Oxidatives Verfahren zur Herstellung kurzkettiger Carbonsäuren aus ungesättigten Fettsäuren

Oxidative Procedure for Production of Short-Chain Carbon Acids from Unsaturated Fatty Acids For decades, the oxidation of oleic acid to acelaic and pelargonic acid has been carried out in industrial scale by ozone. The high costs of ozone production are a problematical point in this procedure. Thanks to the high selectivity the procedure is today still economic. Efforts to replace the ozone oxidation by an oxygen one haven't yet led to a procedure which can be applied in industry. In this work the oxygen oxidation of oleic acid with aldehyds as intermediary carrier of oxygen is reported.     

Wiederveresterung von Konzentraten mehrfach ungesättigter Fettsäuren

Reesterification of Polyunsaturated Fatty Acid Concentrates Fatty acids of the n-6 series such as γ-linolenic acid (C18:3) and of the n-3 series such as α-linolenic (C18:3), stearidonic (C18:4), eicosapentaenoic (C20:5) and docosahexaenoic acid (C22:6) are of great nutritional interest. These acids can be obtained by urea fractionation in concentrated form from natural sources like blackcurrant seed oil, borage oil, evening primrose oil, linseed oil and fish oil, respectively. Certain dietary applications require a reesterification of these fatty acid concentrates with glycerol to triglycerides. Industrial scale methods of reesterification could not be applied as such for the present polyunsaturated fatty acid systems. Therefore reaction conditions had to be adapted to these highly sensitive substances. A one step reesterification method, using ZnCl₂ as catalyst, was optimized for three different fatty acid concentrates composed of the above mentioned acids. Under the given reaction conditions, it could be observed that α-linolenic acid is much more sensitive to polymerization than γ-linolenic acid. Different purification methods of the crude triglycerides have been evaluated, obtaining best results by liquid chromatography methods, in particular with respect to decoloration of the final products.     

Verfahren und Anlagen zur Fraktionierung von synthetischen Fettsäuren

Processes and Plants for the Fractionation of Synthetic Fatty Acids Synthetic fatty acids, prepared by oxidation of paraffins, can be used to save valuable edible fats. Fractional distillation of these fatty acids enable their manifold application. For this, the paraffins have to fulfil certain criteria of quality. In a multiple stage vacuum fractionation process provided with material balance regulator, high boiling complex mixtures can be processed to distillates of high purity. Such a multi-column plant is equipped with stills, fractional columns and rectifying columns, and the plant is controlled by feeding machines. Many years of experience and production data have shown that synthetic fatty acid distillates can be produced economically and these products meet the technical requirements of soap and detergent industry.     

Zur Hydrocarboxymethylierung von ungesättigten Fettsäureestern

On the Hydrocarboxymethylation of Unsaturated Fatty Acid Esters The hydrocarboxymethylation of technical oleic acid and eruca acid methyl ester was tested in the presence of the catalyst system cobalt/4-picoline. It was known for non terminal olefins that the formation of unbranched carboxylic acid derivatives is facilitated with the cobalt/picoline system. So up to 75% of the unbranched product is obtained during the hydrocarboxymethylation of μ-olefins. It was shown in the case of the unsaturated fatty acid methyl esters that here, too, by precise control of the reaction temperature, promoter/catalyst ratio and CO pressure the hydrocarboxymethylation can be carried out in such a way that up to 60% of the α, ω-dicarboxylic acid dimethyl esters are obtained.     

Fraktionierung mehrfach ungesättigter Fettsäuren aus verschiedenen natürlichen Rohstoffen

Fractionation of Polyunsaturated Fatty Acids from Various Natural Oil Sources Blackcurrant seed oil, borage oil and evening primrose oil are known to be sources of γ-linolenic acid (GLA) with values of up to 25% for borage oil. These GLA concentrations are sufficient for most of the applications of these oils as such but some particular utilisations require higher concentrations of up to 70% γ-linolenic acid or more. Different fractionation techniques have been evaluated. Distillation as well as fractionated crystallization at various temperatures did not give any reasonable results. Preparative high performance liquid chromatography gives only separations on reversed phase columns of the RP 18 type. However, specific enrichment in γ-linolenic acid is obtained by urea fractionation in methanol, also with blackcurrant seed oil which contains up to 14% α-linolenic acid. On a large scale basis of around ton scale it was possible to enrich blackcurrant seed oil fatty acids to 70-80% γ-linolenic acid in a preferably 2-stage fractionation process.     

Spurennachweis von mehrfach verzweigten Fettsäuren in Fetten

Detection of Traces of Polybranched Fatty Acids in Fats A method for the detection and quantitative determination of saturated polybranched fatty acids in animal and vegetable fats is described. The method is based on gas-chromatographic determination of polybranched fatty acid methyl esters in the methyl esters which do not form urea adducts. The following amounts of polybranched fatty acids were determined in animal fats: whale oil 15 000 ppm., fish oil 6000 ppm., butter fat 4000 ppm., beef tallow 2000 ppm. and lard 110 ppm. In different vegetable oils and fats upto 200 ppm. of polybranched fatty acids were found. Not only the difference in total content of polybranched fatty acids but also differences in their percentage composition and retention volumes in gas-chromatograms were found. This method therefore offers the possibility of identification of some of the animal fats.     

Die katalytische Metathese von ungesättigten Fettsäureestern

Catalytic Metathesis of Esters of Unsaturated Fatty Acids Several active and selective catalysts have been developed for the metathesis of unsaturated hydrocarbons in homogeneous medium. These are based on WCl₆ and MoCl₅ with Sn(CH₃)₄, Sn(C₆H₅)₄ and Pb(C₆H₆)₄ as the most important co-catalysts. These catalyst systems also permit the metathesis of compounds having functional groups, such as esters of fatty acids and halogenated hydrocarbons. The metathesis of esters of fatty acids enables the synthesis of numerous compounds, which so far were either unknown or difficult to synthesize. Such compounds are, for instance, certain long chain unsaturated dicarboxylic acids which are derived from monoenoic fatty acids, such as oleic acid and erucic acid. From technological viewpoint the unsaturated dicarboxylic acids might be significant as raw material for the preparation of unsaturated polyesters and polyamides, as well as for the synthesis of certain flavoring agents. The metathesis of fatty oils (glycerides) leads to the formation of high molecular weight compounds. The metathesis of semi-drying and drying oils offers the possibility to prepare stand oils having good drying properties.     

Der Einfluß der Chloroplasten auf die Bildung von ungesättigten Fettsäuren in reifenden Rapssamen

Influence of Chloroplasts on the Formation of Unsaturated Fatty Acids in Maturing Rapeseeds In general, seeds that store fats, contain only C₁₈-fatty acids which are desaturated upto linoleic step. Exceptions to this general pattern are the seeds of cruciferae, legumenae and linaceae. Embryos of these seeds develop, especially during the initial stages of maturation, photosynthetically active chloroplasts with a high content of linolenic acid. Therefore, for the breeding of rapeseed plants (cruciferae) having low linolenic acid content in the seed oil, one has to select either such seeds in which very little chloroplasts are formed during maturation, or seeds in which chloroplasts are reduced at an early stage.     

Verfahren zur Anreicherung von Stearidonsäure

Preparation of Stearidonic Acid Concentrates Fatty acids of the n-3 series are precursors of the biochemical synthesis of prostaglandins which are known as inhibitors of blood platelet aggregation. The parent compound of this series, α-linolenic acid (ALA), is transformed to stearidonic acid C18:4 δ6.9, 12.15 (SA) by catalysis by the liver enzyme δ6-desaturase. SA is found in few natural materials such as fish oils and blackcurrent seed oil (BCO) and only at low concentrations. In this context the oil extracted from entrails of squids caught in warm-water seas is reported to present an interesting source of arachidonic acid with contents of up to 8%. A two-step procedure was developed for the preparation of SA concentrates with 15% SA was obtained by urea fractionation. Simultaneously the γ-linolenic acid (GLA) concentration was increased to 80%. Subsequent separation of SA from GLA was carried out by preparative HPLC yielding SA concentrates with a purity of ≧ 90%. These SA concentrates were used for a comparative investigation of the inhibiting effects of some polyunsaturated fatty acids such as GLA, ALA or eicosapentaenoic acid on blood platelet aggregation. It was found that, compared with the other fatty acids. SA inhibits more specifically the aggregation stimulated by thrombine.     

Selektive Härtung mehrfach ungesättigter Fettsäuren in der Flüssigphase

Selective Hydrogenation of Multi-Unsaturated Fatty Acids in the Liquid Phase Fatty acids and esters which contain only one double bond have interesting properties such as high oxidation stability or favourable pour points. For these reasons such products find a broad field of application for instance in the sections cosmetics, textile finishing agents or oilfield chemicals. However, natural fats and oils contain often multi-unsaturated fatty acids such as linoleic and linoleinic acid which are able - even in minor amounts - to change substantially the physical and chemical properties of the fatty material. Therefore, a hydrogenation procedure is needed which enables the selective conversion of multi-unsaturated into mono-unsaturated fatty acids without formation of completely saturated compounds. After a review of the general possibilities in selective hydrogenation a new method is described to hydrogenate with solvent-stabilized palladium colloid catalysts. A remarkable high selectivity was obtained applying very mild reaction conditions. By use of the liquid-liquid two phase technique an easy and complete catalyst recycle is possible.     

Gaschromatographische und dünnschichtchromatographische Untersuchung von Fettsäuren: Die Anwendung von gepackten Glaskapillarsäulen zur Trennung von cis- und trans-ungesättigten Fettsäuren

Gas Chromatographic and Thin-Layer Chromatographic Studies on Fatty Acids: The Application of Packed Glass Capillary Columns for Separation of cis- and trans-Unsaturated Fatty Acids from Saturated Fatty Acids Packed glass capillary columns were used for the quantitative determination of trans- and cis-unsaturated fatty acids in the presence of saturated fatty acids by gas chromatography. The fatty acids were analyzed as methyl esters after interesterification of the triglyceride samples. The conversion of glyceryl esters of fatty acids into methyl esters could be followed using short GC columns and by thin-layer chromatography.     

Produkte der Dimerisierung ungesättigter Fettsäuren VI: Untersuchungen zur Kinetik der Bildung dimerer Fettsäuren

Products of Dimerisation of Unsaturated Fatty Acids VI: Kinetic Studies about the Formation of Dimeric Fatty Acids During the dimerisation reaction of a mixture of 60% oleic acid and 40% linoleic acid samples were collected in time intervals. The samples were converted into their dimethylates by diazomethane and separated by thin layer chromatography in one fraction of monomers and one of dimers. The monomeric fractions were further separated by GC, the dimeric fractions by HPLC. First linoleic acid reacts, either by cyclisation or by attacking another molecule of linoleic acid. Thus linoleic acid has already disappeared nearly completely at the end of the heating up period (after 60 min). The less linoleic acid is present, the more molecules of linoleic acid react with oleic acid molecules. The primary cyclic dimerisation products are slowly converted to aromatic compounds as well as cyclohexane derivatives. The oleic acid is transformed already in the heating up period into its isomer, elaidic acid and isomers thereof with double bonds in other positions of the chain. These products are converted slowly partly to stearic acid, partly to isostearic acids. Dimeric compounds of MW 592 (methylates) are produced as well by reaction of 2 molecules of oleic acid. They are slowly converted to open chain dimeric acids of MW 594 (methylates).     

Neues schonend wirkendes und energiesparendes Verfahrensprinzip zur Geradeausdestillation von überwiegend ungesättigten vegetabilischen Rohsäuren

New Mild Acting and Energy Saving Process for Straight-Run Distillation of Mainly Unsaturated Vegetable Raw Acids A remarkably gentle and newly-developed process for effective first running- and pitch separation especially suitable for the reconditioning of highly unsaturated raw acids as those derived from soybean-, cottonseed-, sunflower- and linseed oil is being discussed. The process is characterized by effective degasification at low temperatures, efficient dehydration with first running separation and high reflux ratio and extremely low evaporation temperatures for the main- and pitch stage of < 220°C or <230°C respectively by maintaining low consumption rates. The first-quality main run fatty acid yield of one flow for a splitting degree of 95 %regarding the free fatty acid content in the raw acid will amount to > 97.5%. The waste water quantity arising per hour and per to of distillate amounts to < 100 1 and only contains < 40 ppm organic substance to be decomposed.     

Produkte der Dimerisierung ungesättigter Fettsäuren IX: Kinetische Untersuchungen zur Dimerisierung von Linolsäure

Products of the Dimerisation of Unsaturated Fatty Acids IX: Kinetic Studies about the Dimerisation of Linoleic Acid To clarify the dimerisation process of linoleic acid, we investigated samples taken in different time intervals. The first reaction step is a water addition at double bonds of the starting material and not double bond isomerisation as previously assumed. The resulting unsaturated monohydroxy fatty acids can cyclize with the second double bond in an intramolecular reaction forming 2,5-disubstituted tetrahydrofuran respectively 2,6-disubstituted tetrahydropyran derivates. Linolenic acid, present nearly always in small amounts in linoleic acid, reacts to first dimerisation products with linoleic acid by formation of a C-C-bond. The aliphatic dimers cyclize in an intramolecular reaction to mono-cyclic compounds. No dimeric acids, which would result from a Diels-Alder-reaction, could be identified. Bicyclic and aromatic dimeric acids can also be found in the early phase of the dimerisation. In the further progress of the reaction isomerisations, hydrogenations and dehydrogenations of the primary reaction products occur, thus the content of aromatic substances increases steadily.     

Produkte der Dimerisierung ungesättigter Fettsäuren V: Die Aromatenfraktion dimerer Fettsäuren

Products of Dimerisation of Unsaturated Fatty Acids V: The Aromatic Fraction of Dimeric Acids The aromatic fraction of dimeric fatty acid esters can be separated according to a decreasing grade of unsaturation by HPLC using an UV-recorder. Hydrogenation experiments of the collected fractions allowed the determination of the number of rings. If the aromatic fraction are oxidized with KMnO₄ using a phase-transfer catalyst benzene 1,2,4- and 1,3,5-tri-, 1,2,4,5-and 1,2,3,5-tetra- and the pentacarboxylic acid were obtained as main products. Consequently we have to conclude that the catalyst causes intramolecular extensive migration of alkyl chains. Finally 2,3-dihydrobenzofurantetracarboxylic acids with different position of the carboxylic groups were detected in the mixture of oxidation products.     

Untersuchungen über die Entstehung von Kohlenwasserstoffen in erhitzten gesättigten Fettsäuren und Fettsäureestern

Studies on the Formation of Hydrocarbons in Fatty Acids and Fatty Acid Esters on Heating The investigations on the volatile compounds of the unsaponifiable matter and the steam distillate of heated saturated fatty acids have shown that on heating in the presence of air, along with other substances, hydrocarbons having a chain length 1 to 2 C atoms shorter than the corresponding fatty acids are formed. The splitting proceeds so slowly in the case of esters that even after 4 hrs of heating at 160°C no reaction products could be detected. By heating palmitic acid under the same conditions, except that vacuum was employed, no perceptible quantities of hydrocarbons were found.     

Übergangsmetallkatalysierte Oxidationen ungesättigter Fettsäuren — Synthesen von Keto- und Dicarbonsäuren

Transition-metal Catalyzed Oxidation of Unsaturated Fatty Acids — Synthesis of Ketocarboxylic Acids and Dicarboxylic Acids Terminal unsaturated C₁₀–C₁₄-fatty acid methylesters (9-decenoic-, 10-un-decenoic-, 13-tetradecenoic methylesters) were converted to methylketocarboxylic methylesters (yields: 60–75%, isolated) by oxidation with O₂/H₂O at roomtemperature under catalysis of PdCl₂/CuCl₂. Using RhCl₃/FeCl₃ at 80°C yields of 40–60% were obtained. For the first time methyl oleate was converted directly to a mixture of 9-oxo- and 10-oxo-stearic acid methylester by palladium catalyzed oxidation. In DMF/H₂O the selectivity to these two ketoesters was 85% (15% isomers), in dioxane/H₂O the selectivity droped to 55% while the yield of the oxostearic acid esters climbed to 70%. The Mn-catalyzed oxidative cleavage of methylketocarboxylic acid esters with O₂ at 115°C led in each case to a mixture of two dicarboxylic acid esters in a molar ratio of 2 : 1. Starting with 9-oxodecanoic acid azelaic and suberic acid were obtained at a conversion rate of 90%. Analogous 10-oxoundecanoic acid led to C₁₀/C₉- and 13-oxotetradecanoic acid led to C₁₃/C₁₂-dicarboxylic acids. The oxidative cleavage of 9-/10-oxostearic acid methylester yielded mixtures of C₈–C₁₀-monocarboxylic acids and methylesters of C₈–C₁₀-dicarboxylic acids.     

Cis-trans-Isomerisierung ungesättigter Fettsäuren im Laufe der Alkydharz-Herstellung

Cis-trans Isomerisation of Unsaturated Fatty Acids during the Preparation of Alkyds We studied the influence of the preparation conditions of alkyd resins with the help of infrared spectroscopy of soya and linseed oil on the cis-trans-isomerisation of the unsaturated fatty acids present. The most important of all conditions was the temperature. The higher content of trans-isomers can be seen in the properties of alkyd resins.     

Regioselektive C-H-Funktionalisierung von Fettsäuren und Fettsäuremethylestern

Regioselective C-H-Functionalization of Fatty Acids and their Methyl Esters Fatty acids and thier methyl esters can be chlorinated preferentially at the terminal methylene groups with N-alkylchloroamines in sulfuric acid. With capric acid and its methyl ester the optimal reaction conditions for the selective chlorination were elaborated and then transferred to longer fatty acids up to stearic acid. The influence of the solvent, the temperature and the nature of different chlorinating reagents on the selectivity was studies. The capillary GC/MS-analysis of the isomeric chlorinated fatty acids is described.     

Über die Reduktion ungesättigter Fettsäuren und deren Ester zu ungesättigten Fettalkoholen durch selektive katalytische Hochdruckhydrierung V: Die katalytische Wirkung von Mischoxiden und reinen Oxiden

Reduction of Unsaturated Fatty Acids and Their Esters to Fatty Alcohols by Selective High-Pressure Catalytic Hydrogenation V: Catalytic Action of Mixed and Pure Oxides The catalytic action of mixed oxides and pure metal oxides such as zinc-chromium oxide, zinc-iron oxide, magnesium-iron oxide and zinc oxide, chromium oxide, titanium dioxide and zirconium dioxide in the high-pressure hydrogenation is described. Substances taken for testing were methyl oleate, butyl oleate, oleic acid, methyl undecenoate and methyl linolate. Optimum combinations of catalysts and the corresponding reaction conditions are reported for oxidic catalysts. The previously postulated hypothesis on the catalytic action in the selective hydrogenation is supported by considering the semiconductor properties of the metallic oxides.