Exudate Flavonoids in Several Asteroideae and Cichorioideae (Asteraceae)* Eckhard Wollenweber, Marion Dörr, Hannelore Fritz 3 and Karin M
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Exudate Flavonoids in Several Asteroideae and Cichorioideae (Asteraceae)* Eckhard Wollenweber, Marion Dörr, Hannelore Fritz 3 and Karin M. Valant-Vetscherab a Institut für Botanik der Technischen Hochschule, Schnittspahnstraße 3, D-64287 Darmstadt, Germany b Institut für Botanik der Universität Wien. Rennweg 14, A-1030 Wien, Österreich Z. Naturforsch. 52c, 137-143 (1997); received October 21/November 27, 1996 Asteraceae, Exudate Flavonoids, Polymethoxyflavones and -flavonols, Flavanones, Phloracetophenones Introduction tanical Garden Darmstadt; coll. K. Mann, August 1990. In the course of continuing studies on the occur Artemisia diffusa: Iran, coll. A. Rustayian, 1992. rence and distribution of exudate flavonoids on higher plants (Wollenweber, 1990; 1996), many Asteriscus sericeus: Botanical Garden, Darm stadt; coll. H. Groh, September, 1991. Asteraceae have been found to produce and accu Helichrysum aureum: Katberg pass, Seymor Dis mulate flavonoid aglycones externally on leaves, stems, and inflorescences. The Asteroideae in par trict, Republic of Ciskei, coll. by E. H. Graven, 13.03.91 . ticular are a rich source of flavonoid aglycones Helichrysum bracteatum: Botanical Garden which accumulate externally on the plant surfaces (Wollenweber and Valant-Vetschera, 1996). The Darmstadt (seeds from Australia; J. G. West 5142); species dealt with in the present paper belong to coll. E. Wollenweber, June 1989. eight different tribes, some of them placed in the Hieracium amplexicaule: Metnitztal, Nord- subfamily Cichorioideae (according to Bremer, Kärnten, Austria; coll. 23.08.1989 (Leute & Kniely, 1994). 8951/3). Inula brittanica: Iran, coll. A. Rustaiyan, June 1993. Material and Methods Inula ensifolia: Quarry near Lindabrunn, Nie Aerial parts including inflorescences were col derösterreich, Austria; coll. K. M. Valant-Vetsch- lected either in the field or in Botanical Gardens era, 16.09.95. and air-dried. The collection data are as follows. Inula germanica : Seeben, near Halle/Saale, Achillea eriophora: Iran, coll. A. Rustaiyan, Germany; coll. K. M. Valant-Vetschera, 16.09.95 July 1993. Inula germanica: Mettenheim, near Worms, Achillea millefolium ssp. lanulosa. 3 miles North Germany; coll. Th. Andreef, 20.09.96. of Mindenmines, Barton Co., Minnesota, coll. Inula helenium: Botanical Garden Darmstadt; G. & K. Yatskievych 20/05/88 (G. Yatskievych 88- coll. Th. Andreef, 25.08.96. 33, K. Yatskievych). Inula salicina : Botanical Garden, Vienna; coll. Arctotis venusta: Botanical Garden, Vienna; K. M. Valant-Vetschera, August ‘96. coll. K. M. Valant-Vetschera, September 1989; Bo Oncosiphon grandiflorum : Botanical Garden, Darmstadt (seeds from Vienna, ST 181); coll. M. Dörr, August 1996. Pulicaria dysenterica: Bessunger Forsthaus, near * Part II in the Series “ Exudate Flavonoids in Miscella neous Asteraceae” . Darmstadt; coll. E. Wollenweber, August 1987. Reprint requests to E. Wollenweber. Senecio viscosus: Darmstadt, growing as a gar Telefax: # 06151/166878. den weed; coll. E. Wollenweber, July 1992. 0939-5075/97/0300-0137 $ 06.00 © 1997 Verlag der Zeitschrift für Naturforschung. All rights reserved. D Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. 138 E. Wollenweber et al. ■ Exudate Flavonoids in Asteraceae, II Tanacetum balsamita : Botanical Garden, V i were kept to a minimum since this seems prema enna; coll. K. M. Valant-Vetschera, October 1993. ture at this stage. For more detailed information Tragopogon pratensis : Darmstadt, weed among on this subject, see Wollenweber and Valant- railway lines at freight depot; coll. K. D. June;. Au Vetschera (1996). gust 1995. Flavones Xanthium strumarium: Botanical Garden, R1 = R2 = H: A pigen in Darmstadt; coll. K. Polin, September 1991. R 1 = OH, R2 = H: Scutellarein Vouchers are kept at the Herbaria of the Botan Rl = H, R2 = OH: L u te o lin ischer Garten der TH Darmstadt, Institut für Bo Rl = R2 = OH: 6-OH-Luteolin tanik der Universität Wien (W U ), Department of Botany at Shahid Beheshty University in Teheran, Rl = R2 = r3 = H; Galangin Missouri Botanical Garden (M O ), and in the R1 = R2 = H, R3 = OH: Kaempferol Kärntner Landesherbar (K L ) at Klagenfurt. R l = R3 = OH, R2 = H: 6-OH-Kae Austria. OH 0 R 1 = H, R2 = R3 = OH: Quercetin R i = R2 = R3 = OH: Quercetagetin Air-dried plant material was briefly rinsed with acetone to dissolve the lipophilic exudates. Con Flavanones centrated solutions were defatted (M eOH, -10 °C; centrifugation) and passed over Sephadex LH-20, R1 = H, R2 = OH: Naringenin R1 = R2 = OH: Eriodictyol eluted with methanol, to separate the flavonoids OH 0 from the prevailing terpenoids. Flavonoid portions Fig. 1. Core structures of flavones, flavonols and flava were subjected to column chromatography on sil nones found in the present study. ica and/or polyamide SC- 6, eluted with toluene and increasing amounts of methylethyl ketone and methanol (cf. Wollenweber et al., 1996). Fractions were monitored and comparisons with markers Subfamily Asteroideae were made by TLC on polyamide D C -11 with the Anthemideae solvents petrol100_i40 - toluene - methylethyl ke tone - methanol 12:6:1:1 , toluene - petrol]00_i40 - Achillea eriophora DC. Aerial parts of this plant MeCOEt - methanol 12:6:2:1, toluene - dioxane- yielded apigenin-4’-Me and ap-7,4’-diMe, scutel- methanol 8:1:1 and toluene - methylethylket- larein-6,7,4’-triMe, 6-OH-luteolin-6,7,4’-triMe and one - methanol 12:5:3 and on silica with the 6-OH-lut-6,7,3’,4’-tetraMe,6-OH-kaempferol-6,7,4’- solvents toluene - methylethylketone 9:1 and tol triMe and 6-OH-kae-3,6,7,4’-tetraMe, querceta- uene - dioxane - glacial acetic acid 18:5:1. Chro getin-3,6-diMe and quercetagetin-3,6,7-triMe. By matograms were viewed under U V before and af and large this pattern fits the “ usual” flavonoid ter spraying with Naturstoffreagenz A (N A ). pattern in Achillea sect. Achillea (Valant-Vetsch- Unless otherwise stated, identifications were made era and Wollenweber, 1994), to which this species by direct comparisons on TL C and in some cases belongs. However, apigenin-4’-Me, ap-7,4’-diMe confirmed by UV-spectra and by mass spectra (re and quercetagetin-3,6-diMe are new compounds corded at 70 eV). for species of this section. Achillea millefolium L. ssp lanulosa (Nutt.) Piper. This species exhibited luteolin, four methyl Results ethers of 6-OH-kaempferol (3,6-diMe, 3,6,7-triMe, As in the previous paper (Wollenweber et al., 3,6,4’-triMe and 3,6,7,4’-tetraMe), and the 3,6- 1996), the results are reported for each species se diMe and 3,6,7-triMe of quercetagetin. The pre quentially, since presentation in tabulated form sent analysis is in good agreement with an earlier did not appear feasable. The species are grouped study including species of the North American A. according to their tribal affiliation within the Ast millefolium complex (Valant-Vetschera and Wol eraceae (Bremer, 1994). Abbreviations O H = hy- lenweber, 1988). However, the earlier studies droxy- and Me = methyl ether are used through yielded less complex profiles for collections from out. In most cases, references to chemotaxonomy the same taxon. E. Wollenweber et al. ■ Exudate Flavonoids in Asteraceae, II 139 Artemisia diffusa Krasch. ex Poljak. The fla vo cetagetin-3,6-diMe) (Gonzalez et al., 1990) and noid pattern of this species was reported earlier from T. albipannosum (scutellarein-6,7,4’-triMe, 6- (Valant-Vetschera and Wollenweber, 1995). In OH-luteolin-6,7,3’,4'-tetraMe) (Gören and Jaku- that paper, the presence of a phloracetophenone povic, 1990) are in good agreement with the gene was mentioned. It should be added here that its ral substitution trends observed in Tanacetum. structure corresponds to the 4,6-dimethyl ether of Only two aglycones (quercetagetin-3,6,4'-triMe phloracetophenone. Its N M R data agree with and quercetagetin-4'-Me-7-acetate) were reported those measured previously for the same product, for T. microphyllum (Abad et al., 1993), which isolated from Artemisia aucheri (Wollenweber et might be due, however, to the activity-orientated al., 1992). Phloracetophenone-4, 6-dimethyl ether nature of that publication. The 3,7-dimethyl ethers (xanthoxylin) has also been found in Artemisia of 6-hydroxykaempferol and of quercetagetin as brevifolia (called brevifolin). p-Hydroxyacetophe- well as 6-OH-kae-3,7,4’-triMe and queg-3,7,3’- none was reported from A. scoparia (Liu and Ye, triMe have recently been reported from the exu 1991), and several acetophenone derivatives were date of T. parthenium (Williams et al., 1995). None reported for Artemisia campestris subsp. glutinosa of these four compounds (queg-3,7,3’-triMe is very (de Pascual-Teresa et al., 1984). Those species ac rare and 6-OH-kae-3,7,4’-triMe is a novel com cumulating this groups of compounds belong pound) has so far been reported for any other spe either to sect. Seriphidium {A. diffusa, A. aucheri, cies of Tanacetum. Several 6-methoxyylated flava- A. brevifolia) or to sect. Dracunculus (A. camp nones have been isolated from Tanacetum estris, A. scoparia). Its further distribution among sibiricum (Stepanova et al., 1982), differing mark Artemisia might prove to be of systematic value. edly from the other known flavonoid structures so Oncosiphon grandiflorum (Thunb.) Källersjö. far known from Tanacetum spp. However, this spe (syn. Pentzia grandiflora Thunb.). The lipophilic cies was segregated from Tanacetum as genus Fili- exudate of this species contained scutellarein 6- folium which is claimed to be related to Artemisia Me, scut-6,7-diMe and scut-6,4'-diMe, the 6-Me, (Bremer and Humphries, 1993).