After eliminating the free acid in cuttle-fish oil, brominated glycerides were isolated and purified by utilizing the difference of solubility against various solvents. When melting point and bromine content were fixed constant, it was assumed to be pure. This was then hydrolysed with concentrated hydrochloric acid to form the brominated acid and these were again isolated and purified with organic solvent. Then this was debrominated with zinc powder, concentrated sulphuric acid and methanol, and formed fatty acid was identified. Thus, the composition of the fatty acid in glyceride was investigated. Considering the proportion with regard to the quantity, it was supposed that the composition of the sample will be as follows; Cuttle-fish oil (Free fatty acid) (10%) 1) Palmito-palmitoleo-olein 10% 2) Palmito-oleo-gadolein 12% 3) Myristo-palmitoleo-olein 10% 4) Stearo-palmitoleo-eicosatrienin 12% 5) Palmito-oleo-eicosatrienin 7% 6) Trieicosatrienin 4% 7) Octadecatrieno-eicosatrieno-eicosatetraenin 9% 8) Trioctadecatrienin 6% 9) Octadecatrieno-eicosatrieno-octadecatetraenin 8% 10) Other polyunsaturated glycerides 12%
High boiling fraction in fatty acid methyl ester of cuttle-fish oil was re-distillated to separate into further fractions. With each fraction, saponification value, iodine value, bromination and ultraviolet absorption were measured. As a result, it is considered that a little of C24 acid, C26 acid and C28 acid exist in it and that the most unsaturated acid of these fatty acids was F6 acid. Inasmuch as author could not detect the F2 unsaturated fatty acid in the every research of this report from No-I to No-X, it does not probably exist in C24 acid, C26 acid and C28 acid. It is supposed that the F5 acid and F6 acid would be comparatively little and that the F1 acid, F3 acid and F4 acid would be contained much more.
Claisen condensation of higher fatty acid methyl esters was studied by using sodium methylate as the condensing agent. The condensation resulted in high yields of β-keto esters at reduced pressure, however it was difficult to proceed at normal pressure. Some properties of higher β-keto esters, including the reaction with hydroxylamine hydrochloride and KOH ethanol solution were discussed. The ketonic decomposition of higher β-keto esters was so quantitative that this may be easily utilized to analysis. Claisen condensation of C6C18 fatty acid methyl esters was little affected by the chain length. By the infrared spectroscopic study, some structural informations were obtained. These are as follows : Higher β-keto esters have no resonance structures characteristic to enolic form, and the tautomerism is far on the side of ketonic form with increase of chain length. β-Keto esters derived from C12C18 fatty acid esters are almost in the ketonic state. Properties of higher ketones which were prepared quantitatively from ketonic decomposition products were studied.
The marine oils such as whale oil are the important raw materials in the hardened oil industry in our country. They are used as the edible fat products and soap etc., although none of these are considered as desired raw materials such as ordinary vegetable and animal fats because of their fish liked odor. We have succeeded in gaining the completely deodored and low melting hydrogenated whale oil by the copper-chromium-manganese oxide catalyst. In addition to the results, we have found that about 50% of cholesterol contained in whale oil has dehydrogenated to cholestenone during the hydrogenation of whale oil by the copper-chromium-manganese oxide catalyst.
Although it is known that the isolated double bond of unsaturated fatty acid is changed to the conjugated isomer by the action of heat, no investigation has been made in this process detail. The thermal isomerization of pure cis non-conjugated methyl linoleate and methyl linolenate was described in this paper. Almost pure cis non-conjugated methyl linoleate was obtained from methyl ester of cotton seed oil by combining the both of urea complex method and low temperature crystalization. Preparation of high purity isomer of methyl linolenate was reported in the previous report. The results of thermal isomerization of these pure isomers at 145, 190, 245 and 300°C, can be summerized as follows : 1) Cis non-conjugated methyl linoleate forms trans-trans conjugated isomer and trans non-conjugated isomer at any temperature. The conjugated isomer is produced at the earlier stage even at relatively low temperature, and the trans non-conjugated accumulates as the isomerization proceeds. 2) Methyl linolenate gives cis-trans conjugated isomer and trans non-conjugated isomer. However, cistrans conjugated isomer decreases and trans non-conjugated isomer accumulates as the isomerization proceeds. 3) Against expectation that the methyl linolenate will be isomerized more easily to be conjugated isomer than methyl linoleate, the latter was more sensitive to thermal treatment even at relatively low temperature.
The specific reaction rates of epoxidations of various unsaturated fatty acids with per-acetic acid in acetic acid solution were calculated by measuring the concentration decrease of per-acetic acid in reaction solution. The specific reaction rate of epoxidation of cis-acid was higher than that of trans-acid. It was not affected by carboxyl group at the θ-position to ethylenic double bond, but it was affected a little by that of β-position to ethylenic double bond. The specific reaction rate of epoxidation of dienoic acid to monoepoxy acid may be similiar to that of monoenoic acid, but that of monoepoxy acid to diepoxy acid was very slow. It was not affected by sulfuric acid in reaction solution, but it was increased by the presence of water in the solution. The specific reaction rates, K×103 (l·mol·-1 min-1) at 30°C were as follows; oleic acid 180, elaidic acid 149, ricinoleic acid 133, monoepoxy octadecenoic acid 91.1, linoleic acid 230 and erucic acid 207. The activation energy of oleic acid and elaidic acid were 7970 cal and 8660 cal respectively. They were calculated with Arrhenius' equation from value of the specific reaction rates at 22.5, 25, 27.5 and 30°C.
In the operation of urea dewaxing plant the corrosion problem for the plant material (metal) caused by urea decomposed substances must be considered. We studied the corrosion rate in the most severe conditions proposed by our process [Journal of Japan Oil Chemists' Society, vol.6, 17 (1957)], to discover the suitable corrosion inhibitor. We have tested several kinds of test pieces according to the above condition. Then, we tested the corrosion inhibiting effects of small quantity of additives to mild steel. We found that it was most effective to add 0.1% order of (NH4) 2HPO to the urea mixture, and by this we could overcome the corrosion trouble of plant materials.