High resolution gas chromatography of fatty acid methyl esters prepared from ten samples of refined vegetable oils was carried out on glass capillary columns. Effective separations of the positional isomers of monounsaturated fatty acids, the trans-9, cis-12 isomer of linoleate, and the cis-9, cis-12, trans-15 and trans-9, cis-12, cis-15 isomers of linolenate were performed on a Silar-5 CP or SP 2300 column. Additionally, the cis-9, trans-12, isomer of linoleate was separated on a Silar-10c or SP 2340 column. The cis-9, trans-12, cis-15 isomer of linolenate has not been detected in this study. Conversion of linolenate to the trans isomers during the refining process was 1329%, and that of linoleate was about 10% of the conversion of linolenate to the trans isomer. The fatty acid composition of refined vegetable oils is presented in detail.
Crude tall oils imported from five countries were analyzed by glass capillary gas chromatography. The 5-olefinic fatty acids they contained consisted of cis-5, cis-9-octadecadienoic acid (5, 9-18 : 2), 5, 9, 12-18 : 3, 5, 11-20 : 2, and 5, 11, 14-20 : 3; the proportions varied widely among the samples. For the effective separation of a specified 5-olefinic acid, it is important to select suitable crude tall oils as original material. The contents of the 5-olefinic acids in the total fatty acids increased with increasing contents of linoleic acid and with decreasing oleic acid in the samples analyzed.
Reversed phase high performance liquid chromatography (HPLC) on methyl silica column was used for the separation of phospholipids including phosphatidyl choline (PC), phosphatidyl ethanolamine (PE), phosphatidyl inositol (PI) and phosphatidyl serine (PS) in naturally occurring samples. Hexane/2-propanol/water (1 : 60 : 39) was one of the best eluents for the separation of these phospholipids which were detected at 210nm. The molar extinction coefficient of each phospholipid is not yet known and it is very difficult to obtain an authentic sample, so that purified soybean phospholipids, quantitated by Reinecke's salt method for PC and by 2, 4-dinitro-1-fluorobenzene (DNFB) method for PE, were used as standard samples for the determination of PC and PE. The calibration curves between the amount and the peak height in the HPLC were obtained with good linearity ranging from 3.7 to 74μg for PC and from 0.7 to 6.6μg for PE. PC and PE in some phospholipids such as soybean, egg yolk, pig liver and dry yeast (Saccharomyces cerevisiae sp.) phospholipids were determined with reliable accuracy under the conditions employed. The present method can be used for the routine quantitation of PC and PE in various phospholipids prepared from plant and animal sources.
To compare the effects of various metals (periodic group VI) on the autoxidation of methyl oleate and the decomposition of methyl oleate hydroperoxide in methyl oleate, the substrates were kept with metal carbonyls [Mo (CO) 6, Cr (CO) 6 and W (CO) 6] at 80°C. The effects of the catalysts were investigated by observing the changes in peroxide value, iodine value, saponification value, refractive index, molecular weight, and trans isomer content. The identification of autoxidation products of methyl oleate and decomposition products of methyl oleate hydroperoxide were carried out by gas chromatography of trimethylsilyl ether derivatives. Mo (CO) 6 showed marked effect on the autoxidation of methyl oleate and the decomposition of methyl oleate hydroperoxide. The products were found as methyl cis-epoxyoctadecanoate and methyl hydroxyoctadecenoate, which were produced by intermolecular reaction among methyl oleate and methyl oleate hydroperoxide. Moreover, methyl hydroxyepoxyoctadecanoate was also produced by intramolecular reaction of methyl oleate hydroperoxide itself. Cr (CO) 6 showed more marked effect than Mo (CO) 6. The autoxidized products of methyl oleate were identified as methyl trans-epoxyoctadecanoate, methyl cis-epoxyoctadecanoate, methyl hydroxyoctadecenoate and methyl oxooctadecenoate, but methyl hydroxyepoxyoctadecanoate was not produced. Methyl oxooctadecenoate and methyl hydroxyoctadecenoate were produced by decomposition of methyl oleate hydroperoxide in the presence of Cr (CO) 6, but W (CO) 6 showed almost no effects.
The stabilities of 20% fluorocarbon (FC) /water emulsions containing 5% fluorinated nonionic surfactants were determined by measuring the variation of droplet diameter distribution with time (up to 10 months). For comparison of less effective emulsifiers, the rate of phase separation was also used. O/W emulsions containing HCF2 (CF2) 3CH2O (C2H4O) 9.7H showed low stability, but those stabilized by HCF2 (CF2) 7CH2O (C2H4O) 10.5H showed excellent stability. Although emulsions containing HCF2 (CF2) 5CH2O (C2H2O) 10.3H separate a minor proportion of the aqueous phase in a relatively short time, the distribution of FC droplet diameter changed little over a long period. In the present investigation, emulsions stabilized by CF3 (CF2) 6CH2O (C2H4O) 10.3H exhibited the highest stability, indicating the importance of a greater affinity of the terminal CF3 group for FC. The percentages of the aqueous phase formed 5h after preparation of emulsions containing various surfactants were as follows : HCF2 (CF2) 7CH2O (C2H4O) 10.5H (0%), CF3 (CF2) 6CH2O (C2H4O) 10.3H (00.3%), CF3 (CF2) 5CH2O (C2H4O) 10.3H (00.6%), HCF2 (CF2) 3CH2O (C2H4O) 9.7H (01%), HCF2 (CF2) 5CH2O (C2H4O) 10.3H (12.613.4%), CH3 (CH2) 11O (C2H4O) 8H (6670%).
6, 10-Dimethyl-2-undecanone (10), a key intermediate for squalane and isophytol, was effectively synthesized from prenyl chloride (4a, b) via telomerization with isobutylene and hydroformylation with cobalt catalyst followed by aldol condensation with acetone. Telomerization of (4a, b) with excess amount of isobutylene was carried out in the presence of zinc chloride catalyst to obtain 6-chloro-2, 6-dimethyl-2-heptene (5) in 63.5%. Dehydrochlorination of (5) was investigated under various conditions. A mixture of 2, 6-dimethyl-1-heptene (7a) and 2, 6-dimethyl-2-heptene (7b) was obtained from (5) by hydrogenation followed by dehydrochlorination. Hydroformylation of the mixed products (7a, b) with cobalt catalyst proceeded with migration of the double bond to yield 3, 7-dimethyloctanal (8) as the sole product which was converted to (10) by aldol condensation with acetone and by selective hydrogenation.
Fluorination of various terpenic alcohols and fatty alcohols with N, N-diethyl-1, 1, 2, 3, 3, 3-hexafluoropropyl amine (PPDA) was carried out. A mixture of 2- (2'-fluoroethyl) -6, 6-dimethyl-bicyclo [3.1.1] hept-2-ene (2) and nopyl 2, 3, 3, 3-tetrafluoropropionate (3) was obtained from the reaction of nopol (1) with PPDA. Similar results were obtained from other terpenic alcohols and fatty alcohols.