Phytochemistry, Vol. 29, No. 3, pp. 877-879, 1990. 0031-9422/90 $3.00 +O.

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Printed in Great Britain. 0 1990 Pergamon Press plc

SESQUITERPENES AND FLAVONOIDS FROM TESSARIA SPECIES

E. GUERREIRO, M. J. PESTCHANKER, L. DEL VITTO* and 0. S. GIORDANO

Departamento de Quimica OrgBnica, Universidad National de San Luis, 5700-San Luis, Argentina; *Herbario, Universidad
National de San Luis, 5700-San Luis, Argentina

(Received 17 May 1989)

Key Word Index--Tessaria ambigua; T. integrijoh; T.fastigiata; Compositae; sesquiterpenes; flavonoids.

Abstract-The investigation of aerial parts of Tessaria ambigua afforded two known flavonoids. The aerial parts of T.
integrifilia gave two known flavonoids and the aerial parts of T.fastigiata afforded three new and three previously
reported eudesname derivatives.

INTRODUCTION penes reported by Bohlmann from samples of Ecuador

[4] nor cauthemone derivatives isolated from samples of
The segregation between the Tessaria and Pluchea genus
Costa Rica [9]. The only products isolated were the
(Pluchinae, Inuleae, Asteraceae) have been attempted
flavonoids casticine and artemisine.
several times. Thus, Robinson and Cuatrecasas [l] con-
In the case of T. ambi&u, two samples, one coming
sidered Tessaria integrifolia as the only species belonging
from Entre Rios and another from Catamarca prqvince,
to this genus, concluding that all South American species
were studied. From the former, cc-amyrine and the flavon-
belong to the Pluchea genus. Later, Espinar [2] in his re-
oids penduletin, and 3,6,7-O-trimethylquercetagetin were
examination of the Tessaria genus, described Tessaria
obtained, but only artemisine was isolated from the later.
dodoneaefolia Tessaria absinthioides and T. ambigua (the
Six eudesmane derivatives (3-8) were isolated and
last one has been considered by Cabrera [3] as T.
characterized from T.fastigiata. The sesquiterpenes were
integr@lia var. polyandra) and assigned them to the
isolated by conventional chromatographic methods from
Tessnria genus. In view of the different criteria and
the chloroform extract. They were in order of elution
conclusions of the taxonomists, it was clearly interesting
from silica gel: 3a-angeloyloxy-4a-acetoxy-eudesm-&one
to see if the chemical data would contribute to this
(3), 3a-epoxyangeloyloxy-4a-acetoxy-eudesm-8-one (4),
classification. In this paper we described the study of the
9-0x0-4,1 l( 13)-eudesmadien-12-oic-acid (5), 9P-hydroxy-
different Argentinian species, T. ambigua, T. integrfolia
4,l l( 13)-eudesmadien-12-oic-acid (6), 3a-(2’-hydroxy-3’-
and T. fastigiata, as well as the re-examination of the
species already studied T. dodoneaefolia [&6] and T.
absinthioides, the last one in view of the different analyti-
cal results of Chilean [7] and Argentinian samples [8].

DISCUSSION AND RESULTS

In the first examination of T. absinthioides [S] samples

coming from the province of Mendoza (Argentine) an
eremophilane, tessaric acid, was isolated. In a later invest-
igation of the samples, 3-desoxytessaric acid was also
found. This compound had already been isolated, to-
gether with the alcohol acetate derived from it, and the
eudesname, carissone from a Chilean sample [4]. In our
recent examination of samples from San Luis province 3 R = Ang 5 R = O(l21
(Argentine) we isolated tessaric acid and for the first time 4 R = Epang 6 R = BOH,H
three flavonoids identified, as casticine, artemisine and 6~ R = 80Ac,H[l2]
chrysosplenetine.
In our first analysis of T. dodoneaefolia from Mendoza OP?
province we isolated one eremophilane, tenedodiol, and
the flavonoids sakuranetin, eriodictyol, 7-O-methyl erio-
dictyol, 4’,7-0-dimethylnaringenin, dihydroquercetin-3-
acetate, luteolin, 3-0-methylquercetin and 3,6-O-dimeth-
ylquercetagetin. In a second study the isomeric mono-
terpenes 1 and 2 were isolated beside the above
products. 7 R’ = 2. Hydroxy-3a -WetOXy .2- MeBu, 8
A sample of T. integr$olia from Entre Rios province R’ = Me
was examined. In this study we did not find the triter- 78 R’ = Epang, R’ = H 1141

877
878 E. GIJERREIRO et al

Table I. 13CNMR data of compounds 4-6,6a and 7 (90 MHz, methylbutyrate residue [b 1.29 (3H, d, 5=6 Hz), 1.30 (3H,
CDCI, TMS as int. standard) s), 1.95 (3H, s) and 5.03 (1 H, (1. J= 6 Hz)]. The mass
spectral fragmentation pattern and “C NMR data also
4 5 6 6a 7 supported this structure. It seemed possible that the C-8
hydroxyl was methylated during the extraction pro-
1 32.9 34.7 27.5 31.2 33.4 cedure.
2 23.1 27. I 27.0 23.7 23.2 When this paper was being prepared the results of the
3 73.5 32.0 31.8 31.3 74.2 phytochemical study of Plucheu.filstigiuta were published
4 82.8 144.3 144.7 144.6 82.5 by X. A. Dominguez [ 161. The different products isolated
5 46.5 125.2 124.5 124.7 50.4 were reported without mention of spectral or physical
6 23.0 31.5 31.4 31.2 22.1 data. In our study, we found only one of the reported
7 55.5 39.5 39.5 38.4 158.4 products. The proton signals of compounds .%8 were
8 209.8 36.0 38.6 38.3 105.5 assigned by COSY experiments. The ‘H shifts were then
9 59.1 216.12 78.2 x0. I 53.1 used in a two-dimensional heteronuclear ‘H-‘“C correla-
10 38.4 47.0 39.3 39.4 35.3 tion experiment.
11 25.X 133.5 132.9 132.6 124.4 A number of compounds have been isolated from
12 19.2 125.2 124.6 124.8 173.5 Plucheu species, the most characteristic are eudesmane
13 20.6 172.4 171.9 170.8 8.5 derivatives, cuauthemone and their derivatives, lactones
14 17.8 22.1 17.2 18.3 19.2 and 1 l( 13)-eudesmen-12-oic-acids. In addition to the
15 18.2 18.9 18.9 18.9 18.2 eudesmane, triterpenes and highly oxygenated flavonoids
OAc 168.1 172.1 169.0 were obtained. The comparison of the results from the
22.1 21.2 22.2 two genus show clearly that they are very closely related
OCOR 169.3 169.5 and that it is impossible it make any segregation employ-
59.8 75.6 ing the results obtained from chemical investigation.
59.4 74.5
1x.7 21.2
13.8 13.1 EXPERIMENTAL
169.6
22.3 ‘H NMR: 360 MHz. CDCI,, TMS as int. standard; ‘-‘CNMR:
OMe 50.4 90 MHz, CDCI,, TMS as standard. MS: 70 eV, direct inlet. CC:
silica gel. TLC: silica gel, C,H,-dioxane_HOAc (45:5: 1,
90:25:4 and 90:25:6).
Plunt ~~lurinl. Voucher specimens w’ere deposited in the
acetoxy-2’-methylbutyryloxy)-4a-acetoxy-8~-methoxy- Herbario de la Universidad National de San Luis (UNSL),
7(11)-eudesmen-12,8-oIide (7), and 4-hydroxy-11(13)- Te,ssaricrfu.sti!/iutn collected in El Cadillal (Tucum2in) [Del Vitto
eudesmen-12-oic-acid (ilicic acid) (8). 2179); 7: umhiyun. collected in Parani(Entre Rios)(IJNSL 5) and
The spectroscopic data of 3 and those of the major a second sample collected in Las Pirquitas (Catamarca) (UNSL
compound 4 were different only in the nature of the acyl 35); T. inteqr(/o/iu collected in Paran;i (Entre Rios) (UNSL 6): T.
residue at C-3. Comparison of the data with those of the ahsinthioidrs, collected in El Volclin (San Luis) (Petenattl 136)
compound previously isolated from P/u&a showed that and 7’. rlorlo,trcrrli,lrtr collected in El Challao (MendoTa) (UNSL
3 and 4 were saturated derivatives of 3r-angeloxy-4a- 48).
acetoxycuauthemone isolated from Pluchea suat’eolens Extractioncodisolution.The aerial parts of ~e.s.strrra,~u.\ri~iatcr,
[lo] and 3x-epoxyangeloxy-4-acetoxycurthemone iso- Griaeb (3 kg) were air-dried, finely ground and extracted at room
lated from P. orloratu [l 11,respectively. Effectively the ‘H temp. with MeOH (3 x 48 hr). The crude extract obtained by
and ‘“CNMR spectra confirmed the presence of one evapn under red. pres. was dissolved in McOH containing H,O
isopropyl group C60.91 (3H, d, 5=7 Hz), 0.98 (3H, d, J (10 and 30%) and partitioned between n-hexane and CHCI,,
= 7 Hz)] and [S 19.2, 20.6 (two secondary methyl)]. respectively. The CHCI, extract was adsorbed on silica gel
The ketoacid 5 and the hydroxyacid 8 were identified packed in C,H, and eluted with C,H,-EtOAc mixtures of
by comparison of their spectral properties with reported increasing polarity.
data [12, 131. The structure of hydroxyacid 6 was elucid- Fraction 4 (C,H,) provided a gummy residue which by
ated from spectroscopic data. The ‘HNMR spectrum successive chromatography over silica gel gave 1 I mg of 3.
was identical with that of the acetate isolated from Fractions 5 -9 (C,H,--EtOAc, 44: 1) provided a crude residue of
Artemisia tournefortiana [12], except for the absence of 4, which was rechromatographed affording 2.47 g. Fractions
the acetate absorption at 62.06 and the expected shift (A6 10~ 11 (C,H,-EtOAc. 19: 1) contained the products 4, and 5,
=1.24) of the H-9 C63.50 (lH, dd, 5=8.3, 7.3 Hz), 4.74 which were separated by extraction with 5% NaHCO, from
(1 H, dd, J=8.3, 6.8 Hz)]. In fact, acetylation of 6 furni- Et,0 soln. Fractions 11-13 (C,H,-EtOAc. 19: 1) contained
shed a monoacetyl derivative 6a, with identical [aID MS crude 5 which was purified by treatment with 5”10. NaHCO, in
and ‘H and 13C NMR spectra to those of the compound the usual way and chromatography over silica gel, yielding
from Artemisia tuornefortianu [12]. Compound 5 was 850 mg. Fractions 16-20 (C,H,-EtOAc, 9: I) provided a solid
obtained almost quantitatively when the hydroxyacid 6 residue which by crystallization from Ccl, gave 75 mg of 6.
was oxidized with Jones reagent in the usual way. Fractions 22-24 (C,H,-EtOAc. 17: 3) afforded a gummy resi-
Lactone 7 exhibited a ‘HNMR spectrum similar to due which was rechromatographed over silica gel to give crude 7.
that of 7a from P/u&a roseu [14] except for the signals as a solid. Crystallization of 7 from Et20-EtOAc afforded pure
due to the methoxy group instead of the hydroxyl group material. Fractions 27.-32 (C,H,--EtOAc. 3: 1) provided a
at C-8 C63.15 (3H, s)] and the signals due to the ester side solid residue which wasextracted with NaHCO, and crystallized
chain at C-3, characteristic of a 2-hydroxy-3-acetoxy-2- from EtOH--HZ0 affording 1.25 g of R.
 Sesquiterpenes and flavonoids from Tessaria 879

3a-Angeloyloxy-4a-acetoxyeudesm-g-one (3). Gum; IR 1.90 (3H, d, J = 1.1 Hz, H-13), 1.95 (3H, s, OAc), 1.98 (3H, s, OAc),
v$;cm-I: 1715 (C=O), 1725 (C=CCO,H), 1750 (HOAC) MS 3.15(3H,s,OMe),5.03(1H,q,J=6HgH-3’),5.85(1H,t,J=2.5,
m/z (rel. int.): 378 [Ml+ (> l), 318 [M-HOAc]+ (4), 235 [318 H-3), [alo -2.01” (CHCI,; c 12.6).
-RCO]+(9),219[318-RCO,]+(15),218[318-RCO,]+(ll), Tessaria ambigua from Entre Rios (2.4 kg) and from Cata-
176 (5), 175 (lo), 147 (3), 135 (6), 119 (8). 116 (12), 43 (100); marca (1.8 Kg), T. integrifolia from Entre Rios (2.3 kg), T.
‘H NMR (360 MHz, CDCI,): 60.88 (3H, s, H-14), 0.90 (3H, d, J absinthioides from San Luis (2.5 kg), and T. dodoneaefolia from
=7 Hz, H-12), 0.98 (3H, d, 3=7 Hz, H-13), 1.50 (3H, s, H-15), Mendoza (3.6 kg), were extracted as described above for T.
1.87(3H,s, H-4’), 1.92(3H,s,OAc), 5.70(1H, t,J=2,5Hz,H-3), fastigiata. Known compounds were identified by comparison
6.05 (1 H, qq, J = 1.5, 7 Hz, H-3’). with authentic materials (mp, IR, UV, ‘H and ‘%NMR).
3a-Epoxyangeloyloxy-4a-acetoxyeudesm-S-one (4). Gum; IR
vtz: cm-‘: 1720 (C=O), 1750 (OAc, CO,R); MS m/z (rel. int.): Acknowledgements-The authors thanks Prof. J. Kavka and Dr
394 CM]’ (> l), 334 [M-HOAc]+ (3), 291 [334-43]+ (l), 235 F. H. Guidugli, LEA [UNSL), for the mass spectra. The work
[334-RCO]+ (7), 219 [334-RCO,]+ (14), 218 [334 was supported by a grant from CONICET.
-RCO,H]+(12),176(11),175(5),163(4),161(4),147(5),135(7),
121 (6), 119 (12), 116 (12), 106 (8), 99 (3), 97 (6), 95 (lo), 43 (loo),
REFERENCES
‘H NMR (360 MHz, CDCl,): 60.90 (3H, s, H-14), 0.91 (3H, d, J
=7 Hz, H-12), 0.98 (3H, d, J=7 Hz, H-13), 1.34 (3H, d, J 1. Robinson, H. and Cuatrecasas, J. (1973) Phytologia 27, 277.
=5.5 Hz, H-5’), 1.55 (3H, s, H-15), 1.59 (3H, s, H-4’), 2.00 (3H, s, 2. Ariza Espinar, L. (1979) Kurtziana 12, 13, 47.
OAc), 3.08 (lH, q, J=5.5 Hz, H-3’), 5.88 (lH, t, 5=2.5 Hz, H-3); 3. Cabrera, A. L. (1939) Lilloa 4, 181.
[a& 204.3” (CHCl,; c 2.13). 4. Bohlmann, F., Zdero, C. and Silva, M. (1977) Phytochemistry
9fi-Hydroxy-4,l l( 13)-eudesmadien-12-oic-acid (6). MP 16, 1302.
131-132” IRvkt: cm-‘: 3500-2500, 1690, 1620 (-C=CCO,H); 5. Giordano, 0. S., Guerreiro, E., Romo, J. and JimBnez, M.
MS m/z (rel. int.): 250 [M]’ (46), 232 [M - H,O] + (90), 217 [232 (1975) Reo. Latinoam. Quim. 6, 131.
-Me]+ (38), 206 [H-C,H,O]+ (38), 199 [217-H,O]+, 191 6. Guerreiro, E., Kavka, J. and Giordano, 0. S. (1973) An. Asoc.
[206-Me]+, 163 [191-CO]+, 133 (24); 119 (64), 107 (30), 105 Quim. Argen. 61, 161.
(57), 93 (84), 91 (64), 79 (47), 77 (48), 43 (100); ‘H NMR (36O.MHz, 7. Kavka, J., Guerreiro, E. and Giordano, 0. S. (1977) An. de
CDCI,): 6 1.05 (3H, s, H-14), 1.60 (3H, s, H-15), 2.39 (lH, dddd, J Quim. (Madrid) 73, 305.
=12, 12,3,3Hz,H-7),3.50(1H,dd,J=8.3,7.3 Hz,H-9),5.69(1H, 8. Guerreiro, E., Kavka, J. and Giordano, 0. S. (1979) An. Asoc.
s, H-13’), 6.32 (lH, s, H-13); [alo 70.1” (CHCI,; c 127). Acetyl- Quim. Argen. 67, 112.
ation (Ac,O-pyridine at room temp.) afforded 6a, identical with 9. Jakupovic, J., Misra, L. N., Chau Thi, T. V., Bohlmann, F.
the natural acetate [12]. and Castro, V. (1985) Phytochemistry 24, 3053.
Oxidation with Jones reagent gave the corresponding ketone, 10. Bohlmann, F., Ziesche, J., King, R. M. and Robinson, H.
identical with the isolated product. (1980) Phytochemistry 19, 969.
9-0x0-4,1 1(13)-eudesmedien-12-oic-acid (5). Identification was 11. Nakanishi, K., Crouch, R., Miura, I., Dominguez, X., Zamu-
made by comparison of [a]o value, IR and ‘H NMR spectra with dio, A. and Villareal, R. (1974) J. Am. Chem. Sot. 96, 609.
those previously reported. 12. Rustaiyan, A., Bamonieri, A., Raffatrad, M., Jakupovic, J.
3a-(2’-hydroxy-3’-acetoxy-2’-methylbutyry~oxy)-4a-~cetoxy- and Bohlmann, F. (1987) Phytochemistry 26, 2307.
Ij?-methoxy-7(1 l)-eudesmen-12,8-elide (7). Mp 210-212”; IR 13. Herz, W., Miroaki, C. and Tether, L. R. (1966) J. Org. Chem.
v:E cm-‘: 1770, 1650 (y-lactone), 1740 (OAc, CO,R); MS m/z 31, 1632.
(rel. int.): 496 [M]’ (18), 409 [M-87]’ (lo), 350 [409-OAc]+ 14. Dominguez, X. A., France, R., Cano, G., Villareal, R.,
(24), 322 [350-CO]’ (2.5). 306 [350-44]+ (5),279 [322-431’ Maringanti, B. and Bohlmann, F. (1981) Phytochemistry 20,
(20),263[350-87]+(21),232[263-31]+(100),217[232-153+ 2297.
[47), 201 (25); ‘H NMR (360 MHz, CDCI,): 6 1.17 (3H, s, H-14), 15. Dominguez, X. A;, Sanchez, H., Vazques, G. and Grenz, M.
1.29 (3H, d, J=6 Hz, H-5’), 1.30 (3H, s, H-4’), 1.58 (3H, i, H-15), (1988) Rev. Latinoam. Quim. 19, 91.