Alklaloids of Alphonsea sclerocarpa

Journal of Natural Products
1987.0

Abstract

The genus Alphonsea (Annonaceae) comprises about 30 species of small trees and shrubs distributed in India, Sri Lanka, Southeast Asia, and the Malaysian region. Only Alphonsea milreu has been chemically studied previously, containing glaucine, norglaucine, and a large number of long-chain furanic diacetylenes. We now report the chemical examination of Alphonsea sclerocarpa Thw. from Sri Lanka. The bark contains 0.036% nonquaternary alkaloids, including liriodenine (12% of crude bases), anonaine (5.5%), norushinsunine (5.0%), ushinsunine (4.5%), stepharine (2.0%), and stepholidine (7.0%). It also yields 0.09% quaternary alkaloids (as crude chlorides), with candicine (30%), phenethyltrimethylammonium (9.0%), and magnoflorine (4.7%) characterized. The leaves contain 0.135% nonquaternary alkaloids, with crotsparine as the main constituent (25%), accompanied by its rearrangement product sparsiflorine (4.0%), laurotetanine (7.0%), isoboldine (5.5%), liriodenine (5.0%), and petalinemethine (4.0%). Most of these alkaloids are frequent constituents of Annonaceae. Notably, candicine, a simple biogenetic derivative of tyrosine, is reported for the first time in this family. Phenethyltrimethylammonium ion, derivable from phenylalanine, was previously only recorded in the orchid Erythrorchis (4). Petalinemethine, previously isolated from Leontice leontopetalma (Berberidaceae) (5,6) and believed to be an artifact from quaternary petaline, has an unusual 7,8,4'-trioxygenation pattern of benzylisoquinolines, which is first observed in Annonaceae. Cotula L. (Compositae), the largest genus in the tribe Anthemideae, is a widespread Southern Hemisphere group of about 80 species. The Anthemideae was arranged into seven provisional subtribal groups by Reitbrecht (2), following Bentham's original scheme (3). Cotula and its relatives are placed in the "Cotuleae" by Lloyd (1972) (4), with generic affinities remaining unclear despite the genus being well-defined (3). Cotula cinerea L. had previously been studied, with kaempferitin, quercetrin, quercetin, and kaempferol reported (5). We now describe different flavonoids from another population of this species: the 7-O-β-D-glucoside (6), 7-O-β-D-diglucoside, and 6-hydroxy-7-O-β-D-glucoside of luteolin (7), luteolin itself, and apigenin 7-O-α-L-rhamnoside (8). These, along with 6-C-arabinosyl-8-C-glucosylapigenin (isoxhafcoside), are the primary flavonoid constituents. Minor amounts of quercetin 3-O-β-D-glucoside, quercetin 3-O-β-D-galactoside, quercetin 7-O-β-D-glucoside (9), and 5,3',4'-trihydroxy-3,6,7-trimethoxyflavone (10) are also isolated. Although 5-O-glycosylated flavonoids (11) usually distinguish Cotula from other Anthemideae members, none were detected in this study. However, glycosylated flavones like those described have been reported in other tribe members (1).

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