A study of fatty acid methyl esters with epoxy or alkyne functionalities

Described are the physical and chemical properties of the methyl esters of two uncommon fatty acids: vernolic acid, containing an epoxy group, and crepenynic acid, containing a triple bond. The incorporation of an epoxy or alkyne group into the fatty acid structure is shown to greatly affect the properties compared to conventional unsaturated fatty acids. The methyl esters have been characterized and compared with ordinary fatty acid methyl esters (i.e., methyl oleate and linoleate) with respect to spectroscopic characterization [¹H nuclear magnetic resonance (NMR)], ¹³C NMR, and Fourier transform infrared), rheological properties, and oxidative reactivity (using chemiluminescence). Both methyl vernoleate and methyl crepenynate could successfully be produced by transesterification under basic conditions without reaction of the epoxy or alkyne groups. Rheological measurements showed that the methyl esters had a significantly lower viscosity compared to their triglyceride analogs. Smaller differences were seen when comparing the different methyl esters where methyl vernoleate had the highest viscosity due to the presence of the more polar oxirane group. Very large differences were found with respect to the oxidation rate of the different methyl esters. Methyl crepenynate was shown to oxidize extremely rapidly, whereas methyl vernoleate was very stable toward oxidation.     

Summary of the technology for the manufacture of higher alpha-sulfo fatty acid esters

Interest in α-sulfonated higher molecular weight (up to C₂₀) fatty esters has increased in recent years in the surfactant industry due to the advent of economical sulfonation processes and methyl esters of fatty acids. In this paper, the authors present a review of the chemistry of the sulfonation of fatty esters and the two-step mechanism leading to α-sulfonation. Laboratory and pilot plant scale preparation of long chain fatty acid α-sulfoesters with vaporized SO₃ without the use of solvents are also summarized. Work on the falling film equipment with hydrogenated methyl tallowate with vaporized SO₃ is described along with procedures for neutralization and bleaching. Analytical methods for defining the α-sulfonates are discussed. A larger scale unit to continuously manufacture α-sulfo fatty esters from long chain fatty acid is described. A review of the commercially available continuous processes for sulfonation of the fatty acid esters with vaporized sulfur-trioxide have also been included. The properties of the salts of α-sulfo fatty esters including the hydrolytic stability, aqueous solubility, lime soap dispersing ability, and biological properties have been tabulated. Uses of these surfactant range α-sulfo esters are included in this discussion. Presented at the AOCS Meeting, New Orleans, April 1976.     

Esterification of ethylenediaminetetraacetic acid

The esterification of ethylenediaminetetraacetic acid (EDTA) in a hot acidic medium gives rise to impure products. The impurities have been identified and shown to be esters of various acids: nitrilotriacetic acid; iminodiacetic acid; piperazine-1,4-diacetic acid; N-methylethylenediaminetriacetic acid; N,N- and N,N′-dimethylethylenediaminediacetic acids and 2-ketopiperazine-1,4-diacetic acid. The reactions for the formation of these impurities are discussed and a method for the preparation of pure esters of EDTA is described. Details of some crystalline derivatives, ¹H-n.m.r. and infrared spectra of a series of esters of EDTA are presented. The determination of the molecular weights of the esters by saponification is discussed.     

α-Sulfonated fatty acids and esters: Manufacturing process,properties, and applications

α-Sulfonated fatty acid esters, because of their wide-range of application and biological properties, represent an interesting class of surfactants. A technical method for the preparation of α-sulfonated fatty acid esters is described. By using special reaction conditions it is possible to α-sulfonate saturated fatty esters directly without the use of solvents. The use of gaseous SO₃ gives the product in greater than 97% yield. A process for the bleaching of the α-sulfonated fatty esters has been developed, whereby a product of faultless color is produced without the necessity of further purification or separation techniques. The sulfonation and bleaching processes operate continuously. The process has been tried successfully on a commercial scale using the methyl esters of technical fatty acids. Methods for the preparation of α-sulfonated fatty acids are given. The chemical, technical, and biological properties of the α-sulfonated fatty acids and their esters are discussed. α-Sulfonated fatty esters possess good washing and foaming properties, have good biological degradability, possess good skin compatibility and low acute toxicity. They can be considered as surfactant components for phosphate-free or low-phosphate detergents. α-Sulfonated fatty acids and esters also possess other favorable technical properties which allow them to be used in cosmetics, as auxiliary agents in the production of fibers, plastics, and rubber, and in leather manufacture.     

Alkali-isomerized linoleic acid

Summary Alkali-isomerized linoleic acid and its methyl ester have been found to have boiling points higher than the corresponding normal C₁₈ acids and esters. By careful fractional distillation of methyl esters of alkali-isomerized C₁₈ cottonseed acids, methyl linoleate of 95% or more purity is obtained consisting of 75% conjugated methyl linoleate and some 20% of methyl ester of an altered linoleic acid. Paper No. 69, Journal Series, Research Department, General Mills, Inc. (Presented at the 19th Annual Fall Meeting of the American Oil Chemists’ Society, Nov. 7–9, 1945, in Chicago, Ill.)     

Chromatographic analysis of polyglycerols and their fatty acid esters

Polyglycerols and their fatty acid esters have been analyzed by gas-liquid chromatography (GLC) as trimethylsilyl ether derivatives. Linear diglycerols and triglycerols were isolated from commercial polyglycerols by vacuum distillation. Mono- and di-fatty acid esters were synthesized in the laboratory. Two isomers of diglycerol have been separated and identified. GLC analysis was carried out on columns packed with 3% JXR on Gas Chrom Q. Response factors for diglycerol and triglycerol relative to glycerol have been established. Commercial polyglycerol esters are shown to be mixtures of glycerol, free fatty acids, mono- and diglycerides, and mono- fatty acid esters of diglycerol and triglycerol. Separation of free polyglycerols and their esters is also demonstrated by thin-layer chromatography on Silica Gel-G containing 4.0% boric acid.     

Effect of food emulsifiers on crystal structure and habit of stearic acid

Several food emulsifiers have been found to serve as crystal structure modifiers for stearic acid crystallized from various organic solvents. Stearic acid that usually precipitates under appropriate crystallization conditions as the B- form is converted into the C- form when 1- 5% of sorbitan esters or ethoxylated sorbitan esters of fatty acids are present in the solution. Other emulsifiers such as polyglycerol esters, bdsubstituted monoglycerides and sucrose esters of fatty acids consisting of bulky hydrophilic groups are also effective emulsifiers in preserving the C- form of the crystallized stearic acid. The active emulsifiers modify the external crystal habit of stearic acid. Mass spectrograph analysis indicates that sorbitan monostearate (Span 60) is precipitated with the stearic acid.     

Paper chromatography of unsaturated fatty acid esters as their mercuric acetate addition compounds

Summary A method is described by which unsaturated fatty acid esters can be separated and identified by reversed-phase paper chromatography. The procedure is based upon the formation of the mercuric acetate addition compounds of the esters and the detection of the compounds on the chromatograms, using the sensitive color reaction with diphenylcarbazone. The application of this technique to the analysis of the component unsaturated acids of natural fats has been examined, and tetradecenoic acid in olive oil and hexadecenoic acid in linseed oil both formerly unidentified have been detected as the minor component acids by means of the method. The preliminary investigation on the absorption spectra of diphenylcarbazone complexes derived from the addition compounds has been made to bring the method into quantitative use.     

The seed oil ofBernardia pulchella (Euphorbiaceae) —A rich source of vernolic acid

The fatty acids from the seed oil ofBernardia pulchella (Euphorbiaceae) have been analyzed by gas chromatography (GC) and GC-mass spectrometry (MS) analysis of their methyl esters. Vernolic acid is the main compound (91%), along with other usual fatty acids. In addition to the quantitation by GC analysis,¹H-nuclear magnetic resonance (NMR) signals from the seed oil have been used to estimate the total epoxy fatty acid content. The structure of vernolic acid has been proven by spectroscopic methods (infrared,¹H, and¹³C-NMR) and by GC-MS analysis of the corresponding silylated hydroxy-methoxy derivative. The 4,4-dimethyloxazoline derivatives of the fatty acid mixture have also been examined by GC-MS, and it was shown that this derivazation reaction is not suitable for the structure analysis of vernolic acid.     

Analysis of sorbitan fatty acid esters by HPLC

Sorbitan esters of several fatty acids have been analyzed by high pressure liquid chromatography (HPLC) using an RP-18 column. No derivatization was necessary. Mono-, di- and trisorbitan esters of palmitic, stearic, oleic, isostearic and sesquioleic acid have been separated using isopropanol/water as the elution mixture.     

Fatty acids of Thespesia populnea: Mass spectrometry of picolinyl esters of cyclopropene fatty acids

Thespesia populnea belongs to the plant family of Malvaceae which contain cyclopropane and cyclopropene fatty acids. However, previous literature reports vary regarding the content of these compounds in Thespesia populnea seed oil. In this work, the content of malvalic acid (8,9‐methylene‐9‐heptadecenoic acid) in the fatty acid profile of Thespesia populnea seed oil was approximately 7% by GC. Two cyclopropane fatty acids were identified, including dihydrosterculic acid. The methyl and picolinyl esters of Thespesia populnea seed oil were also prepared. The mass spectrum of picolinyl malvalate was more closely investigated, especially an ion at m/e 279, which does not fit the typical series of ions observed in picolinyl esters. It is shown that this ion is caused by cleavage at the picolinyl moiety and contains the fatty acid chain without the picolinyl moiety. This type of cleavage has previously not been observed prominently in picolinyl esters and may therefore be diagnostic for picolinyl esters of cyclopropene fatty acids. The NMR spectra of Thespesia populnea methyl esters are also discussed. Practical applications: The work reports the fatty acid composition of Thespesia seed oil whose derivatives have not yet been extensively utilized for industrial purposes, for example, biodiesel. Knowing this composition is essential for understanding potential uses and, for example, in case of biodiesel the fuel properties. Besides this issue, some data (mass spectrometry and NMR) crucial for obtaining the composition information are analyzed in detail. The biodiesel properties of methyl esters of Thespesia populnea will be reported separately.     

Enzymatic fractionation of fatty acids: Enrichment of γ-linolenic acid and docosahexaenoic acid by selective esterification catalyzed by lipases

Immobilized lipase preparations from seedlings of rape (Brassica napus L.) andMucor miehei (lipozyme) used as biocatalysts in esterification and hydrolysis reactions discriminate strongly against γ-linolenic and docosahexaenoic acids/acyl moieties. Utilizing this property, γ-linolenic acid contained in fatty acids of evening primrose oil has been enriched seven to nine-fold, from 9.5 to almost 85% by selective esterification of the other fatty acids with butanol. Similarly, docosahexaenoic acid of cod liver oil has been enriched four to five-fold, from 9.4 to 45% by selective esterification of fatty acids (other than docosahexaenoic acid) with butanol. As long as the reaction is stopped before reaching equilibrium, very little of either γ-linolenic acid or docosahexaenoic acid are converted to butyl esters, which results in high yields of these acids in the unesterified fatty acid fraction.     

On the behaviour of nitrate esters in acid solution. III. Oxidation of ethanol by nitric acid in sulphuric acid

The oxidation of ethanol as a model of the alcohols produced in the hydrolysis of nitrate esters, by nitric acid in aqueous sulphuric acid solutions has been studied with the aim to obtain information on the decomposition reaction of “spent acids”. The results show, in agreement with previous suggestions from this laboratory, that ethanol is firstly oxidized to acetaldehyde via a reaction initiated by nitric acid but carried on by NO₂ radical. The latter is formed by the interaction of nitric and nitrous acids. The acetaldehyde is then oxidized by two independent paths leading one to acetic acid and the other to oxalic acid and eventually to CO₂. The relevance of these findings on the understanding and on the control of „spent acids”︁ is briefly discussed.     

Synthesis and characterization of synthetic lubricants based on dibasic acid

Synthetic esters have long been used in a variety of applications due to their excellent thermal stability, excellent cleanliness, natural lubricity, and polarity. In the present work, we aimed to prepare some synthetic base oils through preparation of different dibasic esters by esterification of dicarboxylic acids (adipic acid and azelaic acid) with different linear alcohols (hexanol, octanol, and decanol) and branched alcohol (2-ethyl hexanol) at 120°C. The reaction yield ranges between 85% and 94%. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy were used to analyze the structures of the produced compounds. Using thermo gravimetric analysis (TGA), the heat stability of the produced esters was determined, and it was found that the prepared esters have high thermal stability. The degradation of the prepared esters takes place in the range between 300 and 600°C. The rheological behaviour of prepared esters shows Newtonian behaviours, which means that Newtonian fluids obey viscosity Newton's law. The viscosity is independent of the shear rate. The results showed that the lubricity properties, based on their pour point, flash point, and oxidation stability of the esters, were significantly affected by the linear and branched alcohols used. There is a slight increase in kinematic viscosity and viscosity index values with decreasing the internal chain length of the dibasic acid. The esters which were based on adipic acid such as C₁ exhibited maximum values of VI: 187 compared to those which were based on azelaic acid such as F₁ with VI: 182. Viscosity and viscosity index increases with increasing the number of carbon atoms of the used mono-ol alcohols. Using branched alcohols gave almost the same viscosity results compared to using linear alcohol with the same number of carbons. Almost all prepared esters give pour point results ≤ −30°C.     

Fatty acid content of marine oil capsules

The use of dietary ω3 fatty acid capsules has been associated with a decrease in plasma triglyceride levels. In addition, populations consuming diets rich in fish appear to have a decreased incidence of cardiovascular disease. Eicosapentaenoic acid (EPA, 20∶5ω3) and docosahexaenoic acid (DHA, 22∶6ω3) are major fatty acids in fish oils. It is believed that fish oils exert their biolotic effect through these fatty acids. Many individuals are currently taking fish oil capsules to lower lipids, increase bleeding time, and possibly decrease cardiovascular risk. These capsules also have been classified as food additives with less stringent controls on content. We assessed the fatty acid, cholesterol, and vitamin A and E content of eight commercially available capcules along with cod liver oil. The content of EPA was found to range from 8.7–26.4% (wt%) with a mean of 17.3% (82.4% of labeled content), and that of DHA from 8.9–17.4% with a mean of 11.5% (90.0% of labeled content) as assessed by capillary column gas-liquid chromatography. The mean content of the polyunsaturated ω3 fatty acids was 31.9%, and that of the ω6 fatty acids was 1.4%. The content of saturated fatty acids was 32,0%, and that of monounsaturated fatty acids was 25.1%. Cholesterol content was low, with a range of 0.7–8.3 mg/g, the α-tocopherol range was 0.62–2.24 mg/g, and the range of retinyl esters was 0.4–298.4 μg/g. Cod liver oil had substantially more retinyl esters (2450.1 μg/g) than did fish oil capsules. Our data serve as an independent guide to fish oil capsule fatty acid content upon single lot analysis, and indicate that these capsules contain as much saturated fat as they contain ω3 fatty acids.     

Synthesis and characterization of poly(aspartic acid) derivatives conjugated with various amino acids

Novel derivatives of poly(aspartic acid) conjugated with various amino acids and their amphiphilic copolymers were synthesized and characterized. Methyl esters of various amino acids (in their hydrochloride form) were synthesized from the reaction of amino acids with methanol in the presence of chlorotrimethylsilane (TMSCl). Aminolysis reaction onto polysuccinimide (PSI) using various amino acid methyl esters in the presence of catalyst and the followed hydrolysis provided the corresponding amino acid-conjugated poly(aspartic acid) derivatives in high reaction yield. Amino acid—conjugated amphiphilic analogs were also prepared by introducing hydrophobic alkylamine along with amino acid using a similar procedure. The chemical structures of copolymers were confirmed by FT-IR and ¹H NMR spectroscopy. The physicochemical properties of amphiphilic copolymers were characterized using dynamic light scattering (DLS), fluorescence spectroscopy and field emission scanning electron microscopy (FE-SEM). In addition, the in vitro cell viability of the copolymers was examined. These polymers have potential applications in the pharmaceutical and cosmetic fields as delivery vehicles for bioactive molecules.     

Cholesteryl ester compounds containing alkyl branched acyl groups — their preparations,properties and applications

Cholesterol having a reactive hydroxyl group at C₃-position can react with fatty acids to give the corresponding cholesteryl esters. Most of the natural cholesteryl esters consist of straight alkyl chain fatty acids with a high melting point. In oleochemistry it is well known that alkyl branched fatty acids, which are derived from petroleum or the fat and oil industry, have low melting points (mp.) and are chemically more stable if they are saturated acids. We designed alkyl branched fatty acid cholesteryl esters by means of common esterification and found some esters having a low mp. (mostly as a liquid). They had no irritative effect on both animal and human skin. They showed characteristic emulsification properties, namely the formation of either O/W or W/O emulsion coexistence together with other lipid components. Applying them onto human skin, they were able to penetrate towards the stratum corneum and improve the water-retaining ability and the barrier function of the stratum corneum. Based on these properties we have been applying the alkyl branched fatty acid cholesteryl ester, especially the methyl branched isostearic acid cholesteryl ester (IS-CE), to a shampoo and a rinse as hair cosmetics, skin care cosmetics and bath-additive products in the past decade.     

Characteristic properties of cutting fluid additives derived from the reaction products of hydroxyl fatty acids with some acid anhydrides

Several adducts were prepared from the thermal reaction of hydroxyl fatty acids (ricinoleic acid oligomers, 12-hydroxystearic acid oligomers, oleyl alcohol, dehydrated castor oil fatty acids, and dimer acid) with maleic anhydride and screened as water-soluble cutting fluids. For example, aqueous solutions of triethanolamine salts with the products of ricinoleic acid oligomers, 12-hydroxystearic acid dimer, and 12-hydroxysteric acid hexamer showed good antirust properties for waterbased cutting fluids. Various half esters of hydroxyl fatty compounds with acid anhydrides were prepared. Aqueous solutions of triethanolamine salts of half esters of maleic anhydride and succinic anhydride and phthalic anhydride with hydroxyl fatty acids gave good antirust and antiwear properties for waterbased cutting fluids.     

Stability of cyclopropane and conjugated linoleic acids during fatty acid quantification in lactic acid bacteria

Seven methods commonly used for fatty acid analysis of microgrganisms and foods were compared to establish the best for the analysis of lyophilized lactic acid bacteria. One of these methods involves fat extraction followed by methylation of fatty acids, while the other methods use a direct methylation of the samples, under different operating conditions (e.g., reaction temperature and time, reagents, and pH). Fatty acid methyl esters were identified by gas chromatography-mass spectrometry and quantified by on-column capillary gas chromatography. Two reliable methods for the analysis of fatty acids in bacteria were selected and further improved. They guarantee high recovery of classes of fragile fatty acids, such as cyclopropane and conjugated acids, and a high degree of methylation for all types of fatty acid esters. These two direct methylation methods have already been successfully applied to the analysis of fatty acids in foods. They represent a rapid and highly reliable alternative to classical time-and solvent-consuming methods and they give the fatty acid profile and the amount of each fatty acid. Using these methods, conjugated linoleic acids were identified and quantified in lactic acid bacteria.     

Identification of nine acetylenic fatty acids, 9-hydroxystearic acid and 9,10-epoxystearic acid in the seed oil ofJodina rhombifolia hook et arn. (Santalaceae)

In addition to some usual fatty acids, the seed oil ofJodina rhombifolia (Santalaceae) contains nine acetylenic fatty acids [9-octadecynoic acid (stearolic acid) (1.1%),trans-10-heptadecen-8-ynoic acid (pyrulic acid) (20.1%), 7-hydroxy-trans-10-heptadecen-8-ynoic acid (2.3%),trans-10,16-heptadecadien-8-ynoic acid (0.7%), 7-hydroxy-trans-10,16-heptadecadien-8-ynoic acid (0.1%),trans-11-octadecen-9-ynoic acid (ximenynic acid) (20.3%), 8-hydroxy-trans-11-octadecen-9-ynoic acid (12.2%),trans-11,17-octadecadien-9-ynoic acid (1.5%), 8-hydroxy-trans-11,17-octadecadien-9-ynoic acid (1.3%), 9-hydroxystearic acid (<0.1%) and 9,10-epoxystearic acid (0.7%)]. The fatty acids have been analyzed by gas chromatography/mass spectrometry of their methyl ester and 4,4-dimethyloxazoline derivatives. The hydroxy fatty acid methyl esters have been examined also as trimethyl-silyl ethers. Furthermore, the fatty acid methyl esters (FAME) have been fractionated according to their polarity (FAME-A: nonhydroxy; FAME-B: hydroxy fatty acids) and to their degree of unsaturation (FAME-A1/A2; FAME-B1/B2) by preparative thin-layer chromatography and argentation chromatography, respectively. All of these fractions have been analyzed by ultraviolet and infrared spectroscopy, and the fractions FAME-A and FAME-B have been analyzed further by nuclear magnetic resonance (¹H,¹³C, 2D H/C, attached proton test) spectroscopy and gas chromatography/mass spectrometry. This work is dedicated to the 65th birthday of Prof. Dr. K. Pfeilsticker, Institut of Food Science, University Bonn (Germany).