It was thought that cacao butter like fat would be prepared by palm kernel oil, removing the composition of low melting point. This paper was investigated with fractional crystalization, specially on organic solvent. Selecting aceton and n-hexane as the solvent of fractional crystalization, we tested washing effect of crystal, concentration of solution, and the temperature of segregation. The results were given as follows, n-hexane is inferior to aceton in necessiating low temperature to segregate, in the state of crystal and in the washing effect, and also the yield decreases considerably which proves itself unsuitable for the segregation of palm kernel oil. Of the fractional crystalization in aceton, twice crystal washing was sufficient, the yield was about 40 per cent, and had quite satisfactory melting point as cacao butter like fat. In the consideration of industrialization tests were made on the segregation with methyl ethyl keton of various purities, and confirmed that 95 per cent methyl ethyl keton can afford to the purpose.
The authors have studied on the activtiy and selectivity of the copper-chromium-manganese oxide catalyst for the hydrogenation of carbon-carbon double bond and carbonyl radical of “wet” crotonaldehyde in the vapor phase. It was found that in the presence of excess hydrogen (H2 : crotonaldehyde=over 6 : 1mole) at the temperature of 170200°C and LHSV (liquid hourly space velocity) at 0.4, croton-aldehyde was almost completely hydrogenated to butyl alcohol and a small amount of higher boiling substances, such as 2-ethylhexenal, were byproduced. The authors also found that in the presence of the limited hydrogen (H2 : crotonaldehyde=1.31.5mol) at the temperature of 170200°C and LHSV at 0.30.5, almost crotonaldehyde was selectively hydrogenated to butylaldehyde with a small amount of higher boiling substance. The amount of the by-products may greatly be reduced by using the “dry” crotonaldehyde or “wet” croton-aldehyde mixed with butyl alcohol (1 : 1) as raw material. From the facts, the authors are considering that the formation of high boiling substances would account for free water present in the reactant and not for the unavoidable side reaction due to the catalyst.
The authors contemplated to find the most suitable conditions to manufacture propylene oxide via chlorohydrine process. It was found that a high yield of propylene chlorohydrine is obtainable in circulating type reaction column. Further investigations were made on the condition for direct utilization of untreated gaseous chlorine from electrolysis of salt water, and 95% yield has been achieved. In manufacturing propylene oxide by the dehydrochloric acid of propylene chlorohydrine optimum conditions on holding time and were achieved when a horizontal type reactor having a providing net at the bottom was employed of the amount of direct blowing steam.
Nonionic surfactants, having polyoxyethylene chain in molecule, react with a ferrocyanic acid to form an addition compound. Schonfeldt presented a method of quantitative analysis of these nonionic surfactants using this reaction, then we call this method “Schonfeldt's Method.” Applying this method to polyethylene glycol stearates (MYS), polyoxyethylene nonylpenyl ethers (NP), and polyoxyethylene lauryl ethers (BL), it was assured the applicability of this method to the derivatives having several ethoxy-units lower than 50 moles in a molecule, as it is reported in Schonfeldt's paper. This method was examined to the extended numbers of ethoxy-unit up to 160 moles in a molecule, MYS-100 and MYS-160, and it was found that this method is well applicable for these derivatives. Mole ratio in these addition compounds, numbers of ethoxy-units per unit mole of ferrocyanic acid, was determined from these experiments, which was 6.8 for MYS series (from 25 to 160 ethoxy-units in molecule), 7.0 for NP series (from 21 to 50), and 6.3 for BL series (from 17 to 25). These ratios found in our experiments differed slightly from the ratio of about 6 which was reported by Schonfeldt.
Distilled and purified tetra-, penta-, and hexa-ethyleneglycol capric mono esters were synthesized, and were purified further by repeating cromatography, molecular distillation and some other processes. The aqueous solutions of the above samples and their mixtures were prepared and measured their cloud points, lathering properties and CMC. It has been recognized a near linear relationship between the cloud points and the HLB of a series of non-ionic surface active agents in which additional oxyethylene mole numbers merely vary. In the case of the purified samples and their mixtures, similar relations were obtained. The relation between the lathering properties, the cloud points and the CMC of the purified samples and their mixtures seemed to be continuous. Consequently, it is considered that the experience obtained from the measurements of the samples which were purified and limited the additional oxyethylene mole distribution can be applicable to analogize the properties of a simple substance.
From the discovery of higher dibasic acids in Japan wax, many investigations were carried out about the structure of the glycerides of dibasic acids. However, these investigations were mainly concerned with the separation of dibasic acid glycerides from Japan wax, and no definite conclusion has yet been established whether it would be monomolecular type or bimolecular type. The purpose of this investigation is determining the structure of higher dibasic acid glycerides synthetically prepared. Synthesis of dibasic acids (C12C22) was carried out according to four different methods and pure C22 dibasic acid was obtained. The paper chromatography of the dibasic acids has been carried out by the reversed phase method using several kinds of stationaly phases, and a linear relationship was observed between Rf value and the carbon number of the acids. By applying this analytical method to the dibasic acid which was separated from Japan wax according to the Tsujimoto's method, it was found that arachidinic acid was also present besides C20 and C22 acids which were previously known, and the ratio of those three acids was determined by molecular distillation.
Some ferulates as phenolic substances have been confirmed in rice germ oil. These ferulic acid esters are resemble to that from rice bran oil. The unsaponifiable fractions from these ferulates were confirmed to consist mainly of two triterpenoid alcohols (C30H50O and C31H52O) and sterol.
Having previously found that the corn (maize) -germ oil contains an inhibitor in determining the tocopherol content by the method of Emmerie-Engel reaction, the authors isolated the dihydro-β-sitosterol ferulic acid ester, C39H60O4, mp 156157°C, [α] D+13.1°, ε231mμ max. 12270, ε290.5mμ max. 18380, ε314.5mμ max. 21460 from the oil. And also dihydro-γ-sitosterol ferulic acid ester, C39H60O4, mp 155156°C, [α] D+13.6°, ε231mμ max. 13040, ε290.5mμ max. 18440, ε314.5mμ max. 21460 has been isolated from the wheat-germ oil. It is interesting that such water insoluble lipid as sterol exists in the vegetable oil as a hydrophilic ferulic acid ester, and that the esters are a new state of sterols existing in nature. As to ferulic acid ester in vegetable oil, Kaneko and Tsuchiya had found it from rice-bran oil and named it “oryzanol”, reporting that it has such actions as furtherance of growth, recovery from fatigue and cure of aged disturbances. As the alcoholic components of oryzanol, cycloartenol and 24-methylene-cycloartanol were confirmed by Ota and Shimizu. Thus, it was found that ferulic acid esters are contained in few kinds of vegetable oil, and ferulic acid is similar to lignin etc. in its structure. Therefore its ester might be widely distributed in vegetable oils. In this work, the authors examined 5 kinds of vegetable oil : soy bean oil, linseed oil, sesame oil, rapeseed oil and safflower oil. Alkali carbonate and caustic alkali solutions have been adapted for separation and phenolic concentrate was obtained from those oils, and then refined repeatedly by chromatography and recrystallization (Fig. 1, curve AD). As a result, the authors could not confirm the presence of ferulic acid ester in soy-bean oil, sesame oil and safflower oil, but succeeded in isolating the eicosanol ferulic acid ester from linseed oil (content in the soap stock was 0.006%). The ester, C30H50O4 with mp 5354°C was positive in the Emmerie-Engel reaction and colored green with ferric chloride and yellow with potassium hydroxide, UV in heptaneε231mμ max. 14621, ε290.5mμ max. 17421, ε314.5mμ max. 20317 (Fig. 1, curve D), IR of the film showed phenolic OH (at 2.84μ), ester (at 5.73μ and 9.69μ), asymmetrical 3 substitute bond of benzene (at 11.80μ and 12.17μ) and methylenic chain (at 13.83μ) (Fig. 2). Eicosanol with mp 6566°C, IR : 9.44μ (OH), 13.84μ [- (CH2) n-] (the acetate : mp 3637°C) and ferulic acid with 167169°C (Emmerie-Engel reaction, UV, no depression with pure sample in mp) were obtained by hydrolysis of this substance. Then the authors separated a mixture of ferulic acid esters from rapeseed oil (Fig. 3) and further confirmed eicosanol as a conponent by examining the hydrolytic products of the mixture. Therefore the presence of eicosanol ferulic acid ester in rapeseed oil was found (content of the mixture in the soap stockwas 0.007%).
Soybean proteins are liable to undergo denaturation by heating. Particularly, when the moisture content of soybeans is high, protein denaturation takes place readily even at relatively low temperature levels. Even in the case of butane extraction, the occurrence of protein denaturation is conceivable when extracted flakes from soybeans of a high moisture content is subjected to a local overheating in the commercial desolventizer. Extracted flakes from raw soybeans without preliminary drying also have invariably too high moisture content to be accepted normally in the market. It is therefore necessary to reduce the moisture content of soybean flakes by drying without causing any denaturation of their proteins. In this paper, results of studies on drying soybean flakes using a through circulation dryer were reported. This dryer operated under the optimum condition has been found very effective, giving dried flakes of a moisture content of about 8% or less. The decrease of soluble proteins during drying is only 1% or less (on the basis of total proteins). Also the data on the design of a 200 tons per day dryer are presented.
Bouveault et Blanc reduction of oleic, erucic, debrominated linoleic and linolenic acid methyl esters was studied for the purpose of examining the properties and isomerization of unsaturated fatty alcohols. No geometrical isomer was observed by the infrared spectroscopic study in the case of esters of monoethylenic acids such as oleic and erucic acid. With increase of the number of double bonds the yield of the fatty alcohol slightly decreased. It shows that Bouveault et Blanc reduction has a little effect on the double bond of dienoic and trienoic acid esters. From the ultraviolet spectroscopy linolenyl alcohol contains more conjugated double bonds than linoleyl alcohol, showing that the higher content of double bonds favors the more rapid conjugation when reduced under the same condition. If the alcohol produced would be treated during a prolonged period in the reaction vessel, the conjugated double bonds contained in the alcohol decrease to be lower than that of the raw ester. When methyl linoleate and linolenate are reduced with excess of reducing alcohol, metallic sodium reacts priorly with raw ester and reducing alcohol, resulting more conjugation compared with the case whereby reducing alcohol is not excess. Isomerization reaction on the reduction of dienoic and trienoic acid esters was discussed.
By ingestion of food with heated lipids, not adenocarcinoma but abnormal growth like tumors is produced in gastric mucous membrane of rats. In general, carcinogenic agents have a close connection with protein and combine with it. Lipids having oxidized unsaturated fatty acids and protein form complexes. Because of their strong linkages, the complexes are not decomposed by solvent extraction. Would the oxidized lipids form complexes with nucleoproteins, the status of cell-division may probablly change. It is thus assumed that the cancerous cells may be produced. In such a case, cancerous tissues may contain oxidized lipids. From this point of view, lipids were extracted from cancerous tissues, such as gastric scirrhous carcinoma, gastric adenocarcinoma, rectal adenocarcinoma and mammary carcinoma indicated the picture of carcinoma simplex tissues. Then fatty acids and their methyl esters were obtained. All procedures were carried out at room temperature under the atmosphere of nitrogen without exposing samples to direct sunlight. From ultra-violet spectrum, fatty acids composition was calculated. It was ascertained that trans-trans conjugated diene hydroperoxide exists in the methyl esters obtained from cancerous tissues, and that trans-trans nonconjugated dienoic acid also exists in some such esters from the results of infrared spectrum analysis.