Japanic acid (C22 acid), a main constituent of dibasic acid portion in japan wax, and palmitic acid were reacted to form monomolecular-type glycerides ; α-, α'-japanin-β-palmitin and α-, β-japanin-α'-palmitin of those melting points were 61.2 and 68.3°C, respectively. Japanic acid used in this work was a pure material of which synthetic procedure has been reported previously.
Two moles of glycerin were reacted with one mole of japanic acid to form a bimolecular-type glyceride in which two moles of glycerin were bridged by japanic acid in α-, α-positions. The tetrapalmitate of this glyceride was prepared by esterifying it with palmitic acid, and the product melted at 59.6°C.
A methylsterol, C31H52O, mp 120122°C, [α] 590+44.7°, Liebermann-Burchard reaction : yellow to orange-red, the acetate mp 116-117°C, [α] 590+56.9°, was isolated from the unsaponifiable matters of wheat germ oil by fractional crystallization, repeated liquid chromatography (Table 2 and 3), refining through the digitonide and subsequent recrystallization. The IR spectrum of this compound showed the presence of vinylidene group (at 3.247μ, 6.10μ and 11.29μ), cyclopropane linkage (at 3.292μ and 9.80μ or 9.97μ) and gem-dimethyl group (at 7.331μ) (Fig. 1). The properties of this compound were agreed with those of 24-methylenecycloartanol which was originally isolated from rice bran oil by Ota and Shimizu. The methylsterol was also presumed as 24-methylenecycloartanol from the NMR spectrum compared with those of cycloartenol and cycloartanol. Because, it was assumed that those substances have the same skelton structure. NMR spectrum of cycloartenol (Fig. 2) had a signal at 9.05τ (or ppm) (shown as M2), which seemed to indicate the intensity of two methyl groups, and also had two signals at 9.11τ (M3) and 9.20τ (M4) which seemed each one methyl group respectively. Besides, the signal at 8.32τ and 8.39 would be corresponded to the dimethyl group, and this signal seemed to be shifted to lower τ magnetic field by the effect of ethylene bond connected with C-25. From the spectrum of cycloartanol (Fig. 3), each signals at 9.03τ (M2), 9.09τ (M3) and 9.19τ (M4) seemed to indicate two methyl groups respectively, and those were correspended to C-4 dimethyl, C-13 methyl, C-14 methyl and C-25 dimethyl groups. The signals owing to dimethyl groups connected with C-25 which had a proton atom were shown at M3 and M4, and they were summed up to become the intensity of two methyl groups. NMR spectrum (Fig. 4) of the methylsterol, isolated in this work and being presumed as 24-methylenecycloartanol, had a signal of which intensity were equivalent to 3 methyl groups at 9.04τ (M2), and also had 3 signals at 8.93τ (M1), 9.11τ (M3) and 9.20τ (M4) respectively. Intensity of each signals was equivalent to one methyl group. Those 4 signals were derived from C-4 dimethyl, C-13 methyl, C-14 methyl and C-25 dimethyl. The signals of C-25 dimethyl had been shifted about 0.15τ to lower magnetic field, owing to the ethylene bond connected to the vicinal carbon atom of C-25. The doublet signals appeared at M1 and M2. Besides, 4 signals at around 9.56τ shown in Fig. 24 were presumed to be corresponded to methylene of cyclopropane ring. While, the authors could not get the pure compound mentioned as “tritisterols” in literature, but the properties of the crude fraction of 24-methylenecycloartanol in the refinning stage at this time, were agreed with those of “tritisterol”. As the other compoment of this oil, β-amyrin was isolated. Methylsterol, agreed with 24-methylenecycloartanol in its properties, was also isolated from soy bean oil by the similar procedures described above.
Dye dispersing power and antistatic power of polyoxypropylene polyoxyethylene glycols prepared from polypropylene glycols, the molecular weight being 1200, 2000, 3000 and 4000 respectively, were investigated. The rates of dye-absorption and migration were also observed, using the copolymers as dyeing assistants. For the dyeing of wool with 2 : 1 metal complexes dyes, the copolymers of polypropylene glycol, the molecular weight being 2000 with 400 moles of ethylene oxide, showed excellent results. For Tetron, the copolymers of polypropylene glycols having molecular weight of 12000 with 100 moles and 200 moles ethyleneoxide showed good results.
The surface activity of the α-substituted higher aliphatic acids was studied. These compounds were prepared by reaction of α-bromo-fatty acid with various compounds, such as sodium hydroxide, N-methyltaurine, monoethanolamine, diethanolamine, glycine, n-butylamine, ethylenediamine, potassium cyanide (The obtained α-cyano-fatty acid was hydrolyzed into dicarboxylic acid.), ammonia, trimethylamine and thiourea (The obtained pseudothiohydantoin was decomposed into α-mercapto-fatty acid.). These reaction products were surface active and some of them were stable for metallic ion. It was proved by IR spectrum that α-trimethyl ammonium bromide-stearic acid was decarboxylated by heating into heptadecyl trimethyl ammonium bromide. It was found that the decarboxylation reaction was first order and the activation energy was about 32.9 kcal/mol.
Purified samples which had similar average viscometric degree of polymerization were selected from polymerization products obtained by solution polymerization of vinyl acetate in ethyl, benzyl, dodecyl and octa-decyl alcohol. Their chemical constitution was studied by general analysis, determination of molecular weight, elemental analysis and infrared spectroscopy. It was made clear that the principal component was hydroxy-alkylated polyvinyl acetate or hydroxy-alkylated polyvinyl alcohol.
The chemical constitution of polymer and its saponified product obtained by solution polymerization of vinyl acetate in dodecyl chloride was studied by general analysis, determination of molecular weight and infrared spectroscopy. It was made clear that their chemical constitution were more complicated than those in case of higher alcohol used for solvent, since the former had more complicated terminal groups.
In the studies on performance tests of surface active agents, a new semimicro continuous method of wetting test, the “Semimicro Hydrometer Method”, has been developed in our laboratory. In this method the change of apparent density of a tape (2cm×7cm), immersed in a test solution, is measured with a hydrometer. The change is plotted against time on semilog paper, and entire progress of wetting is clearly shown by the apparent density-time curve. The method necessitates only 100 ml of test solution, while the original macro-method needs 1 liter. The apparatus and operation have been improved.
For the improvement of foaming properties of surfactants, the effect of the addition of alkylolamides has been investigated. The foaming power and foam stability of sodium alkylarylsulfonate, sodium sperm alcohol sulfate, PEG-nonylphenylethers (P=12, 18) and PEG-laurylether (P=17) have been remarkably improved by adding more than 30% by wt. of lauric diethanolamide or coco-fatty diethanolamide.