n-Propylester method was studied to establish a simple and convenient method for gas chromatographic determination of fatty acid composition of fats and oils, such as butter fat, containing both low and high molecular weight acids. The conditions of the preparation of propylesters were examined with the mixtures of butyric and capric acids. It was found that the following procedure was appropriate to prepare the propylesters for GLC analysis. 0.25g of acids and 1.25g of alcoholysis reagent (0.3% sodium in n-propyl alcohol) were placed in a 100ml volumetric flask and the mixture was gently agitated at room temperature for 5 minutes. Then the flask was filled up with 20% aqueous solution of sodium chloride to separate ester, and after vigorous shaking the mixture was allowed to stand at 40°C. Propylesters were obtained with a small amount of propyl alcohol as an upper layer. This procedure was further applied to triglycerides containing low molecular weight acids and the results were satisfactory.
The photo-dimerization reactions of methyl β-eleostearate were studied. When irradiated with light of high pressure mercury lamp, methyl β-eleostearate was also observed to form the dimer in CCl4 and in CCl3H solutions as well in n-heptane. However, the dimer of the eleostearate obtained by illumination with light in CCl4 or CCl3H was chlorinated. It is therefore considered that the eleostearate reacts with CCl4 or CCl3H to give chlorinated dimer in these reactions. From the results of analysis of kinetic data obtained, the disappearance of the eleostearate was observed to be in closest agreement with first order reaction in CCl4 as well in n-heptane, but that in CCl3H does not agree with the first order reaction. The rates determined showed that the disappearance of the eleostearate in CCl4 is about six times as fast as that in n-heptane.
This report deals with the preparation of some esters and N-substituted amides of the following three dibasic acids, di (carboxy) methyl ether, di (carboxymethoxy) ethyl ether, di [β- (carboxy-methoxy) ethoxy] ethane, which were respectively obtained from di-, tetra-, and penta-ethyleneglycols by the oxidation with nitric acid; and also deals with the study on their charateristics as plasticizers for polyvinyl chloride resins. Esters, mentioned above, were generally excellent in low temperature performance and also gave good antistatic properties to the plastics. But the resins plasticized with those esters exhibited a poor thermal stability (Table-4). N-substituted amides didn't seem to be good plasticizers because of the low compatibility with resins and especially in the poor thermal stability (Table-5).
In this paper, the side reactions in the reaction of lauryl chloride (RCl) with sodium hydrogensulfide (NaSH) in a protic solvent, n-butanol (n-BuOH), and a dipolar aprotic solvent, dimethylformamide (DMF), were mainly investigated. The absorbances of 425 and 620mμ of electronic spectrum of NaSH-DMF solution decreased proportionally with added amount of water in this solution. Moreover, from other spectroscopic results, namely the increase in absorbance with concentrations of NaSH or the dependence of absorbance on time, and the synthetic results in n-BuOH and DMF, the presence of solvated complexes, for instance, HS-…DMF and HS-…DMF…Na+ was implied. It was clear that the following reactions occur more easily in n-BuOH, than in DMF : RCl+Na2S→RSNa+NaCl [1a] RSH+NaSH_??_RSNa+H2S [1b] RSH+NaOH_??_RSNa+H2O [1c] RSNa+RCl→RSR+NaCl  The formation of RSR followed by reactions [1c] and  is almost quantitative in n-BuOH. These experimental results were well explained in terms of the difference in solvation power of each solvent for Na+. In DMF, lauryl chloride reacted with sodium sulfide to yield RSH and a small amount of disulfide (RSSR). It was confirmed that the following reaction occurred : _??_ As a cause of disulfide formation, the oxidation reaction of mercaptan in the presence of dimethylamine was examined.
A series of sodium polyoxypropylated laury phosphates was synthesized and the change in their surface activities such as surface tension, foaming properties, wetting power, dispersing power and emulsifying power, by the difference in the number of moles of propylene oxide added, was discussed. The surface tension of propylene oxide adducts, especially 315 mole adducts, is lower as compared with lauryl phosphate. The foaming power and the foam stability are generally low. Addition of propylene oxide greatly improves the wetting power of lauryl phosphate, especially, 3, 10 and 15 mole adducts are excellent. The dispersing power of propylene oxide adducts is superior than that of lauryl sulfate. The emulsifying power of the products is small.
The addition reaction of 1, 2-butylene oxide to lauryl alcohol was investigated. Some sodium polyoxybutylated lauryl sulfates were prepared and the change in their surface activities such as surface tension, foaming properties, wetting power, dispersing power and emulsifying power, by the difference in the number of moles of butylene oxide added was discussed in comparison with sodium lauryl sulfate. 1) In the case of using KOH as catalyst, more than 5wt% of the catalyst must be added to alcohol and the proper reaction temperature is 170°C. 2) As compared with surface activities of sodium lauryl sulfate, the surface tension and c.m.c. values of sodium polyoxybutylated lauryl sulfates were lower, with increased foam stability, and the dispersing power was superior. The wetting power of the products having less than 3 moles of butylene oxide was excellent, and the products having more than 10 moles of butylene oxide had good emulsifying power.
Method for determination of mono- and diglycerides by gas liquid chromatography as their TMS derivatives or acetates were examined. Chromatograms which show completely separated and sharp peaks were obtained for the both derivatives. Calibration factors for glycerides of fatty acids of carbon numder 14, 16 and 18 were determined by using standard materials. Peak areas observed for diglycerides were relatively small in comparison with those for monoglycerides. Five sorts of commercial products of monoglycerides were used for investigation. Saponification value and hydroxyl value calculated from the GLC composition of the products well agreed with those values determined by chemical analysis, respectively. Contents of monoglyceride of the products determined by GLC and chemical analysis also showed good coincidence.