Synthesis and copolymerization of methacryloyl hydroxamic acids

Three methacryloyl hydroxamic acids were prepared and homopolymerized yielding polymers which readily formed complexes with Fe³⁺. The amount of hydroxamic acid available for complexation was found to be low (29–32% of theoretical). Copolymers of methacryloyl hydroxamic acid with methyl methacrylate were also synthesized. The low amount of free hydroxamic acid functionality in the copolymers was ascribed to transfer reactions in the radical polymerization which resulted in branching and deactivation of the hydroxamic acid functionality. In addition, methacryloyl hydroxamic acid was copolymerized with N‐isopropyl acrylamide to yield thermotropic polymers capable of complexing with metal ions. At low concentrations of hydroxamic acid functionality, the lower critical solution temperature of the copolymers remained similar to that reported for poly(N‐isopropyl acrylamide). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 751–758, 2000     

Surface active hydroxamic acids. I. Preparation and properties of long-chain alkyl[oligo(oxyethylene)] oxymethylenehydroxamic acids

For the development of surfactants having an ability to interact with metal ions, hydroxamic acids containing a long-chain alkyl[oligo(oxyethylene)] group were prepared. Any hydroxamic acid with an octyl, decyl or dodecyl group was made readily soluble in water by introducing four oxyethylene units into the molecule. These water-soluble hydroxamic acids had a micelleforming ability and acted as polyoxyethylene-type nonionic surfactants under acidic and neutral conditions. Additionally, those compounds were found to form a water-soluble complex with ferric ion at pH 2, and these complexes also showed surface active properties.     

Synthesis of fatty hydroxamic acids catalyzed by the lipase ofMucor miehei

Biotechnological synthesis of a new class of amphiphilic molecules—fatty hydroxamic acids—was carried out using the lipase ofMucor miehei by reacting hydroxyl amine with the fatty acids in their free or methyl ester form. Concurrently with enzymatic synthesis, chemical synthesis of hydroxamic fatty acids has also been developed by adapting methods that already existed for water-soluble acids. Different parameters were studied to determine the optimum operating conditions: temperature, molar ratio of reagents, quantity of biocatalyst and length of reaction. A general method, whatever the type of fatty acids used, is described.     

Long-chain fatty acids containing ether linkage. I. The antibacterial and fungicidal activities of some new β-alkyloxypropionic acids and their methyl esters

β-Alkoxypropionic acids and their methyl esters were made with alkoxy groups ranging from C₄H₉O to C₁₈H₃₅O: R-O-CH₂CH₂COOH (CH₃). Methyl esters and acids were also made with one and with two oxyethylene groups between the alkoxy group and the propionic acid group: RO (CH₂ CH₂ O) n-CH₂CH₂ COOH(CH₃). The compounds were tested againstStaphylococcus aureus and againstPenicillium for growth inhibition. The optimum size of the alkoxy group appears to be R=C₁₂H₂₅. Oxyethylene groups enhanced the activity againstS. aureus, but had relatively little effect againstPenicillium.     

Sulfonated branched chain fatty acids and esters

In continuation of work reported a year ago describing branched chain fatty acids, a series of monosodium methyl 2-sulfo-2-alkylalkanoates [RR'C (SO₃Na) CO₂CH₃] were synthesized. The surface active properties of these compounds were evaluated and compared with the corresponding disodium 2-sulfo-2-alkylalkanoates [RR'C (SO₃Na)CO₂Na]. Alkaline hydrolysis rates show that the sodium methyl esters are stable. Relative to the disodium salts, these compounds exhibit better wetting properties and more stable foams. Presented at the AOCS Meeting, Cincinnati, October 1965. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Precombustion of fatty acids and esters of biodiesel. A possible explanation for differing cetane numbers

Fatty acids of C₁₈ chainlength as well as their methyl, ethyl, n-propyl, and n-butyl esters were injected into a constant-volume combustion apparatus suitable for collecting material from the fuel spray prior to the onset of ignition. The collected material from this precombustion phase of the injection event was analyzed by gas chromatography-mass spectrometry. Compounds identified as forming during the precombustion phase were straight-chain and branched alkanes, alkenes, and cyclic hydrocarbons, as well as aldehydes, ketones, esters, substituted benzenes, and other species, such as furans. Some of the compounds formed during precombustion have low cetane numbers (CN). Low-cetane aromatic compounds were found more prominently for more unsaturated fatty compounds. Thus, the low CN of the intermediary precombustion species may constitute a possible partial explanation why some compounds, for example the more unsaturated fatty compounds, have relatively low CN. Presented in part at the 88th AOCS Annual Meeting, Seattle, Washington, May 1997.     

Stereospecific hydration of unsaturated fatty acids by bacteria

Three new 10-hydroxy fatty acids, all optically active, have been prepared by the anaerobic microbiological hydration of acis-9 double bond. Substrates that formed these new hydroxy fatty acids are linoleic, linolenic, and ricinoleic acids. The hydroxyl group has the D configuration and the methyl esters are levorotatory. Infrared, mass spectral, specific rotation and ultraviolet data on these compounds were determined. There was no migration of the unreated double bonds at C₁₂ and C₁₅ in linoleic or linolenic acids. The presence of a double bond in the 10-hydroxy fatty acids significantly increased the optical rotation of the methyl esters. The hydratase enzyme showed unusual specificity among Δ⁹ unsaturated acids. While it hydrates methylene interrupted and hydroxy unsaturated acids, it failed to hydrate either 9-decenoic, 12,13-epoxy- or 12-keto-cis-9-octadecenoic acids or sterculic acid. Presented at the AOCS Meeting, San Francisco, April 1969. No. Marketing and Nutrition Res. Div., ARS, USDA.     

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.     

Thermoacoustic properties of methyl esters ofn-alkanoic acids

A number of thermoacoustic parameters, including the Sharma constant S₀, the isochoric temperature coefficient of volume expansivity (d Inα/d InT)_V, the isochoric temperature coefficient of internal pressure (d InP _i/d InT)_V, reduced volume V, reduced compressibility β and the Huggins parameter F, are estimated by using only the volume expansivity α from the density temperature data for a number of methyl esters ofn-alkanoic acids. The methyl esters give excellent separation of saturated fatty acid mixtures. The Sharma constant, which relates the molecular constantn and other thermoacoustic parameters, is a constant with a characteristic value of 1.11+0.01 for all these esters.     

Production of branched-chain fatty acids from sterculia oil

Methyl sterculate was rearranged by use of 0.5% of rhodium catalyst to isomeric conjugated diene fatty acid methyl esters containing both methylene-and methyl-branched isomers. The rearanged products were hydrogenated directly to saturated, methyl-substituted, branched-chain fatty acid methyl esters with the methyl substituent at one of the positions formerly occupied by the cyclopropenoid ring. The crude branched-chain fatty acids from these esters were purified by recrystallization from a mixed solvent of ethanol and water (80:20, v/v) and flash distillation; the product contained about 90% of branched-chain fatty acids (C₁₉:80%, C₁₈:10%). Esters of the branched-chain fatty acid were prepared with 2-ethylhexyl alcohol or trimethylolpropane, and the characteristic properties of these esters were investigated. The branched-chain fatty esters appear to have potential utility in lubricants; other uses may be possible. Presented at the AOCS meeting in New Orleans, May 1981.     

Comparison of silver-ion high-performance liquid chromatographic quantification of free and methylated conjugated linoleic acids

Silver-ion high-performance liquid chromatography was used to fractionate a mixture of conjugated linoleic acid (CLA) isomers (as the free fatty acids, CLAFFA) in commercial CLA mixtures and biological samples. Due to the unchanged retention mechanism, it was assumed that the elution order of the isomers remained the same as that of methyl esters separated on the same column. The most abundant isomers, cis/trans 10,12-18:2 and cis/trans 9,11-18:2, were separated better as free acids on a single column than in the methyl ester form. Quantification of the CLA standard was used as the reference profile to evaluate different methylation methods commonly used to prepare CLA methyl esters for quantitation. Acid- and vuigi base-catalyzed derivatization methods resulted in CLA intraisomerization and losses in total conjugated dienes content. Acid (HCl and BF₃) methylations significantly elevated the level of trans,trans isomers and significantly reduced the cis/trans isomers. Base methylation, tetramethylguanidine/methanol, resulted in loss of trans,trans isomers, and a substantial loss of total underivatized conjugated dienes. Other catalysts such as the trimethylsilyldiazomethane produced additional peaks of unidentified artifacts. The analysis of CLAFFA appears to provide more accurate quantification of CLA isomers in commercial and biological samples.     

Mass spectral determination of aldehydes,ketones, and carboxylic acids using 1,1-dimethylhydrazine

Analyses of nanogram to milligram quantities of aliphatic aldehydes, fatty acids, and unhindered aliphatic ketones such as those typically found in pheromonal blends have been effected by treating these mixtures with 1,1-dimethylhydrazine. The aldehydes and ketones formN,N-dimethylhydrazones, while the fatty acids form methyl esters. Structural elucidation of the reaction products was achieved using EI and CI gas chromatography-mass spectrometry.Mention of a company or trade name is solely for identification of material used and does not imply endorsement by the United States Department of Agriculture.     

Amino acid derived amides and hydroxamic acids as ligands for asymmetric transfer hydrogenation in aqueous media

Amides and hydroxamic acids derived from α-amino acids were evaluated as ligands in combination with rhodium and iridium half-sandwich complexes in asymmetric transfer hydrogenation (ATH) of ketones. The reactions were performed in aqueous media using lithium formate as hydride source. The catalyst systems turned out to be highly efficient and ee's up to 90% were obtained.     

Bromination of methyl esters of soybean fat acids and methyl linoleate with N-bromosuccinimide

1. The reaction of N-bromosuccinimide with methyl esters of soybean fat acids and with methyl linoleate has been investigated, and the influence of changes in the conditions of reaction has been studied.
2. The reaction of brominated methyl esters of soybean fat acids with sodium methoxide produced both methoxylated products and a dimer-like substance.
3. The reaction of brominated methyl esters of soybean fat acids with sodium cyanide and cuprous cyanide did not result in significant replacement of bromine with the cyano group.

     

Analysis of hydroxylated fatty acids from plant oils

A novel process has been described recently for the preparation of hydroxylated fatty acids (HOFA) and HOFA methyl esters from plant oils. HOFA methyl esters prepared from conventional and alternative plant oils were characterized by various chromatographic methods (thin-layer chromatography, high-performance liquid chromatography, and gas chromatography) and gas chromatography-mass spectrometry as well as¹H and¹³C nuclear magnetic resonance spectroscopy. HOFA methyl esters obtained fromEuphorbia lathyris seed oil, low-erucic acid rapeseed oil, and sunflower oil contain as major constituents methylthreo-9,10-dihydroxy octadecanoate (derived from oleic acid) and methyl dihydroxy tetrahydrofuran octadecanoates, e.g., methyl 9,12-dihydroxy-10,13-epoxy octadecanoates and methyl 10,13-dihydroxy-9,12-epoxy octadecanoates (derived from linoleic acid). Other constituents detected in the products include methyl esters of saturated fatty acids (not epoxidized/derivatized) and traces of methyl esters of epoxy fatty acids (not hydrolyzed). The products that contain high levels of monomeric HOFA may find wide application in a variety of technical products.     

Synthesis and chelating properties of some poly(amidoxime‐hydroxamic acid) resins toward some trivalent lanthanide metal ions

The chelation properties of the addition‐type polymers poly(amidoxime‐hydroxamic acid) and poly(N‐methyl amidoxime‐N‐methyl hydroxamic acid) toward some trivalent lanthanide metal ions [La(III), Nd(III), Sm(III), Gd(III), and Tb(III)] were studied by a batch equilibration technique as a function of contact time, pH, and counterion. The effect of the crosslinker, divinylbenzene, was also studied. The selectivity and binding capacity of the resins toward various lanthanide metal ions are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 691–696, 2005     

Cyclopropenoid fatty acids ingnetum scandens and itsterculia pallens seed oils

Seed oils ofGnetum scandens (Gnetaceae) andSterculia pattens (Sterculiaceae) were found to contain sterculic (28.57,6.97) and malvalic (11.27,3.87) acids, respectively. Gas Chromatographic analysis of silver nitrate/meth-anol-treated methyl esters was used to establish the co-occurrence of these two acids.Sterculia foetida methyl esters were used as a reference standard.     

Gas chromatography-mass spectrometry of methyl esters of unsaturated oxygenated fatty acids

Silylation of hydroxyl groups in methyl esters of unsaturated hydroxy acids provides compounds that give mass spectra which can be readily interpreted, whereas spectra of underivatized esters are extremely difficult to evaluate. The relationship of the double bond(s) to the trimethylsiloxy (TMS) group results in specific mass spectral patterns. In esters that have the TMS group separated from the double bond by one methylene group, the ions caused byα-cleavage at the TMS group on the side closest to the olefinic group are much more abundant than those produced fromα-cleavage on the other side of the TMS group. In esters that have the TMS group and the double bond separated by two methylene groups,α-cleavage ions are approximately equal. When the TMS group and the double bond are allylic, no fragmentation results between them. Cleavage does occur on either side of this system, and those ions resulting from cleavage alpha to the TMS group are in greatest abundance. Silylation of esters that have a conjugated diene or ene-yne system adjacent to a hydroxyl group also gives derivatives amenable to gas chromatographymass spectrometry. In these esters, large peaks are observed that arise fromα-cleavage at the TMS group and at the other end of the olefinic system. No fragmentation between the TMS group and the sites of unsaturation occurs. Unsaturated epoxy methyl esters produce spectra difficult to interpret. When the epoxide is converted to methoxy-hydroxy derivatives by BF₃-methanol, the spectrum locates the position of the epoxide group. Silylation of the hydroxyl group produces a compound that gives a less complicated spectrum which also locates the original epoxy group. Mass spectrometry of a series of unsaturated keto-esters, without derivatization, provides spectra that are easily interpretable. Presented at the AOCS Meeting, Los Angeles, April 1972. N. Market. Nutr. Res. Div., ARS, USDA.     

Fatty acids of cows' milk. A. Techniques employed in supplementing gas-liquid chromatography for identification of fatty acids

Milk fat methyl esters were subjected to distillation and silicic acid column chromatography to provide fractions of less complexity for gas-liquid chromatographic analysis. It was still necessary however to employ supplemental techniques for identification. Chromatograms were obtained with polyester columns of different polarity on all the fractions and necessary reference samples. While many of the components were identified in the usual way by plots of relative retention time versus number of carbon atoms, iodine values for total unsaturation and ultraviolet spectrophotometry for conjugated and nonconjugated polyunsaturated acids were essential for positive identification of some components. Similarly, examination by infrared spectrophotometry confirmed the presence or absence of conjugated diene ascis-trans, trans-trans or both. Isolatedtrans or terminal double bonds were also determined in this way. Gas-liquid chromatograms of some fractions showed incompletely resolved peaks attributable to the presence of methyl esters of odd-carbon atom, branched-chain, and unsaturated acids. Hydrogenation and rechromatographing provided more positive determination of the structure of these components. Further confirmation of identity of some peaks on the chromatogram was achieved by collection of the appropriate fractions and examination of the collected material. At least 60 fatty acids were identified, including several not previously reported, such as odd-numbered carbon chain length monoethenoid acids from C₁₅ to C₂₃. Presented at the 53rd Meeting of the American Oil Chemists' Society, October 17–19, 1960, New York. Eastern Utilization Research and Development Division, Agricultural Research Service, United States Department of Agriculture.     

Reactions of conjugated fatty acids. V. Preparation and properties of diels-alder adducts and their esters fromtrans,trans-conjugated fatty acids derived from soybean oil

Summary Soybean fatty acids were conjugated with alkali, and the contained, conjugated dienoic acids were isomerized with iodine to thetrans,trans configuration. Adducts were prepared from thesetrans,trans-conjugated acids by condensation with maleic anhydride and acrylic acid. The adducts were isolated, purified, and converted to esters by using a variety of alcohols, including methyl, ethyl,n-propyl,n-butyl, and allyl alcohols. Esters made from saturated alcohols were converted into the corresponding epoxy derivatives. All of the esters (except allyl) and all of the epoxy esters were compatible with an equal weight of polyvinyl chloride and appeared to be primary plasticizers for this plastic. The epoxy esters were effective in inhibiting heat deterioration of polyvinyl chloride. Presented at fall meeting. American Oil Chemists' Society, September 23–26, 1956, Chicago, Ill.