9-chloro-5,9-dienoic and other fatty acids from marine sponge Penares sp.

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Abstract

The fatty acids and their ethyl esters from an extract of a sponge Penares sp. (South China Sea) were fractionated by high-performance liquid chromatography and analyzed by gas chromatography-mass spectrometry using pyrrolidine, 4,4-dimethyloxazoline, dimethyl disulfide, and hydrogenated derivatives. In some cases, 1Н and 13С NMR spectroscopy was applied for the structural analysis of fatty acids. 71 С12–С28 acids, including 12 new compounds, were found. The new compounds were shown to be (5Z,9Z)-9-chloro-24-methy-5,9-pentacosadienoic, (5Z,9Z)-9-chloro-25-methyl-5,9-hexacosadienoic, (5Z,9Z)-9-chloro-24-methyl-5,9-hexacosadienoic, (5Z,9Z)-9-chloro-25-methyl-5,9-heptacosadienoic, 6-chloro-20-methyl-4-heneicosenoic, 6-chloro-19-methyl-4-heneicosenoic, 6-chloro-20-methyl-4-docosenoic, cis-17,18-methylene-tetracosanoic, 16,21-dimethyldocosanoic, 18,23-dimethyltetracosanoic, 16,18,22-trimethyltricosanoic, and 18,20,24-trimethylpentacosanoic acids. It was shown that the characteristic features of the fatty acid mixture were a high level of constituents with monomethylated chains (over 50%) and the nearly total substitution of common demospongic acids for their chloro-derivatives, previously unknown (5Z,9Z)-9-chloro-5,9-dienoic acids. The presence of analogous structural fragments in the fatty acids from Penares sp. and in some biologically active secondary metabolites from Penares sponges was discussed. The results of this work may be used for the structural, comparative and biosynthetic studies of marine lipids.

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About the authors

Е. А. Santalova

G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch of Russian Academy of Sciences

Author for correspondence.
Email: santalova@piboc.dvo.ru
Russian Federation, 690022, Vladivostok, prosp. 100 let Vladivostoku 159

S. А. Kolesnikova

G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch of Russian Academy of Sciences

Email: santalova@piboc.dvo.ru
Russian Federation, 690022, Vladivostok, prosp. 100 let Vladivostoku 159

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Supplementary files

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2. Fig. 1. New fatty acids (LC) from the sponge Penares sp.

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3. Fig. 2. (a) – Mass spectrometric fragmentation of isomeric ethyl esters (IIa) and (IIIa) (the peak of the molecular ion at m/z 468 [M]+ with 35Cl was low-intensity, the minor peak [M]+ with 37Cl was not recorded); (b) – mass spectrometric fragmentation of bis(methylthio)-derivative of ethyl ether (Ia) (513 [M – Cl]+); (c) – mass spectrometric fragmentation of pyrrolidide (Ib) (479/481 [M]+; to simplify the scheme, less numerous ions corresponding to the elimination of HCl from isotopic fragments at m/z 310/312–422/424) are not shown; (d) – key NMVS correlations for compounds (IIa) and (IIIa).

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4. Fig. 3. (a) – Mass spectrometric fragmentation of pyrrolidide (Vb) (424/425/426/427 [M – 1]+/[M]+); (b) – mass spectrometric fragmentation of ethyl esters (XIa) and (XIIa).

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5. Fig. 4. Hypothetical ways of formation of chlorinated secondary metabolites (XIV) and (XVI) obtained from sponges of the genus Penares.

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