Biochemical Systematics and Ecology 27 (1999) 309 — 311

Two new quercetagetin O-glucosides from

¹agetes mandonii
Felice Senatore*, Mario D’Agostino, Irene Dini
Dipartimento di Chimica delle Sostanze Naturali, Universita% degli Studi di Napoli **Federico II++,
via D. Montesano 49, 80131 Napoli, Italy

Received 3 June 1998; accepted 3 August 1998

Keywords: ¹agetes mandonii, Asteraceae; Flavonol glycosides; Mono and di O-methylquercetagetin 6-O-
glucosides; H and C NMR

1. Subject and source

¹agetes mandonii Sch. Bip. (Asteraceae, tribe Heliantheae) is a herbaceous plant

widespread in the Peruvian Sierra, locally known as ‘‘chick chimpa’’, ‘‘chincho’’ and
‘‘huacatay’’ and it is used in folk medicine as a digestive, an antispasmodic, in the
treatment of respiratory diseases, for gastrointestinal diseases and for its antidiarrhoic
properties (Roersch and Van Der Hoogte, 1988).

2. Present study

¹agetes mandonii was collected in March 1997, at the flowering stage, in the
Sacsayhuman National Park, Cusco Department, Peru (3800 m above the sea level).
Plant material was identified by Dr. Vincenzo De Feo, Facoltà di Farmacia, Univer-
sità degli Studi di Salerno, Italy. A voucher specimen (000132) is deposited in the
Herbarium of Pharmacy Faculty, University of Salerno.

3. Previous work

Isolation of quercetin-3-(3,6-diacetylgalactoside) and quercetin-3-(2,3,4-tri-

acetylgalactoside) from a methanol extract of ¹agetes elliptica (D’Agostino et al., 1992),

* Corresponding author.

0305-1978/99/$ — See front matter  1999 Elsevier Science Ltd. All rights reserved.
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310 F. Senatore et al./Biochemical Systematics and Ecology 27 (1999) 309—311

and quercetagetin-6-O-b-D-glucopyranoside from methanol extract of aerial-parts of

¹agetes mandonii Sch.Bip (D’Agostino et al., 1997).
The air-dried aerial parts (1.5 kg) of plant were sequentially extracted with light
petroleum ether, CHCl , MeOH at room temperature. An aliquot (8 g) of the crude

alcoholic extract (78 g) was chromatographed in 2 g lots on a Sephadex LH-20 column
eluting with MeOH. Fractions of 20 ml were collected and combined for TLC (SiO )

similarity in n-BuOH—HOAc—H O (12 : 3 : 5) and CHCl —CH OH—H O (70 : 30 : 3) in
   
five main fractions: I (895 mg), II (1430 mg), III (1725 mg), IV (587 mg) and V (740 mg).
Fraction IV was further fractionated by HPLC on a C l-Bondapack column by

using MeOH—H O 1 : 1 as eluent, at a flow of 2.0 ml min\ to give two new flavonols:

7-O-methylquercetagetin 6-O-b-D-glucopyranoside (1) (32 mg, R 7 min) and 7,3-di-

O-methylquercetagetin 6-O-b-D-glucopyranoside (2) (19 mg, R 10.4 min). The struc-

tural determination of the compounds was performed by comparing H and
C NMR, negative FAB MS and UV data with those reported in literature (Mabry
et al., 1970; Agrawal, 1984; Aquino et al., 1987; Breitmeier and Voelter, 1989 and
D’Agostino et al. 1997).
Data for 1 were as follows: 1H NMR (CD OD at 500 MHz): d 7.68 (1H, d, J"2 Hz,

H-2), 7.56 (1H, dd, J"2 and 8.5 Hz, H-6), 6.85 (1H, d, J"8.5 Hz, H-5), 6.71 (1H,
s, H-8), 5.1 (1H, d, J"7, 5 Hz, anomeric proton of b-D-glucopyranose), 3.91 (3H, s,
-OMe); 13C NMR: d 149.0 (C-2), 137.3 (C-3), 177.4 (C-4), 153.0 (C-5), 133.2 (C-6), 157.5
(C-7), 95.5 (C-8), 153.0 (C-9), 106.7 (C-10), 124.0 (C-1), 116.4 (C-2), 146.1 (C-3), 149.0
(C-4), 116.4 (C-5), 122.1 (C-6), 61.7 (-OMe) for the aglycon moiety and d 102.1 (C-1),
74.9 (C-2), 78.5 (C-3), 71.4 (C-4), 78.0 (C-5) and 62.7 (C-6) for the sugar moiety; UV
k+-&: 257, 269 sh, 367, 377sh; # AlCl 275, 457; # AlCl # HCl 259, 368, 418 sh;
  
# NaOAc 259, 351 sh, 394; # NaOAc # H BO 260, 376 sh, 387; # NaOMe 275,
 
436; FAB MS: m/z 493 [M-H]\, 331 [(M-H)-162]\.
Data for 2 were as follows: 1H NMR: d 7.73 (1H, dd, J"2 and 8.5 Hz, H-6), 7.72
(1H, d, J"2 Hz, H-2), 6.99 (1H, d, J"8.5 Hz, H-5), 6.84 (1H, s, H-8) 5.1 (1H, d,
J"7,5 Hz, anomeric proton of b-D-glucopyranose), 3.94 (3H, s, -OMe), 3.91(3H, s,
-OMe); 13C NMR: d 148.4 (C-2), 137.7 (C-3), 177.6 (C-4), 150.9 (C-5), 133.3 (C-6), 157.7
(C-7), 95.5 (C-8), 153.0 (C-9), 106.7 (C-10), 122.2 (C-1), 112.4 (C-2), 150.8 (C-3), 147.3
(C-4), 116.1 (C-5), 125.1 (C-6), 61.7 (-OMe) and 56.4 (-OMe) for the aglycon moiety
and d 102.1 (C-1), 74.8 (C-2), 78.9 (C-3), 71.3 (C-4), 78.4 (C-5) and 62.8 (C-6) for the
sugar moiety; UV k+-&: 256, 268 sh, 366, 379 sh; # AlCl 269, 385 sh, 425; # AlCl
  
# HCl 264, 295 sh, 374, 417 sh; # NaOAc 260, 369, 385 sh; # NaOAc # H BO
 
259, 369, 385 sh; # NaOMe 272, 357 sh, 435; FAB MS: m/z 597 [M-H]\, 345
[(M-H)-162]\.

4. Chemotaxonomic significance

The previous and present findings show the presence of quercetagetin, quer-
cetagetin 7-O-arabinosylgalactoside and quercetagetin 7-O-glucoside in ¹. minuta
(Tereschuk et al., 1997), of quercetagetin 7-O-glucoside in ¹. biflora and ¹. perezi
(De Israilev et al., 1991) and quercetagetin 6-O-glucopyranoside in ¹. mandonii
 F. Senatore et al./Biochemical Systematics and Ecology 27 (1999) 309—311 311

(D’Agostino et al., 1997) and indicate that quercetagetin and its derivatives are
important chemical markers in this genus.

Acknowledgements

Many thanks are due to Dr. V. De Feo, Facoltà di Farmacia, Università degli Studi
di Salerno, Italy, for the collection and identification of the plant material. This work
was partially (60%) supported by a grant of M.U.R.S.T.

References

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