In the process of fractionation of methylesters of cuttle fish fatty acids with urea in methanol, highly unsaturated fatty acid esters (I) were able to crystallize at 0°C in the form of urea adducts, but few percent of the total methylesters were used to fail to form adducts. Non-urea-adduct forming fractions (II) showed in almost cases lower iodine values and higher conjugated dien contents, compared with those of (I) and their absorption at 1395cm-1 was scarcely found out. Through autoxidation at room temperature, highly unsaturated esters (I) changed by degrees their properties and turned into the similar materials with (II). NAF (II) is probably a changed product of (I) through autoxidation.
Infrared absorption spectra of polyunsaturated fatty acid esters obtained from cuttle fish oils, showed a characteristic absorption at 1395cm-1, in addition to the typical absorption of normal fatty acid methylesters. This absorption at 1395cm-1 was related to the double bond, since by hydrogenation or autoxidation it was vanished away. Methyl linoleate, -linolenate and -arachidonate gave the suitable absorption at this wave number, while methyl oleate, -eleostearate and cyclododecatrien didn't. This characteristic absorption was assigned to the C-H bending vibration of the center methylene of divinylmethan radical (=CH·CH2·CH=).
Palmitic acid was dissolved in carbon tetrachloride or tetrachloroethylene, and air-sulfur trioxide mixture was introduced into this solution under the various conditions. The absorption coefficient was measured at about 420mμ, to observe the coloring of the reaction mixture. “Teflon” tube showed most resistance to corrosion as gas inlet tubing. The coloring of the reaction mixture in which carbon tetrachloride was used as solvent was almost the same as in the case of terachloroethylene, at the same condition. While, the coloring of the reaction mixture was obviously different according to the method of introducing the gas mixture, namely, either the gas was introduced into the solution or over the surface of the solution, and the latter gave less coloring. The absorption coefficient of the reaction mixture increased linearly when the introduction of sulfur trioxide increased. In the case of such small-scale experiment, we cannot neglect the amount of sulfur trioxide which condensed on the inside wall of pipe and flask during the reaction. The amount of sulfur trioxide in the exhaust gas was only several percent of original sulfur trioxide introduced. The coloring of the solution began before true sulfonation reaction took place.
Bouveault et Blanc reduction of higher fatty acid methyl esters was studied for the purpose of making analysis in reaction system. The yields of reductive condensation products such as acyloins, β-ketoesters in addition to fatty alcohols were determined when C6C18 saturated fatty acid methyl esters were reduced by using ethanol and MIBC as the reducing alcohols. With increase of the length of acyl radicals, the yield of fatty alcohols increased. Inversely, yield of fatty acids and reductive condensation products decreased. The formation of β-ketoesters was trace when used MIBC, but the effect of the chain length was similar to the case of reductive condensation products when used ethanol. Based on experimental results and reactivity investigation about following 4 items, (1) esterketals as sodium ester intermediates, (2) alcoholates, (3) reducing alcohols, (4) generation of hydrogene, the mechanism of reaction system was analysed. It came to conclusion that several reactions in this system are extremely affected by the reducing alcohol.
For the investigation of the influence of various substances on “Methylene Blue Partition Backtitration Method”, (published since Vol.9, No.3, Yukagaku), the titration of anionics was carried out with the following additives. Sodium carbonate, borax, sodium pyrophosphate, sodium hexametaphosphate, sodium heptapoly-phosphate, sodium chloride, sodium sulfate, and tetrasodium ethylenediamine tetraacetate (EDTA (Na4)) show no effect on the titration. In the presence of CMC, over 40% of anionics, the titration is interfered by the formation of stable emulsion, but under 30%, there is no difficulties.
For the purpose of applying “Methylene Blue Partition Backtitration Method” to the analysis of anionis-soap mixtures, the effect of the presence of soap on the determination of anionics by this method has been investigated. The experimental results showed that soap had no influence on the titration, and that anionics in the mixtures could be directly titrated with satisfactory accuracy by “Methylene Blue Partition Backtitration Method.”
For the purpose of applying “Methylene Blue Partition Backtitration Method” to the analysis of anionics-nonionics mixtures, the effect of the presence of nonionics on the determination of anionics by this method has been investigated. While Epton's method suffered influences and showed too low analytical values in the presence of nonionics, our experimental results with various nonionionics, polyoxyethylene lauryl ether (P=10, 15), polyoxyethylene octyl ether (P=13), polyoxyethylene nonylphenyl ether (P=12), polyoxyethylene sperm alcohol ether (P=18), polyethylen glycol laurate (P=15), and polyoxyethylene sorbitan monostearate (P=21), showed that nonionics had no effect on the titration of anionics with the authors' method, and that anionics in the mixtures could be directly and accurately determined by our “Methylene Blue Partition Backtitration Method.”
Classification for activation and inhibition to rice bran lipase was performed by adding dilute aqueous solutions of some 35 kinds of sulfates, nitrates, phosphates, acetates, chlorides and hydrogen peroxide to rice bran. As a result it was found that the activation and inhibition were largely determined by cation and that anion had little effect on it. Salts that have activated are the each salts of sulfates, nitrates, chlorides, and acetates of manganese and magnesium, and the each salts of sulfates, primary and secondary phosphates and acetates of alkalimetal. The salts which show neither activation nor inhibition are the salts of calcium, barium, ferrous salt and nickel. The salts which show inhibition are the salts of aluminum, lead, zinc, ferric salt, cuprous and cupric salts and mercury. Even the salts which show activation when they are dilute aqueous solution show inhibitive action when their concentration is increased. The hydrolytic velocity of lipase due to addition of salts is inversely proportional to the mol-concentration of salts. As for the effect of addition of salts on the particle diameter of rice bran it shows an abnormal action only on 20-mesh residue but on the smaller particle diameter it shows the same degree of activation or inhibitive action. Hydrogen peroxide shows an inhibitive action to lipase in proportion to its concentration.
Rheological properties of some cosmetic creams were compared with penetrobalance (Kambe and Murakami, J. Chem. Soc. Japan, Ind. Chem. Sect., 63, 208 (1960), in Japanese). Cleansing cream of W/O type shows plastic behavior, but cold cream of O/W type has a rather soft surface and shows slight recovery for elasticity. Varnishing cream, which is a suspension of large amount of solid fatty acid is comparatively fluid and soft at its surface. These behaviors are fitted to the condition of application in each case.