Eicosanyl-ferulate mp 5354°C (I) and dihydro-β-sitosteryl-ferulate mp 156157°C (II) were prepared by the condensation of ferulic acid with eicosanol and dihydro-β-sitosterol, respectively. The ferulate (I) was identical to the naturally occurring ferulate isolated in our laboratory from linseed oil and rapeseed oil; and the latter (II) was also identical to that from corn (maize)-germ oil. Ethyl-, mp 4142°C and 57°C, lauryl-, mp 45°C, cholesteryl-, mp 165166°C, β-sitosteryl-, mp 123°C, stigmasterylferulate mp 147148°C and some acyl-derivatives were also prepared, and these characteristics were observed (Table-1). Chlorination_ by oxalyl chloride was mainly applied to this reaction. As a results, acylated ferulic acid chloride was obtained at high yield. The difference between molecular rotations of the above ferulates and those of the original sterols in Δ5-series, were +147+198 in the ranges, and seemed to be obviously greater than the molecular rotation differences in other series (Table-2). The difference in weight increases between those mice ((_??_), 25-days-old) breeded for 28 days by the various feeds in which ferulic acid and its derivatives were added, and the mice breeded by the non-additional standard feed for same days were not recognized (Fig. 1). But, mice ((_??_), 100-days-old), breeded by the feeds in which cholesteryl-ferulate and ferulic acid plus sodium bicarbonate respectively, increased their weight compared with those breeded by the non-additional standard feed, and the results were as follows : non-additional standard feed 100g of standard feed + 12 mg of cholesteryl- ferulate 100 g of standard feed +0.08 mg of ferulic acid and 0.04 mg of sodium bicarbonate after 2 weeks 100.5% 105.1% 107.4% after 4 weeks 105.7% 110.8% feed gathered mold
Authors isolated a new substance and a crude β-sitosterine from distillation residue of rice bran dark oil, in addition to the new ketone compound formerly reported. The former new substance was a yellowish brown solid having extinction maxma of ultraviolet absorption spectra at 268, 280 m (strong) and 300, 315 m (weak). Accordingly it may be one of the steroids having conjugated double bond, otherwise from ergosterine because of its wave length and absorption coefficient inspite of similarity in the form of spectrum. Another substance recognized as crude β-sitosterine had following characteristics, white plate crystal, mp 134.5°C, [α]15D-45.5° (chloroform), molecular formula C29H50O, and was positive in digitonin test. Its acetate, a needle crystal, had mp 128 ; [α]15D-34.5°. The chemical structure of this substance was also discussed by infrared adsorption spectrum. These substances were separated by solvent extraction, column-chromatography and recrystalization.
Higher aliphatic amine or its salt when treated with ethylene oxide reacts to produce the quaternary ammonium compounds as shown in authors' report No. 2 and No. 3. Instead of ethylene oxide, propylene oxide was used in this reaction. Tertiary amine having no or little steric hindrance reacts with propylene oxide to produce the quaternary ammonium compound. But the reaction of secondary amine was difficult and primary amine did not react. These reactivity to produce the quaternary ammonium compounds depends on the back Estrain of 2-hydroxy-propyl radical formed by addition of propylene oxide to secondary and primary amine. Quaternary ammonium salt obtained from this method showed good surface activity.
For the evaluation of dye-dispersing power of surface active agents, “Semimicro Azopigment Electrophotometry” has been established which consists of coupling diazotized base with naphthol in the presence of dispersing agents under definite conditions and determination of the amount of azopigment in filtered dispersion by electrophotometry. It was found that this method is suitable for the accurate determination of dispersing power of surface active agents.
Epoxy fatty acids and their derivatives were heated in nitrogen atmosphere at 70, 95, 120 and 150°C, and oxirane oxygen content (and neutralization value) of each sample was determined. When solid epoxy compound lost about 20% of oxirane oxygen by heating, it was changed into viscous liquid, and when it lost about 70% of oxirane oxygen, it was changed into gel. Cis-epoxy fatty acid lost more oxirane oxygen than carboxyl group by heating, whereas traps-epoxy fatty acid lost more carboxyl group than oxirane oxygen. At experimental temperature, trans-epoxy compound was more stable than cis-epoxy compound, and ester and amide of epoxy fatty acid were much more stable than the epoxy fatty acid. Metal epoxy stearates were not stable except barium salt.
20 samples including control 4 were prepared from AS, AM, BS and BM, where A is coconut oil formulation, B cottonseed oil formulation, S is a standard margarine formulation, and M milk ingredient formulation, to which 0.1, 1.0, 10.0 and 100.0 ppm of Cu were added, and the same experiment as in the previous report was carried out, except that as to AS, and AM, another additional experiment was made by keeping them at 30 for the period, from the 12 th week to the 16 th week. As a result, No. 2 and 3 (0.1 and 1.0 ppm) did not show a considerable change not only in appearance but also in value, almost the same as in the case of Fe. But No. 4 and 5 (10.0 and 100.0 ppm) emitted rancid odor, discolored on the surface and showed several times bad result compared with the case of Fe in P.O.V. No mold was seen during the whole experiment period, due to the good sanitary control in manufacture, so that only a little increase in A.V. was seen. And it was found that a stronger trend for oxidation accompanied an increase in A.V. value, quite contrary to the case where mold came out. It was also found that the existence of milk ingredient was consi-derably effective in curbing the development of P.O.V. but was almost ineffective for CO.V. The experiment at 30°C showed that a relatively large change was observed in CO.V. of all, and in P.O.V. of AS.