The F1 unsaturated fatty acids were isolated by fractional precipitation of Pb salts and Hg salts from ethanol, by fractional precipitation of Li salts from 50% ethanol, by fractional precipitation of the brominated acids from organic solvents. The F1 unsaturated fatty acids were contained about 30% in fatty acids of cuttle-fish oil. By fractional distillation of the methyl esters, tetradecenoic (a small quantity), hexadecenoic, octadecenoic, eicosenoic, docosenoic (a small quantity) and teracosenoic (a small quantity) acids were isolated. The structure of F1 unsaturated fatty acids were determined by ozone-oxidation of the methyl esters in CHCl3, that these acids were 9-tetradecenoic (myristoleic), 9-hexadecenoic (palmitoleic), 9-octadecenoic (oleic), 9-eicosenoic (gadoleic) and 15-tetracosenoic (selacholeic) acids.
Bouveault et Blanc reduction of methyl laurate was studied by using twelve kind of alcohols as the reducing alcohols. The yields of lauryl alcohol, lauric acid, methyl lauro-laurate and reductive condensation products such as lauroin were determined to discuss the effect of reducing alcohol. By products other than lauryl alcohol were formed by two reaction systems, namely, reaction of ester based on ion dissociation of alcoholates and reductive condensation of carboxyl group with metallic sodium.
The change of heat due to mixing n-hexane with various fatty materials, such as fatty oils, soybean oil fatty acid, and soybean oil fatty acid methyl ester, has been measured at 30.0°C in the whole range of concentration by direct calorimetric method. In all cases, heat is absorbed and the value of heat change due to mixing is highest at about 1 : 1 mixture of fatty material and nhexane by weight. The maximum value of heat of the mixing is as follows : soybean oil -0.48, rapeseed oil -0.55, camellia oil -0.62, olive oil -0.64, cocoanut oil -0.67, soybean oil fatty acid -0.26, and soybean oil fatty acid methyl ester -0.67cal/g-mixture, respectively. The viscosity coefficient η of these mixtures has also been measured at 30.0°C in the whole range of composition. Logarithmic plot of viscosity coefficient for every mixtures as a function of mole fraction of fatty material, falls on upper-side of the straight line which is drawn to pass through the point of log η of each component. From these curves of viscosity coefficient versus mole fraction, the parameter “q”, which indicates the shape of the molecule of fatty material in the mixture, can be calculated, provided that the quasi-crystalline model is to be maintained. Furthermore, the coordination number “z” in the mixture can be estimated, and it is found that the value is to be about eight in all these mixtures. Combining the parameter “q” with the heat of mixing “ΔmH”, expressed in cal/mole-mixture, interchange energy “Nw” between fatty material and n-hexane can be calculated. The interchange energy has value of about +260cal/mole for all fatty oils and for fatty acid methyl ester, but has smaller value of +120cal/mole for fatty acid. Using the values of “q”, “Nw” and “r” which represents the ratio of molar volume of fatty material to that of n-hexane, vapor pressure of n-hexane in the mixture can be calculated. But, if one takes the value of “Nw” found above, higher values of vapor pressure will be obtained than the values measured by experiment. This difference between experiment and calculation may be caused by the fact that the great contraction of volume occurs in the course of mixing. Then, if one takes the value of “Nw” multiplied by the factor of 0.7, calculated value of vapor pressure of n-hexane in the mixture will agree with experimental one.
It is known that the unsaturated fatty acids in natural fats and oils are generally produced in cis-form. However, these acids change from cis to trans-form by physical or chemical treatments, -heat, light and various catalysts. The purpose is to study the origin and mechanism of these isomerizations. The fatty acid methyl ester of linseed oil was used as sample. The separation methods of the unsaturated fatty acid in this study were urea complex method, bromination-debromination method, hydroxamic acid method and low temperature crystallization. The isomerization degree of these esters by the above methods were compared. The result was as follows; 1) Urea complex method : Methyl linolenate was concentrated up to 69% by this method, but the efficiencey of separation was not high. More than 2% of conjugated diene was yielded, it was found to be cis-trans conjugated isomer. 2) Fromination-debromination method : This is an effective method for separating the methyl linolenate of high purity, estimating from iodine value. The yeild was about 22%. Even by the careful treatment, it gave about 0.6% conjugated diene which was found to be trans-trans conjugated isomer. It was also found that the trans non-conjugated isomer was formed by this method. 3) Hydroxamic acid method : Methyl linolenate of high purity was obtained in 26% yield by this method. Formation of conjugated isomer was not observed, but little amount of the trans non-conjugated isomer was detected. 4) Low temperature crystallization method : Although the yield of pure material was only 8.4%, this method was found to be the best, since any isomer was not formed by this treatment. Then, the most practical method will be the combination of this method with urea complex method.
Synthesis of aldehydes were tried by four methods as follows; A) the Rosenmund's reaction, B) reaction of alkylbromide and dimethyl-sulfoxide, C) the Stephen's reaction, D) dehydration of dialkyl selenious acid ester. Aldehydes were obtained by method A and B. Quaternary ammonium salts were obtained by reaction of various aldehydes, dimethyl aniline and ethyl bromide. Aldehyde sodium bisulfite adducts were prepared to test the properties as surfactants. Aldehyde was reacted to urea, melamine and n-butyl amine. Cotton fabrics were treated by these products and water repellent effects were measured. It was found that these products are useful as repellent agents.
This report is based upon 25 samples of margarine, 3 of butter, 15 of shortening, and 18 of lard, totaling 61. Margarine was tested in oil content, moisture, salt, solid milk content and vitamin A. With the separated fats test was made for A.V., P.O.V., S.V. and M.P., Oleic, linoleic, and saturated acids were calculated from I.V. and Th. V., of separated F.A. Further X, σ, and σ/X were calculated by classifying the above measured values. Among samples of margarine, 2 have contained butter, 4 were of pure vegetable margarine and the rest consisted mainly of hardened whale and fish oils. As a whole, 13 contained lauric oil. X of 11 kinds of typical household margarine showed 80.8% for oil content, 15.5% for moisture, 2.6% for salt, 1.1% for solid milk content and 26, 740 IU/450g for vitamin A. 25 samples were estimated to contain 42.7% of oleic, 15.2% of linoleic and 42.1% of saturated acid. With 10 kinds of ordinary shortening, the composition was 47.0, 14.6, and 38.4, and with 12 kinds of lard based on imported hog grease, the composition was 43.4, 12.9, and 43.7 respectively. Due to the elapse of 78 months the quality is lower in A.V. and higher in P.O.V., in respect that the margarine showing 3.35→8.95, shortening 0.47→0.85, and lard 0.87→2.04. Thus, stability is seen in shortening. (We give notice to the readers that above english abstract only was attached have althongh the original paper in japanese character had been issued in Yukagaku, 383-392, (1960, July).) This report is based on 18 samples of margarine, 7 of shortening, 3 of butter, totaling 30. Average value for margarine was 79.9% in oil content, 15.8% in moisture, 2.8% in salt, 1.6% in solid milk content and 11, 400 IU/450g in vitamin A. Solid milk content was identified by reaction of nitrogen, fehling, osazone, and shown as an ingredient other than oil, moisture and salt. Due to the elapse of more than one year, the quality changed either in hydrolysis (A.V.) or oxidation (P.O.V.). As a whole, there was little change. Among 18 samples, 8 were estimated as soybean oil type, 7 of cottonseed oil type, 2 contaning butter, 1 of lauric oil type. Oleic, linoleic, saturated acid in % were calculated from I.V., Th. V. of separated F.A. As to the 14 samples other than lauric type and other specialities, they were 58.2, 18.2, 23.6% respectively. For shortening, it was found that 1 is of cottonseed oil type, 3 of soybean oil type, 3 of animal and vegetable oil type, and linoleic content is increasing from 10 to 25% in this ordder. Saturated acid was 3050%, considerably higher than in margarine. As to the 3 samples of butter, they were 24.2, 7.3, 68.5%, and 2 samples of lard, were 42.2, 14.0, 43.8% respectively.