A little previous work has been published on X-ray diffraction of acid potassium soaps. Piper reported a paper which gives only the long 'spacings for a series of acid potassium soaps and recently, Dumbleton reported the lattice constant of acid potassium myristate. In this paper, X-ray investigation on acid potassium caprate, laurate, palmitate, stearate are reported. Acid potassium caprate and laurate were grown from ethanol solution in elongated parallelepiped form (Fig.-1·1), and acid potassium palmitate and stearate were in plates (Fig.-1·3). Acid potassium myristate is crystallized from hot alcohol in the elongated parallelepiped form (Fig. -1·2), but by slow precipitation it gives plate form (Fig.-1-3). The X-ray diffraction patterns showed remarkable difference between the elongated parallelepiped forms and the plates (Fig.-3·1). The cell dimensions for parallelepiped form were determined (Table-1). It was concluded that there were two phases in acid soaps, one was elongated parallelepiped form (pseud-orthorhombic), and another was plate form (triclinic). It seemed that the stable phase for laurate and caprate was the former, while that for myristate, palmitate and stearate was the latter.
In the previous paper*, the authors reported that the most toxic compound in thermally oxidized oil (TO) is presumably the dimer of glycerides with several fanctional groups. In this paper the authors studied the digestibility of the toxic compound and the distribution of this compound into several organs of rats. The results obtained are as follows : (1) From the results of feeding experiments, the digestibility of the toxic dimer was higher than that of original TO. (2) Lipids extracted from liver, intestine, stomach and adipose tissue were fractionated by silicic acid column chromatography. After several analytical experiments (IR, TLC etc.), it was found that the toxic dimer was almost hydrolyzed to mono- or diglycerides in digestive organs. However, it was believed that a part of toxic dimer accumulated in liver and blood. (3) A marked inactivation of the pancreatic lipase was observed when the toxic dimer was added to the substrate. (* Yukagaku, 21, 13 (1972))
In the previous paper*, the authors observed that the presence of toxic substance in thermally oxidized oils. We have wondered the presence of this toxic compound in used commercial frying oils. Therefore, we checked the amount of toxic compound in used frying oils which were collected from manufacturers. Most of the samples used for frying (soybean oil used for vegetables and shrimps, rice oil for dough-cakes, lard for instant-cook Chinese noodle and pork cutlets) contained trace amount of toxic compounds, however, rape-seed oil used for beancurds and soybean oil used for fish ball contained fairly high amounts of toxic dieter (1.5 and 0.6%, respectively). The results of feeding experiments of those oils indicated that the weight gain of rats decreased with increase of the toxic compounds in oils. (*Yukagaku, 21, 13 (1973))
In the previous paper*, the authors reported the presence of toxic compound (dimer of glycerides) in used frying oils. There is considerable doubt whether the commercial fats and oils form dimer of glycerides during their processing. Therefore, we determined the amount of dimer glycerides in those fats and oils. The dimer was not found in most of fats and oils used for experiments. However, a small amount of dimer glycerides was found in seasame oil and margarine (animal fat origin). After the fractionation of the margarine by silicic acid column chromatography, dimer of glycerides (MAP) (0.2%) was obtained and the molecular weight was 1900, but the functional groups of this dimer were poor. It is still not clear whether this dimer of glycerides is toxic or not. (*Yukaggaku, 21, 73 (1972))
Reaction of maleic anhydride with linoleic and oleic acids in the presence of organic peroxides was investigated. The peroxides used were benzoyl peroxide (BPO), di-tert-butyl peroxide (DtBPO), and dicumyl peroxide (DCPO). The maleinization reaction was accelerated by the presence of organic peroxides, and was carried out at a temperature that the peroxides decompose (about 130°C). The orders of the activities of the reaction were as follows : (i) On the peroxides DCPO ≥ DtBPO >> BPO (ii) On the maleic anhydride and its related compounds maleic anhydride >> maleic acid > dimethyl fumarate ≥ fumaric acid > dimethyl maleate (iii) On fatty acids linoleic acid > oleic acid In the case of the reaction of linoleic acid with maleic anhydride, a product of resinous powder (mp ; about 130°C) was obtained. On the structure of maleinized product it was presumed that the main product was dimer, crosslinked by maleic anhydride, of maleic anhydride added to linoleic acid (III), and that the by-product was ketonic compounds derived by decarboxylation from two acid anhydride groups in the main product (III). (III) From the results obtained, a biradical addition reaction mechanism was postulated.
Chlorophosphonations of some methyl carboxylates were carried out under the condition ; 1 : 5 of the mole ratio of methyl carboxylate to PCl3, 200 ml/min of the flow rate of oxygen, -15-0°C and 3 hrs. The products were esterified with ethanol, and the diethyl esters were used for G.L.C. analysis, using a 3 m × 3 mmφ, Ucon LB 550 X column. The G.L.C. peaks of the products were identified by the comparision of their retention times with those of the peaks of authentic samples synthesized by other methods independently. Isomer distributions were calculated from the area ratios of the G.L.C. peaks. The relative reactivities of C-H bonds of the methylene group to the C-H bond of the terminal methyl group as reference standard, are shown in the following Table.
The sodium polyoxybutylated ethyl and octyl sulfates, which had 1, 2, 3, 5, 7, and 10 units of butylene oxides, were prepared by adding 1, 2-butylene oxide to the corresponding alcohols, and the relation of their surface activities, such as surface tension, foaming properties, wetting power, dispersing power and emulsifying powers, and the length of oxy-butylene chain was studied. The following conclusions were obtained. 1) Sodium polyoxybutylated ethyl sulfates having less than 3 moles of butylene oxide had little surface activities, but the products having more than 5 moles of butylene oxide had good surface activities. The surface tensions of the products having over 5 moles of butylene oxide were low, and their c.m.c. values were more than 0.25% approx. The foaming properties, except 10 mole adduct, and dispersing powers of all products were inferior. The wetting powers of 5, 7 and 10 mole adducts and emulsifying power of 10 mole adduct were superior. 2) As compared with sodium octyl sulfate, the surface tensions of sodium polyoxybutylated octyl sulfates were lower in the low concentration, and their c.m.c. values were also lower. The foaming properties and emulsifying powers of the products having over 5 moles of butylene oxide were excellent. The products having 5 and 7 moles of butylene oxide had good wetting power. All products had poor dispersing power.
Purposing for precise evaluation of water-repellency of surface active agents, authors have devised the following new simple method. A filter paper (5 × 5 cm2) for use of paper-chromatography is treated under definite conditions with aqueous solution of the surfactant to be tested, then dried and conditioned in a desiccator. A small amount of water (0.01-0.04 ml) is made flow down upon the treated paper from the graduated capillary tube (the inner diameter : 0.4-0.6 mm), inclined at 10-30 degrees and equipped perpendicular to the paper so as to lightly touch the paper with its sharpened tip (the outside diameter : 1.0-3.0 mm). By recording migration of meniscus in the capillary at every time interval, the wetting time of the paper is determined. The results measured for several cationics and commercial water-repellent products, indicated that this method gives satisfactorily reproducible data and also could serve efficiently for examining the structural effects of hydrophobic part of a surfactant on the water-repellency.