Abner Eisner

Further studies on methanesulfonic acid catalyzed additions to oleic acid

Infrared study of the products of the addition of m-cresol to oleic acid in methanesulfonic acid, revealed the presence of both the m-creasoxy and hydroxytolyl substituted stearic acids. By employing a modified extractive procedure to recover the products of the reaction, followed by chromatography on a Florisil column, a separation of the two types of addition products was effected.The methanesulfonic acid catalyzed addition reaction was extended to include aryl thiols. Among the sulfur analogues of the previously used phenols that were added are: benzenethiol, p-t-butyl-benzenthiol, 2-naphthalenethiol, o-, m-, and p-toluenethiol. The yields of addition products (which were unobtainable in sulfuric acid media) ranged from 37–70%. In contrast with the results obtained when phenolic nuleophiles were employed no evidence for the formation of rearranged addition products has been found. Thioethers were the only products identified.

Improved yields in the acid catalyzed addition of phenols and phenyl ethers to oleic acid

Phenols may be added to oleic acid in methanesulfonic acid solution to give the corresponding hydroxyphenylstearates in good yield. With phenol not only is the yield (ca 80%) better than that reported previously using other reagents but considerably less color is developed also. Surprisingly good yields (35–60%) were obtained with such complex phenols asp-t-butylcatechol and 2-naphthol.

Isolation of an hydroxy acid concentrate from wool wax acids

SummaryThe fractionation of the methyl esters of wool wax acids by partitioning between two immiscible solvent layers has been described. Three fractions were obtained: a fraction rich in hydroxyl content, a fraction low in hydroxyl content, and a small amount of hard, transparent, highly colored material. The same procedure when applied to the free wool wax acids did not yield a satisfactory hydroxy acid concentrate.The preparation of wool wax acids with an essentially zero ester number, that is, in a form free of estolides, lactides, and lactones has also been described.

Nonvolatilealpha-branched chain fatty esters. II

A group of nonvolatilealpha-branched esters was prepared by the di-tertiary butyl peroxide-promoted addition of normal esters to terminal olefins containing methyl branches or aryl groups. Methyl stearate was added to 3,7-dimethyl-1-octene, 3,5,5-trimethyl-1-hexene, and 4-phenyl-1-butene. The reaction with 2,4,4-trimethyl-1-pentene, a terminal alkene with a methyl branch at the internal ethylenic carbon, was not successful. Benzyl 2-(4-phenylbutyl) octadecanoate was prepared by transesterification of the corresponding methyl ester. Benzyl 2,2-dimethylpropanoate, which has no α-hydrogen in the acyl portion of the molecule, was added to 1-hexadecene to form α-hexadecylbenzyl 2,2-dimethylpropanoate. Lubricant evaluation data were obtained on the above compounds.

Derivatives of long chain fatty acids as lubricant components

Soaps ofcis-9,10-epiminostearic acid have been synthesized and tested as components of lubricating greases. The lithium, sodium and potassium soaps were obtained by the reaction ofβ-iodocarbamates with the proper alkali metal hydroxides in the ring closure step of the iodine isocyanate (INCO) procedure for the synthesis of internal aziridines. The soaps of other metals, namely barium, lead, aluminum and indium, were prepared from the alkali metal epiminostearates by metathetical reactions. As a result of this method of preparation, the aluminum and the indium soaps were isolated as the dicarboxylates rather than as the tricarboxylates. For the purpose of comparison a sample of lithium 9,10-epiminostearate was also prepared from theβ-chlorocarbamate obtained by the addition of dichlorourethane (DCU) to methyl oleate. Since DCU addition is nonstereospecific, the soap obtained in this preparation was a mixture ofcis- andtrans-aziridines. Evaluation of the metal soaps as grease thickeners was made. The lithium derivative showed considerable promise as thickener having additional desirable properties.

Methanesulfonic acid catalyzed additions to oleic acid and cyclohexene. III. Addition of acids and substituted phenols

Benzoic acid adds to oleic acid in methanesulfonic acid as catalyst-solvent to form an addition product in 30% yield. Saponification studies on the product reveal that the addition is made via the carboxyl group and no rearrangement of the initial product takes place. A number of substituted benzoic acids were also tried but the yield of addition product was nil. Data are included for the experiments with a number of phenols not previously reported. These include: o-chlorophenol,2,6-di-tert.-butylphenol, 2,4,6-trichlorophenol, resorcinol, 5-n-pentadecylresorcinol, hydroquinone, methyl salicylate, and 3-n-pentadecylphenol. Good yields of addition products of cyclohexene are obtained using methanesulfonic acid as catalyst-solvent and the same nucleophiles employed previously.

Conjugated dienes and trienes from methyl oleate and methyl linoleate

Methyl oleate and methyl linoleate were converted to conjugated dienes and trienes, respectively, by selecting and modifying the conventional procedures usually applied to the generation and characterization of fatty hydroperoxides. Conditions have been studied in the laboratory for: (a) the optimum production of hydroperoxides with a minimum of by-products, (b) the effective separation and concentration of the resulting hydroperoxide, (c) the economic reduction of the hydroperoxide mixture, (d) simple dehydration of the reduced product, and, (e) recovery of the resulting polyene-rich material. If the processing sequence is halted after the reduction step, the resulting product,is a mixture of allylic hydroxy monoene or diene methyl esters. Our investigations have been extended to include studies on the methyl esters of commercial oleic acid and the mixture of methyl esters resulting from alcoholysis of lard oil. Products containing 20–25% conjugated diene and lesser proportions of conjugated triene were obtained.

Preparation and solubility of metal soaps of wool wax acids

The preparation and solubility determination of the cupric, magnesium, nickel, cobalt, cadmium, lead, barium, manganous, ferric, and chromic soaps of the wool wax acid fraction are described. Solubilities, at 25°, were determined in: ethanol, methanol, isopropyl alcohol, acetone, ethyl acetate, carbon tetrachloride, and petroleum ether. Barium and cadmium soaps of hydroxy and nonhydroxy acid fractions, obtained by partitioning the whole wool wax acid fraction, were also prepared and subjected to the same study.

The fractionation of lanolin with urea

SummaryA fractionation of lanolin was effected by contacting lanolin with urea in the presence of methyl alcohol. About 6–8% of the lanolin formed a urea adduct which, upon decomposition, yielded a hard, nontacky wax fraction. In addition to the wax fraction, a fluid fraction and a sticky semi-solid were also obtained. The latter two fractions were obtained by the solvent extraction of the nonadduct-forming material from the urea adducts.The fluid fraction, obtained in 71% yield, is a viscous liquid at room temperature. The fluid properties of the fraction can be improved by acetylation.

Rubber swell as a function of fatty acid ester chain length

A study was made of the relationship between the structure of some fatty acid esters of varying chain length and their swelling effect on standard nitrile rubber samples. The esters evaluated were: methyl esters of caprylic, capric, lauric, myristic, palmitic and isostearic acids;n-butyl, isobutyl,n-octyl, octadecyl, “tallow” and 2,2-dimethyl-1,3-propanediol esters of lauric acid and tetradecyl acetate. Federal test methods for aircraft turbine lubricants were used for the evaluations. In the esters the swelling was higher with type L rubber than with type H. The lower the equivalent weight of the ester, the higher the swell with both types of rubber. Branching in the alcohol moiety lowered the swell. Deswelling (desorption) in air of the swelled samples was also investigated. Methyl myristate, methyl palmitate and the long chain laurate esters meet MIL-L-23699 military specifications for type H rubbers. In type L rubbers the swelling is too high to meet specifications.