Phyrochemir~ry,Vol. 22, No. Printed in Gnat Britain. 6, pp. 1417- 1420, 1983. @ISi-9422/83/061417-04$03.00/O Q 1983Pergamon Press Ltd. COMPARATIVE STUDY OF THE FLAVONOIDS OF SOME LOCAL MEMBERS OF THE UMBELLIFERAE NABIEL A. M. SALEH, SABRY I. EL-NEGOUMY, MOHAMED N. EL-HADIDI* and HASNAA A. HOSNI* National Research Centre, El-Dokki, Cairo, Egypt; *Department of Botany, Faculty of Science, Cairo University, Egypt zyxwvutsrqp (Revisedreceioed 13 September 1982) Key Word Index-Umb4iferae; Apioideae; flavonoid glycosides; chemosystematics. Abstract-Thirty-six species belonging to 27 genera of the sub-family Apioideae, family Umbelliferae, were investigated for their leaf and stem flavonoids. Fourteen flavonoid glycosides of the aglycones kaempferol, quercetin, isorhamnetin, apigenin and luteolin were identified. Chemosystematic In the Umbelliferae, flavonoids, phenylpropanoids, acetylenes, terpenoids and coumarins are characteristic chemical constituents [l, 21. Kaempferol, quercetin, apigenin and luteolin are the most common flavonoid aglycones. Isorhamnetin, chrysoeriol, diosmetin and acacetin occur less frequently and flavanones rarely [3]. Glycosylation is common in position 3 for flavonols and position 7 for flavones [3]. Sulphated flavonoids have also been reported in the family [4]. On the basis of fruit morphology, taxa with spines on both the primary and secondary ridges of the fruits, are grouped in the Caucalideae by Bentham and Hooker [S] and Boissier [6]. But Drude [7] divided these species between two tribes: the Scandiceae (sub-tribe Caucalinae) and the Dauceae. The largest genus in the Caucalinae is Torilis and in Dauceae is Daucus. At the tribal level, Harborne [3] from the flavonoid evidence, divided the family into two broad groups: the first group of nine tribes in which flavones are rare or absent; and the second group of four tribes in which flavones are common or predominant (Apieae, Dauceae, Laserpitieae and Scandiceae sensu Drude). Similar patterns were observed in the present study of 36 species belonging to the sub-family Apioideae (Table 1). Harborne [3] carried out a detailed study of the flavonoid constituents of the tribe Caucalideae sensu Boissier. The study concentrated on the fruit flavonoids and to a lesser extent on those in leaf and flowers. A correlation between flavonoids and evolutionary progression within the Caucalideae was based on the presence or absence of flavones versus flavonols. It has been suggested that flavones represent advancement by loss mutation over the corresponding flavonols [8]. This correlates with advanced and primitive characters in the Umbelliferae [3] and the Oleaceae [9]. The data reported in the present study correlate with the results previously reported in the fruits by Harborne [3] as well as the survey of aglycones by Crowden et al. [lo]. The most common flavonol glycoside is the 3glucoside followed by the 3-rutinoside, while the most common flavone glycoside is the 7-glucoside (Table 1). Although the chromosomal data [l l] do not correlate with the tentative grouping of the tribes of the Apioideae based on the presence or absence of flavones and flavonols relationships are discussed. [lo], a close similarity between the distribution of numbers in the Scandiceae and Dauceae support their close relationship based on chemical evidence [3, lo]. Furthermore, serological data confirm that in the Scandiceae and Dauceae greater changes in protein chemistry have occurred [12]. Also, both tribes have evolved stomata1 characters [13]. The serological evidence, however, did not support Bentham and Hooker’s [S] treatment of placing Torilis and Daucus in the tribe Caucalideae. Both species contain flavone 5-glycosides, which indicate a rather specialized character (Table 1 and results in ref. [3]) It is interesting to note that all Torilis species examined only contained flavone glycosides, while species proved to contain both flavone and flavonol glycosides (see Table 1 and ref. [3]). Serological data indicated a great protein similarity between tribes Coriandreae and Ammineae, as well as a close correspondence among both tribes and Peucedaneae [12]. All three tribes contain mainly flavonols as their major glycosides, with the exception of Pimpinella etbacia, Cuminum cyminum and Ammoides Daucus pusilla which contain grain characters flairone glycosides (Table 1). Pollen indicated that Bupleurum species (tribe Ammineae) showed primitive characters [ 141. All species investigated in the present study only contained flavonol glycosides, and similar results are also reported in the literature for other Bupleurum species [lo]. It is interesting to note that in the case of Bupleurum semicompositum two chemical races exist, one with the 3rutinosides of quercetin and isorhamnetin as the major glycosides and the second with the 3-glucosides as well as the 3-rutinosides. Similarly, Foeniculum uulgare also proved to have two chemical races [15]. EXPERIMENTAL Plant material. Fresh material was used whenever possible. Herbarium samples of all investigated taxa are deposited at the Herbarium, Department of Botany, Cairo University. Isolationand identification ofjavonoid constituents. The plant material (leaf and stem) was extracted with 707; EtOH. Flavonoid glycosides were isolated using elution techniques, and identified according to standard methods [16, 171. 1417 z E Table 1. Distribution of flavonols and Savones in the sul+family Apioideae Flavones? Flavonols* Sub-family Apioideae (sensu Drude) No. of samples Kaempferol 3Glc 3Glur Quercetin 3Glc 3Gal 3Glur 3Rut 3Poly 3Glc 3Rut Tribe I : Echinophoreae zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA _ Py concy cla tomentosa Decne 1 +++ Tribe II : Scandiceae Subtribe 1: Scandicinae L. (Sol.) Thell. var. hirsutum (C. Koch.) Thell. Subtribe 2: Caucalinae Torilis nodosa (L.) Gaertner Torilis radiata Moench Torilis bracteosa Bianca ex Nym. Torilis arvensis (Hudson) Link Caucalis tenella Del. Pseudorlaya pumila (L.) Grande Tribe III: Coriandreae Coriandrum satioum L. Scandix pecten- ueneris Apigenin Isorhamnetin Luteolin 7Glc 7Glur 7Glc 7Glur 5Glc - - - - - _ 1 - - - - - - _ _ - + - +++ - 1 - - _ - - - - - - + - +++ _ 1 2 2 1 1 1 _ - _ _ - _ - - - - - _ - _ - - _ + + + + + + + + - +++ +++ +++ + ++ +++ + + + ? + - +++ +++ 1 - + + ++ +++ ++ - - - - - 1 - - - - - +++ _ - +++ - - - - - 1 1 4 {4 - - ++ +++ +++ +++ _ + + +++ ++ t++ t++ +++ - - - - - + + + +++ - - - - 1 3 1 1 1 1 - _ - - - ? - +++ + ++ - _ - - - t+t _ - - - - +++ + - +++ +++ +++ - - 5 2 1 1 ++ ++ ++ +++ +++ ++t - +++ - - - - + - Scandicium stellatum Tribe IV: Ammineae Subtribe 1: Carinae Bupleurum lancifolium Homem. Bupleurum falcatumL. var. (Boiss.) Tackh. Poir. lineargolium Bupleurum nanum Bupleurum semicompositum Pituranthos tortuosus L. (Desf.) Benth. & Hook. f. L. Ammi oisnaga (L.) Lam. Berula erecta (Hudson) Coville Pimpinella etbacia Schweinf. Rido&a segetum (L.) Moris Apium leptophy llum (Pers.) F. Muell. ex Benth. Apium graveolens L. Helosciadium nodz@ orum (L.) Koch Carum carvi L. Ammi majus +++ - - + + + - - t+t - - 5Glur L. (Brot.) Breistr. Subtribe 2: Seselinae Foeniculum vulgare (L.) Mill. sub. piper&urn (Ucria) Coutinho Foeniculum uulgare (L.) Mill. sub. Cuminum cy minum Ammoides pusilla vulgare L. L. Crithmum maritimum Anethum graveolens Tribe V : Peucedaneae Subtribe 1: Ferulinae Ferula marmarica Asch. & Taub. Ducrosia ismaelis Asch. Subtribe 2: Tordylinae M alabaila suaveolens Coss. Zosima orientalis Hoffm. _ +$ - - +++$ +++ - - - - _ - - _ - - ++ ++ - - - 5 1 1 - - - _ + - - 2 _ ++ + - +++ - - 1 1 1 - ++ - + + - - +++ +++ - + - 1 1 - - +++ +++ - - - 1 1 - - - - - - +ll 1 - - 1 - +II _ - - - - - +++ - - - - - - - _ - - - - _ - - - _ - +** - - - - - - - - - Tribe VI: Dauceae Daucus littoralis Sibth. & Sm. Tribe VII: Smyrnieae Astoma seselifolium DC. +++ - - - - - - - - - - - *3 Glc, 3-glucoside; 3 Gal, 3galactoside; 3Glur. 3glucuronide; 3 Rut, 3-rutinoside; 3 Poly, 3polyglycoside. t 7 Glc, zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA 7-glucoside; 7 Glur, 7-glucuronide; 5 Glc, 5glucoside; 5 Glur, 5-glucuronide. $7-Polyglycosides also present. §Isorhamnetin is the major aglycone. 11 Quercetin Fglucoside. T[Quercetin 3,7diglucoside. **Traces of a C-glycoside were detected. +++ co k s 8. B 1420 N. A. M. REFERENCES 1. Heywood, V. H. (ed.) (1971) in The Biology and Chemistry of p. 31. Academic Press, London. Hegnauer, R. (1973) in Chemotaxonomie der Pjanzen Vol. 6, p. 554. Birkhatiser, Basel. Harborne, J. B. (1971) in The Biology and Chemistry of the Umbellijerae (Heywood, V. H., ed.) p. 293. Academic Press, London. Harborne, J. B. and King, L. (1976) Biochem. Syst. Ecol. 4, 111. Bentham, G. and Hooker, J. D. (1867) Genera Plant. 1,859. Boissier, E. 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