It had been found that some particular fish of several different families contain the wax esters as their major lipid type. The interest in deep sea organisms and advancing survey techniques have permitted to extend the occurrence of the wax esters in their lipids. In the fish there is a characteristic pattern in the presence of waxesters in the tissue lipids; namely, the wax esters are the major lipid, type in the muscle but are present trace in its roe, while this pattern is reversed in some fish. As the representative example of the latter, the mullets caught off coast of Mokuzu, Sukumocity, Kochi-prefecture, were collected and analyzed to understand the properties of ovary and other tissue lipids and thereby, to get some informations on the formation of wax esters during the process of maturing. From the biological measurement of mullet, the maturity of roe can be well expressed by the gonad index (gonad weight/body weight ×100, G.I.). It was further found that there is a relation between the gonad index and the wax ester content in roe lipids. Upon measurement of eleven gonads with different gonad indices from 0.28 to 17.65, the wax ester contents in roe lipids varied from 4.6% to 65.4%. This relation was expressed by the following empirical formula, y=62.6 (1-e-x/1.78), where x is the gonad index and y is the corresponding wax ester content in roe lipids. The wax esters of mullet roe lipids consist mainly of C26 to C40 with even chain-lengths. The major esters are C32 and C34, and the sum of both acids exceeds 70% of total, and a little amounts of odd numbered esters exist. The acid moiety of wax esters contains over 30% of C16 : 1 and C18 : 1 as main acids, respectively, while the alcohol moiety consists of C16 : 0 dominantly, as much as 61%. The fatty acid composition of triglycerides is similar to those of the free fatty acids, and the composition of free alcohols rather resembles those of the alcohol moiety of wax esters. Composition of various tissue lipids obtained from the immature (G.I. 0.28) was contrasted with that of mature mullets (G.I. 17.65). In the former there were no particular differences among the various tissue lipids but a small amounts of wax esters were detected in the lipids of liver, intestine contents etc. as well as ovary, while from the latter the wax esters more than 60% were found only in the lipids of ovary. There were no significant differences in other tissue lipids of both the mature and immature mullets.
As a result of the supplemental test of the Hoover's method (U.S. 3, 231, 390), in which magnesium oxide was used as an adsorption agent on the removal of free fatty acids in frying oils, the method was concluded to be unpractical because magnesium oxide formed a soap with free fatty acids in frying oils, and the soap could dissolve in the oils and promote their hydrolysis significantly. When some reagents were examined for their effects on the adsorption of free fatty acids in the oils, dried aluminum hydroxide gel (AHG) was found to be the most exellent reagent as an acid adsorbent, that is, it had a strong ability of adsorbing free fatty acids and was almost insoluble in the oils. After the adsorption tests had been repeated ten times, the amount of aluminum dissolved in the oil was very small (max. 1.5ppm). A practical test of AHG adsorption was carried out by using an automatic test fryer and the changes in the amounts of free fatty acids and of aluminum in the oils and in the properties of the oils were followed at varied time intervals. As a result of this experiment, it was revealed that the amounts of free fatty acids in the oils had been maintained at a very low level for a long time and aluminum did not dissolve into the oils so much (max., 15ppm). The properties of the oils were maintained in better conditions than those of frying oils which were not treated with AHG. Therefore, AHG was proved to be an excellent acid adsorbent even when used practically. The difference between the preliminary and practical tests in the amount of aluminum in the oils seemed to be due to the incompletion of filtration (the oils were sucked by a pump through filter paper) and to the effect of moisture in the oils coming from frying materials (potato) in case of the practical test. The mecanism of the adsorption of fatty acids on AHG was discussed. It seems that the adsorbed layer is monomolecular and the fatty acids are chemisorbed on the surface of AHG and further reaction between adsorbate and AHG (production of the metal soap which dissolves into the oil) does not occur. This is the major reason why the amount of aluminum dissolved in the oil is very small.
When methyl linoleate is heated in the presence of iodine, a large amount of a substance, which has the same retention time as methyl oleate, forms. To identify this substance, this was concentrated from reaction products by means of adsorption chromatography with alumina and of subsequent urea adduct method, then analyzed by GLC, IR and GC-MS. The concentrated substance was also analyzed by oxidative ozonolysis. It is concluded from these analytical results that this substance is a mixture of positional isomers of octadecenoate of which double bonds are mainly trans form.
The substituent effects on the carbonylation reaction of cobalt hydrocarbonyl with polar olefins such as ethyl vinyl ether, vinyl acetate and N-vinyl compounds (N-vinylcarbazole, N-vinylindole, N-vinylpyrrole and N-vinylpyrrolidone) were studied. These olefins were carbonylated selectively on the α-carbon to give the branched-chain acyl complexes, though the α-carbon is more sterically hindered than the β-one. The branched-chain acyl complexes formed did not isomerize into the straight-chain one, though it is known that acylcobalt complexes easily undergo such a skeletal rearrangement. The branched-chain acyl complexes derived from ethyl vinyl ether, vinyl acetate, N-vinylindole and N-vinylpyrrole showed the great tendency to be reduced by cobalt hydrocarbonyl and to be transformed into the corresponding aldehydes. The oxo reactions of these olefins as well as phenyl vinyl ether were also studied with dicobalt octacarbonyl as the catalyst. The branched-chain aldehyde (and/or the corresponding alcohol) was produced with high selectivity from each olefin used. The effects of the reaction conditions (reaction temperature, partial pressure of carbon monoxide or hydrogen) on the distribution of the products (the straight or the branched-chain one) were very little. From these results, it was concluded that the distribution of the products in the oxo reaction of those olefins with electron-donative substituents such as alkoxy, acyloxy, and N-carbazolyl is mainly decided by the direction of the addition of cobalt hydrocarbonyl to the carbon-carbon double bond, and that the attack of cobalt occurs on the α-carbon from the substituent to give the products of the branched-chain structure.
As a fundamental study on the solvent-dying, the solubility of disperse dyes in nonpolar solvents and in nonaqueous surfactant solutions was measured. The solubility of dyes nonpolar solvents was from 10-5 to 10-3 (mol/kg solvent) and was in the order of benzene>cyclohexane>n-heptane. Furthermore, a linear relation was observed between logarism of the solubility and inorganic/organic properties of dye molecules. On the other hand, the solubility of dyes in surfactant solutions was estimated in terms of the number of dye molecule dissolved by a surfactant molecule present. The solubility of an azo dye in benzene solutions of surfactants was in the order of cationic>nonionic>anionic surfactants. The solubility in anionic surfactant solutions was independent on the counter ions and bulkiness of hydrocarbon chain of surfactant molecules, but those in cationic and nonionic surfactant solutions depended on the counter ions and the ethylene oxide chain length, increasing in the order Cl-salt>Br-salt>I-salt and NP=10>NP=6>NP=4. The solubility of aminoanthraquinone dyes in anionic surfactant solutions decreased with increase of the number of amino group of dyes. The effect of solvents on the solubility of an azo dye in anionic surfactant solutions was in the order of benzene>cyclohexane>n-heptane, but it was not remarkedly affected by temperature.
The authors synthesized two series of dibasic acids containing ether linkages, oxadiacetic acids and oxadipropionic acids, which were respectively obtained from polyethylene glycols by the air oxidation and from water or formaldehyde or ethylene glycol by the cyanoethylation and subsequent hydrolysis. Disodium salts of dibasic acids were prepared and compared to the sodium tripolyphosphate (STPP) and sodium citrate with their detergency building action. The detergency tests were carried out on naturally soiled cotton fabrics and the comparison was made by Scheffe's method. The builders employed were sodium tripolyphosphate (STPP) or disodiumsalts of dibasic acids, or sodium citrate, or the mixture of STPP and disodiumsalts of dibasic acids, or the mixture of STPP and sodium citrate. As a result, the oxadiacetic acid series achieved better building performance than oxadipropionic acid series, and in each series, the smaller molecular weight of the test builder showed the better building power. The reason of these results can be explained that oxadiacetic acid formed a five membered ring with calcium, while oxadipropionic acid probably formed a six membered ring and stability difference between the two chelate ring systems caused the difference of their building actions. Another reason is the difference of the molecular weight. This is interpreted as the “Chelating value” or C.V.. To chelate a given amount of metal it requires less quantity of the minor molecular weight builder than that of the higher.
It has long been believed that a peroxide (PO) such as methyl linoleate hydroperoxide (MLHP) was the major contributor to the toxicity of autoxidized oils. It was found however, in a previous paper*) that hydroperoxyalkenals (HPA) ranging in carbon chain from five to nine were the most toxic when the toxicity was compared in terms of a single compound. Furthermore, low molecular weight compounds yielded in autoxidized oils were found to have powerful enzyme-deactivating abilities in the succeeding paper**) . Although studies on the toxicity of PO were conducted extensively, no information is available on the toxicity of HPA. Some attempts were made in this paper to cast light to the toxicity of HPA in comparison with that of MLHP. 1) LD50 of HPA and MLHP was determined by both oral administration (OA) and intraperitoneal injection (II). HPA was found to be 87 times as toxic as MLHP in the case of OA. There was no discrepancies in LD50 between OA and II for HPA, whereas MLHP was found less toxic in OA than II. 2) P.O.V. s and CO.V. s of tissue lipids of mice to which maximum amount for survival of HPA and MLHP were administered, were determined. Although the amount of HPA administered to mice was far smaller than that of MLHP, P.O.V. s and CO.V. s were found much higher in HPA-administered mice than in MLHP. 3) The enzyme-deactivating abilities of HPA and MLHP were compared in vitro using lipase, succinate dehydrogenase and thiokinase. It was evident that HPA deactivated these enzymes more severely than MLHP. 4) Hemolysis rates of red blood cells by HPA and MLHP were determined in vitro. HPA was found to have greater hemolytic potentials than MLHP. From these results authors concluded that HPA appeared to be absorbed from intestine to some extent and transported into tissues where it exerted adverse effects such as deterioration of tissue lipids, deactivation of enzymes and destruction of membranes. MLHP, on the other hand, seemed to be absorbed with greater difficulty than HPA. MLHP also had far less significant effect on enzymes and membranes, if absorbed entirely.