conjunction with related experiments [40]. The CNMR spectra offive pairs of IX/I- and 182-l Ioxo-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-

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 techniques 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 USCof n-BuOH -Na-metal at water bath temperature (95%) for 48 hours afforded the genuine triterpenoid anagalligenin B [29] as the major product which, however, 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 elucidation of natural products which. in most cases, is now successfully achieved without resorting to the convcntional chemical degradative procedures. Although the widespread adoption of these techniques in structure elucidation studies may appear to have created a limitation 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 analysis 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-resonante 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 assignment of 13C and H NMR spectra of three isomerlc taraxasterol, triterpenoids, 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 Kesslers COLOC sequence [33]. The ability of XCORFE to distinguish two-and three-bond connectivities 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

Triterpenoids 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~/18/3pentacyclic 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 membrane 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 1,3diplanar 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 flexibility at the level of ring C which may be important for the membrane properties of the triterpene.
CD spectroscopy

2201

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 isolated 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 additional 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 cyclizations.
Siphonellane

Siphonellinol, a triterpene, possessing the new carbocyclic 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 cyclization of one half of the molecule.
Polypodane

The circular dicroism spectra of C-8 and C-14 substituted 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 8psubstituent 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 compounds without an 8fi-oxygenated substituent was almost solvent independent. These conclusions were supported 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 3-0x0lupane-28-nitrile exists 40% in the boat form from comparison 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-oxotriterpenoids and from isomerization of 2a- and 2fl-substituted ketones.
NEW SKELETONS OF TRITERPENOIDS

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 lentiscus. 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 isolation of these bicyclic triterpenoids supports the postulation of van Tamelen and his co-workers [Sl], that the cyclization of squalene proceeds via a series of discrete conformationally rigid carbocationic intermediates.
Spirosupinane

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 structure of spirosupinanonediol, a new triterpenoid isolated from Euphorbia supina has been established by spectral and X-ray analyses as 7(8+9)abeo-9SD:C-friedo-B:A-neogammaceran-8-one-3S,7S-diol with a novel skeletal system for which the name spirosupinane (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

The sipholane skeleton (21) consists of a cis-octahydroazulene linked via an ethylene bridge to a trans-

Radermasinin, a novel cytotoxic triterpene lactone isolated from Radermachia sinica was shown to have

2202

S. B.

MAnAT er al.

23 24 Olcanonc

( I)

23

24

Serratone
30-&g

(6)

Urosonc

(2) 30

Lupone

(7)

. 22 Y2g 30

23 24

Toroxastonc (3)

23

24 Hopone (8)

23 Frrcdelone (4)

24 Fernone (9)

23

24 Gornmocerone (5)

26 29 Dammorone (IO)

structure 31 by spectral data and single-crystal X-ray analysis of its monohydrate. It possesses a yem-dimethylvinyl group at C-18 in addition to a spiro y-hydroxy-ylactone moiety at C-17 and its possible biogenetic pathway involving 21-hydroxy-l8z-olean-28-oic acid derivative as precursor has been suggested [S3].

Baccharane The structure of hosenkol-A. the first example of the natural baccharane (23) triterpenoid of the missing intermediate shionane (25) and lupane (7). has been determined [54] by spectroscopic methods as well as by X-ray crystallographic analysis. The isolation of hosenkol-A

Triterpenoids

2203

.
28 2e (30) (31) Lanortone (II) Apotlrucollone (b)

26 27

Cucurbitonc

(12)

Glutonc

(I71

_
2i) is Euphonc 21 (13) 23 24 Toroxeronc (I@)

Tirucollnc

(14) Moloborlcone 26 27

26 27 (19)

23 24 Protortonc (IS)

Onocerone

(20)

which has a unique Spiro-ring strongly supports postulated biogenesis of lupane and shionane baccharane.

the via

Rearranged lanostanes
Some new rearranged lanostanoids having carbon skeletons, such as 17.14-friedolanostane novel (35),

17,13-friedolanostane (36) and 8 (14+13R)abeo-17,13friedolanostane (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 dehydroxylation of OH-17 followed by successive l.tshifts of methyl group(s) and a ring bond.

S.

B. MAHATO

er al.

Slpholone

(21)

Polypodone (26)

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 aqueous 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 regarded as a pentanortriterpene. Two other new nortriterpenes. glycinoeclepins B (42) and C (43) possessing a similar ring system to that ofglycinoeclep~nA. 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 isolated from Pheffinus pomaceus [61] and their structures were determined by a combination of chemical and

Trtterpcnotds

2205

26 27

AcO-

Radtrmor~n~n

(31)

Rearranged

bnortanr

(36)

26 27

24

Sorghumot

(32)

Rearranged

Ianostone

(St)

l-4 :,
4-hgwmonol

(30)

Rcarraflgcd

fcrnanr

(33)

f - Ir~gcrmanal (39)
Rearranged Ianostane (34)

27

Y
HO
Rearranged Ianostanr (35)

(CH2)2CH=CM~(CH2)2CH-CM~CH~H(OHJCH-CM~2 Mr

spectral analyses. The new carbon skeleton of these two triterpenes was confirmed by X.ray crystallographtc ana. lysib of the dimethyl ester of Jareroic acid.

and monocychc carbon skeletons. have btcn isolated from rhizome5 of Iris yermanica [62]. The compounds are closely related to ambrcinc.

Carotenoid-like

triterpenes Swertane 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 analysis. 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.

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.

New

tkeleton

monocyc lit. and bit v( lit triterpenoidc a-irigermanal (38). ;-irigerma(40). possessing novel bicyclic

Three new triterpenoids. nal (39) and iridogermanal

2206

S. B. MAHATO er al.

H02C Glyctnocctcpin A (41) Joverolc acid (44)

Glyctnoccleptn

3 (42) Phellmc ocld (45)

Glyclnoecleptn

C (43)

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. Subsequently, four new pfatfane-type nortriterpenes were isolated from P. puherulenra [65] together with pfaffic acid and its fi-D-glucuronopyranosidc.

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 chemical modifications for a variety of purposes.

Skeletal

rearrangemenrs

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

There have been considerable activities during the years on the studies of skeletal rearrangements of triterpenoids which have made valuable contributions to our knowledge of triterpcnoid chemistry. A detailed discussion 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 introduced the Westphalen rearrangement for the transformation of lanostane to cucurbitane. 3/l-Acetoxy-9ahydroxy-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 rearrangement [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 influencing the course of dehydration under Westphalen conditions of 9a-hydroxylanostane derivatives were discussed. Unusual autooxidation and dehydrogenation

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=pMeC,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-

AcO

AcO

AcO

AcO
XI XII

S. B. MAHATO er al.

xv

I?

4
Cl+OH

o
0

--f0l-l

Me

CH2-CH2-CO

- CHMe2

-K
. H 0
XVII

HO

(0

XVI

Me2CH -CO- CHZ- CH2

7f

Me

-.

-_

OH

OO

.o:F

XVIII

XIX

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 1Ir, 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 cucurbitatins. An intramolecular carbonyl-mediated electrochemical oxidation was shown to occur during the anodic oxidation [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.

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 aglycone (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

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

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/uriica 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 backbone 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

(XxX111. R = AC).

Tritcrpcnoids

2209

AcO

AcO

&
Br /

XXIV

AcO

/ 0 @ ,
XXVII

2\
XXIX

XXVI

x XVIII

monoacetate (XXXIX, R=Ac), hydrolysis of which finally yielded isomultiflorenol. The dihydro derivative (XLIII) of the novel triterpenoid thysanolactone (XLIV) was synthesized [Sl] from the readily available pentacyclic triterpenoid, hydroxyhopanone (XLV). Some 29-norlanostane derivatives, e.g. 29-norlanostan24one and -23-one, 29-norlanost-9( 1l)-en-24-one, -23one and 3-one, 29-norlanost-7-en-3-one, and 29-norlanostan-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 conveniently 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

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 elaboration. 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 presence 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 reactions 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 intramolecular y-alkylation to give the cyclopropane derivative (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 differcnt sugars arc present in various body organs. the synthetic 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 Agzeolite or Hg(CN), in various solvents gave the mixture containing the 3-O-. 25O-monoand 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-.

Triterpenoids

2211

AcO

AcO

XLlll XLIV

R= CHMc2 RC<$
l-4

XLVI

XLVII

XLVIII

XLIX

Me6

LI

LII

3,2@di-0-/?-D-glucopyranosides. However, glycosidation by the Hellerich reaction was accompanied by a dehydration in the side chain which led to the corresponding 20dehydroxy 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 described by Dev et al. [913. The method was illustrated by conversion of cyclolaudanone (LX) into methyl 3-0x0cyclolaudan-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

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 degradation 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-dimethylcholestan-3-one gave the lactone (LXIX), which on methylation by MeLi gave hemiacetal (LXX). Oxidation of this hemiacetal by pyridinium dichromate or pyridinium chlorochromate yielded the secocholestanedione

2212

S.

B. MAHATO

er al

LXIl,R-H,

f?.Me

HOW2

e
\

-A

O-4
LXIV

_b,-#
-Y
*. \

-.
l-i

\
{fi

RO

;
0

LXlll

LXV

LXVI

LXVII

LXVlll

LXIX

LXX

(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 1la,l2a-epoxy 28+ 13glactone (LXXIV) and 12a-hydroxy 28+ 13/&lactone (LXXV). According to the authors the CO,H-28 group was first converted into C(O)O,H, which epoxidized the Adouble bond. H,O,-Se02 in Me,C-OH was found to be a good reagent for the preparation of I la,l2aoxidotriterpenoids with the oleanane and ursane skeletons [95]. Anodic oxidation as the key reaction converted olean12-ene sapogenols into olean- I 1-en-28.13/I-olide,

1la, 12z-epoxyoleanan-28,13/I-olide and 13/3,28_epoxyolean-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 derivatives gave expected 13/?,28-epoxyolean- 11-ene derivatives c971. Epimerization ofsome pentacyclic triterpene acid aglycones 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 arjungenin. The mechanism of this transformation involving

Tritcqxnoids

2213

L-XIoJx~co&2H@j
0
LXX1 LXXII , LXXIV

LXXX, LXXVII LXXVIII, ,R = R=H, R= OH R lR =H,R-OH

R=OH,

R=

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 evaluation 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 anticancer activity of some pentacyclic and tetracyclic triterpenoids was studied by Ling et a/. [99]. The anticancer effects were tested against human cancer cell lines ME180, u-87MG, SK-HEP-1, CAL&l, CAMA-1, SK-OV-3 and HEC-1-A. Among the pentacyclic triterpenoids, epimanidiol (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 required 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/?,22fidihydroxyolean-12-ene) was cytotoxic only against ME180 at IOO~gml~. This result suggested that the presence of a 16a-hydroxy group is important for the

appearance of cytotoxicity of 12-oleanenes. Glycyrrhetinic acid (3/?-hydroxy-1 I-oxo-olean-12cn-30-oic acid) and 1I-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-Dioxotrinortirucall-&enoic acid and ( k )-3fl,7-dihydroxy- lloxotrinortirucall-8-enoic acid were inactive. Several oleanane-type triterpenoids which were chemically derived 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 stimulation 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 ( erythrodiol), 18~-olean-l2tne-3~,23,28-triol, 18a-olean-12enc-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 antileukemit 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 significant cytotoxicity in the lymphocytic leukemia cells P388 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-hydroxyursolic acid demonstrated significant in cirro cytotoxicity 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. Glycyrrhizin 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 inhibition of glycyrrhetinic acid is the result of inhibition of transfer from G, to S phase. Olean-I 1.13( l8)-diene-3b,30diol and its derivatives were found [104] to inhibit tumour-promoting agents such as TPA. These compounds 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 inhibiting Yoshida sarcoma cells in vitro. An injection formulation containing 10 mg of plumeric acid and 5 mg of glucose was prepared. The anticancer activity of anwuweizonic acid, a new lanostane. triterpene, and manwuweizic acid, a new ring-A-srco-lanostane triterpene isolated from Schisandra propinqua [ 1061. was tested. Manwuweizic 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 derivative 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 ursanetype 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/%oleanl2-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-glucuronopyranosyl-(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-28oic 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 nortriterpene 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, netzahualcoyone was found to be most active antitumour agent.

Action

on metabolism

The mechanism of mineralocorticoid action of carbenoxolone ( I I -oxo-olean-I 2-en-30-oic acid 3/?-succinate) was studied by Armanini et al. [ 1143. In cirro and in cit:o studies showed that carbenoxolone has demonstrable affinity for rat renal mineralocorticoid receptors, intrinsic mineralocorticoid activity in the adrenalectomizcd 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 adrenalectomized rats. The influence of oral carbenoxolone on prostaglandin E2 release mto gastric juice was examined [ 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 glycyrrhetinic 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 atherosclerosis (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 IRdehydroglycyrrhetic acid orally (50 mg kg- day _ for six days) to rats with experimental gastric ulcers stimulated 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 anticholesteremics [ 1181. In I;irro experiments with rat liver homogenates indicated that both the compounds inhibited the formation of cholesterol by the liver. The inhibition 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 collagen levels were significantly decreased, whereas the serum /I-lipoprotein level was increased by administration of cucurbitacin B. The hepatic damages, including

Trircrpenoids fibrosis and cirrhosis, were also markedly reduced by this triterpene. The serum CAMP to cGMP ratio was increased 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. Ganoderic acid and its derivatives isolated from Ganoderma lucidurn were shown to be inhibitors of cholesterol biosynthesis [ 1203. These compounds were tested for their effect on cholesterol biosynthesis from 24,25-dihydrolanosterol by rat hepatic subcellular IOOOOysupernatant fraction. The lanosterol (4OpM) with 7-0~0 and 15ahydroxy groups potently inhibited the biosynthesis of cholesterol. In a similar study [ 121),27-nor-24-dihydrolanosterol was found to be markedly active in depressing cholesterol biosynthesis from lanosterol.

2215

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 derivatives of 18&olean- 12-ene-3~,30-dial, 18/j-olean-9( II), 12diene-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 nordihydroguaiaretic 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 administration 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 reaction. Glycyrrhetinic acid and deoxoglycyrrhetol, the parent compounds of the derivatives, showed no detectable 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. 1I-Oxooleanolic acid and 1I-oxohederagenin inhibited 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, 1l-keto-triterpenoids 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 1l-oxo-triterpenes tested inhibited 11.19-diketo-18,19-secoand corticoid-5fi-reductase ursolic acid was found to have the highest inhibitory potency. Gly~yrrhetinic acid inhibited carragenin-induced edema in the rat paw and inhibited leukocyte migration in the pleural space induced by dextran injections [126]. The acid did not prevent prostaglandin release by phag~ytosing leukocytes or slowing the contraction of isolated ileum strips induced by PGE*. The mechanism of the anti-inflammatory action of papyriogenins A and C. two triterpenoids isolated from Tenapanax papyri$erum was studied by Sugishita ef al. [ 1271. The cotton-pellet granuloma test in normal and adrenalectomized 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-inflammatory effects of papyriogenin A or C (10 and 50 mg kg _ ) against ~rotonin-indu~d paw edema. Actinomycin D (1 and 2 mgkg- ) or cycloheximide (6 mg kg- ), given twice during the latent period, completely 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 papyriogenin 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,~-dihydroxycinnamoyloxylup20(29)-en-28-oic acid was tested for its anti-inflammatory 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 permeability, as induced by intra peritoneal injection of acetic acid. The active principle thus isolated was characterized as cucurbitacin B. This is the first report that cucurbitacin B has a significant anti-inflammatory activity. Triptotriterpenic acid A, a new oleanane triterpene isolated from the roots of Trjpferyg~um wi~ford~jwas 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 guineapigs in a dose-related manner. In patch tests in human subjects, dipotassium glycyrrhizinate or disodium glycyrrhetinylsuccinate added to the lotion of a cold hairwaving 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-inflammatory, 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 experimental 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 Table 1. Tritcrpenoids

S. B. MAHATOet 01. isolated from the plant kingdom and other sources Structure Triterpenotd mp. [alo spectra: X-ray analysis reported 2 (Pinaccae) 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 Basic skeleton 3 11

Source 1 Abies /inna

Groups 4 3,23-0x0; 26COrH; (24E)A,.; 961-H 3 23-0x0; 9;1-H 26C0,H: A=*;

Refs 5 Cl451

II

[1451

II 11 35 36 35 36 37

3-0x0: A..; 17.23-epoxy: 26-+23-lactone; 98-H; 17% 23s 3-0x0: A.2; 26-23-lactonc; 17.23-epoxy; Y/?-H; 17s; 23R 26COrH; 26-CO,H;

[1451 r1451 [561 [561 [551 [561 1561

3a-OH; 23-0x0; A7.1.2.: 9,3H 3x-OH; 23-0x0; A.!z.z.: 98-H

A. mariesii

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

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

31

3.23-0~0; 26-CO>H; A7.1..>.: 9fi_H

1561

A. sibirica

Abtesolidoic analysis Abiesonic Tnterpene Triterpene Triterpenoid Triterpenoid Triferpenoid Triterpenoid Triterpenoid Triterpenoid

acid, X-ray actd. X-ray analysis acid. IR. NMR. acid. IR. NMR. MS MS

11 37 II II I1 I1 11 35 35 35

3.4~&co: 26-23-lactonc; A.irs1: 3_CO,H 3.4Sew 23-0~0; A.,~1(1.:.,.,~~,.r. 3.23-0x0; (24E)A,. 3.23-0~0; (24Z)A.r. 3,26CO,H:

[1461 r1471 [14*1 [14*1 [1491 r1491 A c15tJ [571 c571 c571

26-CO,H; 26-CO,H;

3-0x0; 26-23~lactone; (222) A.z.2.; 9jl-H 3-0x0; 26--23~lactone; (22z)A.>.. 3a-OMe; 3z-OMe; A~.... 26-23~lactone; 23-0x0;

26-COaMe; 3,26CO,Me;

3,4-Seco; 23-0x0; A.,~s,&s,,.,.s. 3.4~Seco; 3-CO,Me; 26-+23-lactonc; A.,,.6.8...

Abrotanella

forsterioides

(Compositac)
Abrus canroniensis

Seco-dammaradiene, H NMR. MS

IR.

IO 1 I

3* 4-Seco. * 3-OAc; A..z. 38,228,24.29-OH; 3&22fi.3O-OH; A A*

[1511 [1521 v521

(Lcguminosae)

Abrisapogenol B, 278 -280. +26.1. C NMR Abrisapogenol + 76.7 D. 29&291.

Triterpenoids Table I. (Continued) 1 2 Abrisapogenol E. 249-252. +67.7. MS Abrisapogenol F, 66-67, + 15.4, IR, CNMR Abrisapogenol G. 231-233. -5.3. H, C NMR, X-ray analysis
A. precarorius

2217

3 1 1 1

4 3&22/l.24.3O-OH; A* 3jl-OH; 22-0x0; A 38.228-OH; Aa

5 ~1521 ~1521 [I521

Abrusgenic acid, X-ray analysis Abruslactone A

trijoliatus

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 2 2 1 2a,3a-OH; 24-OAc; 28C0,H; A 2/I,3(9,23-OH; 28C0,H; 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; 3O-nor 3a-OH; 30-nor 28-CO,H; Az~o9; A

Cl531 Cl531 Cl541 [lSS, 1561 Cl561 Cl571

Acanthopanax

(Araliaceac)
Actinidia erianrha

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

Aesculus

hippocasranum

(Hippocastanaceac)
Aglaia roxburghiana

Hippocaesculin 254-256, + 25, IR. H, C NMR, MS Roxburghiadiol A Roxburghiadiol B Triterpenoid Triterpenoid

11 11 11 11 2 2
10 1

Cl581 Cl581 11591 Cl591 116tY WtJl Cl611 C1621

Agrimonia

pilosa (Rosaceae)

Triterpcnoid acid; Me ester, +32.2, IR. H, CNMR, MS Triterpenoid acid; Me ester, + 30.0. IR. H. C NMR, MS

Ailanthus malabarica (Simarubaceae) Akebia quinara

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

(Lardizabalaceae)

A12.2q19i;

C1621

1 1 15

38-OH; 28-CO,H; A; 29/3OCHO 3a,24-OH; 28-COsH;

A12.10(19); Bnor

C1621 Cl631 WI

Alisma

plantago-aquatica

(Alismataceae)

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

3.0~0; 1ljI,l6fi-OH; 23-OAc; 24.25-epoxy; AlJo 3-0x0; 1l&OH; 168.OMe; 23-OAc; 24,25qoxy; At 3-0x0; I lb-OH; 23-OAc; 13/?,17jI-.24.25diepoxy 3a-OH; 20,24-epoxy 3/I-OH; 2424-epoxy 3-0x0; 28-CHxOH

IS

cw

15
10

Cl651 Cl661 11661 Cl673

Alnasterfruticosus

a-Alnincanol, 202-203 b-Alnincanol, 228-229 Miricolone

IO 18

2218

S. B.

MAHATO

er al.

Table 1 Alnus japonica (Betulaoeae) 2

1. (Continued) 3 IO
10

4 3.4~Sew; (24E)A4z8~0~; 3C0,Me; 26-CO,H 3.4~Seco; (24E)As 3.26~CO,H .;

Seco-triterpene acid, + 61.2. UV 3IR , H * 13CNMR, MS Seco-triterpene acid, 1685169.5, +44.0. UV. IR 7 H * CNMR. MS Sew-triterpene C NMR. MS acid, IR. H,

[I681 11681

10 10 10 10 10

3.4~Seco; 20@),24(S)-OH; A*11s.s5; 3_CO,H 3,CSeco; Zo(S),ZS-OH; (23E)AzB~z; 3-CO,H 3.4~Seco; 2O(S),25,26-OH; (23E)A4s? 3-CO,H 3.4.Seco; 12/?.2O(S).ZS-OH: (23E)A41~3; 3-CO,H 3/I-OH; 20.24-epoxy 3.0~0; 20-OH Alt2s; A*

11681 [1681 [I681 [I681

[I691 L1691 11701 [I711

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 4. maximowiczii fi-Alnincanol Monogynol
A. pendula

7 IO 2

12-Deoxyalnustic acid, + 36.7. IR. H. C NMR. MS dicromnus (Labiatac) Zla-Hydroxyursolic acid; Me ester, 214 + 24. H. CNMR. MS Cuachalahc acid

3.4~Seco: ZO(StOH: 24-(=CH,): 3C0,H 3&21x-OH;

Amaracus

28-CO,H;

Amphyretygium
Amsonia

adsrrinyens

14 7 17 17 1 7 14 7 8 30 30 30 11 11

3a-OH;

26-CO 2H.* A.zz.2 A(iz9

~721 [I731 [I741 11751 I1761 [I771

grandij7ora

(Apocynaceae)
Andrachne cordijolia

Lupeol octadecanoate, + 22.98a. IR, H NMR. MS Triterpenoid, 265-268, H NMR. MS IR.

3/I-octadecanoyloxy. IfI-OH; AcO 3-0x0; A

(Euphorbiaceae)

Androsace

saxifbgijolia

(Primulaceae)
Anlidesma pentandrum

Trterpenoid. 25&254. IR, H NMR. MS Androsacenol, 262-264, + 23. IR . H . CNMR, MS Lupeolactone. X-ray analysis Aphananin, C NMR. Triterpenoid Triterpenoid, >305, IR. H, C NMR. MS Pouoside CNMR A; aglycone, IR, H. IR. H. IR. H. NMR. MS. IR. H,

38,16a-OH; 22/I-OAc; 3tKHO; 13fi.28-epoxy 24+3/&lactone; AzO A;

(Euphorbiaceae)
Aphanamixis polystachya

(Meliaceae)
Apocynum Aschersonia venerum

151-152. MS

3/I-OAc; 218.24.25-OH: 21.23(Skpoxy 3/I-arachidoyloxy; 3fi.l5%22-OH 2-0x0; 8,11,22a-OAc; (9E.13E)A4.9.3 2-0x0; 8, 222-OAc; (9E.13E)A4,.s 2-0x0; 11.22a-OAc; (9E.13E)A~~ 3fi-OH. 3x-OH; 26-22~lactone; 26-22.lactone;

[I783 [I791 I1801

A*o29

aleyrodis sp

Asteropus

19/I-OH: 11,19/Y-OH; 19/I-OH; As A*

[341 [341 [WI ll811 [I811

Pouoside B; aglycone. C NMR Pouosde C; aglycone, C NMR

Astraeus hygromerricus (Gasteromycetes)

Astrahygrol, 186187. + 18.0. IR 3 H , CNMR, HRMS 3-EpiastrahygroI, 193-194. + 101.0. IR. H. CNMR. HRMS Astrahygrone. 168-169. + 58 0. IR. H. C NMR. HRMS

II

3-0x0;

26-22~lactone;

A*

Cl811

Astragalus

glycyphyllos

Sapogcnin

I II

3/?,22/?,24-OH;

19-0x0;

[I821 Cl831

(Leguminosae)
A. taschkendicus

Cycloasgenin

Triterpenoids Table I. (Continued)

I Atroxima afieliana

2219

2 Atroxigenic acid Atroxigenic acid lactone Preatroxigenin; dimethyl ester

3 1 1 1
14 14 14 14 14 4 16 13114 13 1

4 2~,3/I,22/I-OH; 23,28-CO,H; Asi4; 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 3-0x0; 215-OH; A.24; 215,23kpox~ 3x-OH; A..; 21+23(-lactone 3-0x0; A***; 21+23<-lactone 3.23-0x0; 22C-OH; A.r 2-0x0; 3-OH; As; 29-CO,H 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

5
Cl841 Cl841 [If351 Cl863 Cl871

Aucoumea klaineana

(Burseraceae)

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
Austropleuckia populnea Azadirachta indica (Meliaceae)

CWI
Cl871 ClUl CW Cl891 119W P9~1

Triterpene acid, UV, IR, H, sC NMR, MS Azadirachtol Nimbocinone, 7678. + IO, H, i3C NMR, HRMS
Nimolinone

Bawingtonia speciosa (Barringtoniaceae)

Anhydrobartogenic acid; dimethyl ester, 276272,

[l92, 1933

UV. IR, H NMR, MS l9-Epibartogenic acid; dimethyl ester, 252-254. + 100. UV, IR, H NMR, MS Bartogenic acid
Betula exilis (Betulaceae) B. maximowicriana B. nana 1

2&3/I,19b-OH; 24,28_CO,H; A2 2~3/?,19z-OH; 24,2&CO,H; Al2 3%20(S)-OH; AZ3 3j?-tram-3.4-Dihydroxycinnamoyloxy; 2028-08 3a-malonyloxy; 12&25-OH; 20.24epoxy 3-0x0; 12/3,2O(Q25-OH; A23 3z,l2~,17a,2U(S),24(R)-OH; A2 3~12/?,17~2a(S),24(S)-OH; A2 3-0~0; As 3/$OH; A(i)

[I92 1931

1 10 7 10

Cl931 Cl941 11951 Cl961

3-Epiisofouquierol Triterpenoid, IR, H, CNMR 3-0-MalonylbetulaIolientriol oxide, 1688172, - l.o, IR, H, 3C NMR, FABMS Triterpenoid Triterpenoid Triterpenoid

B. pendula

10 10 10 33 33

Cl971 Cl971 Cl973 Cl981 Cl981

Boehmeria excelsa (Urticaceae)

Boehmerone, 176-178. + 12.3, IR 3 H . +ZNMR, MS Boehmerol,215-217, +47, IR, H, C NMR, MS, X-ray analysis

Boswellia cartmii (Burseraceae) B. freerana Botryococcus braunii var. showa

4(23bDihydroroburic

acid

2 10 Squalene 7 2

3,CSeco; 3C0,H;

A 2

Cl991 C2W C2W c2021 PO31

Triterpene, 183-185. + 25, IR, H NMR, MS Tetramethylsqualene, % NMR, HRMS +6, H,

3/l-OAc; 16/7,20(R)-OH;A2* 3,7,18,22-Me 3/.?.16/?,28-OH; A2tz9) 3g-OAc; A19(r9)

(Chlorophyceae) Calendulo ojicinalis (Compositae)

Calotropis procera (Axlepiadaceae)

Triterpene MS, of its triacetate Calotropenyl acetate, 198. +8.9, IR, H, sCNMR, MS

2220

S. B. MAHATO et al.

Table 1
Caltha palustris

I. (Continued) 3 4 38,23-OH; 3fi,18/GOH; 28-nor 3.16-0x0; 28 + 13-lactone 16-0x0; A*; 5

2 Palustrolide. (Theaceae) 310 (dec.). IR, MS

1 1 1

w41
~2051

(Ranunculaceae)
Camellia

japonica

Camelienodiol, 215-216.5. + 30. IR, H NMR Camelledionol. + 49, IR, H NMR, 232-233. MS

18/3-OH; A12; 28-nor

PO51

Maragenin, 228-228.5, + 41c, UV , IR > *H 3 CNMR, MS Canarium

album (Burseraceae)

1 2 1 4 4 I 2 41

3/?-OH;

16-0x0;

A.;

28-nor

PO51 w41 PW ~2071 ~2071 WI PO91 PlOl

Triterpenoid, 127-128. H, sC NMR, HRMS Triterpenoid, 29&292, H, 13C NMR, HRMS

+43, + 5 I,

3a,16/.?-OH; A2 3a,l6/3-OH; AL2

Cassine halae

Baknol, 139-140, UV, IR, H, sC NMR Balaenonol, 2OS-208, H, )C NMR UV, IR, ether, UV, IR,

3,21/3-OH; 2-0x0; IS-Me; As*s.7.1w).4; 24,26,29_nor 3,21/?-OH; 2,22-0x0; 1S-Me; A355.7.o(1.4; 24,26,29_nor 3/l-OMe; 38,23-OH; A 2(29; 19z_H 28-CO,H; A

Chionochloa

bromoides

19aH-Lupeol; methyl X-ray analysis Triterpenoid, 283-287, H NMR, MS

Cigarrilla

Mexicana

(Rubiaceae) Cimic@ga acerina (Ranunculaceae)

Cirrhopetalum elatum

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, H NMR. MS Triterpenoid, 233-234. H NMR, MS IR, IR,

11 20 20 10 10 10

(Orchidaceae)
Cissus quadrangularis

3/?-p-Coumaryloxy: 9/?,19-cyclo; 2q=CH,) 3a,ZI,%OH; A

c2111 P121 WI ~2131

(Vltaceae)

3/.?,21z-OH; A 3-0x0; 248-OAc; 20(%25epoxy 3-0x0; 24j5OH; Zo(S),ZS<poxy

Cistrus

libanotis

(Rutaceae)

Triterpenoid Triterpenoid

~2131 ~2141

Cieome brachycarpa

(Capparidaceae)
Cnidosculos elasticus

Deacetoxybrachycarpene, 185-186, +47, UV, IR, H, )C NMR, MS Lupeol; p-phenylpropionate, 211. IR, HNMR, MS, X-ray analysis Hirsudiol, 238. -25. H, 13CNMR. MS Jessie acid, 196202, UV 2IR 9 H 1 CNMR UV, IR,

3.4-Seco; 3-w&, 24-+20(R)dilactone; 25.26.27~nor 3/3-3-phenylpropionyloxy; A029

~151

(Euphorbiaceae)

Cocculus hirsutus (Menispermaceae)

Combretum elaeagnoides

1 11

2zx,3a-OH; A3cs

C2161

+ 55.5.

(Combretaceae)

la.3/?-OH; 24-(=CH,);

23-0x0; 28-COIH; 9/?,19_cyclo

Methyl jessate, 22&223, + 60.4. UV. IR, H. C NMR. MS Methyl jessate,

11

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; 3-0x0; 3a-OAc; 29-CO,H; A= A*

I a,I la-oxide

11

P-181

C. imberbe

Imberbic acid, 286288. + 70.0, H, C NMR. MS

dalzielii

1 10 10

~91 c.w WOI

Commiphora

(Burseraceae)

Isofouquierone, 13C NMR, MS

+ 34. IR, H, 155. MS

20.25-OH;

Cabraliadiol-3-acetate, + lo, IR, H NMR,

ZS-OH; 20.24-epoxy

Triterpenoids

2221

Table 1 C. incisa 2 Triterpenoid, Nortriterpenoid. H, %NMR,

Corchorus capsularis

1. (Continued) 3 4 la-OAc; 3j&OH; Az4; s/3,19-cycle lz,2a,3j?-OH; A8v2*; 29-nor 5

H NMR,

MS IR,

11 11 10 1 1 1

WI WI c=21

+38.2, MS

(Tiliaceae)

Capsugenin, 23&232, - 7.65. IR 3 H 3 13CNMR, MS Triterpene acid, 21 l-212. % NMR, MS Triterpene acid, 209. H, % NMR, MS Triterpene CNMR, Triterpene %NMR, Triterpcne %NMR, Triterpene MS acid, 223. H, MS acid, 205-207, MS H, H,

3j?,l2/3,25,30-OH; 2o(sx24vkpoxY 3a-OH; 3-0x0; 27-CO,H; 27_CO,H; 27-CO,H; 29-CHO, Al2 Al1 Al2

Cordia alliodora (Boraginaceae)

cu31 c2231 I?31 ~2231 ~2231 12231 ~2241

3.29-0x0; 3a-OH; AI

1 1 1 5 1 1 14 14 I

27-CO,H; d Al2

acid, 219, H, MS, X-ray analysis acid, H, 13C NMR,

3a, 29-OH;
~K-OH;

27-CO,H;

27,29_CO,H, 1 l&ZlC-OH 27-CO,H;

Coriandrum sativum (Umbelliferae) Corttulaca monacantha (Chenopodiaceae)

Coriandrinonediol, 285-290, + 38.3, UV, IR, MS Cornulacic Monacanthic MS acid, IR. NMR, MS acid, IR, NMR, IR,

1-0x0; 3p-OH;

612; 18&H

c2251 c2251 CW CW cwl I2281

c2293

3/I-OH; 28-CO,H; A12; 15s 27-cycle; 18&H 3-0x0; 38-OAc; A7*24; 21.23-epoxy A7s2*; 21.23-epoxy A2029

Cornus capitata

(Cornaceae)

Triterpenoid, 188, -24. H, 13C NMR, MS

Triterpenoid, 176. - 6. IR, H NMR, MS Triterpenoid Triterpenoid, Corynebacterium Cunila lythrifolia Dammar resin XG (Labiatae) IR, H NMR, MS

3/?-OAc; 23/24-CHO, 2/?-OH; 3a-OAc; 28+ 13-lactone 2-Me; 22-OH 2B,3/?,19a-OH; 3-0x0; 12u-OH; 28+ 138-lactone 2,16s20.25-OH;
A1.3.23

7 8 2 1

Triterpenoid, 184-186. +0.64, IR 3 H 3 %NMR, MS 2-Epitormentic acid; Me ester, + 16.3, IR, H NMR, MS Hydroxyoleanonic 304-306. +60.4. CNMR, MS lactone, IR, H.

28-CO,H;

A*

cw Cl391

Desfontainia

spinosa

(Loganiaceae)

1 I-Deoxocucurbitacin I, 212-213. UV, IR, H, CNMR. MS 2CHydroxytormentic H, %NMR, MS 7a-Hydroxytormentic H, C NMR, MS 7a.23-Dihydroxytormentic IR 3 H 9 CNMR, MS acid, IR, acid, IR, acid,

12

3,22-0x0;

~2311

2s3/3,19a,24-OH; A2 2u,3/?,7a,l9u-OH; AL2 2~,3/?,7a,l9a,23-OH; A2 11 3/l-OH; 29-nor

28-CO,H; 28-CO,H; 28-CO,H;

24(R)-Me;

c2321 c2321 c2321 12331

Douglas

fir sapwood

(24R)Cycloeucalanol; 107.5-108. +70.9, H NMR, MS

acetate, IR,

9/?,19cyclo;

Enkianthus
Enterolobium

cernuus (Ericaceae)
contorstisiliquum

6/l-Hydroxyursolic acid, 230-235. IR, H NMR. MS 21/?-E-Cinnamoyloxyoleanolic acid, 270. IR, H, CNMR. MS

2 1

3/?,6/?-OH; 28-CO,H; 3/?-OH; 28-CO,H;

cw 12351

(Leguminosae)

21/?-E-cinnamoyloxy; Al2

2222

S. B.

MAHATO

et al.

Table 1
Euonymus revolulus

I. (Continued)
3 IR, IR, IR, IR, IR, 7 4 4 4 1 4 4 4 11 11 18 I1 17 MS 2 11 21 3P_OH; AS,,.1 4 2z.3z-OH; 22-OH; 2-0x0; 3-0x0; 2%CO,H; Arotr9 5 12361 [237]

2 Triterpene acid, 298-300^. H, C NMR, MS Triterpene H NMR, Tritcrpene H NMR Triterpene H NMR, Trterpene H KMR. acid. MS acid, acid, MS acid, MS 258-260. 288-290). 288.-290. 3OC-302,

(Celastraceae)

3-0x0; 32-OH; 29-OH:

28-CO,H 28-CO,H 2%CO,H A

I2371 CW
[238] [239]

2z,3z-OH; 3fl,30-OAc 3&OH;

28-CO,H;

Euphorhia

antiquorum

(Euphorbiaceae)

Triterpenoid. 268- 269. + 23.5. IR. H NMR, MS Triterpznoid, 238-240. IR, H NMR Tritcrpenoid, 31 l-312. IR. H NMR + 27.5 62.8. IR. H.

30-OAc

[2391 L2391 L2401

24-(0Me),; A42J.4

3/I-OAc; 30-OH 3/GOH; 9~,19-cyclo; 24.25~epoxy 3p-OH; 98.19~cycle; 25,26,27-nor 3.4-Srco: 3C0,Mc; 3~OH;

E. hroteri

Triterpenoid, +28.5, C NMR, MS

Trterpenoid; acetate, 98-lOO-, + 50.3-. IR. H, C NMR, MS Triterpenoid, MS

E. caudicifolia

Pa c2403
~2411 ~2421 ~2421

H, CNMR,

3-Epicyclolaudenol. 140. - IO. IR, H NMR, MS Triterpenoid, 190- 191.5 , + 76.8. IR, H. C NMR,

24-Me; A; 9/J,19-cycle

E. maculara

3/I-OAc; A

Triterpenoid, 150-151.5. +362.6, I:V, IR. H NMR, MS E. niculia

E. supina

Triterpenoid, 85-, H NMR, MS

+23,

IR,

3/j-OH;

Az5; 9/?,19-cycle 8-0~0

WI
~521

Spirosupinanonediol, 248-250. -3.8.. IR, H. C NMR, MS, X-ray analysis &Amyrinformate, 254-256. + 15.2., IR, H, C NMR. MS Trterpenoid, 193 - 196.5. H NMR. MS I la,l2a-Oxidotaraxerol, 286.-288) - 38.9, IR, H. CNMR. MS Triterpenod, 242-244. IR . H . CNMR, MS Espnendiol A, 194-196, +90.7, IR, H, CNMR, X-ray analysis Espinendiol B, 1922193.5. - 17.1. IR, H, CNMR. Espinenoxide, 215-218, + 7.8., H, 13C NMR, MS, X-ray analysis Trisnorsoespnenoxide, 209213. -2.9,, H. C NMR, MS IR.

32,7x-OH;

1 9 18

3P-formyloxy:

A3s

P441 w41 L2441

3,&OH; A.(

3,&OH: A?

11%Zz-epoxy I

I I,
9 MS, 9 MS 9

3P.9r.l lz-OH; 3,4-Seco; 2%nor; 3.5~OH; A 3,4-Seco; 25-nor; 3,5/GOH; A4

A l&-H; 9/I-Me;

[245]

[2461

IOa-H; 9/i-Me;

[2461 [2461

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 3/&OH: 9/I. 19-cycle: A;

C2461

E. rirwalli

Cycloeuphordenol,

105-106.

11

C2471

Tritevoids

2223

Table 1 2

1. (Continued) 3 4 24/3-Me; 29-nor 11 18 1 1 3/?-OAc; 6p-OH; Aw111.12 3B-OH; 9/?,19cyclo; 248-Me &OH; A A; 5

+39, UV, IR, H, C NMR, MS Cyclotirucanenol, 13C NMR H,

cw CW
c2501

Euphorginol, 168- 170, +22.35, IR. H, C NMR, MS Fe&a link, (Umbelliferae) Triterpenoid, 223-226. UV 9IR 9 H 7 =CNMR, Triterpenoid, 224-229, H NMR, MS Gaderma applanatum (Polyporaceae) + 315. MS IR,

cw
12511

Ganoderenic acid F, + 93. UV, IR . H I 13CNMR, MS Ganoderenic acid G, UV, IR, H, C NMR, + 189, HRMS

11 11 11 11

3,7,11,15,23-0x0; (20E)AB.2q22

26-CO,H;

3,7,11,23-0x0; 15,sOH; 26-CO,H; (20E)A**2022 3/?-OH; 7,11,15,23-0x0; 26-CO& (20E)A8*2022 3,?,15wOH; 7,11,23-0x0; 26-CO,H; (20E)A.2q22 3,7,11-0x0; 15a-OH; A8.20s22; 21,23cpoxy 3,7,11,23-0x0; 2fX0,H; A8 26-CO,H;

WI
c2511

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 G. luclhm Ganoderic acid A, + 153.8. IR, H, C NMR, MS Ganoderic C NMR acid B, IR, H,

WI

11 11

c2511 c2511

12/?,15a&OH;

11 11 11

3,11,23-0x0; 78,15a-OH; 26_CO,H; Aa 3a.7jI-OH; 26-CO,H; 11,15,23-0x0; A 7j-OH;

c2521 c2521 C2531

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 l40-144=, 13CNMR, Lucidenic 208-211. C NMR acid E; Me ester, +86, UV, IR, H, MS acid F, Me ester, +195, UV. IR, H,

3,11,15,23-0x0; 2K0,H; A

11

3,11,15-0x0; 7/I-OH; 24-CO,H; AO; 25,26,27-nor 3,11,15-0x0; 7/?,12-08; 24-CO,H; A; 25,26,27-nor 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 3/3-OH; 12/?-OAc; 7,11,15-0x0; 24-CO,H; A*; 25,26,27-nor 3,7,11,15-0x0; 24-CO,H; A8; 25,26,27-nor 3/?,78,15a-OH; 26C0,H; A* 3,7,11,15,23-0x0; 11.23-0x0;

C2531

11

C2531

11 11

C2531 cw

11

WI

11

C2541

Ganoderic acid D; Me ester, 199-200. +98, UV, IR, H NMR, MS Ganoderic acid E, Me ester, 206-208, + 167, H, CNMR

11

C2541

11

ZCCO,H;

cw

2224

S. B. Table

MAHATO

et ol.

I. (Continued) 3 11 II 4 3.7.11.15.23-0x0: 26.CO,H: As IZfl-OAc; 5

2 Ganoderic acd F; Me ester. III. UV. H. C NMR. MS Ganoderic 155-156. C NMR, Ganoderic 134-135. C NMR. Ganoderic 279-281. CNMR acd H; Me ester. +55, UV. IR, H, MS acid G; Me ester. +64. UV. IR. H. MS acid I; Me ester, + 132. UV, IR, H.

WI
[2541 A* L2551

3fi-OH; 12jLOAc; 7. I I, 15.23-0x0; 26-CO,H; 3fi,7~,12j?-OH; 26-CO,H; As 11.15.23-0x0;

11

II

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; 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~zo2z 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 (24E)A7~Y~z

W51

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, UV, H NMR. MS Ganoderol B, 171-173. UV. H NMR. MS + 33. +61.

11

WI

11

WI

11 11 11 11 11 I1 11 11 11 II 11

C2561 As 12571 [2571 [2571 [2571 [Ial [14(Jl L1401 [14w []@I [2581

38.26-OH;

Ganodenc acid S. 168-169. UV. H NMR. MS Ganoderic H NMR. acid K. +48, UV. MS

3-0x0: 26-CO,H; (24~)A~.Wlhu 3/L7fi-OH; 12B-OAc; 11.15.23-0x0; 26-CO,H;A* 3&26,27-OH: A7..z4

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 8 H * 13CNMR. MS Ganoderic acid Mb. -4.0. IR . H . CNMR, MS UV.

11 II 11 11 11 II

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; (24E) A*. 26-CO,H:

[2591 [2591 [2601 c26w [2Wl C2@1

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

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 3 CNMR, MS

11

[2@1

Triterpenoids Table 1 2 Ganoderic acid Mf. +42, IR , H 3 CNMR, MS UV, 1. (Continued) 3 4 3a-OAc; 15a-OH; 26CO,H; (24E)A7*9*112* 3/?,24.25,26-OH A.9111 5

2225

c2w WI WI

Ganoderiol A, 232-234, + 20. UV 9IR . H 7 CNMR, MS 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 13C NMR, B9, UV. IR, H, MS 11

3-0x0; 15x,26,27-OH; AT.%11,.2. 3-0x0; 24(s). 25-OH; A7.90 )

CW

3-0x0;

24(5),25,26_OH;

A.9011

CW

11

3/?,15a-OH; 7,11,23-0x0; 26C0,H; A 7a,lSa-OH;3.11,23-0x0; 26CO,H; A* 3/?,7a,15a-OH; 26C0,H; A8 11,23-0x0;

C381

11

C381

11 11

C381 c391

Compound C5, 118.5-121.5, + 101. UV, IR, H, CNMR, MS Compound C6, 14&148, IR , H 3 CNMR, MS UV,

3.1 I.1 5.23-0x0; 78,12/?-OH; 26CO2 Me; Aa 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 3,7,11,15,23-0x0; 26CO,Me; Aa 20C-OH;

11 11 11

c391 C2631 C2633

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. IR, H NMR, MS, CD UV,

11

C2631

11 11

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 3/?,28-OH; 24CO,Me; 7,11,15-0x0; A; 25.26.27~nor

C2631 12631

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 H NMR, MS M, UV, IR,

11 11 11 11 11 11 11 11 11

C2631 C2631 C2631 C2631 C2631 c2641 P541 cw c2641

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; 24CO,Me; 7,11,15-0x0; A; 25,26,27-nor

3/?,7a,lSa-OH; 11-0~0; 24C0,Me; Aa; 25,26,27-nor 3-0x0; 3-0x0; 7x,26-OH; 26-OH; A.91 I;

Epoxyganoderiol A, +65, H, 13CNMR, MS, CD Epoxyganoderiol IR, H, CNMR,

A*; 24(s),2Ys)epoxy 2YSL2Ys)ePoxY 3&26-OH; 3-0x0; A*9; 26CHO; 24(s).2Ys)epoxY 7a-OH;

B, + 35, UV, MS, CD

Epoxyganoderiol C, +43, UV, IR 9 H 9 13CNMR 9MS * CD Ganoderal B, +94, UV, IR,

2226

S. B. MAHATO er (11. Table 1. (Continued) 3 MS Ja UV, H, 11 II II II 4 (24.k-)A8~ 3a.l %-OH; 26_CO H. AT.911I.24 2 7 38.1 %-OH; A7.%,.Z4 26-CO,H; 5

2 H NMR,

Ganodertnic acid lC NMR, MS

C2651 I2651 I2651 P651 WI 12661 W71 P71 W71 W71 C2571 CW

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 9IR 9 H * 13CNMR. MS Triterpene CNMR, acid, UV, H, MS

3a,22/1-OAc; 1Sa-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-.rc1).24

I1
II II 11 II

36.1 Sa-OAc; 26-CO,H; AT.% b.21 3sOH; 1Sz-OAc; 23-0x0; 26_CO,H; A7.%L?.* 3sOAc; 1Sa-OH; 23-0x0; 26_CO H. A7.%).2* 2 . 3a. 1Sa-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; AT.%).24 26-CO,H;

Triterpene acid. UV, H. C NMR, MS Triterpene acid, UV, H. C NMR, MS Triterpene acid, 198-199, H, 13C NMR, MS Triterpene acid lJV, H. C NMR, MS Ganodermic acid T-N, 145-146. UV, H, CNMR, MS Ganodermtc acd T-O, 16&162.. UV. H. 13CNMR, MS Ganodermic acid T-Q, CNMR, MS Ganoderiol 13C NMR, diacetate Ganoderiol C, HRMS UV. H, UV.

II II II

3/1-OH; 1Sa-OAc; 26C0,H; AT.911 1.24

11

3/?-OAc; 15a-OH; 26_C01H; A7.%l.24

W81

II I1

3-0x0; 15sOH; 26_CO,H. A.YlJ.24 3-0x0; AR 3.7-0~0; 7a-OEt; 24,25,26OH;

W81 W91

IR, H, of its 24, 26-

D, CNMR

11 11 II I1 II

24.25.26OH; 7-0x0;

As AR.24

C2691 W91 W91 P91

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 acd, 178-180. H, C NMR, MS Triterpene acid, UV. H, C NMR. MS UV,

3/?.26,27-OH; 3-0x0;

26,27-OH;

A.91 .*

3-0x0; 7z-OMe; 24.25,26-OH; A 3/?,24,25.26-OH; 7-0x0; A*

I391

II II 11 11 II

3-0x0; 15,26,27-OH; 7sOMe; A*.* 3.11-0x0; (24E)A. 15x-OH; 26-CO,H;

C2691 V91 12701 c2701 ~2701

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.

Triterpenoids

2227

Table 1 2 Triterpene acid, UV. H, C NMR, MS Triterpene acid, UV, H, C NMR, MS Triterpene CNMR. Triterpene CNMR, Gardenia jasminoides (Rubiaceae) Gentiana jlavo-maculata (Gentianaceae) Glycyrrhiza uralensis (Leguminosae) acid, UV, H, MS acid, UV, H, MS

1. (Continued) 3 11 11 11 11 11 4 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; A*; 9~,19-cyclo 3/?-Palmityloxy; 28-CO,H; 5

Gardenolic acid. 212-214. + 38.3. UV, IR. H, % NMR, MS Triterpenoid 24-Hydroxy Uralenolide, Glyuranolide glabrolide 302-303

28-OH; A*;

Cl411 ~2721 C2731 I2741

38,24-OH; 1 I-0x0; 30-+22/Llactone 3/j24_OH; 1

AlJ3f;

30+22/?-lactone 3/l-O@ 1 I-0x0; 27-CO,Me; Al; 29+22a-lactone 38. 24-OH; 28,29-CO,H; Al2

Guaiacum oficinale (Zygophyllaaae) Gynocardia odorata (Flacourtiaceae)

Triterpene acid, 290. +66.66, UV, IR, MS Odolactone, 304-305. 47.06 IR, H NMR, C NMR, MS Odollactone, 303-304, H NMR, MS IR,

1 4 4 4

C2751 C2761 C2761 C2751 c2773

3-0x0; 3a-OH; 3a-OAc;

26+ l2g-lactone 26-t 12b-lactone 26+ 12/l-lactone

Acetylodollactone, 302-303. - 19. IR, H NMR, MS Gyrinops walla (Thymelaeaceae) 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 l80-182, H NMR, acid; +50.8, MS Me IR, ester,

14

3-0x0;

24-(=CH,);

25-Me; A

Hedyolis

lawsoniae

(Rubiaceae)

3&23-OH;

28-CO,H;

C2781

3/J,24_OH; 28-CO,H;

A*

C2781

Triterpene acid; Me ester, 51. IR, H NMR, MS Heteropanax jiiagraus Hoya lacunosa (Asclepiadaceae) Triterpene acid acid; methyl MS + 37.4. + 26.7.

h,3fl,24-OH;

28-CO,H;

C2781

7 1 18 8 8 1

38,23-OH;

27,28-CO,H; A* A

A2o29)

C2791 Wl WOI WI WI

Dihydronyctanthic ester, MS Seco-triterpenoid,

3,4-Seco; 3-CO&e; 3,4-Seco; 3-CO,Me; 3/?-OH 3/?-OAc Z&38,24-OH;

Humata pectinata (Davalliaceae)

Triterpenoid, 236-238. IR, H NMR, MS Triterpenoid, 324-326. IR, H NMR, MS

Hyptis

capitata

(Labiatae)

Hyptatic acid A, 298-304, + 57, IR, H NMR, MS, X-ray analysis Hyptatic acid B, 225-228. +28, IR, HNMR, MS

2&CO,H;

Al2

WI

2 2

2~,3/?,19s24-OH; AL2 3a,l9a-OH;

28C0,H; A

cw L-21

H. mutabilis

Triterpene MS

acid

IR, HNMR,

28_CO,H;

2228

S. B.

MAHATO

et al.

Table

I. (Conrinued) 3 1 7 2 2 23 4 3/?-OAc; 28 -+ 13/l-lactone 3/l-OH; 27-CO,H; Azo29 Al2 A 5

2 Triterpenoid lactone, 292-294. + 18.8. IR. H. sC NMR, MS

C28-7 C2831 12841 L-41 [543

H. suaveolens flex rorunda (Aquifoliaceae)

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

3j?,l9a,24-OH; 38,19n-OH;

2%CO,H; 23,28-CO,H;

Impariens balsamina (Balsaminaceae) Inonotus obliquus

Hosenkol-A. 225-227. + 78.9. UV > IR . H . CNMR . MS . X-ray analysis Triterpenoid, 145-146. C NMR, MS Triterpenoid Triterpenoid. MS Triterpenoid, MS Triterpenoid. MS IR, C NMR. IR, C NMR, IR, H, 13CNMR, IR, H NMR, MS MS +36, MS UV, IR. + IO, IR. H,

3/?.17@,26,28-OH: 21,24wePOXY

11 ll I1 11 11 7 7 38 39

3/?-OH; 21-CHO;

As.*

C2851 PW I?871 ~2871 C-2881 I2893 US91 C6.21 C621

3~,22_OH; A.q(* .2* 3fl.21-OH; As. A8.z3 7-0x0: Asz4 16/l-OH; 16/8-OH;

3P.22,25-OH; 3g,22-OH;

Inuh

britannica (Compositae)

Triterpenoid, Triterpenoid,

3fLPalmityloxy; Aro,z% 3/LMyristyloxy; Ar0,29 _

Iris germmica (Iridaceae)

z-lrtgermanal, H, 13C NMR,

y-lrigermanal, 74-75. UV I IR . H 9 13CNMR X-ray analysis Iridogermanal, H, CNMR, I. missouriensis Missourin +41, MS

9MS ,
UV, IR, 48 8 IR, +22.8. MS 8 19

_&-OH; 6a-OAc; 30-CO,H; 21/l-OH; Azzfz9 A2229

CQI cwl c2901 ~2911

Missouriensin, 213-216. H, C NMR, MS Jaspis siellifera Triterpene I; Me ester, UV , IR 3 H . CNMR,

3fi-OH; 12-0x0; 28-CO,H; (13Z.l5E,17E,22E)

413.13.*7,2lw2.2*

Triterpene II; Me ester, - 154, UV 9IR 3 H 3 CNMR. MS Triterpene III, -32.7, H, 13C NMR, MS Triterpene IV, -66.7, H, %NMR, MS
Kadsura coccinea (Schisandraceae)

19

3fi-OAc; 12-0~0; (13Z,15&17E,22E) A&% 12eL22.21

28-CO,H;

~2911

UV, IR, UV, IR,

19 19

3&28-OAc; 22-OH; 12-0x0; (13Z,15E,17E)A~~7~0~2 38-OH; 12-0x0; (13Z,lSE,17E,22E) 3-0x0; 3-0x0; 2W0,H; 26C0,H;

~2911 c2911

A13.15.17~20~.21.21

Coccinic

acid

11 11 34 34 34

A9.s* (242)Ae.s

~2921 c591 c591 C581

K. heteroclita

Triterpene acid, 95-97. + 69.95. 13C NMR, MS Neokadsuranic acid A, -35.0. UV . H 1 13CNMR, MS

3-0x0; 26-COzH; (24Z)As I. 3118Ltd 3-0x0; 26C0,H; (24Z)A 8.13,18,.2. 3-0x0; I38-OH; (24Z)Asz4 26CO,H;

K. longipedunculata

Neokadsuranic H, 13C NMR. Neokadsuranic H, 13C NMR,

acid B, + 37.4, MS, CD acid C. +42.0, MS, CD

C581

2230

S. B. MAHATO el al. 1. (Continued) 3 + 62, I 1 7 23 24 25 10 14 26 20 20 20 20 19 MS 19 MS IR, A&14( (17~ 24~)Al*~s),7l20l.2*. 138-H (17~ 24~)A*s.l7ZO).2*. 13a-H 3/I-OAc; A; 30-nor 3-0x0; 9B,19-cycle; A24; As*; c3091 C3lOl C3lOl C3lOl C3lOl C3lOl [3lOl AT.14 A7.13 4 3/I-4-Hydroxycinnamoyloxy; 28-OH; Al2 3/?,30-OH; 38,30-OH; A12.21 AY.2. A3.21 A*&* AT.24 A2s9 20s 5 [3041 c3051 c3051 c3w c3w c3w c3w c3w [491 c3071 c3071 c3071 [3071 C3W C3081

Table 1 2 Triterpenoid, 287-289, UV, IR, H NMR, MS kwsonia iwrmis (Lythraceae) Hennadiol, Triterpenoid, Lemmaphyllwn microphyllum (Polypodiaceae) H NMR, MS

H NMR, MS

Triterpene. 103- 104. +46.6, H NMR, MS Triterpene, MS -39.8. H NMR, + 16.1.

Triterpene, 93-94. H NMR, MS

Triterpene, + 57.1. IR, H NMR, MS Triterpene, MS -24.8. H NMR, +27.4, MS +3.1,

a-Polypodatetraene, IR . H 3 %NMR,

Triterpene, 155-156. H, C NMR. MS Triterpene, CNMR, Triterpene, + 87.8. H, MS 83-85.

+ 15.6. H,

"CNMR,MS
Triterpene, 174 175. + 94.8, H, % NMR, MS 13/IH-Malabaricatriene, + 16.3. IR. H. -CNMR, 13aH-Malabaricatriene, - 23.3. IR, H NMR, Liartris microcephalo (Eopatotiaceae) Lindheimera texana (Compositae) Nortriterpenod. H NMR, MS Triterpenoid. MS

228-233, H,

%Z NMR, IR,

l6B.2YS)epox~ 3-0x0; 9/?,19cyclo; 16&23(R)-epoxy

Triterpenoid, 160-162.5. H, sC NMR, MS, CD

Triterpenoid, 214-217. IR, H, C NMR, MS, X-ray analysis Triterpenoid, Triterpenoid. H, % NMR H, %Z NMR

3-0x0; 9/3,19-cycle; 168,23-, 23.25-diepoxy; 23R 3/?-OH; 9jI,19cyclo; 168,23(S)-epoxy 38-OH; 9/?,19cyclo; A=; l6B>2YR)-epoxy 6;

Triterpenoid, 228-23 1. IR, 1 H, C NMR, MS, CD Triterpenoid, 185-187, C NMR, MS, CD Triterpenoid, H. CNMR Lufla amara (Cucurbitaceae) Lygodium Jexuosum (Polypodiaceae) Macaranga peltara (Euphorbiaoeae) Amarinin Triterpenoid Cyclopeltenyl acetate, H NMR, MS IR, 225-228 IR, H, (dec.) 11 11

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

[3lOl C3lOl

12
8 11

El431 C3lll

~3121

Triterpenoids

2231

Table 1 Madhuca butyracea (Sapotaceae) Manggera indica (Anacardiaceae) 2 Butyracic acid

1. (Continued) 3 1 +30.6, 10 4 2)9,38,23-OH; 3-0x0; 28-CO& Ar (24E)A** 5 C3I31 c3141

Triterpenoid, 116-118. IR, H NMR

20(S),26_OH;

Triterpenoid, 109-l 1 l, +64.9 IR, H NMR, MS Triterpenoid, 154-155. IR, H NMR, MS +51,

10 11 11 11 11 11 11 11 11 8 2 2

3-0x0; 2qSbOH; (24E)A 3&26-OH; (24E)A

260Ac;

c3141 c3141 A* 13141 c3141 c3141 c3151 c3151 c3151 c3151 c3151

9/?,19_cyclo; 9/?,19<ycl0; 9~,19cyclo 25-OH; 26C0,H; (24E)A

Triterpenoid, 19t- 192, + 18.8. IR, H NMR, MS Triterpcnoid, IR, H NMR 154-156. +O,

3/?,24(,27-OH; 3&24<,25-OH; 3/?,24{-OAc; 98,19-cycle 3x,22{-OH; 9/?,19-cycle;

Triterpenoid, 16% 163, +42.5, IR, H NMR, MS Triterpenoid, 218-220, UV 3IR 9 H 7 13CNMR, Triterpenoid, MS Triterpenoid, MS + 27.5. MS

IR, H, iJC NMR, IR, H, 13C NMR, +21.5, MS IR, MS

3j?,22C-OH; 26-CO,H; 9/?,19-cycle; (24E)A* 3/?,23(-OH; 9~,19cyclo; 26-CO,H; (24E)A*

Triterpenoid, 205-207, UV . IR 3 H 7 CNMR, Triterpenoid, Maprounea africano (Euphorbiaceae) 253-255.

3x,27-OH; 26CO,H; 9/?,19-cycle; (24E)A* 1/?,3/7,22-OH 3j3-OH; 29C0,H; A*

Maprounic acid 305-307. + 12.8. IR, MS Maprounic acid 3-p-hydroxybcnroate, 308-31 l, + 32.5. UV, IR, MS 7B-Hydroxymaprounic 3-ghydroxybenzoate, UV, IR, MS Triterpenoid, acid + 8.0.

ClW CW

3/?-O-(p-hydroxybenzoyl); 29C0,H; Ai* 38-O-(phydroxybenzoyl~ 7fi-OH; 29-CO,H; A 2q3p-(p-hydroxybenzoyl),; 29C0,H; A* 3-0x0; 28,29-OH 29-CO,H; Ai*

ClW

UV, IR, MS

CW C3161 c3171

Maytenus con&rtiJora (Celastraceae) M. diwrsifolio

Confertiflorol Maytenfolic acid, 281-282. +34.2. IR, H, i3CNMR, MS, X-ray analysis Maytenfoliol, 290-291. - 12.8. IR, H, 13C NMR, MS, X-ray analysis Maytensifolin A, 234-236, -29.5. IR. H, sCNMR, X-ray analysis Maytensifolin B, 280-282. -21.8 . IR . CNMR, MS MS,

3f?,22a-OH;

3-0x0;

28,30-OH

c317l

3-0x0;

I7-OOH;

28-nor

C3181

4 1 4 7

16-0X0 1~,3/?.1 la-OH; 3-0x0; A*

C3I91 13201

M. horrida M. octogona M. orbiculata Melia toosendan (Meliaceae)

Triterpenoid, Triterpenoid Triterpenoid

H NMR. MS

28-CO,Me A20t29)

~3211 ~3223
C3231

38.29-08;

Lipomelianol, 5455, H, 13C NMR, MS

- 3, IR,

14

3fi-OCO(CH,),Me; 21<-OH, 21,23-, 24,25diepoxy; A where n= 10,12,14,16 3a,7a-OH; 21-OAc; 2123-24.25diepoxy A;

21-0-Acetyltoosendantriol, )CNMR, X-ray analysis

16

C3241

2232

S. B. MAHATO et al. Table I. (Conrinued) 3 46 + 28. 5 4 31,32,33,34-OH; 38-OH; 3-0x0; A 98.19~cycle; A; 29-nor 29-nor 35-NH, 5 ~3251 13261 C3271 (I3281 C3291 [3301 c3301 c3311 [3311 [3321 [3321 27-nor A A A [3331 c3341 [3351

1
Methylosinus Monechma tricosporiwn debile (Acanthaceae)

2 Triterpenoid Monechmol, 292-294. IR, H NMR, MS Triterpenoid, Triterpenoid, MS

Musa paradisiaca

(Musaceae)

IR, H NMR, MS 135. + 72. IR.

11 11 II 11 11 11 II I1 II 1 1 2

3/I-OH; 24-Me; A.;

Muscari

comosum (Lihaceae)

Nortriterpcnoid. 194-195. +67.2, H, CNMR, MS Nortriterpenoid. C NMR, MS Nortriterpcnoid, C NMR. MS Nortriterpenoid, H NMR, MS 196-l 98. I84- 186. 234-236.

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; 17z,23(S)-epoxy; 15-0x0; A; 27-nor

H. H,

Nortriterpenoid, 195-197, -22 . H 1 CNMR. MS Nortriterpenoid. 18 I- 183. UV, IR > H 7 -CNMR, MS Nortriterpenoid. 221.-224. IR, H NMR. MS
Myrianthus arboreus

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.; 3/%6P-OH. 29-CO,H; 2&3/1,24-OH; 3/1,19x-OH; 28-CO,H; 24.28-CO,H;

UV,

(Cecropiaceae)

Myrianthinic actd; Me ester, 145 -147. IR, H NMR, MS Arboreic actd: Me ester, 239-230. IR, H NMR. MS Myriabortc 2%260, MS acid: dimethyl ester, IR. H, 13CNMR. -0.2,

Myrica

rubra (Myricaceae)

Triterpenoid. 225-227, IR 3 H 3 %INMR, MS Triterpcnoid, 213-215. IR, NMR, MS

18

3-0x0;

2X-CO,H;

[336]

Nardia

scalaris

+81,

6 14
14

3-0x0:

21x-OMe;

c3371 [3381 C3381 c3391

(Marchantiopsida)
Neochamaelea pulwrulenta

(Cneoraceae)

Protolimonoid I, 229. IR > H I CNMR, MS Protolimonoid -89. MS II,

66.3.

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

187-189.

Nepeta,

hindosrana

(Labiatae)

Nepetidone 300 (dec.), -28.13. UV, IR, H. r3C NMR, MS Nepedinol, 282. (dec.), - 18.67, UV, IR, H, 13CNMR, MS Triterpene 210-212. MS acid; Me ester, IR, H, CNMR,

1/7,3/I,lla,

30-OH;

A2029

II3391

2j,3a,

23-OH;

28-CO,H;

At*

c3401

Nerium oleander (Apocynaceae)

Kaneric acid. 122. + 16.66. UV . IR 7 H . 13CNMR. MS Ncriucoumaric Oleanderen, %NMR, acid

l/I,3/I-OH;

28-CO,H;

c3411 c3421 c3431

3fi-OH; 2x-cis-p-coumaryloxy; 28-CO,H; A A2 + 6.15. MS 3/1,27,28-OH; 3/?,5a-OH; A4,23,.te Az~2029) 24-nor;

H NM R,

Oleanderol, 206.-208. UV . IR 1 H . CNMR,

[3441 c3451

Kamerin, 280-28 1. + 14.28, UV, IR, H NMR, MS

28-CO,H;

Triterpcnoids Table 1. (Continued) 1 2 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 Neroilia purpwea (Orchidaceae) 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
Nothohzena

2233

4 3/LOH; 28-CO,H 3a-OH; 28-CO,H; A1*. 3B-pHydroxylphenoxy; 1lx-OMe; 12a-OH; 28-CO,H; AZ0

5 13451 c3461 13473

7
11 11 11 11

3.7-0x0; 28-OH; A2029) 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; A6*21;28-nor 3fi_OH; 16_Me; A1s.1(22); 28-nor 3!-OH; lCCH,OH; 28-nor A6*21;

P-473 C3481

C3481 C3481 C3481 WI c3491 c3501 c3511

11 8
1

candida

(Pteridaceae) Orthopterygium huancuy (Julianaceae) Orthosphenia mexicana (Celastraceae)

Triterpenoid, 234-236. IR, H, 13CNMR, MS Triterpenoid, 204-205, - 7. IR 7H , CNMR, MS 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

C3521

c3531 c3541 c3541 c3551 c3551 C3561 c3571

Pachysandra

terminalis,

(Buxaceae)

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

4 4 4 4 8 18 11 11

3/?-OH; 16-CH,OH; A16; 28-nor 3/J-OAc, 12/7,22-OH 3/&24-OH; Al4 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; 1Sa-OAc; 2226-epoxy; A7.9(11).2*; 22s; 26s

Parmelia Parsonslo (bowa==)

tinctorwn laevigata

Triterpenoid Triterpenoid, 320, IR, HRMS Fruticin A, 217-218, +75, IR, HNMR, MS Fruticin B, 235-236, +12.9, IR, H NMR, MS, X-ray analysis

(Parmeliaceae)

Partheniumfruticosum

(Compositate)

C3581 C3581

P. lozanianwn

Desoxyprefruticin B, IR, H NMR, MS Desoxyisofruticin B, IR, H NMR, MS

11 11 11

c3591 c3591 c3fw

Perenniporia

ochrokuca

(Polyporaceae)

Perenniporiol, 186187, + loo, UV, IR, H, I CNMR, MS

2234

S. 0.

MAHAT~

er al.

Table

1. (Continued)
3 + 138. MS + 174. II 4 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 5 [3W

2 Triterpenoid, 188-189. UV 9IR . H 1 CNMR, Triterpenoid, 208-209. UV . IR 7 H 9 CNMR X-ray analysis Triterpenoid, 208-210. UV 3IR , H 1 13CNMR,

II

c3m1

. MS 3
+ 117. MS 11

38.1 Sa-OAc; 26-OH; 22,26-epoxy; A.9fJ~24; 22s;26S 3fi-OH; 2GOMe; A; 22x26s 22,26epoxy;

c36(Y C3Wl C3@1 C3611

Triterpenoid. I70- 171 .I, + 68. IR , H . -CNMR, MS Triterpenold, 187- 188. + 43. IR 3 H I +ZNMR, MS 12/&Acetoxyperenniporiol, 217-218. -2.6. UV. IR, H, C NMR, MS Triterpenoid. 197-200,. IR , H 3 CNMR, MS Periandra d&is (Leguminosae) Triterpenoid, 290-296. + 123.68, IR, H NMR. + 102, 11 I MS I 1 29

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

C3611 C3621 [3621 C3631 WI

Triterpenold, 283-292, + 1.52. IR, H NMR, MS Triterpenoid. 260-263. + 183.36. IR, MS Pfajia panicuiata (Amaranthaceae) P. puluerulenta Pfaffic acid, 285-286. + 109.2. IR, H, % NMR, MS, X-ray analysis Nortriterpenoid Nortriterpenoid Nortrrterpenoid Nortriterpenoid Phase&s vulgaris, (Leguminosae) Glycinoeclepin A, H, C NMR, MS, X-ray analysis Glycinoeclepin B, H, C NMR, FDMS Glycinoeclepin C, H, C NMR, FDMS Phellinus pomaceus Javeroic acid; dimethyl ester, 125-126. +lOl, IR, HNMR, MS, X-ray analysis Phellinic acid, 218-220. IR, H NMR, HRMS Phellodendron chinense (Rutaceae) Niloticin, 147, -62, C NMR, MS UV,

3-0x0; 25-CHO; 29-CO,H; A 3-0x0; 25-OH; 30-CO,H; 3@-OH; 28-CO,H; A A

29 29 29 29 41 42 43 44

3/LOH; 3-0x0; 3,lI-0x0; 3.11-0x0; A2 -

I I-0x0; 28-CO,H;

28-CO,H; Al2 AL2 28-CO,H;

C651 C651 C651 [653 WI c371 c371 C611

28-CO,H; 72-OH;

45 13/14 13114 13/14 11 11

_
3-0x0; 23&OH; 24(,25epoxy; A 3-0x0; 23(-OAc A 2%. 25cpoxy; A

C611 c3641 c3641 c3641 C3651 C3651

IR, H. -75.

Niloticin acetate, 157. IR, H NMR. HRMS Dihydroniloticin, IR , H . CNMR, Pholidota chinensis Cyclopholidonol Cyclopholidone

174, -47. MS

3/?,23<-OH: 24(,25_epoxy; 38-OH; 9/3,19-cycle; A; 29-nor 3-0x0; 9/?,19-cycle; A; 29-nor

24, 24Me; 24,24-Me;

2236

S. B. MAHATO et al. Table 1. (Conrmued) 3 MS VI, UV, MS IR. 12 1 3 MS 3 6 6 6 11 3/?,23,27-OH; 28+20,3-lactone Al4 A* c3771 13781 [3781 4
epoxy;

2 C NMR,

5 As. c3751

Picfeltarraegenin H, % NMR,
Pittosporum breuicalyx

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

Pittobrevigenin 27-Desoxyphillyrigenin, 294-297, IR, H NMR, 23-Hydroxyphillyrigenin, 330-332. + 19,. IR, MS

CW
13771

(Pittosporaceae)
P. phillyraeoides

Pinus monf icola (Pinaceae)

Triterpenoid, MS Triterpenoid, MS Triterpenoid, MS

IR, H. C NMR, IR, H, CNMR, IR,H, CNMR,

3@-OMe; 2Ia,30-OH; 3/I-OMe; 21a.29-OH; 3/I-OMe;

21@,30-OH; Al4

WI
c3791

Pisolithus

rinctorius

(Sclerodennataceae)

Pisolactone, 279-280, + 60, IR, H, CNMR, MS, X-ray analysis Triterpenoid, Triterpenoid, IR. H NMR IR, H NMR

3/I-OH; A; 24-CO-O-22

11 11 11 11 11

3,!7,235-OH; 22<-OAc; 24-(=CH,); A* 3&23<-OH; 22C OAc; 24-(=CHMe); A* 3-0x0; A; 24-C0-O-22 24-(=CH); 25-OH; As

C361 C361 C3801 C3801 C3801

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. H NMR, MS Psracia lentiscus (Anacardiaceae)
PIectranthus rugosus (Labiatae)

3/l,22(S)-OH; 32,22(R)-OAc;

A*=

IR,

11 26 2 2 2 1

3x,25-OH; 38,8z-OH;

22 (R)-OAc; A= A13.7.2

C3801 c5w

Triterpenoid, CNMR

H NMR,

Plectranthoic acid, 296. + 42, IR, H NMR, MS Acetylplectranthoic acid, + 58. IR, H NMR, MS Plectranthadiol, H NMR, MS 258.

3a-OH; 19s 3x-OAc; 19s 3a,29-OH.

29-CO,H; 29-COH;

A; A;

18a-H; 182-H;

C38Il C38Il C38Il

220. + 26 IR,

3A. 9 18a-H; 19s

28-CO,H; A

Polygala

chomaebuxus

Triterpenoid Triterp-ene, MS - 14.4. H NMR, + 27.4. MS

38,23,27,29-OH; A% 17b.2.;
20R

C3821 [3831 c491

(Polygalaceae)
Polypodium jauriei

10 26 11

(Polypodiaceae)

a-Polypodatetraene, IR 9 H . CNMR,
P. .formosanum

(24R)Cyclolaudenyl acetate 127-128. + 53.5. IR, H NMR, MS (24R)Cyclomargenyl acetate 144-145. 50.5. IR, HNMR, MS (24R)Cyclolaudenol. 123-124. + 36.5, IR, H NMR, MS (24R)-Cyclomargenol,

3/3-OAc; 24(R)-Me; As 3/I-OAc; A=s 24(R)-Et;

9/?,19-cyclo;

C3841

11

9/?,19cyclo;

[3841

11 11

3/I-OH; 24 (R)-Me; 9/?, 19cyclo; Al5 3/?-OH; 24(R)-Et; 9~.19cyclo;

C3841 C3841

Triterpenoids Table 1. (Continued) 1 2 Triterpenoid, 2-264. IR * H , sCNMR. MS

S. nicolsoniana

2239

3 + 69.
7 1 1 1 18

4 l/I,1 la&OH; 3-0~0

5 c4101 c4111 A* c4111 ~4121 [4131

Triterpene acid, > 300. IR. H NMR, MS Triterpene acid, > 300. IR, H NMR, MS

3a, 24-OH; 28-CO,H; A 301.24OH; 28, 3OC0,H; 2a3B.l la-OH; A &3a-OH; 28-CO,H; A14; 12a.27~cycle 2a,3r-OH; 28-CO,H; 12z,27cyclo; 24-nor; A423.4 3B-OAc; lla-OH; A. 38,25-OH; Azo** 3/7,25-OH; Ax 2a,3p-OH; 28-CO,H; Al4 3rI?.16/?-OH; As 3/I.l6/.7-OAc; As 3-0x0; 168-OH; As 3-0x0; 16a-OH; As

S. pinnata S. przewalskii

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

18

c4131

Santolina oblongi$Aia

(Compositae)

Triterpenoid, 136137, +48.8, IR , H . sCNMR, MS Triterpenoid, 161-162. + 58.6, IR 9H , %NMR, MS 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 3H 3sCNMR, MS Triterpenoid, 230-232. + 6.35. IR ?H * +ZNMR, MS Triterpenoid; acetate, 208-210. +31.5, IR, H, %NMR, MS Triterpenoid; acetate, 210-212. +37, IR, H NMR, MS

10 10 10 18 1 1 1 1

c4141 14141 c4141 c4151 C4161 C4161 C4161 C4161

Sapium sebjr-

(Euphorbiaceae) Schaefferia cunejrolia (Celastraceae)

Scheflera octophylla

(Araliaceae)
Schisandra propinqua

Triterpene acid, 213-214. -2.0 IR 3 H 3 CNMR.

MS

301.1 la-OH; 23,28-COzH; AZOW% 3-0x0; 26CO,H; Air.

c417l

Anwuweixonic acid Manwuweizic acid

11 11 11

CIW ClW C4181

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; 4a,lOj?,l9~-OH; A A*

Schizandra species

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

Schizandra grandijlora

11 11 11

c4191 ~4201 ~4211

(Schixandraceae) Scilla scilloides (Liliaceae)

11

~4211

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

~4221 c46.471

21

PWm 3117-O

2240

S. B. MAHATO et al. Table 1. (Continued)

Sipholenone A, 187-188, -29, IR, H, CNMR, MS Sipholenone B, + SC, IR. H, 13C NMR, MS Sipholenone C, + 13C NMR, MS Sipholenol 13CNMR, Sipholenol 13C NMR, Sipholenol HNMR Sipholenol CNMR.

21 21 21

40x0;

lOfl,19,!?-OH; A

t46 471 t471 t471 t471 t471

40x0; 10/3,19/?-OH; 152,l &-epoxy 4.16-0x0; A%%% 10/?,19/?-OH;

1. IR,
IR, IR. H. H,

B. -37, HRMS C, -28-, HRMS

21 21 21 21 22 10

&3 3 10-s 19B-OH; A 4a,lO/3,19/&OH; (13E,Z)A13 42.10/3,19~-OH; Al4 4z,lO/LI6~,19~-OH; 4a,lO~,16~-OH: 16-0x0; A*

D, - 3 1_.IR, E, IR, H, HRMS

t471 t471 [4Rl ~1421

Siphonellinol, 109-I 11. - 52. IR . H > CNMR, HRMS Skimmia japonica (Rutaceae) Skimmiarepin A, 164.S-165.5-, -22.7. CNMR. MS IR, H,

A.*

3a-Isovaleryloxy; 7z,21{-OH; 21,23-, 24.25-diepoxy; 30,13acycle 3a-Decan-2,4,6-trienoyloxy: 7x,21(-OH; 21,23-.24,25diepoxy; 30,132~cycio _

Skimmiarepin B, 1688169, -39.8. UV, IR, H, CNMR

Sorghum bicolor

10

~1421

(Gramineae)

Sorghumol, 277-282. H NMR. MS 3_Epimesembryanthemoidigenic acid, H NMR, 3-0-Acetyl-3-cpmesembryanthemoidigenic acid. + 106.7. IR, H, C NMR. MS 3-O-Acetylmesembryanthemoidigenic acid 3-0-Acetylserratagenic acid, > 290. H, C NMR. MS 3-0-Acetyl-3-epi-serratagenic MS acid, H. CNMR, MS

32

t4231 28-CO,H; 29-OH; A A t4241 [424]

Stauntonia

hexaphylla

3z,29-OH; 3z-OAc:

28-CO,H:

3fi-OAc; 29-OH;

2X-C&H: Al2 A

L4241 t4241 t4241 t4251

3fi-OAc; 28.29~CO,H; 32-OAc; 19 2X,29-COH;

Stellet ta species

Triterpenod. 258.-260. + 87, UV, H. CNMR. MS, X-ray analysis Triterpenoid, 200 202 , + 28.2. UV . IR . H > CNMR. MS Triterpenoid, 178-180. UV . IR , H . %NMR, + 33.3. MS

3.12-0x0: 26-22~lactone; AJ.%W,.ZZ.L4; 8x_Me(30,

Stirophyllum

riparium

2 2 2 28

(Bignoniaceae)

38-OH; 24rrans-fcrulyloxy; 28-CO,H; A* 3/I-OH; 24-cis-ferulyloxy: 28-CO,H; Al2 3/J,l9-OH; 28-CO,H: 3-0x0: A 24-rrans-ferulyloxy: A

t4261 t4261 L4261 t631

Trterpenoid, 195-197. + 1.58. UV, IR, H, 13CNMR, MS

Swertia chirata

(Gentianaceae)
Terminalia alata

Swertanone. 270-272. -98.12. IR, H, CNMR, MS, X-ray analysis 3-Acetylmaslinic 192 195. ~32. acid, IR, H NMR

2%~OH; 3/I-OAc: 28-C&H. 2a,3j,23,24-OH: A2 3jI,25,30-OH;

2O(R),24(R)-epoxy

t4271 t4281 [429]

(Combretaczae)
T. bellerica

Belleric acid > 300. + 77. IR, H. 13C NMR, MS (Rhamnaceae) Trevoagenin A, 297-300. -49, IR, H NMR, MS, X-ray analysis Trevoagenm B. 243-246. - 31 II,

I
10

28-COH: 16-0x0;

Treooa trinercis

10

3/?.25,30-OH;

16-0x0:

t4291

2242

S. B. MAHATO er al. 1. (Continued) 3 IR. H, UV, II II I I 46 4 3-0x0; 23/3-OMe; 98.19~cycle; 16/3,23-. 24,2S-diepoxy 3-0~0; A.; 22.25epoxy 23,28XO,H; 5 [444]

Table I
2

Triterpenoid, 21 l-212. lJCNMR, MS Wjzrhia mollis (Compositae) Triterpenoid, IR, H NMR, Zanhic Zanhic %ymomono mobilis acid acid-a,,-lactone 168.5-171, HRMS

c4W

Zanha golunyensis

28.3/?.16z-OH; A2

C4461 C4461
c4471

2~.3~,16+OH: 23-CO,H; 28+ 13/I-lactone 32-0x0; 33,34,35-OH

Triterpenoid

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 aglycone, glycyrrhetinic acid (5 mg kg- , intravenous) induced interferon (IFN) activity in the blood serum ofmice [137]. Glycyrrhizin was found to be more effective than glycyrrhetinic acid. The antitussive and expectorant activities 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 antitussive effect of this compound was slightly less than that of codeine at a dosage of 3 mg kg- . Intraperitoneal injection 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. Glycyrrhetinic acid choline did not suppress the histamine- or acetylcholine-induced contraction of isolated tracheal smooth muscle of guinea-pigs but suppressed the acetylcholine-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 triterpenoids was investigated by Poehland et al. [139]. Nine triterpenoids isolated from dammar resin showed antiviral 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 continuously 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 antimicrobial activity [SS, 561 against Gram-positive bacteria and actinomycetes. The results suggested that not

only the carboxylic group, but also the hydrophobic moiety, played an important role in revealing the inhibitory activity. The inhibitory effects of 10 lanostane triterpenes (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 Filczewski 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 hypertension 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 concentration during the whole period (four weeks) of treatment remained unchanged. Although the principal aldosterone-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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78. Nishizawa, 79. 80.

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