In previous papers, the authors reported that peroxides in oils are decomposed by hydrogenation into hydrocarbons, aliphatic alcohols and ketones as volatiles, and into ω-hydroxy acids and lower fatty acids in the glycerides.
In this paper, the soybean oil with peroxide value 230 was hydrogenated and the polymerized products were isolated as non urea adduct fraction (NAF). The NAF was further fractionated by LC and TLC.
When the oil was hydrogenated under industrial condition the polymerlized products were increased. They were non-polar dimer acids, keto-dimer acids, hydroxy-dimer acids and trimer with hydroxy groups. When the oil was hydrogenated with Pd catalyst at lower temperature, NAF did not increase. But keto acid and hydroxy acid were found in urea-adduct fraction.

抄録全体を表示

In the previous papers, the authors reported that the decomposition of tocopherol in oxidative rancid oil increases more than those in non-rancid oil.
In this paper, the influence on decomposition of tocopherol by oxidation products of oil was investigated. That is for the effect of free fatty acid and peroxide in oil on the decomposition of tocopherol. For examination the following kinds of lard were prepared, namely, without addition of dl-α-tocopherol; with addition of tocopherol by 0.2%; 0.2% tocopherol plus 0.32.3% fatty acid; 0.250.5mg% iron (some iron salts) added thereto; and 13% benzoyl peroxide added thereto; and they were heated at 180°C for 24hrs.
The results obtained were as follows;
1. Fatty acid and iron in oils did not promote the decomposition of tocoehhrol.
2. The decomposition of tocopherol was apparently promoted by the peroxide of oil and the addition of benzoyl peroxide.

抄録全体を表示

The effect of the natural tocopherol mixture on the Fried Noodle was compared with that of butylated hydroxyanisole. (BHA) by using the test fryer which reduced to a scale of one-twentieth of the commercial apparatus at almost the same conditions as those of the commercial operation.The effect of the protection of fat surface from the air by means of hood method on the loss of antioxidant and on the fat deterioration was also examined.
The following results were observed. Tocopherol, as was expected from the previous paper, showed a better thermostability and its content was kept in a constant level of about 80% during frying when the fat surface was protected from the air as shown in Fig.-2 (A). On the other hand, it was about 50% in the case of the use of BHA. The reason why BHA showed a considerably good thermostability like this might be due to the low frying temperature and the higher fat turnover rate in the case of the Fried Noodle.
As shown in Fig.-2 (B) and (C), BHA rather maintained a higher level of the fat stability than that of tocopherol in the frying conditions. This is considered to be caused by the difference of efficiency of antioxidant, that is, BHA has stronger effectiveness than tocopherol as shown in Table-1. As shown in Fig.-2 (H), this tendency became more and more marked on the shelf-life of Fried Noodle.
From the results of Fig.-2 (A), (B), (C), (E) and (H), it was recognized that the protection of fat surface from the air by the hood method was an effective method to prevent the loss of antioxidant and the fat deterioration.

抄録全体を表示

It was found that KLS precipitates in NaLS-KCI mixtures in low NaLS concentrations, and precipitate decreases and finally disappeares as the NaLS concentration increases. As this phenomenon is important in biological systems, e.g. those involving the interaction of metal ions with micellar bile salts in solution, it was of interest to us to observe this phenomenon and to study its mechanism.
The phenomenon was studied by measuring LS and potassium ion concentrations in filtrates of KCI-NaLS mixtures. As a result, the precipitation and dissolution zones were influenced by KCl concentration and temperature, and the precipitation zone was not observed above the Kraft point of KLS. It was further observed that as soon as the LS ion concentration reaches to the cmc, the KLS precipitate begins to decrease. Therefore, it was found that the dissolution zone was closely related to the micelle formation of LS ions.
But it was suggested that the KLS precipitate was not solubilized in the hydrocarbon core of micelle in the dissolution zone, because KLS was hydrophobic but not oleophilic as revealed by the measurement of solubilities of NaLS and KLS in several solvents.
Plot of Δκ (=the difference between the calculated conductivity of KCl+NaLS and the observed conductivity of mixtures of KCl-NaLS) against the NaLS concentration showed that Δκ increased until the maximum precipitate was reached and then decreased in the dissolution zone.
The decrease in Δκ stopped at the point where the KLS precipitate disappeared and Δκ remained constant there after.
Therefore, it was assumed from the above-mentioned results that the precipitate dissociates into potassium and LS ions in the dissolution zone, and LS ions take part in the micelle formation. Moreover, it was suggested that potassium ions are adsorbed on the surface of micelles because of their low hydration degree.

抄録全体を表示

Most of the S-thiostearates (C₁₇H₃₅COSR') were prepared by heating the appropriate alkyl halides with S-potassium thiostearates in ethanol-ether. The S-thiostearates prepared were as follows : R'=methyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl, heptyl, octyl and dodecyl. S-sec-butyl, S-heptyl and S-octyl thiostearates thus prepared are believed to be new compounds and they showed the melting points of 24.424.6, 45.045.2 and 44.545.0°C, respectively. S-n-hexyl thiostearate showed the melting point of 37.337.5°C, which was lower than that reported before.
Earch of the series of the S-thiostearates shows an alternation of the melting points. Fig.-5 represents the plot of the melting points of S-thiostearates against the number of carbon atoms (R') in the S-thiostearates. The odd members in the S-thiostearates melt at higher temperature than the even members.
The ultraviolet absorption spectra of the S-thiostearates were also measured in cyclohexane solution, and the effect of R' on the π→π* band (234mμ) and n-π* band (270300mμ) was studied. The λmax and εmax did not appear which might be affected by the R' (Table-2).
Further, the infrared absorption spectra of the S-thiostearates were measured in a KBr disk. The S-thiostearates having straight chain R' give no influence on the νmax of νC=O band and νC_??_S band, but νmax of the νC=O band seems to shift toward small wave numbers (cm_-1) according to the branches of R' (Fig.-2).

抄録全体を表示

Chlorophosphonations of some n-alkylbenzenes were carried out under the condition; 1 : 5 of the mole ratio of n-alkylbenzene to PCl₃, 200ml/min of the flow rate of oxygen, -150°C and 3hr.
The product mixtures were esterified with ethanol and analyzed by GLC, using 3m×3mmφ, Ucon LB 550X column.
Isomer distributions were determined.
In the chlorophosphonation, relative reactivities of C-H bond of the methylene group in the alkyl chain to the terminal methylene group, as reference standard, were shown as follow.

抄録全体を表示

Author reported a method in the previous paper on the determination of the critical micelle concentration (cmc) of a surfactant, in which a strongly ultraviolet absorbing organic substance (I), such as diethylaniline, was added to the aqueous surfactant solution and the cmc was obtained as the breaking (minimum) point on the curve of the λmax in ultraviolet region vs. surfactant concentration.
In the present work, this method was applied to more complex cases, and good results were obtained.
When a surfactant had little or no ultraviolet absorption characteristics, such as tetradecyldime-thylbenzylammonium chloride or sodium dodecyl sulfate, the λmax vs. surfactant concentration curve similar to that given in the previous report was obtained even when it contained a builder or impurities, and the concentration at the breaking point agreed well with the cmc determined by other methods. A similar curve was also obtained and the cmc was clearly determined in the case of a binary or ternary surfactant system among these surfactants.
Although it is often difficult to determine accurately the cmc of impure or commercial surfactant, it is possible with this method. For example, the cmc of somewhat purified Tween 20 was determined to be 0.11₇g/100ml at 22°C.
When a surfactant had strong ultraviolet absorption characteristics, a slight breaking point appeared on the curve of λmax vs. surfactant concentration, and although the determination of cmc was possible, the types of surfactants to which the method is applicable were limited to pyridinium salts, polyoxyethylene nonyiphenyl ethers etc. (II). The determination was also possible by the addition of (I) to (II), but it was unsuitable when λmax of (I) and (II) overlapped. For example, acetophenone was suitable as (I) for the determination of alkylpyridinium salts. In regard to the determination of alkylphyridinium salt, two breaking points appeared on the curve and the concentration of the lower point agreed with the cmc obtained by another method in the case of both single system and mixed system with other substances.
This method is based on the solvent effect for (I) or ultraviolet absorbing portion of the surfactant molecule, and from the results of above-mentioned measurements, it was assumed that the pyridin nucleus of the molecule of alkylpyridinium salt forming the micelle was partially contracted to the water phase, and the micellar state changed considerably with the change of the salt concentration above the cmc.

抄録全体を表示

Various surfactants including linear alkylate sulfonate (LAS), alpha olefin sulfonate (AOS), sulfate of synthetic alcohol (AS), and a formulated detergent for kitchen use were applied on the clipped back skin of guinea-pigs, and after 24hr or 1week the histopathological reactions on those skin were observed.
The degrees of the reaction obtained were as follows : In 30% aqueous solutions of surfactants, AOS showed remarkably weaker reaction than LAS or AS, and the reactions of LAS and AS were approximately the same.
In 1% solutions of surfactants or in 10% solution of the detergent, every sample did not show any reactions on the test skins.

抄録全体を表示

Chelate surfactants were synthesized which had hydrophobic alkyl group and hydrophilic metal ion, the ion being bonded to the former in chelate configuration, and their properties were investigated.
Some N-alkyl ethylenediamines (alkyl group : octyl, decyl, dodecyl) were used as the chelating agents and they were treated with salts of some transitional metals, and some pure chelates were obtained. There were some chelate surfactants having good surface activities, in those chelates. Above all, N-octylethylenediamine-Fe (NO₃) ₃ (2 : 1) chelate and some other chelate surfactants had good dispersing power for TiO₂ in organic solvent.

抄録全体を表示