The formation of a π-diene-iron tricarbonyl complex and also the dimerization of fatty acid residue in the process of hydrogenation of cotton seed oil with iron pentacarbonyl catalyst have been reported in the previous paper. In order to confirm the complex formation and further to investigate the catalytic behavior of this complex, a new π-C18-conjugated-diene-carboxylic acid methyl esteriron tricarbonyl was firstly isolated from the reaction product of fatty acid methyl ester of dehydrated castor oil with iron pentacarbonyl. Its structure was discussed from its IR-, UV-, and NMR-spectra and also from its ligandexchange reaction with triphenylphosphin. By treating above its decomposition temperature the complex polymerized with the coexisting dienecarboxylic acid ester mainly into the dimer, and by high pressure hydrogen-cracking it was converted mainly into methyl stearate.
A number of preparation methods of unsaturated higher alcohol have been reported, but the production of unsaturated higher alcohol on an industrial scale by these methods has not been susceeded in Japan. In this report, the authors report the results of a new method using the combined catalyst Cu-Cr-O and cadmium soap. This method can be expected to have the following merit on the industrial production; the Cu-Cr-O catalyst has been used for the preparation of saturated higher alcohol in factory for long time and the cadmium soap is soluble in raw fatty esters, then this new method can be performed with the equipment and the technique established for the preparation of saturated higher alcohol. From the result of this investigation, it was recognized that desirable unsaturated higher alcohol for detergent can be prepared over 93% yield under such conditions : reaction pressure; 218205kg/cm2, reaction temperature; 290±3°C, reaction time; 2hrs, used catalyst; Cu-Ba-Cr-O catalyst 0.4g and cadmium soap 1.5g, for 4g of raw methylester.
The authors contemplated to find the most preferable method for preparation of methyl hydrogen azelate by the esterification between azelaic acid and methanol. In the first place, authors decided the equilibrium constant, then, specified the composition consisting of azelaic acid, methyl hydrogen azelate and dimethyl azelate in equilibrium with one another at 90°C and 1 atm. By putting the result to practice, authors could establish the condition to obtain the suitable equilibrium composition of the product for preparing methyl hydrogen azelate. The hydrolysis of dimethyl azelate was also discussed by using sodium hydroxide and barium hydroxide in methanol respectively. The result of the experiments showed that the equilibrium method was superior as compared with the latter two cases.
Hydrocarbon (mp 68.068.5°C (uncorrected); molecular weight 435) was obtained from crude sterol of soybean oil deodorizer scum by extraction with n-hexane and column chromatography. It was suggested by IR-spectrum, gas chromatography and NMR-spectrum etc. that this hydrocarbon was constituted by n-C32H66, n-C30H62, and small amounts of n-C28H58, n-C29H60 and n-C31H64. Therefore, extraction with paraffinic hydrocarbon solvents is necessary when soysterol of deodorizer scum is used for the syntheses of steroidal hormones.
It has already been reported that Japan wax contains higher dibasic acids such as docosanedioic and eicosanedioic acids, but no detailed reports including the lower dibasic acids have been found yet. The purpose of this investigation is to determine accurately the fatty acid and dibasic acid compositions of the wax by gas-liquid chromatography using a hydrogen flame ionization detector. Gas chromatographic analyses were performed on a gas chromatograph of Shimadzu GC-1 B type equipped with a flame ionization detector. U-shaped stainless steel columns of 150cm×4mm i.d., and another 75cm×4mm i.d. for the specified analysis of higher dibasic acid dimethyl esters, were packed with 10% polyethyleneglycol adipate on Diabase B (Kotaki-seisakusho Co., Ltd.), 80-100 mesh. The flow rates of helium as the carrier gas, hydrogen and air for the detector were approx. 60ml/min, 40ml/min and 1.0l/min, respectively. The inlet heater was kept at 280°C, the column temperature was at 215°C for the analysis of fatty acid methyl esters and lower dibasic acid dimethyl esters, and at 220°C for the long-chain dibasic acid dimethyl esters. As a result, different dibasic acids (C5, C6, C7, C8, C9, C10, C11, C12, C14, C16, C18, C20 and C22), various fatty acids (less than C10, C14, C15, C16, C17 C18, C20 and C22) and considerable amounts of unknown materials were found in the free acids responsible for the high acid value (21.5) of the wax. In addition, the methyl esters, obtained by direct methanolysis of the wax and subsequent removal of the free acids, contained small amounts of C14-, C16-, and C18- as well as C20- and C22- dibasic acids. The thin-layer chromatography on silica gel was also applied to the analysis of the wax; namely, it was observed that the dibasic acids were separable from the fatty acids and other materials and that each constituent can be examined in detail.
The object of this study was the quantitative determination of oil losses during the deep fat frying of soybean curd, “Tofu”. The possibilities for the loss of oil during the deep fat frying result from the formation of volatile products of fat degradation and absorption of oil in fried foods. The chief factors governing the amount of oil lost during the deep fat frying were the time of cooking, the temperature of oil used, and the composition of the food. 15 cakes of Tofu were fried in 1kg of oil. They were fried for a minute one after another; one side for 30 seconds, the other for 30 seconds. Then the oil losses and the weight of fried Tofu were measured, and from these data, vapourized water was calculated. The fried Tofus were wiped with dried filter paper and the amount of oil attached to the food surface was measured. The results were as follows : Our frying tests did not reveal any significant differences in oil absorptions among the soybean oil, cottonseed oil and rapeseed oil used. Being cooked for 1 miunte at 240, 220, and 200°C, significant differences were seen in oil temperature. The longer they were fried, the more the oil was lost. When deteriorated oil or foaming oil were used, oil decreased significantly. It was mostly caused by their sticking to the surface of food being fried, whereas the amount of oil absorbed in the food was rather small.