Furanoid Fatty Acids Research Articles

Separation of the Fatty Acids in Menhaden Oil as Methyl Esters with a Highly Polar Ionic Liquid Gas Chromatographic Column and Identification by Time of Flight Mass spectrometry

The fatty acids contained in marine oils or products are traditionally analyzed by gas chromatography using capillary columns coated with polyethylene glycol phases. Recent reports indicate that 100 % cyanopropyl siloxane phases should also be used when the analyzed samples contain trans fatty acids. We investigated the separation of the fatty acid methyl esters prepared from menhaden oil using the more polar SLB-IL111 (200 m × 0.25 mm) ionic liquid capillary column and the chromatographic conditions previously optimized for the separation of the complex mixture of fatty acid methyl esters prepared from milk fat. Identifications of fatty acids were achieved by applying Ag(+)-HPLC fractionation and GC-TOF/MS analysis in CI(+) mode with isobutane as the ionization reagent. Calculation of equivalent chain lengths confirmed the assignment of double bond positions. This methodology allowed the identification of 125 fatty acids in menhaden oil, including isoprenoid and furanoid fatty acids, and the novel 7-methyl-6-hexadecenoic and 7-methyl-6-octadecenoic fatty acids. The chromatographic conditions applied in this study showed the potential of separating in a single 90-min analysis, among others, the short chain and trans fatty acids contained in dairy products, and the polyunsaturated fatty acids contained in marine products.

ChemInform Abstract: Catalytic Isomerization of 1‐Alkynyl‐2,3‐epoxy Alcohols to Substituted Furans: Succinct Routes to Furanoid Fatty Acids and Difurylmethanes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Catalytic Isomerization of 1-Alkynyl-2,3-epoxy Alcohols to Substituted Furans: Succinct Routes to Furanoid Fatty Acids and Difurylmethanes

A versatile procedure for the preparation of synthetically valuable 2,5-disubstituted and 2,3,5-trisubstituted furans via mercury(II)-mediated isomerization of 1-alkynyl-2,3-epoxy alcohols is described. Mercury(II)-catalyzed isomerization of alkynyl epoxides 3a-k derived from cyclic Phi-alkynyl allylic alcohols furnishes 2,3,5-substituted furans bearing an aldehyde or keto group on the C-2 side chain. The reaction is used in a succinct and efficient synthesis of the furanoid fatty acid F-5. In contrast, the mercury(II)-catalyzed reaction of a series of alkynyl epoxides 3m-p lacking ring fusion affords difurylmethanes 5, presumably by the dimerization of intermediate 2-(alpha-hydroxyalkyl)furans 4.

The impact of furanoid fatty acids and 3‐methylnonane‐2,4‐dione on the flavor of oxidized soybean oil

AbstractOils from soybeans with high or low contents of furanoid fatty acids were evaluated during storage for flavor intensity of soybean oil (SBO) off‐flavor, but no significant differences were found. In addition, the compound 3‐methylnonane‐2,4‐dione (MND), a breakdown product of furanoid fatty acids suggested by other researchers to contribute to reversion flavor of SBO, was evaluated for its contribution to off‐flavor. The compound was synthesized in the laboratory and purified by gas chromatography (GC) on a Silar 10 C column. GC analysis of the purified MND on a nonpolar SPB‐1 column showed two well‐separated main peaks that have been suggested to represent keto and enol forms. Between these two peaks, a bridge of poorly resolved compounds may have represented various possible enol forms or an equilibration among these forms during the GC separation. MND had an intense straw‐like and frulty odor when evaluated at the outlet of a gas chromatograph. Sensory evaluation of MND in a mineral oil/water emulsion system showed that its flavor intensity increased almost imperceptibly with increased concentration (from 0.09 to 2.56 ppm). An explanation for this unusual flavor response may be that, when molecularly dispersed in air, MND has an intense odor, but when placed in a mineral oil or soybean oil emulsion, MND may exist in a form with relatively low flavor intensity, or it may be bound by the media. The concentrations of MND in SBO at various peroxide values were measured at 0 to 0.804 ppb, which were far less than concentrations tested in mineral oil/water emulsions during sensory evaluation and below published odor threshold values for MND in oil. Therefore, these results do not support the theory that furanoid fatty acids or MND contribute strongly to the reversion flavor of SBO.

ChemInform Abstract: Total Synthesis of the Naturally Occurring Furanoid Fatty Acid, F5.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Hay-like off-flavour of dry parsley

The flavour of parsley was found to change during drying and storage. Quantification of 27 potent odorants, selected by dilution experiments and calculation of odour activity values, indicated that 3-methyl-2,4-nonanedione was mainly responsible for the hay-like off-flavour. Two furanoid fatty acids, known to be precursors of 3-methyl-2,4-nonanedione, were detected in dry parsley. The decrease in the intensities of the parsley-like, metallic and green notes in the odour profile during storage of dry parsley was due to losses of p-mentha-1,3,8-triene, myrcene and (Z)-6-decenal. Sulphurous cabbage-like and malty notes were caused by dimethyl sulphide, methylpropanal as well as 2- and 3-methylbutanal. The effect of the water activity (at a w levels of 0.15, 0.25, 0.35) on the changes in the concentrations of all these compounds during storage of dry parsley was investigated.

Total synthesis of the naturally occurring furanoid fatty acid, F 5

The furanoid fatty acid F 5 has been synthesized using a mercury( II) catalyzed isomerization of 2-(1,2-oxiranylcyclododecyl)-3-nonyn-2-ol.

Stability of furanoid fatty acids in soybean oil

AbstractAnalysis of the positional distribution of the furanoid fatty acids, 10,13‐epoxy‐11,12‐dimethyloctadeca‐10, 12‐dienoic acid (F20) and 12,15‐epoxy‐13,14‐dimethyleicosa‐12,14‐dienoic acid (F22), in soybean oil (SBO) indicated that they were preferentially esterified with the primary‐OH groups of glycerol molecules. Hydrogenation of SBO reduced the concentrations of F20 and F22 somewhat. During exposure of SBO to daylight, F20 and F22 were completely degraded within two days, whereas linoleic acid and linolenic acid were not affected. β‐Carotene inhibited both the degradation of the furanoid fatty acids and their oxidation to the odorant 3‐methyl‐nonane‐2,4‐dione (MND), which contributes strongly to the light‐induced off‐flavor of SBO. A model experiment indicated that two days of light exposure of SBO, followed by filtration through silica gel and further refining, prevented the formation of MND during subsequent storage of the oil.

Conversion of unsaturated fatty acids — Nucleophilic additions to methyl (E)‐12‐Oxo‐10‐octadecenoate [1

AbstractMethyl ricinoleate is converted in 57% yield into methyl (E)‐12‐oxo‐10‐octadecenoate (4) by oxidation of the 12‐OH group and conjugation of the double bond. The enone fatty acid methylester 4 reacts in high yield with anions of 1,3‐dicarbonyl compounds, nitroalkanes, acylanions from aromatic aldehydes and cyanide to new C10‐functionalized fatty acids. The nitroalkyl adducts can be converted into pyrroloid and furanoid fatty acids.

Furanoid fatty acids in oils from soybeans lacking lipoxygenase isoenzymes

AbstractThe concentrations of 10, 13‐epoxy‐11, 12‐dimethyloctadeca‐10, 12‐dienoic acid (F20) and 12,15‐epoxy‐13, 14‐dimethyleicosa‐12, 14‐dienoic acid (F22) were determined by a stable isotope dilution assay in oils extracted from the soybean cultivar Century and from five soybean genotypes that lacked one or two of the three lipoxygenase isoenzymes. The concentrations of F20 and F22 ranged between 190–225 mg/kg oil and 91–132 mg/kg oil, respectively. The concentration differences were not correlated to the differences in lipoxygenase activities of the soybeans.

Chemical and enzymatic preparation of acylglycerols containing C18 furanoid fatty acids.

C18 furanoid triacylglycerol [glycerol tri-(9,12-epoxy-9,11-octadecadienoate)] was prepared by chemical transformation of triricinolein isolated from castor oil. The procedure involved oxidation, epoxidation and cyclization of the epoxy-keto intermediate with sodium azide and ammonium chloride in aqueous ethanol. The furanoid triacylglycerol was also obtained by esterification of C18 furanoid fatty acid with glycerol using Novozyme 435 (Novo Nordisk A.S., Bagsvaerd, Denmark) as biocatalyst. When Lipozyme (Novo Nordisk A.S.) was used, a mixture of the furanoid 1(3)-rac-monoacylglycerol and 1,3-diacylglycerol was obtained. In order to obtain the C18 furanoid 1,2(2,3)-diacylglycerol, selective hydrolysis of the furanoid triacylglycerol was achieved using porcine pancreatic lipase in tris(hydroxymethyl) methylamine buffer. Interesterification of triolein with methyl C18 furanoid ester in the presence of Lipozyme showed maximum incorporation of 34% of furanoid fatty acid. Extension of the interesterification to vegetable oils (olive, peanut, sunflower, corn and palm oil) allowed a maximum of 24% furanoid acid incorporation to be achieved.

Synthesis of dimethyl‐substituted C18 furanoid fatty ester

Reaction of a C18 furanoic fatty acid with dimethyl dicarboxylate (DMAD) furnished the corresponding bicyclo Diels‐Alder adduct, which was partially hydrogenated over Pd/BaSO4. Heat treatment (160–180°C) of the partially hydrogenated product caused a retro‐Diels‐Alder reaction to yield a furanoid fatty acid derivative containing methoxycarbonyl (COOCH3) substituents at the 3‐and 4‐positions of the furan nucleus. Reduction of the COOCH3 substituents with LiBH4 gave the corresponding CH2OH‐substituted furanoid fatty acid. Hydrogenation of the latter over Pd/C furnished the desired dimethyl‐substituted furanoid acid derivative (overall yield 60%). The spectroscopic properties of the intermediates and product are reported.

Detection of Furanoid Fatty Acids in Soya‐Bean Oil – Cause for the Light‐Induced Off‐Flavour

AbstractThe following furanoid fatty acids were detected in soya‐bean oil (SBO), wheat germ oil, rapeseed oil and corn oil: 10,13‐epoxy‐11‐methyloctadeca‐10,12‐dienoic acid(I),10,13‐epoxy‐11,12‐dimethyloctadeca‐10,12‐dienoid acid (II), 12,15‐epoxy‐13,14‐dimethyleicosa‐12,14‐dienoic acid (III). A model experiment indicated that II and III were quickly photooxidized with formation of the intense flavour compound 3‐methyl‐2‐4‐nonanedione (MND) as secondary product. MND causes the light‐induced off‐flavour of SBO. A method for the quantification of the three furanoid fatty acids in vegetable oils was developed. The amounts of II and III were relatively high (0.02‐0.04%) in unprocessed and refined SBO and in one sample of wheat germ oil and quite low (0.0015–0.0035%) in corn oil and rapeseed oil. The furanoid fatty acids I, II and III were absent on olive and sunflower oils.

Furanoid Fatty Acids and Lipids

AbstractThe furanoid fatty acids and furanoid lipids are reviewed, present in nature in testes and liver of many fishes, or produced through autoxidation or photo‐oxidation of linoleic and linolenic acids. Some recent working hypotheses are examined and analyzed about the bio‐synthesis of furanoid fatty acids in fishes.

Studies on lipids of crayfish, Procambarus clarkii. I. Furanoid fatty acids.

The fatty acid compositions of crayfish hepatopancreas lipids have been studied. Seven homologous unusual furanoid fatty acids, detected by gas chromatography-mass spectrometry, accounted for 18% of the cholesteryl ester fatty acids. The major component among them was 12, 15-epoxy-13, 14-dimethyleicosa-12, 14-dienoic acid (47%), and the hitherto unknown 8, 11-epoxy-9, 10-dimethylhexadeca-8, 10-dienoic acid was also present. These acids were concentrated in cholesteryl esters, and only trace amounts were found in triglycerides and phospholipids. The distribution of furanoid fatty acids in crayfish did not correspond to that in fish. This is the first report of fatty acids containing a furan ring in crustaceans.

ChemInform Abstract: Chemical Synthesis of Furanoid Fatty Acids (38 Literaturangaben).

Chemischer InformationsdienstVolume 13, Issue 22 Reviews ChemInform Abstract: Chemical Synthesis of Furanoid Fatty Acids (38 Literaturangaben). L. K. JIE, L. K. JIESearch for more papers by this authorS. F. MARCEL, S. F. MARCELSearch for more papers by this author L. K. JIE, L. K. JIESearch for more papers by this authorS. F. MARCEL, S. F. MARCELSearch for more papers by this author First published: June 1, 1982 https://doi.org/10.1002/chin.198222363AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue22June 1, 1982 RelatedInformation

32] Chemical synthesis of furanoid fatty acids

This chapter discusses the chemical synthesis of furanoid fatty acids. The occurrence of furanoid fatty acids in nature seems to be more widespread than initially expected, at times in high concentrations and localized in certain organs or tissues. It is found that coupled with their unknown properties, the synthesis of furanoid fatty acids not only reconfirms the material that had been characterized by degradation and spectrometric methods. The classical approach to furan ring formation consists of acid-catalyzed cyclodehydration of dimethylene-interrupted dioxo compounds. Methyl linoleate, linolenate, ricinoleate, and a few other less common naturally occurring fatty acids— namely, vernolic, and ximenynic acids, have been used as starting material for furanoid fatty acid production. Methyl ricinoleate has proved to be the most potent substrate in selectively producing a single positional furanoid derivative, as the hydroxy function in natural ricinoleic acid is localized at C-12. Alkylation of furan at its relatively more reactive 2- or 5-position of the ring was achieved by initial treatment of furan with a molar equivalent of butyl lithium to form the 2-1ithiofuran derivative, which was condensed with 1-bromoalkane of the required chain length.

Fatty acid composition and the characterization of a novel dioxo C 18-fatty acid in the latex of Hevea brasiliensis

The fatty acids of the triacylglycerol fraction of the latex of the rubber plant consists of 97% of a C 18 furanoid fatty acid, 10,13-epoxy-11-methyloctadeca-10,12-dienoic. The free fatty acid fraction is composed of a more equally distributed mixture of 16:0, 18:0, 18:1, 18:2 and the furanoid acid. A novel dioxo fatty acid, 10,13-dioxo-11-methyloctadecanoic, was also isolated and characterized.

Synthesis of a fish C20 furanoid fatty acid from the lipid extract of the latex of the rubber plant (Hevea brasiliensis)

10,13-Epoxy-11-methyloctadeca-10,12-dienoic acid, isolated from the latex of the rubber tree, was chain-extended by two carbons to give the naturally occurring 12,15-epoxy-13-methyleicosa-12,14-dienoic acid in high yield.

Synthesis of three-, five-, six-membered carbocyclic and furanoid fatty acids

This review covers the various synthetic routes to the carbocyclic and furanoid fatty acids, and examines numerous refinements to such schemes to improve the yield or to permit extension of the procedure to novel compounds. The occurrence of these unusual fatty acids in nature is also briefly reviewed.