Dehydromatricaria ester

Several nematicidal acetylenic compounds have been isolated. Most are from the Asteraceae (127). Recently isolated are (8R,9R, 10S)-9,10-epoxyheptadec-16-ene-4,6-diyne-8-ol and other compounds from Cirsium. iaponicum (128,129). 1-Phenylhepta-l,3,5-triyne and 2-phehyl-5-(1 -jjropynyl)-thiopene, from Coreopsis lanceolata and cis-dehydromatricaria ester from Soli dago altissima have been shown to be fly ovicidal substances (130,131). 

Conyza canadensis (L.) Cronq. Xiao Fei Peng (aerial part) Essential oils, matricaria ester, dehydromatricaria ester, linoleyl acetate, limonene, linalool, centaur X, dephenyl methane-2-carboxylic acid, cumulene, O-benzylbezoic acid.48 Relieve swelling, itchiness, treat intestine and liver infection, a detoxicant, externally for skin eczyma, wounds, pain caused by arthrritis, toothache. 

Although the compound known today as dehydromatricaria ester (1) was obtained crystalline from essential oils as long ago as 1826 the first correct structure assignment for a natural acetylene, tariric acid (octadec-6-ynoic acid), a component of the seed fat of the Simarubaceae Picramnia tariri DC., was published in 1902". The elucidation of the structure of lachnophyllum ester (2) from the Compositae Lachnophyllum gossipinum Bge. appeared in 1935 and was followed from 1941 onwards by those of several acetylenes from Compositae species headed by matricaria... 

Another example of the specificity encountered in plants is found in the difference between the pathways leading to CH3C=CR and CH3CH=CHR polyacetylenes. Unlike the case of dehydromatricaria ester (1) for which 46 and the Cjs triynene keto ester 48 are precursors , the Cig enediyne skipped-ene ester 45 (Scheme 2) is... 

A pattern similar to that in Figure 6 is believed to apply in higher plants" and microorganisms The more effective conversion of the C16 compound (65 Figure 9) than the C18 compounds (49 and 66) into dehydromatricaria ester (3) in Artemisia spp discredits a hypothesis that a direct Baeyer-Villiger type of oxidation of a Cig-precursor... 

Polyynes (polyacetylenes). Compounds with very diverse structures containing several C/C triple bonds are produced mainly by fungi (basidiomycete cultures) and plants of the families Asteraceae, Apiaceae, and Araliaceae. In addition to conjugated triple bonds the R often also contain C/C double bonds, allene units, thiophene and furan rings. On account of the close biosynthetic relationships between these compounds, the term R is used as a collective name even when only one C/C triple bond is present in the molecule. As result of the work of Bohimann, E. R. H. Jones, Sorensen, and others more than one thousand natural R are now known. The antibiotically active mycotnycin (C H, g02, Mr 198.22, mp. 75 °C) from basidiomycete cultures, dehydromatricaria ester (CiiHgO, Mr 172.18, mp. 105-106°C) from Asteraceae, and the thiarubrins may be mentioned as typical examples (see also ter-thienyls). 

Me ester Dehydromatricaria ester. Occurs in Artemesia vulgaris. Cryst. (pet. ether). Mp 114-115°, 112°. 

A large series of compounds are derived by modification of crepenynic acid and related Cig acetylenic fatty acids. Whereas these acids may be accumulated in seed oils as components of triacylglycerols, modified derivatives usually are found in vegetative portions of plants. The biosynthesis of matricaria ester (4) and dehydromatricaria ester (5) (both with 10 carbon atoms in the acid portion of the molecule) (Fig. 3.1) is typical for this series of compounds. In this instance, fatty acids with chain lengths of less than 18 carbon atoms do not serve as precursors. 

Kobayashi, a., Y. Shibata, and K. Yamashita A Novel Preparation of 1-Acetoxy-cw-pent-2-en-4-yne A New Synthetic Route to c -Dehydromatricaria Ester. Agr. Biol. Chem. 39,911 (1975), and refs, cited therein. 

Biosynthesis.—Bohlmann and Burkhardt have examined the biosynthesis of matricaria ester (49) in both Matricaria trichophylla and Grindelia robusta and have established that (49) is not formed in an analogous manner to the dehydromatricaria ester (50). Feeding experiments showed that (49) is formed from oleate according to Scheme 4. 

Thioethers (XL—XLII) closely related to dehydromatricaria ester, (XLIII) (Stavholt and Sorensen, 1950 Bohlmann and Mannhardt, 1955) which occurs widely in the Anthemideae, have been isolated from Anthemis species (Bohlmann, Arndt, Bornowski and Kleine, 1963). 

Recently, the lactone (LXI) was isolated from a species of Anthemis, a genus in which the corresponding straight chain dehydromatricaria ester (XLIII) is found (Bohlmann, Kleine, Arndt and Kohn, 1965). [See also addendum 0]. 

Using dehydromatricaria ester-1(XLIII) as precursor, it was demonstrated for the first time that an open chain polyacetylene could be converted biologically to an aromatic compound (Bohlmann, Bohm and Rybak, 1965). In this instance, the reaction apparently involved, in addition, migration of the end methyl group. Thus, when XLIII was fed to Anthemis tinctoria, not only was the thioether XLII which was isolated, radioactive, but also the aromatic compound LXXXIII. All of the activity was in the carboxyl carbon. [See also addendum ]. 

Stavholt, K., and N. A. Sorensen Studies relating to naturally-occurring acetylene compounds V. Dehydromatricaria ester (methyl n-decene-triynoate) from the essential oil of Artemesia vulgaris L. Acta Chem. Scand. 4, 1567 (1950). 

Hodge, Jones and Lowe (1966) have pointed out that almost one-third of all natural polyacetylenes and 70% of fungal polyacetylenes have 9 or 10 carbon atoms. Using labelled dehydromatricaria ester, they demonstrated in a number... 

Hodge, P., E. R. H. Jones, and G. Lowe Natural acetylenes Part XXII. trans-Dehydromatricaria ester as a biosynthetic precursor of some fungal polyacetylenes. J. Chem. Soc. 1966, 1216. 

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