New synthesis of royal jelly acid

A new synthesis of (E)-10-hydroxy-2-decenoic acid (royal jelly acid) is described, starting from 8-bromo-1-octanol via condensation of malonic acid with 8-hydroxyoctanal or 8-acetoxyoctanal.     

Novel fatty acids from the royal jelly of honeybees (Apis mellifera,L.)

Three new compounds isolated from the royal jelly of honeybees (Apis mellifera, L.) have been identified as 8-hydroxyoctanoic acid, 3-hydroxydecanoic acid and a dextrorotatory isomer of 3,10-dihydroxydecanoic acid.     

Neo acids: Synthetic highly branched organic acids

Neo acids are highly branched synthetic trialkyl acetic acids manufactured by reacting an olefin with high purity carbon monoxide under high pressure in the presence of an acidic-type catalyst. The starting olefins for neopentanoic (C₅, single isomer) and neodecanoic (C₁₀, mixed isomers) acids are isobutylene and nonene, respectively. Commercial quantities of both products have been available since 1964. Neopentanoic acid is used in the preparation of t-butyl peroxy neopentanote (pivilate), a peroxyester initiator used in polyethylene manufacture. The C₅ neo acid also finds use in a variety of other industrial end uses, e.g., pharmaceutical, agricultural chemicals, and reaction of form hindered, very stable esters. Metal salts of neodecanoic acid are used in paint driers, PVC stabilizers, and peroxyester initiators. Other reactions such as esterification, amide formation, and reaction with ethylene oxide will be discussed.     

Chlorinated alcohols: I. Preparation from chlorinated acids

Rhenium, ruthenium and rhodium oxides, hydrogenolysis catalysts for stearic acid at 150 C, were tried for the conversion of 9,10-dichloro-stearic acid to the dichloro alcohol but only ReO₃ was effective in some degree (yield 14%). Dehydrochlorination or hydrogenolysis at the carbon-chlorine bond was the principal reaction. Reductions with diborane or with lithium aluminum hydride, however, were found to be excellent methods for preparing 9,10-dichloro-stearyl alcohol.     

Hyperchlorinated fatty acids: I. Tentative methods of synthesis

The hyperchlorination of fatty acids was studied by four methods using mainly stearic acid. This acid was first submitted to the action of nascent chlorine from NaCl electrolysis, for which the best results never exceeded 43% of fixed chlorine (about 6 Cl atoms per mole of acid), with a yield of 30% based on the acid. Stearic acid was also submitted to electric discharges in CCl₄, and so transformed into various chlorinated and unsaturated compounds, which indicate a near simultaneity of chlorination and dehydrochlorination. However, when the time of contact of the acid with the reactive solution was reduced, formation of only saturated chlorinated compounds occurred, of which the chlorine content, in the best case, was 54% (9 Cl/mole). Direct photochlorination of acid without solvent gave a product containing a maximum of 8 Cl atoms per mole (about 50%). Finally, direct photochlorination of the fatty acid in CCl₄ led to a hyperchlorinated acid containing 68.3% Cl (16–17 Cl/mole), and minor, more or less polymerized products. Although the second and third methods readily afford stearic acid chlorinated to the extent of about 50%, this value, corresponding to an average of 0.5 Cl/C atom, appears to be a barrier that can only be overcome by employing photochlorination in an inert solvent, such as CCl₄.     

Electrochemical perfluorination of organic acids. Contribution to the knowledge of the mechanism

Electrochemical perfluorination of octane-sulphofluoride (OSF) and octanoic-fluoride (OF) to the perfluoro compounds (POSF and POF) has been studied over a wide range of experimental conditions. Significant improvement of the reported yield of perfluoro-product has been achieved with electrolysis at high potential. The results are explained in terms of a model involving simultaneous adsorption of the reactant and of fluorine on a NiF₂ surface.     

Coulometric determination of organic acids

A system has been devised for the coulometric titration of organic acids in a non-aqueous medium. The solvent system is benzene-methanol, 1∶1, containing LiCl as the electrolyte. The acid is titrated by reducing hydrogen ion at a platinum cathode. The anode reaction involves the formation of AgCl on silver. The endpoint is detected by an antimony-glass electrode pair and the derivative of the electrode output is used to effect automatic current shut-off. Alternative reference electrodes are discussed. Usual sample size titrated is 0.01 meq but the method can be applied to both larger and smaller amounts. The method has been applied to the determination of acid value and free fatty acid in fatty materials. The advantages of the coulometric determination are: 1) No standard solutions are required. 2) The titration is conducted without analyst attention. 3) The technique is simple and rapid. Presented at the fall meeting. American Oil Chemists’ Society, Chicago, Illinois, October 30 to November 1, 1961.     

Multicomponent-liquid-membrane permeation of organic acids

The parameters of lactic acid separation from fermentation broths by Emulsion-Liquid Membranes (ELMs) have been optimized. Using these parameters, lactic acid can be separated up to 90%, concentrated up to 3 times and cleared of most of its by-products. Only about 1% of glucose and amino acids is permeated together with the lactic acid. With these parameters, not only lactic acid but also other monocarboxylic acids can be separated, the better and faster the lower the pKa-value of the acid the fewer polar side groups it carries. When separating dicarboxylic acids, the mass transfer is hindered by the second carboxylic group. The smaller the distance between the two carboxylic groups, the slower is the separation of the acid. When several organic acids are separated from the same fermentation broth, their mutual influence is not very strong, at least when the concentrations of the acids are about 100 mmol/l. However, sulphuric acid which is added to the fermentation broth throughout permeation to maintain the broth at a constant pH, does exert a strong influence. In order to reduce the competition between the organic and sulphuric acids during permeation to a minimum, as little as possible sulphuric acid is used. However, a certain quantity of sulphuric acid is necessary to maintain the pH of the fermentation broth during permeation at 4.5, otherwise organic acid separation would become too slow.     

Ethylene adduct of conjugated octadecadienoic acids: I. Peracid oxidation products

8-(4-n-Hexylcyclohex-2-enyl)octanoic acid obtained by the addition of ethylene totrans,trans-9,11-octadecadienoic acid was treated with 28% hydrogen peroxide in acetic or formic acid to give the hydroxyacetoxy or-formoxy derivative. Saponification of the hydroxyacetoxy derivative yielded two crystalline glycols. The hydroxyformoxy fatty acid was converted in one step either to the glycol ester, methyl 8-(4-n-hexyl-2,3-dihydroxycyclohexyl)octanoate, by reaction with anhydrous hydrochloric acid in methanol or to the acetone derivative of the glycol ester by treatment with dimethoxypropane and anhydrous hydrochloric acid in methanol. Epoxidation of the C₂₀ cyclohexene fatty methyl ester gave the oxirane derivative. A ring opening reaction of the diol acid with periodic acid yielded 9,12-diformylstearic acid. Presented in part at the AOCS-AACC Meeting, Washington, D.C., April 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Activation of long chain fatty acids by subcellular fractions of rat liver: I. Activation oftrans-unsaturated acids

The optimal fatty acid to protein ratio for maximum rat liver microsomal or mitochondrial activation of thetrans-monounsaturated acids elaidate ortrans-vaccenate is similar to the ratio for maximum palmitate activation but approximately double the optimal ratio for maximum activation of thecis-unsaturated fatty acids, oleate,cis-vaccenate, or of thetrans-diunsaturated linelaidic acid. However, when the substrate is a fatty acid-albumin complex rather than free fatty acids, optimal fatty acid activation appears to be independent of geometrical configuration or degree of unsaturation. All-trans retinoate, d-α-tocopheryl acid succinate, and dihomogeranoate are not activated themselves, but at low concentrations extensively inhibit activation ofcis-acids (oleate,cis-vaccenate, petroselenate, linoleate, linolenate, arachidonate) and thetrans-diunsaturated linelaidate but do not affect activation of palmitate ortrans-monounsaturated acids elaidate andtrans-vaccenate. Anionic, cationic or nonionic detergents in a pH 7.4 buffered incubation medium were shown to inhibit, have no effect on, or apparently activate oleate activation, respectively, while not affecting or inhibiting palmitate and elaidate activation. The effect observed was dependent on the fatty acid to protein ratio, the fatty acid configuration and the detergent concentration.     

Fatty acids of lard. A. Identification by gas-liquid chromatography

Abstrat A fresh commercially rendered lard was separated into its component fatty acids by subjecting the methyl esters to gas-liquid chromatography on nonpolar and polar columns. The lard methyl esters were first chromatographed on a silicone column. This column achieved separation of the component esters principally on the basis of chain length, and fractions which were represented by a single peak or series of peaks were collected. The collected fractions were then rechromatographed on an ethylene glycol succinate polyester column to separate and identify the saturated and the unsaturated esters. Qualitative evidence was obtained for the presence of 29 fatty acids ranging in chain length from 10 to 20 carbon atoms. Included were the esters of the following: Satrated acids (10,12,14,15,16,17,18,19,20, and 22 C-atoms), monounsaturated acids (14,16,17,18,19, 20, and 22 C-atoms), and polyunsturated acids (18∶2,20∶2,22∶2,18∶3,20∶3,22∶3,20∶4,22∶4,20∶5, and 22∶5).³. Peaks for several additional trace components were also observed. Presented in part at the AOCS meeting, St. Louis, Mo., 1961. Eastern Utiliz. Res. & Dev. Div. ARS, U.S.D.A.     

Lipopeptidic surfactants: I. Neutral N-lauroyl-I-arginine dipeptides from pure amino acids

Neutral N^α-lauroyl-dipeptides such as N^α-lauroyl arginylglycine and N^α-lauroyl-arginylphenylalanine as methyl ester (cationic surfactants) and free acid (amphoteric surfactants) derivatives have been prepared by synthetic methods. Fundamental surfactant properties and antimicrobial activity have been evaluated. The properties of these compounds have been compared to the properties of the monomer derivatives N^α-lauroyl-arginine methyl ester (cationic) and N^α-lauroyl-arginine (amphoteric). These new molecules are very soluble in water, good surfactants, and exhibit a good antimicrobial activity, independently of their ionic character.     

液相色谱-串联质谱法鉴定甲胺基阿维菌素的化学成分

用高效液相色谱法从工业甲胺基阿维菌素中分离出10个馏分，用电喷源－串联质谱法获得各馏分的质谱数据，基于准分子离子和母离子的特征子离子，鉴定出甲胺基阿维菌素中含有21个组分。     

Unsaturated fatty acids. I. Low temperature urea complexes of polyunsaturated acids from bovine tissue

Summary A mixture of fatty acids obtained from autolyzed saline extracts of beef testicular tissue was fractionated by crystallization of the urea complexes at 5°, −20°, and −75°C. Fractions rich in docosahexaenoic and in arachidonic acids were obtained as solid complexes. The filtrate remaining after precipitation of the solid urea complexes contained a high percentage of hexaenoic acid of shorter chain length than docosahexaenoic, probably eicosahexaenoic acid. Presented at the fall meeting of the American Oil Chemists' Society, Minneapolis, Oct. 11–13, 1954. Presented in part before the Lipoid Section, IId International Congress of Biochemistry, Paris, France, Sept. 21, 1952.     

Catalytic oxidation of odorous organic acids

Emissions of volatile organic acids is a significant problem in rural communities. So far no one has considered catalytic solutions to the problem but catalytic alternatives look quite reasonable. In this paper we present the results of the first study of the oxidation of a series of odorous organic acids on copper catalysts. We find that the organic acids are easily oxidized on commercial copper on alumina catalysts. Light-off temperatures vary from 180°C for n-butyric acid to 220°C for acetic acid. The rate of oxidation of acetic and i-butyric acid show simple power law dependence on the concentrations of the reactants. In contrast, the oxidation of n-butyric, i-valeric and n-valeric acids show rates which reach a maximum at intermediate oxygen concentrations. Analysis of the data indicates that the copper can exist in two different states: a more active and a less active state.

These results provide the first evidence that catalytic processes are viable for emissions control in rural communities.     

Radiolysis of lipids in monolayers. I. Saturated fatty acids

In order to study the effect of molecular orientation on the behavior of lipids when exposed to high energy radiation, model systems of palmitic acid or ethyl palmitate adsorbed as monolayers on silica were irradiated with⁶⁰Co at 25 Mrad under vacuum, and the volatile products compared with those of control samples irradiated in bulk. Major quantitative differences were observed. More of the C _n−1 alkane relative to the shorter-chain members of the homologous series were formed in bulk samples as compared to samples in monolayer. The C _n−2 alkene and C _n aldehyde also were formed in greater quantities in bulk. These observations are explained on the basis of a reduced preferential cleavage near the carbonyl group and a restricted mobility of free radical intermediates, in the case of the monolayers.     

Deodorization of vegetable oils. Part I: Modelling the geometrical isomerization of polyunsaturated fatty acids

Laboratory-scale treatments of canola oils similar to deodorization were carried out by applying the following conditions: reduced pressure with nitrogen or steam stripping at different temperatures ranging from 210 to 270°C for 2–65 h. The formation of the group of trans linolenic acid isomers follows a first-order reaction and the kinetic constant varies according to the Arrhenius’ law. Similar results were observed for the trans isomerization of linoleic acid. Based on these experiments, a mathematical model was developed to describe the isomerization reaction steps occurring in linoleic and linolenic acids during deodorization. The calculated degrees of isomerization are independent of the composition of the oil but related to both time and temperature of deodorization. The degree of isomerization of linolenic acid is unaffected by the decrease of this acid content observed during the deodorization. Deodorization at about 220–230°C appears to be a critical limit beyond which the linolenic isomerization increases very strongly. The newly established model can be a tool for manufacturers to reduce the total trans isomer content of refined oils, and was applied to produce a special selectively isomerized oil for a European Nutritional Project.     

Compatibility of polymer blends. I. Copolymers with organic solvents

In this work, we present a theoretical discussion regarding the Flory–Huggins χ interaction parameter for 11 random copolymer‐solvent systems along with their corresponding polymer pairs. Copolymers studied are poly(acrylonitrile‐co‐butadiene) in acetonitrile, poly(styrene‐co‐acrylonitrile) in 1,2‐dichloroethane, poly(acrylonitrile‐co‐butadiene) in hexane, and poly(acrylonitrile‐co‐butadiene) in pentane. For ternary systems, the results are expressed in terms of χ_1,23, which is reduced to the classical Flory–Huggins χ₁₂ interaction parameter in case of binary mixtures. The data on χ_1,23 may be used for an approximate estimation of the χ′₂₃ interaction parameter for the limiting case of zero solvent concentration. For this purpose, at the end of each subsection of tables, the limiting value of is given. The limiting values of , , and χ′₂₃ also appear at the end of each table. It should be noted that these values are obtained by the graphical extrapolation of data to zero concentration of solvent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 492–498, 2006