New Lignans and Isobutylamides fromHeliopsis buphthalmoides

Abstract

A reinvestigation of the aerial parts of Heliopsis buphthalmoides gave in addition to compounds isolated previously four new lignans and two unsaturated amides. Some time ago we isolated some lignans (1, 2) from Heliopsis buphtalmoides. As these compounds show remarkable biological activities (3) we have reinvestigated the aerial parts of the same species which were collected in Peru. While the unpolar fractions afforded a-and 3-farnesene, germacrene D, caryophyllene and phytol the more polar fractions gave seven lignan derivatives (1-7) only three of them being isolated previously, (1) (1), heliobuphthalmin (2) (1) and 4(2). Five highly unsaturated isobutylamides were also obtained, the enynes 8(1,4) and 9, the enyne dienes 10and 11(1) as well as the ynediene 1.2.The structure of 3, molecular formula C22H2209, followed from the 1H NMR spectrum (Table I) which clearly showed that we were dealing with a biscarbomethoxy derivative (8 3.68 and 3.53 s) with two trisubstituted aromatic moieties. A four proton singlet at 8 = 5.93 indicated the presence ot two dioxymethylene groups. However, in contrast to the spectrum of 2, the aromatic signals showed that this compound was not symmetric. Accordingly, the signals of the benzylic protons showed different splitting, one pair of doublets and one pair of double doublets. A broadened singlet at 8 = 3.58 indicated a hydroxy group which could only be placed at C-8. Its presence also followed from the IR spectrum, which further indicated a

Alkamides: a critical reconsideration of a multifunctional class of unsaturated fatty acid amides

“…3). This characteristic group of unsaturation was also reported for C 18 isobutylamides from Heliopsis buphthalmoides and H. helianthoides (124a-127a) Jakupovic et al 1986), and a series of C 16 amides with different amine parts (132k, 133a,k,n,q; 134a) from Achillea ageratifolia . Besides acetylenic C 18 piperidides, A. lycaonica was shown to accumulate also olefinic and saturated C 18 piperidides (30b, 31b,k; 32b) and pyrrolidides (20b,k) as major compounds.…”

“…Their structures were published only tentatively as C 18 -pentaenoic and -hexaenoic acid isobutylamides, respectively (Jacobson 1951(Jacobson , 1957b. As mentioned above they are probably closely related to or even identical with the acetylenic C 18 isobutylamides 124a-127a isolated from that species by and Jakupovic et al (1986).…”

“…They were exclusively reported for the Heliantheae genera Acmella and Echinacea (Nakatami and Nagashima 1992) (Table 4). Apart from two isomeric tetradeca-2,4,10-triene-8-ynoic acid isobutylamides (138a, 139a) from H. buphthalmoides Jakupovic et al 1986) and tetradeca-2-en-10,12-diynoic acid isobutylamide (145a), isolated in small amounts from E. angustifolia (Woelkart et al 2005), the accumulation of acetylenic C 14 alkamides listed in Table 3 was detected solely in the tribe Anthemideae. They were mainly reported for Achillea species (Table 4), where they are characterized by highly desaturated acid moieties, sometimes even leading to fully conjugated systems (147-149).…”

“…Regarding the investigations of H. helianthoides var. scabra and H. buphthalmoides by and Jakupovic et al (1986), it is tempting to assume that the four acetylenic C 18 isobutylamides 124a-127a (Fig. 6) isolated from the aerial parts and roots, respectively, are closely related or even identical with scabrin and heliopsin.…”

Evaluation of Lignans from Heliopsis helianthoides var. scabra for Their Potential Antimetastatic Effects in the Brain

“…This compound has earlier been reported from Heliopsis bupthalmoides, although without 13 C NMR spectroscopic data. 8 In 2D-NMR experiments, the chemical shifts assignment of all the carbons were assigned, as listed in the Experimental Section. It has also been described from Biota orientalis leaves.…”