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Further Compounds from Haplophyllum ptilostylum
Abstract
In addition to previously isolated coumarins and lignans, we have isolated a new coumarin, ptilin and two known lignans, matairesinol and arctigenin from the aerial parts of Haplophyllum ptilostylum.
... References Acutine (1), Dictamnine (25), Leptomerine (38), N-Methyl-2-Phenylquinolin-4-One (43), 2-heptylquinoline-4-one (56), [27] Acutinine (2) [102] Bucharaine (3), Haplopine (9), 4-Hydroxyquinoline-2-one (27) [30] Daurine (45), Folimine (37), Robustinine (26), Robustine (11) [28] Dubinidine (4), Foliosine (28), Foliosidine (48) [31] Dubinine (5), Dubamine (44), Norgraveoline (29) [29] (+)-Dihydroperfamine (33) [32] Edulinine (51) [86] Evoxine (6), Flindersine (22), 3-(3,3-dimethylallyl)-4-(3,3-dimethylalloxy)-2quinolone (54) [45] Glycohaplopine ( 3-b] quinoline (15) [101] ...
The genus Haplophyllum belongs to the large family of flowering plants, Rutaceae. The genus Haplophyllum comprises of about 133 species of low shrubs and perennial herbs in the subtropical and tropical regions of the northern hemisphere of the Old World, markedly in Iran, Turkey and Central Asia. Species from this genus contains a rich sources of secondary metabolites such as quinoline alkaloids, furoquinoline alkaloids, isoquinoline alkaloids, acridone alkaloids, amide alkaloids, quinolone alkaloids, lignans, arylnaphtalene lignans, lignan glycosides, flavonoids, coumarins, saponins, amides and sterols. Extracts and pure compounds isolated from Haplophyllum species have been experimentally shown to have various bioactivities such as antioxidant, anti-inflammatory, antimicrobial, insecticidal, antiprotozoal, molluscicidal, cytotoxic, anti-cancer and anti-HIV activities. This reviews compile the 4455 phytochemical constituents, various pharmacological activities of the different plants of the Haplophyllum genus and the NMR value of different compounds of Haplophyllum genus.
... References Acutine (1), Dictamnine (25), Leptomerine (38), N-Methyl-2-Phenylquinolin-4-One (43), 2-heptylquinoline-4-one (56), [27] Acutinine (2) [102] Bucharaine (3), Haplopine (9), 4-Hydroxyquinoline-2-one (27) [30] Daurine (45), Folimine (37), Robustinine (26), Robustine (11) [28] Dubinidine (4), Foliosine (28), Foliosidine (48) [31] Dubinine (5), Dubamine (44), Norgraveoline (29) [29] (+)-Dihydroperfamine (33) [32] Edulinine (51) [86] Evoxine (6), Flindersine (22), 3-(3,3-dimethylallyl)-4-(3,3-dimethylalloxy)-2quinolone (54) [45] Glycohaplopine ( 3-b] quinoline (15) [101] ...
The genus Haplophyllum belongs to the large family of flowering plants, Rutaceae. The genus Haplophyllum comprises of about 133 species of low shrubs and perennial herbs in the subtropical and tropical regions of the northern hemisphere of the Old World, markedly in Iran, Turkey and Central Asia. Species from this genus contains a rich sources of secondary metabolites such as quinoline alkaloids, furoquinoline alkaloids, isoquinoline alkaloids, acridone alkaloids, amide alkaloids, quinolone alkaloids, lignans, arylnaphtalene lignans, lignan glycosides, flavonoids, coumarins, saponins, amides and sterols. Extracts and pure compounds isolated from Haplophyllum species have been experimentally shown to have various bioactivities such as antioxidant, anti-inflammatory, antimicrobial, insecticidal, antiprotozoal, molluscicidal, cytotoxic, anti-cancer and anti-HIV activities. This reviews compile the 4455 phytochemical constituents, various pharmacological activities of the different plants of the Haplophyllum genus and the NMR value of different compounds of Haplophyllum genus.
The genus Haplophyllum belongs to the family Rutaceae. More than 70 species, growing from the Mediterranean region to eastern Siberia (most of them in western and central Asia), are assigned to this genus (Everett 1981). Only eight species can be found in Europe (Townsend 1968); H. patavinum (L.) G. Don fil. is the only species occurring in Italy (Townsend 1968; Pignatti 1982).
A new furanoquinoline alkaloid named haplotin along with haplophytin A and eudesmin have been isolated form the methanol soluble part of Haplophyllum acutifolium belonging to the family Rutaceae. The structures of all these isolated constituents were elucidated by spectroscopic means. However, the structure of the new constituent (haplotin) was reconfirmed via 2D NMR techniques. Among the all isolated metabolites, eudesmin was found the most active constituent when studied for phytotoxicity, antifungal and antibacterial activities.
In addition to previously isolated coumarins and lignans, we have obtained one new aryltetralin lignan and three new prenylated diarylbutyrolactone lignans from the aerial parts of Haplophyllum ptilostylum. The structures of the new compounds were established by 1H NMR, 13C NMR (BB and DEPT), COSY, HETCOR, COLOC and selective INEPT experiments.
Three known arylnaphthalene lignans (justicidin B, diphyllin and tuberculatin), and one dibenzylbutyrolactone (arctigenin) were isolated from native plants, callus and suspension cultures of Haplophyllum patavinum. The present paper represents the first report on arylnaphthalene lignan production by in vitro cultures; in vitro, the biogenetic potential is strictly dependent on the cell strain.
Four new lignans were isolated from Haplophyllum ptilosyhm, their structures were establihed by spectral data, using COSY, HETCOR, COLOC, selective INEPT experiments. Pharmacological tests were performed on human cell lines and HIV-1 reverse transcriptase. The success of semisynthetic anticancer drugs etoposide (1) and teniposide (2) focused the attention on the availability of podophyllotoxin (3) which was first isolated from PodophyZlum peltaturn L. later in higher quantity from P.hexundium (l). Since the total synthesis of podophyllotoxin is uneconomic, either systematic cultivation of the plant or tissue culture methods could be used to produce compound 3, a third way is to screen seed bearing plants for aryltetraline lignans (2). During the
Haplophyllum telephioides yielded a new alkaloid, 7-hydroxy-9-methoxyflindersine and a new lignan 4-acetyldiphyllin, in addition to haplomyrtin, diphyllin and vanillic acid. The structures were established from spectral data.
The genus Haplophyllum (Rutaceae) comprises about 70 species with rich phytochemistry. The characteristic classes of secondary metabolites present throughout this genus include flavonols, coumarins, lignans and alkaloids, many of them endowed with remarkable bioactivities including antiinflammatory, antiparasitary, anticancer and antiviral effects. To facilitate further research into this genus, and highlight its interest as a rich source of bioactive natural principles, this chapter provides an overview of the occurrence of over 240 different secondary metabolites in about 45 different species, followed by a brief discussion of their pharmacological applications with focus on the anticancer properties of arylnaphthalene lignans and quinoline alkaloids and the biosynthetic capabilities of shoot cultures for the bioproduction of these interesting metabolites.
Although there are a number of Haplophyllum species in the world, H. acutifolium (DC.) G. Don, H. buxbaumii (Poiret) G.Don, H. buxbaumii (Poiret) G.Don, subsp. Buxbaumii, H. cappadocium Spach, H. glabrinum, H. hispanicum Sprach, H. myrtifolium Boiss., H. patavinum (L.) G. D. ON. fil., H. perforatum (M.B.) Vved., H. ptilostylum Spach, H. suaveolens (DC.) G.Don, H. telephioides Boiss., H. thesioides (Fisch ex DC.) G. Don, H. tuberculatum (Forssk.) A.Juss. and H. vulcanicum Boiss. & Heldr. were most studied and a lot of compounds isolated. Only alkaloids, coumarins and lignans of these species are mentioned in this article. In addition some volatile components of H. tuberculatum were also given
In addition to a known derivative, five new coumarin-hemiterpene ethers were isolated from the leaves of Artemisia laciniata, A. armeniaca and A. tanacetifolia and identified by 1H NMR and, in part, by 13C NMR spectroscopy. The coumarin patterns are characterized particularly by compounds with a hydroxylated and saturated isoprenoid unit attached to oxygen at the C-8 position and by 5,7,8-trioxygenated derivatives. The chemotaxonomic significance of the coumarin-terpenoid ethers within Artemisia is discussed.
Gravelliferone methyl ether (I), xanthyletin, furopinnarin (IV), pinnarin (VI), benahorin (VII), limettin, luvangetin, bergapten (V) and a new coumarin sabandinin (X) were isolated from the roots of Ruta pinnata L. fil. The structures of I, IV and VII were confirmed by degradative studies.
The aerial parts of Jurinella moschus afforded the lignane arctigenin, four sesquiterpene lactones, the germacranolides salonitenolide and two new ones as well as a new elemanolide. The structures were elucidated by high field 1H NMR spectroscopy.
Pinoresinol dimethyl ether, secoisolariciresinol, lariciresinol, isolariciresinol and isolariciresinol-4′-methyl ether were isolated from the knots of dead trees of Araucaria angustifolia. The 13C NMR spectra of these compounds, their methyl and acetyl derivatives, and the corresponding one of matairesinol, have been recorded and the signals assigned. On the basis of these assignments, the structure of the new monomethyl ether of isolariciresinol has been established.
The methoxyl resonance of a 5-methoxyfuranocoumarin provides a simple method for distinguishing between an angular and a linear furanocoumarin. The effects of furan substituents on the coumarin nucleus have been estimated.
The aerial parts of both Drummondita hassellii and D. calida have yielded a number of simple furoquinoline alkaloids and polymethoxylated flavonols. Of the latter 3,5,6,7,8,4′-hexamethoxyflavonol (auranetin-5-methyl ether) and 3,5,7,8,4′-pentamethoxyflavonol (flindulatin-5-methyl ether), both isolated from D. calida, appear to be novel. In addition both species produced dihydrocinnamic acid derivatives, including the previously unrecorded trans-avicennic acid [6-(3-methylbut-1-(E)-3-dienyl)-5, 7-dimethoxy-2,2-dimethylbenzopyran-8-propanoic acid]. Finally, three novel coumarins were isolated from D. hassellii and identified as 6,7-di(3,3-dimethylallyloxy)-5-methoxycoumarin, 6,7-di-(3,3-dimethylallyloxy)-5-hydroxycoumarin and 7-(3,3-dimethylallyloxy)-6-hydroxy-5-methoxycoumarin. No coumarins were detected in D. calida. The systematic value of these findings is briefly discussed.
The 1H-nuclear magnetic resonance spectra of more than one hundred natural coumarins were obtained and analysed to provide quantitative spectra-structure correlations based on chemical shifts and coupling constants. These data were in turn used to construct a program whereby the spectra of unfamiliar or novel coumarins could be processed systematically to deduce the probable structure of the unknown. Examples of the use of the method are given and its limitations are discussed.