In the previous paper, the authors reported that more than 55% of the toxic fraction separated from thermally oxidized oil was absorbed through the intestine of rats. The present study is for investigation of the structure and the behavior of this toxic fraction in rats. The toxic fraction prepared from the thermally oxidized soybean oil by chromatography on silicic acid column as described previously, was fed to rats for 2 weeks. The feces were collected, and the fecal lipids were extracted and fractionated by column chromatography. For comparison of the toxicity, each fraction thus obtained and the toxic fraction of original polymerized oils were orally administered to mice. The toxic components derived from the fecal lipids which were eluted into the diethyl ether fracion from silicic acid column, were comparable to dimer of triglycerides in molecular weight, and more toxic than that of the toxic fraction of original polymerized oil. Chromatographic behavior, molecular weight, and the toxicity of the fecal lipids seem to indicate that at least a part of toxic components in the thermally oxidized oil undergoes little change in the body of rat and is excreted in the feces.
Rate constants were determined for thermal addition reactions of methyl methacrylate and methyl crotonate to methyl trans-9, trans-11-octadecadienoate at various temperature, and the results were respectively shown in Table-3. The activation energy of the reactions was also shown in Table-3. The addition was observed to be based on the Diels-Alder reaction by the analysis of the structures of the adducts. From the results of the difference of rate constants, it has been found that methyl methacrylate has about three times as great a dienophile activity as methyl crotonate to trans, trans-conjugated octadecadienoic acid methyl ester.
The thermal addition reaction of methyl vinylacetate to methyl trans-9, trans-11-octadecadienoate was studied by a kinetic method. At the temperature, where the vinylacetate forms addition compound with the conjugated octadecadienoate, the octadecadienoate underwent dimerization. Therefore, the rate constants for the addition reaction were determined by obtaining the ratio to that of the dimerization reaction at 180, 200, 220, 240, and 260°C. From the results of the rate constants, it has been found that the dienophilic activity of methyl vinylacetate is about one-sixth than that of methyl crotonate. Furthermore, from IR, NMR, and Mass analyses, the adduct separated by column chromatography was observed to be the Diels-Alder addition compound between the vinylacetate and the trans, trans-conjugated octadecadienoate.
It has been known that alcohols are oxidized into corresponding salts of carboxylic acids by the action of alkali metal hydroxides. As a method for making fatty acids from easily obtainable synthetic alcohols, the alkaline oxidation is very attractive from the industrial points of view. In order to obtain data for the commercial plant, alcohols were heated in the temperature range of 210320°C with alkali metal hydroxides in an autoclave of 2, 300ml. The alcohols used for the reaction were as follows; straight-chain alcohols having even number carbon atoms from 6 to 18, branched chain alcohols obtained by the oxo-alcohol process, glycols, oleyl alcohol and benzyl alcohol. In general, the reaction proceeded smoothly with evolution of hydrogen, and the conversion to the alkali metal salts of the corresponding acids was more than 90%. 2-Ethyl-1-hexanal was also converted into the corresponding acid by the alkaline oxidation, 2-ethyl-hexylether, however, was not oxidized under the similar conditions. Lithium hydroxide and alkaliearth metal hydroxides did not react with alcohols in the present experimental conditions. A small amount of water in the reaction mixture decreased the yields of acids and the reaction rates. Secondary alcohols, such as 2-octanol and 1, 2-propanediol, were also oxidized for comparison.
Isoprene was dimerised by lithium naphthalene to linear isoprene dimer, a mixture of 2, 6-dimethyl-2, 6-octadiene, 2, 7-dimethyl-2, 6-octadiene, and 2, 6-dimethyl-1, 6-octadiene, in about 80% yield. Hydroboration of isoprene dimer followed by oxidation with hydrogen peroxide gave various new terpene alcohols. Thermal condensation of isoprene dimer with paraformaldehyde in the presence of acetic anhydride gave various acetates of C11-alcohols.
By analyzing natural soil components adherred to collars and undershirts which were worn and soiled in each season, the authors investigated seasonal changes of natural soil components and influence to detergency and foaming. The results is as follows. 1) The amount of the soil on worn undershirts in summer season is about 1% o.w.f., which is one half of that in winter season, and the soil contains less triglyserides and much nitrogen compounds and sodium chloride. On the other hand, no difference was observed between the soils of spring and autumn season. 2) It was found that the soil of summer season was easier to remove with detergent than that of winter season. 3) No difference was observed on foaming property in the soil of each season. This seems to come from no difference recognized in the amount of fatty acids and squalene in the soil of each season, which will give remarkable effect on foaming property.