タラキセラン及びウルサン型のトリテルペンは植物界に広く分布しているが,あせび(pieris japonica D. Don つつじ科)の樹皮から得られたタラキセリルアセタート(1),タラキセロール(2),タラキセロン(3), 3β-アセトキシ-28-ヒドロキシウルス-12-エン(4), 3β, 28-ジヒドロキシウルス-12-エン(5), 3β-アセトキシウルス-12-エン-28-アール(6)及び3β, 28-ジアセトキシウルス-12-エン(7)を用いて1H-NMR及び13C-NMRについて検討した。1H-NMRについては(2)及び(3)のメチル基の帰属を行い,13C-NMRについては(1)～(7)のすべての炭素の帰属を明らかにした。
The dissolution of iron from the iron utensil to the vegetable oil has been studied on using the iron plate and safflower oil with the dissolved water at 180°C. At this experiment, water was added dropwise to the safflower oil contained the iron plate at 180°C, and the relation between the amount of dissolved water and dissolved iron in the oil was investigated. The amount of dissolved water in the oil was 5801168ppm for 13h at these conditions. The ratio of physically and chemically adsorbed water on the iron plate was 9.410.7% of the dissolved water in the oil. On the other hand, the ratio of iron and its oxides on the surface of the plate was 15:85 by measurement with ESCA. The ratio of the iron oxide derivative on the plate surface decreased from 81% to 34% under the same experimental conditions with 13h heating. At the same time, the dissolved amount of iron from the plate in the oil increased from 0.12ppm to 1.23ppm for 13h. From these results, the dissolution process of iron from the iron plate in the oil was found to be that the iron oxides on the surface of the plate dissolved in the adsorbed water on the plate and then diffused into the oil.
It has been believed that chlorophylls are not remained in refined edible fats and oils, because their contents are below the limit of detection by spectrophotometric analysis. In this experiments, photo fluorometric quantification was investigated to evaluate simultaneously the content of chlorophylls and pheophytins in refined edible oils. Chlorophylls a and b, and pheophytins a and b were prepared respectively from acetone extracts of spinach and/or followed by the treatment of oxalic acid. Sixteen mililiters of actone solution of each component (concentration ca. 0.15mgl) was added into 3.64g of blank oil, which was prepared through the removal of photosensitizer in edible plant oils by using a activated carbon-Celite column. By the measurement of fluorescence intensity in four measurement systems (Ex 425-Em 663, Ex 454-Em 646, Ex 404-Em 670 and Ex 434-Em 655nm) by spectrophotofluorometer, the following calculation formulas were introduced; Chl a=(10.8F663425+0.307F646454-3.30F670404-4.91F655434)×10-3mg/kg oil Chl b=(0.566F663425+5.09F646454-0.199F670404-0.950F655434)×10-3 Phy a=(-8.09F663425-0.214F646454+11.7F670404+2.74F655434)×10-3 Phy b=(-4.81F663425-1.71F646454+1.23F670404+7.92F655434)×10-3 In the case of practical evaluation of refined edible oils, the fluorescence intensity of blank oil was subtracted from that of sample solution, dissolving 3.64g oil in 16ml of spectrum grade acetone. Thus, the indentity and concentration of four components may be accurately and rapidly determined within the concentration range from 0.05 to 1mg/kg oil as the total chlorophylls. As the results of fluorometric quantification on several refined edible oils, it was confirmed that “chlorophylls” was presented at 0.06 to 0.3ppm as the sum of four components, in which pheophytin a showed the highest content above 60%.
The telomer-type surfactants containing carbamoyl and/or carboxyl group that had been prepared in the previous paper were evaluated as detergent builder. The detergent solution composed of LAS, builders and Ls-CONH2 telomer, which telomerized l-dodecanethiol with acrylamide, with only carbamoyl group showed more excellent values than that of STPP for Ca2+ sequestration, CaCO3 dispersion ability, orange OT solubilization ability and detergency, and these values were increased with increasing the hardness of used water. This activation was attributed to the mixed micelle formed by LAS with Ls-CONH2. On the effect of carboxyl group in the telomer, chelating value, lime soap dispersion power, orange OT solubilization ability, anti-redeposition ability and detergency decreased with increasing the content of carboxyl group and displayed a minimum at 1020 mol% carboxyl group content. On the other hand, CaCO3 dispersion ability increased by introduction of carboxyl group and the maximal value obtained at 20mol% carboxyl group content. These were interpreted as a result of interaction between carbamoyl and carboxyl groups in telomer aqueous solution and resulted variation of conformation of dissolved telomer chain.
Several new series of aminimides [(3ac, e), (4ah), (5d) and (6a, b) in Scheme-1] were synthesized by Slagel method1). Some surface active properties and the effectiveness on phase transfer catalysis were examined for these compounds. The results were compared with those of several reference compounds. Surface active properties of aminimides (1ae)5) and (2ag)2), and bis(aminimides) (5ac)3) have been reported previously. Substitution of an aromatic group, especially pyridyl group, for an alkyl group (C23) on imino nitrogen of aminimides caused a decrease in cloud point (Cp) and critical micelle concentration (cmc), but an increase in melting point, Krafft point (Kp) and γcmc (surface tension above cmc). Melting point, Cp and γcmc increased with increasing the number of hydroxyl group in an amineimide molecule regardless of the relative position (Table-2). In the case of bis(aminimides), (6a) was similar to (5d), but differed from (6b) regarding to the dissolution behavior (Kp and Cp) (Table-3). It was found that the efficiency of aminimides as phase transfer catalysts in the substitution reaction of 1-bromooctane with aqueous potassium iodide depended on the following structural factors: a) HLB (hydrophilic-lipophilic balance) of aminimides, b) the position on which long chain placed (_??_+N- and/or -N-), c) the number of hydroxyl groups, d) introduction of pyridyl group, and e) the chain length and the steric structure of the linking group between two aminimide groups in bis(aminimides). The series (1) were the most effective among the series examined, and some of (1) had a high efficiency close to that of “Dicyclohexyl-18-crown-6” (Table-4).
The amounts of nonylphenyl poly (oxyethylene) ethers adsorbed at saturation on activated carbons were measured and the area occupied per molecule was calculated by the use of the value of surface area for the pores larger than 8Å in a diameter. For all activated carbons studied, a good linear relation was obtained between the area per molecule and the number of ethylene oxide attached to nonylphenol. This relation is applicable to the estimation of surface area.