Distribution of chromenes and benzofurans in Encelia californica

Two populations of Encelia californica (Asteraceae) were analysed for chromenes and benzofurans on an organ specific basis using HPLC. Both classes of compounds were present in all parts of the plant studied including roots, stems, leaves, capitula and achenes. The distribution patterns were less complex in roots and achenes when compared to stems, leaves and capitula which yielded three chromenes and two benzofurans. In addition to the chromenes and benzofurans the capitula afforded a sesquiterpene lactone of the eudesmanolide type which was absent in the other parts of the plant.     

Chromenes and benzofurans of the asteraceae,their chemistry and biological significance

Chromenes (benzopyrans) and benzofurans are characteristic natural products of certain tribes of the Asteraceae. This review highlights recent findings     

Systematic implications of chromenes and benzofurans from Encelia (asteraceae)

Phytochemical analysis of Encelia species yielded numerous chromene and benzofuran derivatives. Systematic comparison of the chemical profiles revealed three distinct groups of species. The species affinities, as elucidated by the chromene and benzofuran patterns, largely paralleled those based on recent morphological and anatomical findings and are thought to reflect the phylogeny of the genus.     

Quantitative variation of the sesquiterpene lactones and chromenes of encelia farinosa

The components of the two major classes of natural products of the composite Encelia farinosa, sesquiterpene lactones and benzopyrans/benzofurans (chromenes), were resolved and quantified by high performance liquid chromatography. Geographic variation was examined over a range of mesic and xeric populations from California and Arizona (USA). The concentration of farinosin, a sesquiterpene lactone, varies significantly between individuals and seasonally within individuals. Ontogenetic comparisons revealed interpopulation variations within sesquiterpene lactones and chromenes. A geographic survey suggests the presence of two putative chemical races which vary in the amounts of sesquiterpene lactones and chromenes present. The adaptive significance of this quantitative variation is discussed.     

Insecticidal chromenes from the Asteraceae: structure-activity relations

Chromenes (benzopyrans), common to many genera of the Asteraceae, are lethal to the neonate variegated cutworm, Peridroma saucia Hübner, when presented on the inner walls of glass vials at concentrations of 1.0 mol/vial or less. Closely related benzofurans, including some from the same plants, are relatively inactive at these concentrations. The most potent of seven naturally-occurring and four derived chromenes is the well known allatocidin, precocene II, with an LD₅₀ of 0.134 mol/vial or 0.67 g/cm². A more widely distributed chromene, desmethoxyencecalin, is also relatively toxic with an LD₅₀ of 0.98 g/cm².Structure-activity comparisons of the chromenes tested in this study suggest that the presence of a free hydroxyl group at either C-7 or C-11 significantly diminishes activity. Saturation of the 3,4 double bond, which destroys the allatocidal activity of the precocenes, diminishes, but does not alleviate, contact toxicity of chromenes to cutworm larvae. Brief exposure (24 h) of 2-day-old larvae to chromene residues significantly inhibits subsequent larval growth. The degree of chronic growth inhibition (sublethal toxicity) from five different chromenes is highly correlated to their lethal potencies to neonate larvae.

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Zusammenfassung Verschiedene Chromene (Benzopyrane), die in einer Vielzahl von Gattungen aus der Familie der Asteraceae vorkommen, erwiesen sich als insektizid gegenüber frischgeschlüpften Raupen von Peridroma saucia. Die getesteten Substanzen wurden dabei als Film an den Innenwänden von Glass-Scintillationsgefäßen in Konzentrationen bis zu 1 mol/Gefäß appliziert und die Raupen über 24 h in diesen Gefäßen gehalten. Den Chromenen biogenetisch ähnliche Benzofurane, die oft gemeinsam in Asteraceen gefunden werden, weigten im Vergleich keine oder nur schwache insektizide Wirkungen. Von sieben natürlich vorkommenden und vier durch Partialsynthesen getesteten Chromenen erwies sich das bekannte Allatocidin Precocen II als die aktivste Verbindung. Der LD 50-Wert dieses Chromens betrug 0.134 mol/Scintillationsgefäß oder 0.67 g/cm². Das weitaus häufigere Chromen desmethoxyencecalin wies im Vergleich einen LD 50-Wert von 0.98 g/cm² in diesem Biotest auf.Struktur/Aktivitätsuntersuchungen der getesteten Chromene zeigten, daß die Anwesenheit einer OH-Gruppe an den Positionen C-7 und C-11 zu einer deutlichten Aktivitätsminderung führte. Hydrierung der heterocyclischen Doppelbindung, die einen völligen Verlust der allatociden Wirkung von Precocenen bewirkt, verringerte die Kontakttoxizität der Chromene auf 50% der ursprünglichen Aktivität.Ein kurzer Kontakt (24 h) von zwei Tage alten Peridroma-Raupen des ersten Larvenstadiums mit den Chromenen resultierte in einer signifikanten Verringerung des nachfolgenden Wachstums der Raupen auf künstlicher Diät.Die deutlichsten Struktur/Aktivitätsbeziehungen, die in der vorliegenden Arbeit ermittelt wurden, lassen sich wie folgt zusammenfassen: 1) Die Gegenwart eines Furanringes statt eines Pyranringes (Chromen) bewirkt einen zumeist vollständigen Verlust an insektizider Wirkung; 2) die Gegenwart eines OH-Substituenten führt zu einer drastischen Abnahme an Aktivität. Eine Übersicht der bisher vorliegenden Daten sowie laufender Untersuchungen zeigt, daß Chromene ein breites Spektrum an insektizider Wirkung besitzen.

     

Guaianolides and chromenes from Calea species

Chemical analysis of Calea berteriana yielded, besides the known flavonoid acacetin and the sesquiterpene lactone calbertolide C, three new guaianolides, desacyl-8-tiglylsubcordatolide A and 8-epi-8-tiglylrupicolins A and B. C. prunifolia provided acacetin, calbertolide C, desacyl-8-tiglylsubcordatolide A, and two new chromenes, prunichromenes A and B. From C. solidaginea acacetin, heliangine, calbertolide C, 8-epi-8-tiglylrupicolin A and desacyl-8-tiglylsubcordatolide A were isolated. The structures of the new compounds were established by chemical and spectral methods.     

Flavonoids from the external leaf resins of four hemizonia species (asteraceae)

The external leaf resins of four Hemizonia species afforded nine methylated flavonoids, including flavanones, flavones and flavonols. Besides the rare compounds 7-methyleriodictyol and 3,6,8-trimethoxy-5,7,3′,4′-tetrahydroxyflavone the new 6-methoxy-5,7,8,3′,4′-pentahydroxyflavone was isolated and identified by spectroscopic means.     

Dimeric chromenes and mixed dimers of a chromene with euparin from Encelia canescens

The investigation of Encelia canescens afforded, in addition to several known compounds, four new dimeric p-hydroxyacetophenone derivatives, two epimeric chromene dimers and two epimeric mixed dimers of euparin and encecalin. Furthermore, derivatives of tremetone and of encecalin were present. The structures were elucidated hy high field ¹H NMR spectroscopy.     

Seasonal age-specific measurements of the sesquiterpene lactones and chromenes of Encelia farinosa

Age-specific concentrations of farinosin, a sesquiterpene lactone, and encecalin and euparin, both chromenes, were measured in two semi-desert populations of Encelia farinosa in California over a three month period. All three natural products differed significantly in concentration. The average concentration of encecalin is 10 times that of euparin and eight times that of farinosin. Farinosin concentrations did not differ between the two populations, but both euparin and encecalin were in higher amounts in the UC Riverside population than in the Home Gardens population. Seasonal changes in natural products differed at the 0.05 level for all populations and compounds except euparin in the UC Riverside population. Percent nitrogen content of dried leaves was similar in both populations, but differed between collection dates. Water content did not vary significantly with leaf age on one collection date. The significance of these results is discussed in the light of herbivore history.     

External flavonoid aglycones of Viguiera series Viguiera (asteraceae: heliantheae)

Distribution of external flavonoid aglycones supports other data to suggest that Viguiera series Viguiera (series Dentatae Blake) is a mixed taxonomic grouping. Two species, V. dentata and V. potosina, lack external flavonoid aglycones, whereas the remaining species of the series all produce external flavonoid aglycones and appear to form a natural taxonomic group. The latter group, which consists of species from Baja California and nearby xeric areas, exhibits a diversity of flavonoid types, with different diploid species variously producing flavonols, simple flavones, 6-methoxyflavones, 6-hydroxy,7-methoxyflavones and a chalkone as major compounds. Polyploid species exhibit combinations of flavonoid types from possible diploid ancestors. Compounds of the 6-hydroxy,7-methoxyflavone type appear to characterize the group of species from Baja California and nearby areas within Viguiera.     

Chromans from helianthella quinquenervis

Investigation of Helianthella quinquenervis afforded, in addition to several known 6-acetylchromenes, 3-prenyl-4-hydroxyphenone and the benzofuran encecalin, cis- and trans-2,2-dimethyl-3,4,7-trihydroxy-6- acetylchroman.     

Chromenes from ageratina riparia

The reinvestigation of the roots and aerial parts of Ageratina riparia afforded ten new chromenes, their structures being determined by spectral data and chemical transfomrations.     

Molluscicidal activity of affinin and other isobutylamides from the asteraceae

Unsaturated aliphatic isobutylamides from Asteraceae, Rutaceae and Piperaceae are potential agents to control schistosomiasis. Affinin (N-isobutyl-2,6,8-decatrienamide) from Heliopsis longipes has strong molluscicidal activity against Physa occidentalis (ld₅₀ca 100 μM) and the cercariae of the fluke. The amide has also been shown to be present in Wedelia parviceps flowers.     

2-Methyl-2-hydroxymethylchromenes from Artemisia campestris subsp. glutinosa

From the non volatile neutral part of a hexane extract from Artemisia campestris subsp. glutinosa, two new 2-methyl-2-hydroxymethyl chromenes h     

New chromenochalcones from Flemingia

2-Methyl-2-(4′-methylpent-3′-enyl)-5,8-dihydroxy-6-(4-hydroxycinnamoyl)-chromene (flemingin-D) has been isolated from inflorescences of Flemingia congesta, together with the known flemingin-C and two other chalcones. These (flemingin-E and -F) are allylic alcohols which differ from flemingin-D by an additional OH group in the side chain. Photooxidation of model 2-methyl-2-(4′-methylpent-3′-enyl)-chromenes gave pairs of allylic alcohols with the same structural feature. The known flemingin-A, -B, -C and homoflemingins have been isolated from F. grahamiana, and another new chalcone from F. bracteata.     

Detoxification of naturally occurring chromenes in larvae of the generalist herbivore Spodoptera littoralis (Noctuidae)

Five naturally occurring chromenes from the Asteraceae including the insecticidal compounds precocene II (1) and encecalin (2) were administered to last instar larvae of Spodoptera littoralis via the food or by topical contact. Metabolites formed and excreted via the frass were analysed by GC-MS and by direct comparison with reference compounds obtained by partial synthesis. In total 28 different metabolites were identified, many of them reported here for the first time. All metabolites detected originated from phase I reactions (most probably catalysed by Cytochrom P-450-dependent monooxygenases) by hydroxylation, demethylation or reduction of the parent chromenes. The resulting metabolites can be regarded as detoxification products based on previous structure-activity studies. The increased polarity of the metabolites will furthermore facilitate their excretion by the larvae compared to the more apolar parent chromenes. The largest number of metabolites (eight for each compound) was detected following oral treatment with precocene II and encecalin respectively. 3-Monool as well as 3,4-trans-diol derivatives predominated in the frass of larvae treated with the latter compounds whereas the 6-hydroxyethyl derivatives were the major metabolites of the other chromenes investigated. The patterns of metabolites originating from precocene II or encecalin were the same following oral application or topical treatment.     

Antifeedant/insecticidal terpenes from asteraceae and labiatae species native to Argentinean semi-arid lands

To validate the potential as added-value resources of Asteraceae and Labiatae species of Argentinean semi-arid lands, we have selected 13 of their major terpenoids belonging to several chemical classes and tested their insect antifeedant and toxic activity on the herbivorous insects Spodoptera littoralis and Leptinotarsa decemlineata. The antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedant to L. decemlineata was the eudesmane sesquiterpene gamma-costic acid (13), followed by the labdane diterpene 2alpha,3alpha-dihydroxycativic acid (8), the clerodane diterpenes 6-acetylteucjaponin B (5), bacchotricuneatin A (1), bartemidiolide (7), butanolide (4), and the sesquiterpenes ilicic acid (11) and tessaric acid (10) (eudesmane and eremophilane type, respectively). S. littoralis was only affected by the clerodanes and showed the strongest response to salviarin (3) and 5, followed by hawtriwaic acid (6) and 12-epi-bacchotricuneatin A (2). Orally injected S. littoralis larvae were negatively affected by 5. Most of the diterpenes had selective cytotoxic effects to insect-derived Sf9 cells with the clerodane 1 being the most active, followed by the eudesmane costic acid (12), the only cytotoxic sesquiterpene. None of these compounds was cytotoxic to mammalian CHO cells.     

Benzofuran derivatives from enceliopsis argophylla

From the composite Enceliopsis argophylla several new benzofuran derivatives were isolated. The unusual structure of the skeleton comprises an isopropylidene group at C-2 and a keto function at C-3 of the furan ring. An organ specific analysis by HPLC showed the compounds being present in leaves, peduncles, bracts, ray and disc flowers. The absolute amounts, however, differed greatly being highest in leaves and bracts.     

Sesquiterpene lactones from Viguiera deltoidea

Three sesquiterpene lactones, 2′,3′-dihydroniveusin-A, 2′,3′-dihydroniveusin-B and 3-acetylchamissonin, were isolated from the dichloromethane extract of leaves of Viguiera deltoidea. The structures were established on the basis of physical and spectroscopic data and that of 3-acetylchamissonin was also confirmed by X-ray analysis.