Alkaloids ofCocculus pendulus

Planta Medica
1993.0

Abstract

The shrub Cocculus pendulus is found growing in the dry area, climbing on rocks, cliffs, and Acacia trees. Although this species is relatively widespread, phytochemical analysis revealed it is a very rich source of alkaloids mainly bisbenzylisoquinoline alkaloids, with some hypotensive and anticancer activities associated with the alkaloidal fractions of its leaves and stems, and the plant also exerts a diuretic effect. Cocculus pendulus (syn. C. laebe) Diels. (Menispermaceae) was collected on May 5, 1988 from the vicinity of Wadi Arava, identified by Prof. D. Al-Eisawi (voucher deposited at the Herbarium of the Faculty of Sciences, University of Jordan, Amman). The dried, ground leaves and stems were extracted with EtOH, and the resulting extract was fractionated according to accepted methods to afford a basic fraction. Extensive gradient column chromatography (CHCl3-MeOH mixtures on silica) afforded the bisbenzylisoquinoline alkaloid hernandezine (166 mg); this is the first report of isolation of this alkaloid from Cocculus spp., as well as tetrandrine (62 mg), penduline (45 mg), cocsuline (26 mg), and punjabine (60 mg). Punjabine was first isolated from Berberis lycium and this is the second report of its isolation from nature and the first from the genus Cocculus. In addition, quercitol (43 mg) was isolated from the non-alkaloidal fraction; this is the first report of its isolation from this genus. The alkaloids and quercitol were characterized by direct comparison (TLC, IR, 1H-NMR, MS, melting point, optical activity) with authentic samples and/or published data. In the course of a search for biologically active substances from Bulgarian medicinal plants, the petroleum ether extract of the aerial parts of Rosmarinus officinalis L. (Lamiaceae) was found to contain nine pentacyclic triterpenoids. Four of them, α- and β-amyrin, oleanolic acid, and ursolic acid, have been previously found in R. officinalis and are common constituents of Lamiaceae species, whereas α- and β-amyrenone, 3-O-acetyloleanolic acid, and 3-O-acetylursolic acid are now isolated for the first time from Rosmarinus species. In addition, a new triterpenoid rofficerone (1) was isolated and identified as 3-oxo-20,9-hydroxyurs-12-ene. The known compounds were identified by comparing their spectral data with those in the literature and with authentic samples on TLC. The new triterpene (C30H48O2, m/z 440, M⁺) exhibited IR absorption bands at 3620 cm⁻¹ (hydroxy) and 1705 cm⁻¹ (carbonyl). The ¹H-NMR spectrum showed signals for one secondary methyl group (δ 1.09), seven tertiary methyl groups (δ 0.85, 1.06, 1.08, 1.10, 1.22), and a trisubstituted olefinic proton (δ 5.20). There were also two multiplets centered at δ 2.47 and 2.52 (each 1H) assignable to the C-2 methylene protons. The lack of a carbinol proton and the fact that no acetylation occurred on treatment of 1 with Ac₂O/Py at room temperature strongly suggested the presence of a tertiary hydroxy group.

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