Alkaloid composition of the bulbs ofCrinum amabile

Chemistry of Natural Compounds
1982.0

Abstract

At the present time the structure and features of the Conformation of meristotropic acid have been established definitively [8, 9]. All the results presented, and also the conversion of the diacetate of methyl isomeristotropate on oxidation with selenium dioxide into the diacetate or methyl meristotropate, show that the carbonyl group is present in ring E and occupies position 22, as in meristotropic acid. Thus, isomeristotropic acid is 3-hydroxy-22-oxooleana-9(11),12-diene-29-oic acid and possesses the structure (I). At the present time, 130 alkaloids have been isolated from the plants of the family Amaryllidaceae [1-3]. Among them, lycorine and galanthamine have proved to be pharmacologically valuable [4, 5]. We have studied the alkaloids of the hypogeal and epigeal organs of Crinum amabile Donn. (Amaryllidaceae) introduced into the experimental field of the Transcaucasian zonal experimental station of VILR [All-Union Scientific-Research Institute of Medicinal Plants] at Kobuleti. In the leaves and roots at the beginning of the vegetation period the total alkaloids amounted to 0.78% and 0.74%, respectively. In the bulbs at the end of the vegetation period (after the first frosts) about 1.56% of combined alkaloids had accumulated. To isolate the individual alkaloids, the combined alkaloids were extracted from the bulbs with chloroform, and when these were boiled with acetone base (I) separated out with mp 270-272°C, [α]D²⁰--70.6° (ethanol), and this was identified as lycorine. Chromatography on a column of silica gel with elution first by means of benzene and then with benzene-methanol in various ratios gave fractions containing bases (II)-(VII). Base (II), with mp 208-210°C, [α]D +160° (chloroform) was identified by a mixed melting point as tazettine. Base (III), with mp 127°C, [α]D --122 (ethanol) proved to be galanthamine. Base (IV), with mp 184-186°C was identical in its UV and IR spectral characteristics with a racemate of narvedine. Base (V), with mp 130-131°C [α]D--81.5°C (ethanol) was identical with galanthine. Base (VI), with mp 216-217°C, [α]D +160°C (chloroform), hydrobromide with mp 264°C (decomp.), was identified as hippeastrine. Base (VII) had mp 206-207°C, [α]D --38°C (chloroform). The IR spectrum confirmed the presence of a cyclohexane ring (1470 cm⁻¹) and of a methylenedioxy group (930, 1040, 1258, 1490 cm⁻¹). M⁺ 271, 254, 199, 187. The spectral characteristics coincided with those for the alkaloid crinidine [2]. Thus, we have determined the alkaloid content of the leaves, roots, and the bulbs of Crinum amabile Donn. from the combined bases of the bulbs we have isolated for the first time the alkaloids lycorine, hippeastrine, crinidine, galanthine, galanthamine, narvedine, and tazettine. Hymenocallis littoralis Salisb. (tropic American hymenocallis), family Amaryllidaceae, is a perennial bulbar herbaceous plant [1]. This plant growing in America and cultivated in the Buitenzorg (Indonesia) Botanical Garden has been studied previously [3, 4, 6-8]. Two alkaloids have been isolated from the epigeal parts: lycorine and tazettine. Hymenocallis littoralis growing in certain regions, and also cultivated in the gardens of the University of Upper Volta and the Ivory Coast [2, 5] has not been studied previously. We have investigated the bulbs with roots and the epigeal part of the plant collected in the flowering period in the regions close to the mountains of Bobo Dioulasso and Banfora in the Upper Volta and the environs of the town of Abidjan in the Ivory Coast. A preliminary investigation of the alkaloid-containing raw material collected in the two states showed that they did not differ significantly in their alkaloid contents in both the qualitative and quantitative results. We subsequently investigated the raw material collected in the region of the Upper Volta. By chloroform extraction from the epigeal part we obtained 0.25 ± 0.11% and from the bulbs with roots 0.37 ± 0.13% of total alkaloids. A chromatographic study of the qualitative composition of the total material isolated using thin-layer chromatography in a fixed layer of type KSK silica gel with various systems of solvents showed the identical qualitative compositions of the alkaloids of the epigeal and hypogeal part of the plant. In the process of purifying the combined alkaloids, we isolated a base which was identified as lycorine (0.1285 g) [9]. The treatment of the combined alkaloids with acetone also led to the isolation of the alkaloid lycorine (0.1401 g). After the separation of the lycorine, the mother liquor was chromatographed on a column. Elution with benzene and with benzene--methanol yielded the following alkaloids: trisphaerine (0.0938 g), tazettine (0.1813 g), hippeastrine (0.1725 g), pancratine (hemanthidine) (0.1175 g), galanthamine (0.0186 g), lycorine (0.081 g), and the amorphous bases (I) (0.0063 g) and (II) (0.0066 g) [3, 9]. From the bulbs with roots by the same methods we isolated trisphaeridine (0.1237 g), tazettine (0.1822 g), hippeastrine (0.1439 g), pancratine (0.2164 g), galanthamine (0.0311 g), lycorine (0.6937 g), and amorphous bases (I) (0.0091 g) and (II) (0.0094 g).

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