Biochemical Systematics and Ecology 30 (2002) 263–265 www.elsevier.com/locate/biochemsyseco
Alkaloids from Fumaria sepium and Fumaria agraria Rafael Suau a,*, Baltasar Cabezudo b, Rodrigo Rico a, Juan Manuel Lo´pez-Romero a, Francisco Na´jera a a
Departamento de Quı´mica Orga´nica, Universidad de Ma´laga, E-29071 Ma´laga, Spain Departamento de Biologı´a Vegetal, Universidad de Ma´laga, E-29071 Ma´laga, Spain
b
Received 29 August 2000; accepted 21 March 2001
Keywords: Fumaria agraria; Fumaria sepium; Papaveraceae; Fumariaceae; Isoquinoline alkaloids; Chemotaxonomy
1. Subject and source The plants of genus Fumaria L., which encompasses about 40 species (Southon and Buckingham, 1989), are annual herbs which have a wide distribution from India to Macaronesia. Twenty-two species are restricted to the Ibero-Mauritanian Region, which includes Algeria, Morocco and Spain (Lide´n, 1986). Plant material of Fumaria agraria Lag. (Fumariaceae) was collected from Churriana (Ma´laga, Spain) and that of Fumaria sepium Boiss. (Fumariaceae) from Los Barrios (Ca´diz, Spain). Both were identified by the Department of Botany of the Faculty of Sciences of the University of Ma´laga. Voucher specimens (F. agraria MGC-23062 and, F. sepium MGC-31528) are deposited in the Faculty’s herbarium. 2. Previous work F. sepium has not been studied to date, and previous investigations on isolation of alkaloids from F. agraria revealed the presence of protopine (Susplugas et al., 1957). * Corresponding author. Present address: Facultad de Ciencias, Dpto de Quı´mica Orga´nica, Universidad de Ma´laga, Campus de Teatinos s/n, E-29071 Ma´laga, Spain. Tel.: +34-952-13-19-34; fax: +34-952-1319-41. E-mail address:
[email protected] (R. Suau). 0305-1978/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 5 - 1 9 7 8 ( 0 1 ) 0 0 0 7 7 - 1
264
R. Suau et al. / Biochemical Systematics and Ecology 30 (2002) 263–265
3. Present study In this paper, the isolation of alkaloids from F. agraria and F. sepium is described. Total alkaloids, 5.5 g (0.88%) for F. sepium and 4.5 g (0.83%) for F. agraria, were obtained from the air-dried aerial parts of the plant (0.62 and 0.55 kg, respectively) following reported procedures (Suau et al., 1998). Separation of alkaloids was similar for both specimens, and was achieved by column chromatography on silica gel (300 g), by elution with 9:1 CHCl3/MeOH. Preparative TLC was used for further separation and purification on silica gel, using 7:3 EtOAc/hexane and 7:2:1 benzene/EtOAc/Et3N. Crystallization from EtOH was used for purification and separation of protopine and isoboldine. The alkaloid contents in the aerial parts of F. sepium and F. agraria are shown in the following table (Table 1). As can be seen, protopine is the main alkaloid in both. Alkaloids were identified by direct comparison of their physical and spectral properties with reported values or with those for authentic samples (Guinaudeau et al., 1994; Krane et al., 1984; Preisner and Shamma, 1980; Hussain et al., 1983). The GC–MS analysis of these Fumaria alkaloids also revealed the presence of trace amounts of nandazurine (aporphine) and sinactine (protoberberine) in F. agraria, and of africanine (aporphine), fumariline (spirobenzylisoquinoline), adlumidine (phtalideisoquinoline) and cheilantifoline (protoberberine) in both plants.
4. Chemotaxonomic significance Most of the European Fumariaceae can be associated with three chemotypes based on alkaloid contents. Sarcocapnos and Ceratocapnos are distinguished by the presTable 1 Alkaloids contents of F. sepium and F. agrariaa Type
Alkaloid
Aporphine Aporphine Benzophenanthridine Isoquinolone Isoquinolone Protoberberine Protoberberine Protopine Spirobenzylisoquinoline Spirobenzylisoquinoline
Domesticine (+)-Isoboldinea Dihydrosanguinarine Noroxyhydrastinine Oxyhydrastinine Coptisine (⫺)-Stylopineb Protopine Densiflorine (⫺)-Fumaritine-N– oxidec (+)-Parfumined
Spirobenzylisoquinoline a
F. sepium (mg/100 g plant)
F. agraria (mg/100 g plant)
m.p. (°C)
– – 5 14 26 7 53 253 11 42
19 112 3 4 8 – 25 212 – –
120–125 135–138 – 185–189 97–100 – 191–193 202–204 – 200–201
18
36
101–105
[a]24 D : (a) +57.5 (0.2, EtOH); (b) ⫺267.7 (0.3, CHCl3); (c) ⫺35.8 (0.4, MeOH); (d) +5.6 (0.3, CHCl3).
R. Suau et al. / Biochemical Systematics and Ecology 30 (2002) 263–265
265
ence of cularine alkaloids, the genus Platycapnos posses aporphines and morphinanes almost exclusively while Corydalis, Rupicapnos and Fumaria are characterized by the presence of many types of isoquinoline alkaloids that includes mainly indenobenzazepines, spirobenzylisoquinolines, protoberberines and phtalideisoquinoline (Preininger, 1986). Chemotaxonomic investigations of several populations of 10 species of the genus Fumaria resulted in the definition of two different chemotypes based on the presence of either the protoberberine stylopine (group I) or the protopine cryptopine (group II) in the plant (Garcı´a, 1989). The alkaloids contents revealed the presence of the typical Fumaria constituents in both F. sepium and F. agraria (group I). The occurrence of aporphines in F. agraria is not usual in the genus Fumaria. The presence of domesticine and oxyhydrastinine is reported here for the first time in Fumaria.
Acknowledgements This work was supported by Spain’s DGES (Project PB97/1077).
References Garcı´a, A.I., 1989. Ph.D. evaluacio´ n, Aislamiento y Determinacio´ n Estructural de Alcaloides en la Flora de Andalucı´a, University of Ma´ laga, Ma´ laga. Guinaudeau, H., Leboeuf, M., Cave´ , A., 1994. J. Nat. Prod. 57, 1033. Hussain, S.F., Khan, L., Nakkady, S., Shamma, M., 1983. Phytochemistry 22, 319. Krane, B.D., Fagbule, M.O., Shamma, M., 1984. J. Nat. Prod. 47, 1. Lide´ n, M., 1986. Opera Bot. 88, 1. Preininger, V., 1986. Chemotaxonomy of Papaveraceae and Fumariaceae. In: Brossi, A. (Ed.), The Alkaloids. Academic Press, London, p. 1. Preisner, R.M., Shamma, M., 1980. J. Nat. Prod. 43, 305. Southon, I.W., Buckingham, J., 1989. Dictionary of Alkaloids. Chapman & Hall, London. Suau, R., Rico, R., Lo´ pez-Romero, J.M., Na´ jera, F., Cuevas, A., 1998. Phytochemistry 49, 2545. Susplugas, J., Lalaurie, M., Privat, G., Chicaya, P., 1957. Trav. Soc. Pharm., Montpellier 17, 154.
