New Alkaloids from Delphinium andersonii Gray

HETEROCYCLES
1989.0

Abstract

Earlier, we reported the isolation of andersonine and 14-deacetylnudicauline (4) and six known diterpenoid alkaloids (delavaine, aectinine, lycoctonine, methyllycaconitine, nudicauline, and takaosonine) from the aerial parts of Delphinium andersonii Gray. In continuation of our work on the minor constituents of D. andersonii, we report here the isolation of two new and ten known alkaloids, with six of the known alkaloids (14-acetylbrowniine, 14-acetyldelcosine, browniine, delcosine, deltaline, and dictyocarpine) being reported for the first time from this plant. Extraction of the aerial parts with 95% EtOH, followed by treatment with CHCl3, gradient pH fractionation, vacuum liquid chromatography, and centrifugally accelerated radial thin-layer chromatography, yielded 14-acetylbrowniine (1), 14-acetyldelcosine (2), browniine (3), 14-deacetylnudicauline (4), delcosine (5), deltaline (6), dictyocarpine (7), methyllycaconitine (8), nudicauline (9), and two new alkaloids andersonidine (10) and 14-acetylnudicaulidine (11). The plant material remaining after 95% EtOH extraction was further extracted with 75% EtOH, yielding lycoctonine (12) along with 5, 6, 10, and 11. The identity of known alkaloids was confirmed spectroscopically and by comparison with authentic samples. Andersonidine (10), with mp 127-130°C cor. and [α]D +39.1° (c 0.565, CHCl3) and molecular formula C33H46N2O9, was structurally elucidated using IR, ¹H NMR, ¹³C NMR, and mass spectral data, revealing hydroxyl, amine, and ester (anthranoyl at C-18 and acetate at C-14) functionalities, with confirmation from comparison with nudicauline (9). 14-Acetylnudicaulidine (11), amorphous with [α]²² +18.9° (c 0.54, CHCl3) and molecular formula C26H41NO7, had its structure deduced from IR, EIMS, ¹H NMR (CDCl3 and CD3CN), and ¹³C NMR data, supported by similarity to nudicaulidine (13) and spectral shifts around C-14.

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