Higher dialkyl phosphoramidates were synthesized from the corresponding dialkyl phosphite, carbon tetrachloride, and NH3. The alkyl groups were butyl, amyl, hexyl, and octyl. These compounds were purified ccnveniently by means of molecular distillaticn at temp. below 100°C. It has been reported that diethyl and diisopropyl phosphoramidate are hygroscopic crystals. The higher dialkyl phosphoramidates were, however, insoluble in water and soluble in common organic solvents, and were oily liquid at room temperature. The effect of these compounds as plasticizer for PVC was evaluated. They were found to give good antistatic and good flame retarding properties to the plastics, and were also excellent in low temperature performance. Moreover, they were found to have an excellent wear resistant effect and slight extreme pressure effect as additives for lubricating oil.
The reactions of ethyleneoxide (EO) with p-hydroxybenzoicamide and benzoicamide were carried out in the presence of small amounts of NaOH as a catalyst at 80°C in an autoclave. In order to remove polyethylene-oxide by product and to reduce the width of molecular weight distribution of addition polymerisates of EO, the gel-filtration and counter current distribution extraction were carried out. These seperated samples (F.) were analysed by thin layer chromato-graphy, infrared spectroscopy and nuclear magnetic resonance (NMR). Then, the average chain length of the EO units of all F was calculated from the peak area in NMR diagram. Every fractions having 0 to 18 of EO units existed in nearly equal amounts in the products. The physico-chemical measurements of the aqueous sample solution, such as specific gravity, relative viscosity, surface tension as well as the test of emulsification and wettability were carried out. From the above experiments, it was made clear that all above samples were inferior as nonionic surfactant.
Synthesis of β-chloroethyl alkyl sulfide via higher alkanesulfenyl chloride and Strecker reaction of the β-chloroethyl alkyl sulfide, β-chloroethyl alkyl sulf-oxide, and β-chloroethyl alkyl self one were studied. The selfone derivative reacted almost quantitatively to give alkanesulfonylethanesulfonate under following condition ; 1.2 moles of saturated aqueous solution of sodium sulfite to one mole of the chloride, 100°C, 2 hrs. Under this reaction condition, dodecyl chloride gave no dodecanesulfonate. The sulfide derivative gave alkylthioethanesulfonate in about 70% yield. The sulfoxide derivative, however, gave by-product mainly and a small amount of alkanesulfinylethanesulfonate. β-Chloroethyl alkyl sulfide was synthesized from ethylene and alkanesulfenyl chloride which was derived from alkyl mercaptan and sulfuryl chloride. The sulfoxide derivative and the sulfone derivative were synthesized from β-chloroethyl alkyl sulfide by oxidation with 30% H2O2. Sodium dodecylthioethanesulfonate thus obtained reduced the surface tension of water as low as 38-39 dyne/cm at a level of 0.02 wt%.
Authors prepared higher alkyl ethers of pentaerythritol purposing for their utilization as surfaclants. Preparation of three series of the ethers having straight chains of C3-C16 is reported in this paper. Monoalkyl ethers (R : C12 and C16) were prepared by acid-catalyzed alcoholysis of 3, 3-bishydroxy-methyloxetane. Trichloropentaerythritol was treated with an excess of sodium alcoholates togive the corresponding 3, 3-bisalkoxymethyloxetanes (V) in high yields. By sulfuric acid-catalyzed hydrolysis of V in dioxane, dialkyl ethers (R : C4-C8) were obtained in high yields. Trialkyl ethers (R : C3-C6) were also prepared in good yields by alcoholysis of V using a catalytic amount of tin tetrachloride.
In the previous papers, the authors observed the amount of copper adduct to casein increased with the storage days in the systems of aqueous solution and oil. Also it was found that the copper seriously affected on the rancidity of oil, but in the case of casein or copper-casein complex, the peroxide value remained low. In this paper, the relation between the binding ability of various inorganic metal (copper, iron, zinc, magnesium) -casein complexes and the activity of metal-catalyzed autoxidation was investigated. Thus various inorganic metals (copper sulfate, ferrous chloride, ferric chloride, zinc nitrate, magnesium chloride) were mixed with casein in water, or, casein, various inorganic metals and soybean oil were mixed and heated for 1 hour at 180°C and the amount of adduct formed with these materials was measured. On the other hand various inorganic metal salts and various inorganic metal-casein complexes were admixed with soybean oil, and the peroxide values were measured during the autoxidation period at 60°C. The results obtained were as follows : For casein, the amount of adduct with copper or iron was most and that with zinc was found in the followed order, but, no adduct formation was observed with magnesium in the both cases of aqueous solution and oil. The order of activity was Cu > Fe > Zn > Mg. Copper and iron were only metals which will have practical catalytic activities, and zinc and magnesium had little catalytic effect. But in the case of various inorganic metal-casein complexes, the peroxide value remained low. A correlation exists between the binding ability of various inorganic metal-casein and the activity of metal-catalyzed autoxidation.
A lipid fraction having an inhibitory activity against Ehrlich mouse ascites carcinoma was isolated from calf thymus. Thymus tissue was hydrolyzed under N2 with 20% NaOH and the active material was extracted with ether after the hydrolysate was acidified with HCI. The crude material thus obtained was purified by the difference in solubility of its metal salts in organic solvents. The growth of the tumor in mice was inhibited by the administration of either the crude material or the purified one in a dose of 5 mg/mouse/day or 2 mg/mouse/day respectively for 10 days. Further purification was subjected to a silica gel column chromatography as the Hg-complex of an active lipid fraction, and the chemical analyses were made on the fractions with TLC, GLC. and IR. The results indicated that the main component of the most purified fraction was a cis-octadecenoic acid. This fatty acid was similar to oleic acid but it was far more active than oleic acid against Ehrlich ascites carcinoma. The GLC-MS and the result of oxidative cleavage suggested that the principle of the anti-tumor substance from calf thymus might be cis-Δ10- or cis-Δ11-octadecenoic acid differing-from oleic acid in the location of the double bond.