A systematic characterization of the reversion flavor of soybean oil

The volatile flavor compounds in a reverted soybean oil with a peroxide number of 4.3 meq/kg were isolated by a semicontinuous counter-current vacuum steam-distillation process, fractionated by repeated gas chromatography, and identified by infrared and mass spectrometry. A total of 71 compounds were identified, which included 19 acids, 39 nonacidic compounds, and 13 tentatively identified compounds. The acids consisted of eight normal saturated acids, nine α,β-unsaturated acids, a branch-chain acid, one hydroxy acid, two keto acids, three lactones, and one aromatic acid. The nonacidic compounds consisted of two esters, eight normal saturated aldehydes, two branched-chain aldehydes, five 2-enals, three dienals, eight ketones, eight alcohols, six hydrocarbons, and four aromatic compounds. The mechanism of formation of the identified compounds indicated that they were mostly primary or secondary autoxidation products of the hydroperoxides of the unsaturated fatty esters. Since many of the identified compounds were produced from oleic and linoleic acids, it is doubtful that linolenic acid was solely responsible for the reversion flavor. Of the compounds identified two are of unusual interest. They are 1-decyne and 2-pentyl furan. The former is the first acetylenic compound reported as the autoxidation products of unsaturated fatty esters which contained only double bonds. The latter imparts to an oil at concentrations of 5–10 ppm a beany and grassy flavor reminiscent of that of a reverted soybean oil. Since this compound is postulated as being produced by the autoxidation of linolenic acid, it is suggested that the presence of linolenic acid catalyzes the autoxidation of linoleic acid and possibly alters the decomposition pattern of its hydroperoxides.     

Unsaturated C18 α-hydroxy acids inSalvia nilotica

The oil ofSalvia nilotica Jacq. (Labiatae) seed contains 0.6% α-hydroxyoleic, 4.2% α-hydroxylinoleic, and 5.4% α-hydroxylinolenic acids. The first two have not been found previously in seed oils. In addition to the common fatty acids, also identified were small amounts of three unsaturated C₁₇ acids and one branched chain C₁₇ acid. Methyl esters of the component fatty acids were fractionated by both column and thin-layer chromatography. These esters were identified by combination of gas chromatography, GC-mass spectrometry, ozonolysis-GC, infrared, and nuclear magnetic resonance.     

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

Sulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C_16:0, C_18:0, C_18:1, and C_18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO₃ to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and ¹HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.     

Quantification of Nonanal and Oleic Acid Formed During the Ozonolysis of Vegetable Oil Free Fatty Acids or Fatty Acid Methyl Esters

The ozonolysis of unsaturated lipids is a process that has been used to generate aldehydes, acids, alcohols, and other biobased chemical intermediates. Reported here is a method that can be used to measure the formation of nonanal and oleic acid during the ozonolysis of unsaturated vegetable oil fatty acids or their methyl esters to indicate the extent of the ozonolysis reaction. Derivatization was performed using boron trifluoride in methanol solution to transform nonanal and oleic acid into nonanal dimethyl acetal and oleic acid methyl ester, respectively. Undecanal and 10‐heptadecenoic acid were used as internal standards and separation was performed using gas chromatography coupled with a flame ionization detector. The method was validated by performing a standard addition procedure in which nonanal or oleic acid standards were spiked into samples collected during the ozonolysis of oleic acid or canola oil fatty acid methyl ester (FAME). Linear regression results indicated that the measured nonanal and oleic acid are in good agreement with the actual amounts of nonanal and oleic acid added to the sample with at least 98 % recovery. The application of the method was demonstrated by the successful measurement of nonanal and oleic acid formed throughout the ozonolysis process for high oleic canola oil FAME.     

Highly unsaturated fatty acids. II. Fractionation by urea inclusion compounds

Summary 1. Urea segregation has been found to be a useful tool in concentration of highly unsaturated acids and esters. Fatty acids and esters derived from fish oils and methyl esters of hog adrenal fatty acids have been fractionated, and the polyunsaturated acids have been enriched. 2. The tendency for fatty acids and esters to combine with urea decreases with increasing unsaturation. Combination is favored by lowered temperature. Polyunsaturated acids are concentrated in the final filtrate whereas esters of these acids appear in the final inclusion compound fractions. Fatty acid concentrates have been obtained with iodine values ranging from 294 to 356. Bound esters exhibited iodine values as high as 338. 3. The increased chain length brought about by esterification has a minor role in increasing the yield of inclusion compounds. Likewise, shifting of the terminal polar group in an acid toward the center of the molecule by esterification does not explain the higher yield of inclusion compound from esters. 4. The improved tendency of esterified acids to form urea inclusion compounds is probably due to blocking of association of acid groups. This effect is found in unsaturated acids and in short chain saturated acids. In long chain saturated acids and esters this effect is not noticed. Both give high yields of inclusion compounds because the effect of the carboxyl group is overshadowed by the high energy of formation contributed by the long carbon chain. Taken from a dissertation presented by A. M. Abu-Nasr to the Graduate School of Texas Agricultural and Mechanical College in partial fulfillment for the requirements of the Ph.D. degree, May, 1953. Supported in part by contract N8onr-66218 of the Office of Naval Research. Hormel Institute publication No. 93.     

Branched carboxylic acids from long-chain unsaturated compounds and carbon monoxide at atmospheric pressure

Carbon monoxide at atmospheric pressure adds readily to the double bonds of certain long-chain unsaturated compounds in concentrated sulfuric acid to produce branehed carboxylic acids. Unsaturated compounds studied were oleic acid, 10-hendecenoic acid, oleyl alcohol, methyl ricinoleate, and linoleic acid. A major component from the reactions of the last two compounds is the same. Infrared spectrophotometry and gas-liquid chromatography have been the major tools employed in determining composition and structure of the products in addition to the usual chemical and physical determinations. Both the concentration and quantity of sulfuric acid are critically important variables in determining the yields. Water is an essential reactant also and must be available throughout the reaction. Carbon monoxide has been prepared and utilizedin situ by a modification of Koch’s (1) method in which the unsaturated compound mixed with formic acid is added to concentrated sulfuric acid or carbon monoxide from a cylinder is passed through sulfuric acid to which the unsaturated compound is added. A method for preparing methyl and butyl esters of carboxyl groups which are difficult to esterify is described. Reaction mechanisms involving intermediate carbonium and oxoearbonium ions are proposed to account for the products. Presented at the annual meeting, American Oil Chemists’ Society, Dallas, Tex., April 4–6, 1960. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

A rapid method for concentrating highly unsaturated fatty acid methyl esters in marine lipids as an aid in their identification by GLC

The selective solubility of unsaturated fatty acid methyl esters in nitromethane at temperatures down to −20C can be used to concentrate highly unsaturated methyl esters. With a typical sample of marine oils methyl esters having an iodine value of 110–190, a concentrate can be ready for GLC analysis in an hour or less and the nitromethane layer can be injected directly for analysis in GLC apparatus with ionization detectors. Examples of the use of the method in the identification of component fatty acids in herring oil are given.     

Spectrophotometric determination of small proportions of polyunsaturated constituents in fatty materials

Summary Existing ultraviolet spectrophotometric methods have been modified for application primarily to the detection and estimation of low proportions of conjugated and nonconjugated unsaturated constituents in fats, oils, and soaps. The method is applicable also to fatty materials having high proportions of these constituents. Modifications include corrections for absorption by interfering substances, use of alkaline glycerol as an isomerization medium in the analytical procedure, and correction of absorption data on the isomerized product for absorption by conjugated constituents in the material before isomerization. The presence of small proportions of highly unsaturated conjugated and nonconjugated compounds is established in lards, tallows, tallow soaps, and highly purified esters and acids. Tall oil fatty acids are shown to contain approximately 10% of conjugated diene acids and a small amount of linolenic acid. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Chemoenzymatic epoxidation of unsaturated fatty acid esters and plant oils

In the presence of an immobilized lipase fromCandida antacrtica (Novozym 435^R) fatty acids are converted to peroxy acids by the reaction with hydrogen peroxide. In a similar reaction, fatty acid esters are perhydrolyzed to peroxy acids. Unsaturated fatty acid esters subsequently epoxidize themselves, and in this way epoxidized plant oils can be prepared with good yields (rapeseed oil 91%, sunflower oil 88%, linseed oil 80%). The hydrolysis of the plant oil to mono- and diglycerides can be suppressed by the addition of a small amount of free fatty acids. Rapeseed oil methyl ester can also be epoxidized; the conversion of C=C-bonds is 95%, and the composition of the epoxy fatty acid methyl esters corresponds to the composition of the unsaturated methyl esters in the substrate. Based partly on a lecture at the 86th AOCS Annual Meeting & Expo, San Antonio, Texas, May 7–11, 1995.     

On the structure of highly unsaturated fatty acids of fish oils by high resolution nuclear magnetic resonance spectral analysis

Methyl esters of highly unsaturated fatty acid concentrates were prepared from fish oils by the urea-adduct method. The nuclear magnetic resonance spectra of the mixed esters and some related pattern compounds were analyzed. As a result, it was concluded that the structure of highly unsaturated fatty acids has divinylmethane arrangement of the ethylenic bonds and no divinylethane arrangement, and that one methylene group is present between the terminal methyl group and the double bond located at the remotest position from a carboxyl group in the acids.     

Reaction Mechanisms of Lean-Burn Hydrocarbon SCR over Zeolite Catalysts

A large number of novel fatty compounds have been synthesized by catalytic C,C-bond forming addition reactions to the C,C-double bond of unsaturated fatty compounds. Radical reactions such as the solvent-free addition of α-halocarboxylic acid esters initiated by electron transfer, e.g., from copper to give fat-derived γ-lactones are described as well as Lewis acid–induced electrophilic addition reactions yielding new oleochemicals such as alkyl-substituted 4-chlorotetrahydropyrans, primary homoallylic alcohols, β-, γ-unsaturated ketocarboxylic acids and Diels–Alder addition products. New catalysts as, e.g., ligand-modified rhodium catalysts for the hydroformylation and heterogeneous boron-modified rhenium catalysts for the olefin metathesis have been developed. The addition of C-nucleophiles such as dimethylmalonate and nitromethane is possible by palladium-(0)catalyzed additions to unsaturated fatty compounds after conversion of the electron-rich to an electron-poor double bond. More than fifty literature articles are reviewed.     

The isolation of omega-3 polyunsaturated fatty acids and methyl esters of fish oils by silver resin chromatography

Multigram quantities of the highly unsaturated ω3 component from samples of fish oil fatty acids and esters were isolated by silver resin chromatography. An XN1010 resin column saturated with silver ions was utilized. Polyunsaturated fatty acid (PUFA) esters from fish oil concentrate (FOC) were fractionated based on the number of double bonds by using solvent programming (acetonitrile in methanol). Larger samples (4–9 g) of FOC acids and esters and menhaden acids and esters were enriched in ω3 polyunsaturates to 82–99% (95–99% total PUFA) by use of a large 100% silver resin column and isocratic elution with 30, 35 or 45% acetonitrile in acetone.     

Chemical reactions involved in the deep- fat frying of foods: IX. Identification of the volatile decomposition products of triolein

The acidic and nonacidic volatile decomposition products (VDP) pro-duced by pure triolein maintained at 185 C with periodic injection of steam were collected, fractionated and identified. A total of 93 compounds were positively or tentatively identified. A number of the compounds found were identified for the first time in fats or oil VDP. Among these newly identified compounds are: unsaturated acids, keto-substituted unsaturated acids, ω-enals, unsaturated esters and an unsaturated γ-lactone.     

Calculation of iodine value from measurements of fatty acid methyl esters of some oils: Comparison with the relevant American Oil Chemists Society method

A new calculation method for the determination of iodine value (IV) from measurements of fatty acid methyl esters is proposed. The method is based on the quantitative determination of fatty acid methyl esters of vegetable oils by capillary gas chromatography. IV is a measure of the number of double bonds in the unsaturated fatty acids in one gram of oil. The analytical methodology of its evaluation includes the use of rather health dangerous reagents, and for that reason is mostly avoided by laboratory analysts. A calculation procedure to determine the IV of oils from their fatty acid methyl ester composition is in use based on the American Oil Chemists’ Society (AOCS) method Cd 1c-85. A new calculation procedure for IV, based also on the evaluation of the fatty acid methyl esters of oils, was developed. The application of the proposed calculation methodology was checked with olive oil, corn oil, soybean oil, cottonseed oil, and sunflower seed oil. The proposed calculation gave results in better agreement with the Wijs method than with the relevant AOCS method.     

Dilatometric investigations of fats. VI. Melting dilation as a function of chain length in fatty acids and their glyceryl esters

Melting dilations have been determined for the even-numbered, saturatedn-fatty acids in the series lauric through stearic, and some of their glyceryl esters. These data have been correlated with data obtained previously to determine the relationship between melting dilation and the effective chain length of these compounds. The melting dilations of the mono-, di-, and triglyceryl esters of a fatty acid were found to be proportional to the acid residue content of each compound. The melting dilation of a monoglyceride was one-half that of the diglyceride and one-third that of the triglyceride of the same fatty acid. The increment of melting dilation of the fatty acids and glyceryl esters increased regularly with each addition of two methylene groups, with the end group components exerting a contant effect on the volume change. Equations were developed for calculating the melting dilation of then-fatty acids and their glycerides as a function of chain length of the fatty acid radical. The melting dilations of those compounds which are unsaturated, or have less than 10 carbon atoms, cannot be calculated by these equations.     

杨梅核仁油的理化指标和脂肪酸成分分析

采用索氏提取法提取杨梅核仁油,并测定了杨梅核仁油的常见理化指标,同时采用GC-MS法分析了杨梅核仁油中的脂肪酸成分。结果表明,杨梅核仁油的提取率为67%,杨梅核仁油的折光率为1.471,酸价为0.416mg/g,过氧化值为0.023。GC-MS分析共检测出9种脂肪酸,不饱和脂肪酸总含量为85.63%,亚油酸含量为40.36%。     

Industrial chemical uses of polyunsaturated fatty acids

Production of vegetable, animal and marine oils containing more than about 40% unsaturated fatty acids totaled 15,000 million pounds in 1968, almost on the scale of petrochemical production. The greater share (64%) of this nonfossil oil production was directed toward food uses, the remainder toward industrial and animal feed uses. The variety of chemical reactions carried out on these unsaturated fatty acid products include hydrogenation, interesterification, dimerization, sulfation, formation of nitrogen compounds, epoxidation, alkaline cleavage and oxidative ozonolysis. Some of these reactions have been developed at Utilization Research and Development Divisions of the Agricultural Research Service, U.S. Department of Agriculture. Research is continuing in developing new reactions for potential industrial application. An example is reductive ozonolysis of unsaturated fatty esters to produce monofunctional aldehydes and bifunctional aldehyde esters. Presented at the ISF-AOCS World Congress, Chicago, September 1970. No. Market. Nutr. Res. Div., ARS, USDA.     

Chemical Properties and Fatty Acid Composition of Thunbergia fragrans Roxb. Seed Oil

The physicochemical and fatty acid compositions of seed oil extracted from Thunbergia fragrans were determined. The oil content, free fatty acids, peroxide value, saponification value and iodine value were 21.70 %, 2.25 % (as oleic acid), 9.6 (mequiv. O₂/kg), 191.71 (mg KOH/g) and 127.84 (g/100 g oil) respectively. The fatty acid profiles of the methyl esters showed the presence of 90.16 % unsaturated fatty acids and 9.84 % saturated fatty acids. Palmitoleic acid, which is usually found in marine foods and is unique in seed oils of botanical origin, was the major component (79.24 %). The oil can also be used in industries for the preparation of liquid soaps, shampoos and alkyd resin.     

Lewis Acid Induced Additions to Unsaturated Fatty Compounds

Unsaturated fatty compounds such as oleic acid, which are of interest as renewable raw materials, can be functionalized at the C,C-double bond by Lewis acid induced addition reactions. The products are branched and highly functionalized fatty compounds which may have interesting properties. SnCl₄-induced additions of nitriles to methyl oleate and ethyl 10-undecenoate give the corresponding esters of the N-acylamino fatty acids. Alkylaluminium halide induced ene additions of formaldehyde to unsaturated fatty compounds yield primary homoallylic alcohols. β,γ-Unsaturated ketones are obtained in ethylaluminium dichloride induced Friedel-Crafts acylations of unsaturated fatty compounds with acyl chlorides and cyclic anhydrides.     

Solvent-Assisted Crystallization of Fatty Acid Alkyl Esters from Animal Fat

An easy and efficient method for the separation of saturated and unsaturated fatty acid mono alkyl esters, prepared from animal fat, was developed. The most efficient separation was achieved by the use of solvents such as methanol and acetone at low temperatures. The dilution of the alkyl esters with 10 times the amount of solvent (10:1 v/w) and storage of the mixture for 4 h at ?22 °C could be defined as optimum conditions. After filtration of the saturated fraction at the corresponding temperature very pure fractions were obtained. For fatty acid methyl esters deriving from tallow, with an initial content of saturated fatty acids of almost 50 %, a saturated ester fraction with only 5 % unsaturated fatty acids and an unsaturated ester fraction with about 9 % of saturated fatty acids could be obtained. The solvent easily could be recovered by distillation. In addition fatty acid ethyl, 1‐propyl, 2‐propyl, 1‐butyl, tert‐butyl and 3‐methyl‐1‐butyl esters were prepared and separated into saturated and unsaturated fractions. All fractions were analyzed according to the fatty acid compositions and showed similar or slightly worse results compared to the methyl esters. The cold filter plugging points of the unsaturated fractions were measured, showing the lowest value for the unsaturated methyl ester fraction at ?26 °C. The fractionation with the use of solvents is an easy tool in order to obtain fatty acid alkyl esters with excellent cold temperature behavior out of animal fat.