Hydroxyaliphatic acids in branched copolymers with acyl chloride-terminated long side chains: A new shrink-resist treatment for wool

Two synthetic routes were followed to prepare graft copolymers with long side chains containing acyl chloride terminal groups. In the first of these methods acryloxy aliphatic acyl chlorides were synthesized from ricinoleic acid, 12-hydroxystearic acid and 10-hydroxydecanoic acid and then polymerized with other acrylate ester comonomers. In the second procedure, a prepolymer was formed by copolymerizing acryloyl chloride with acrylate esters. The prepolymer then was treated with 12-hydroxystearic acid or 9(10)-hydroxymethylstearic acid to produce polymers with side chains having terminal carboxylic acid groups. These polymers were made more reactive by conversion to acid chlorides. The active polymers were applied to wool fabrics; the imparted shrink-resistance was durable under an accelerated wash test procedure. An added advantage of the treatment is a soft “hand” or feel resulting from internal plasticization of the polymer coating. No. Market. Nutr. Res. Div., ARS, USDA. W. Market, Nutr. Res. Div. ARS, USDA.     

Homogenous catalytic conjugation of polyunsaturated fats by chromium carbonyls

Various arene-Cr (CO)₃ complexes and Cr(CO)₆ are effective soluble catalysts for the conjugation of polyunsaturated fats. Methyl benzoate-Cr(CO)₃ is one of the most active catalysts. The following conjugation levels were obtained: methyl linoleate, 65%; methyl linolenate, 45%; the polyunsaturates in soybean and safflower oils, 73%; and in linseed oil 48%. Conjugated dienes from linoleate were predominantlycis,trans in configuration. Their double bonds were distributed between C₅ and C₁₆ of the fatty acid chain. Hydrogenation and dehydrogenation are side reactions, which seem to limit the yield of conjugated dienes from methyl linoleate. A conjugation mechanism is proposed that involves allyl-HCr(CO)₃ complexes as intermediates undergoing 1,3- and 1,5-hydrogen shifts. Presented at the AOCS Meeting, San Francisco, April 1969. No, Utiliz. Res. Dev. Div., ARS, USDA.     

Chromatographic studies on oxidative and thermal fatty acid dimers

A chromatographic study was carried out to investigate the nature of polymeric products in edible oils. Dimers from low-temp oxidation of methyl linoleate were compared with thermal dimers from high-temp polymerization of conjugated methyl linoleate. The distilled dimers were subjected to liquid-partition chromatographic separations on silicic acid columns as methyl esters, as free acids, and as methyl esters prepared by saponification and reesterification. Chromatographically isolated dimer fractions were also rechromatographed before and after each treatment. When thermal dimer esters are saponified and reesterified, chromatographic recoveries are quantitative, and the expected changes in polarity result; whereas, with oxidative dimer esters, gross changes in polarity occur. Chromatographic separations of dimer esters or their acids fractionate into distinct areas of increasing polarity. Presented at the AOCS Meeting, New Orleans, 1964. Honorable Mention, Bond Award Competition. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, USDA.     

Homogeneous catalytic hydrogenation of unsaturated fats: Cobalt carbonyl

Homogeneous hydrogenation of unsaturated fats by cobalt carbonyl has been compared with the previously reported catalysis by iron carbonyl. Soybean methyl esters, methyl linoleate and linolenate have been hydrogenated at 75–180C, 250–3,000 psi H₂ and 0.02 molar concn of catalyst. The cobalt carbonyl catalyst is more active at lower temp than iron carbonyl. The partially reduced products are similar to those observed with iron carbonyl, but the reaction differs in showing much less accumulation of conjugated dienes, no selectivity toward linolenate, almost complete absence of monoene hydrogenation to saturates, less double bond migration and moretrans isomerization. No evidence was found for a stable complex between cobalt carbonyl and unsaturated fats as previously observed with iron carbonyl. The rates of hydrogenation/double bond were the same for linoleate and linolenate on one hand, and for alkali-conjugated linoleate and nonconjugated linoleate on the other. Presented at AOCS Meeting in Minneapolis, 1963. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, USDA.     

Aminoacyloxy Oligostannoxanes

Oligomeric stannoxanes having the general formula were prepared by treating amino and N-acylamino-acids with polymeric dibutyltin oxide at molar ratios less than 1. Shorter oligomers were built up to higher oligomers by insertion of dibutyltin oxide units.     

cis-bond-producing hydrogenation of polyunsaturates catalyzed by polymer-complexed Cr(CO)3 catalysts

cis-Bond-producing chromium carbonyl catalysts were prepared by complexing conventional or macroreticular, styrene-divinylbenzene copolymers or cross-linked poly (vinyl benzoate) with Cr(CO)₆. With one exception, these polymer-Cr(CO)₃ catalysts were as selective as the corresponding homogeneous arene-Cr(CO)₃ complexes for the formation ofcis-monoenes from methyl sorbate and from conjugated, polyunsaturated fatty esters in cyclohexane. Although several of the polymer catalysts were very active when fresh, they all lost activity on recycling. They could not be recycled more than two times before a marked decrease in activity occurred due to loss of Cr, as shown by elemental analysis and infrared absorption in the recovered catalyst. Thermal analysis indicated instability of the polymer complexes at hydrogenation temperatures.     

Antioxidant activity of grape extracts in a lecithin liposome system

Extracts of 14 different grapes were tested for their antioxidant activities in a copper-catalyzed lecithin liposome oxidation assay and analyzed for their phenolic components by high-performance liquid chromatography (HPLC). The total phenolic contents of the grape extracts varied from 176 to 1236 mg gallic acid equivalents (GAE)/L. Extracts of red wine grape varieties contained higher concentrations of phenolics than other varieties. When compared at the same 20 μM GAE basis, the grape extracts inhibited formation of conjugated diene hydroperoxides by 25.1 to 67.9%, and hexanal formation by 49.3 to 97.8%. Extracts of red table grape varieties Red Globe and Emperor and white wine grape varieties Chardonnay and Sauvignon Blanc gave the highest antioxidant activities. The relative percentage inhibition of conjugated dienes and hexanal correlated with total phenols (r=0.86 and 0.89). HPLC analyses showed that anthocyanins were the most abundant phenolic compounds in extracts of red grapes, and flavonols were most abundant in extracts of white grapes.     

Analyses of lipids and oxidation products by partition chromatography: Hydroxy fatty acids and esters

A liquid-partition chromatographic procedure was used to separate hydroxy fatty acids, their methyl esters, and reduced fatty ester hydroperoxides. Mixtures of methyl stearate, mono- and dihydroxystearate, and mixtures of the corresponding free fatty acids were easily separated. Chromatographic determinations for ricinoleate in castor oils compared favorably with the chemical and infrared analyses. The chromatographic procedure was used to separate hydroxy fatty acids inDimorphotheca andStrophanthus seed oils. The methyl ester of dimorphecolic acid, the principal hydroxy fatty ester ofDimorphotheca oil, behaved like reduced methyl linoleate hydroperoxide and showed a polarity intermediate between methyl 12-hydroxystearate and methyl 9,10-dihydroxystearate. The 9-hydroxy-12-octadecenoic ester ofStrophanthus oil had a larger retention volume than methyl ous hydroxy fatty esters isolated chromatographically. The diene content of the reduced hydroperoxides agrees well with values reported in the literature (1,5,16). The diene content of the chromatographed methyl dimorphecolate is higher than reported by Smithet al. (20) for their preparations but agrees well with the value reported by Chipault and Hawkins (6) for puretrans-trans conjugated methyl linoleate. The extinction coefficient of methyl 12-hydroxystearate at 2.8 μ is higher than that reported for ricinoleate and the absorption band is much sharper. Because of these two conditions no association of the hydroxyl groups is indicated. These results also confirm the purity of the hydroxy fatty esters obtained by LPC. This method has been a valuable adjunct to the study of various oxygen-containing fatty acid and esters and was used to characterize the hydroxy esters obtained from the hydrogenation of methyl linolenate hydroperoxides (9). This work offers a basis for the development of analytical methods to determine the hydroxy and other polar acid content of fatty glycerides and their derivatives.     

Determination of hydroperoxides and structures by high-performance liquid chromatography with post-column detection with diphenyl-1-pyrenylphosphine

A high-performance liquid chromatographic method, using post-column detection with diphenyl-1-pyrenyl-phosphine (DPPP), was developed for the quantitative and qualitative determination of isomeric lipid hydroperoxides (OOH). The OOH eluted from a normal-phase column were passed through a photodiode array detector and then mixed with DPPP solution in a reaction coil heated at 80°C. DPPP oxide formed by the reaction with OOH was determined by monitoring the fluorescence intensity at 380 nm and excitation at 352 nm. The conjugated diene OOH (13-cis, trans- and 9-cis, trans-OOH) and nonconjugated OOH (12-cis-trans- and 10-cis, trans-OOH) from photosensitized oxidation of methyl linoleate were determined in a molar ratio of 31∶29∶19∶21, respectively. However, only the two conjugated hydroperoxides were detected by ultraviolet absorption at 234 nm. Further applications were carried out for the determination of OOH of methyl oleate and methyl linolenate. This method proved to be useful for the determination of the OOH containing both conjugated and nonconjugated diene structures.