The high vacuum residuum of methyl esters of the rice bran oil was treated with methanol and the methanol soluble matter was then repeatedly chromatographed by using active alumina to isolate a new compound, colorless needle crystal, having mp at 95.3°C, molecular weight 444 (Rast) and [α] 15D -46.6°C (chrolof orm). The new compound had extinguishable maximum absorption band at 268 mμ and its E1%1cm was 506. It was positive to Liebermann-Burchard reaction, while negative to Emmerie-Engel reaction and to digitonin reaction. The existence of carbonyl group was confirmed by the infra-red absorption spectrum and by the oxime formation with hydroxylamine hydrochloride. This substance was unstable and its UV absorption spectrum was convertible during preservation, i.e., extinction at 268 mμ decreased, while new extinction maximum at 230 mμ was observed. These properties were similar to that of Calciferol. However, upon investigation by comparing with Oppenauer-oxidized Calciferol, they were not the same substance.
The rates of liquid-phase oxidation of n-dodecene with oxygen using benzoyl peroxide as initiator and the compositions of oxidation products have been studied. At 120140°C the oxidation of n-dodecene was easier than that of n-dodecane, and the concentrations of hydroxyl, peroxide and carbonyl groups were large even at the beginning of the oxidations, but concentration of carboxyl group was gradually increased up to about 25 mole% of n-dodecene used. The concentration of ester group became lager with time, and only about 60% of C=C double bond was consumed. Accordingly, oxygen would attack not only C=C double bond and its α-methylene group but also to the other methylene groups. At above 160°C, random attack of oxygen occurred. However, the compositions of products, in which the concentration of carboxyl group became to 25 mole% of dodecene used, were constant between 120 and 160°C. In the oxidation of dodecene-1, large amount of CO2, volatile acids and others were produced even at the beginning of oxidation. The liquid oxidaton products contained about 25 wt % of carboxylic acid and about 75 wt % of unsaponificable products containing α, β-unsaturated and saturated alcohols, ketones and aldehydes. Most of the carboxylic acids were keto-aids, hydroxyacids and polymeric acids. The unsubstituted fatty acid part contained large amount of lower fatty acids having less than six carbon atoms, and the compositions of higher acids were in the order of C8 ≈ C11 > C9 > C10. When heavy metal salt was used together with benzoyl peroxide, the rate of formation of various groups was different from the case of benzoyl peroxide as the sole initiator.
To clarify the re-odorization mechanism, the refined rape seed oil was oxidized with dried air. The volatile carbonyl compounds were caught in a trap of 2, 4-dinitrophenylhydrazine solution, while the non-volatiles in the oil were extracted with Girard reagent to convert into 2, 4-DNPH compounds. These compounds were then passed through alumina column with benzen to collect only monocarbonyl compounds. Saturated and unsaturated mono-carbonyl compounds were determined by applying paper chromatography and ultra-violet absorption spectrum analysis with the following results : 1) C4 and C6 aldehydes covered over 70% of the volatile carbonyl compounds and over one half of the C8 and C10 components was consisted of unsaturated compounds. 2) The non-volatile carbonyl compounds contained more saturated ones compared with the volatiles.
The authors contemplated to find the most suitable conditions to manufacture butylene glycol via chlorohydrin process. It was found that a substantial good yield of Butylene chlorohydrin was obtained by utilizing natural circulating reaction tower using untreated electrolytic chlorine. Further investigations were made on the dehydrochlorination of butylene chlorohydrin and it was found that butylene oxide was more easily isomerized to butylene aldehyde than propylene oxide to propion aldehybe. In manufacturing butylene glycol by hydration of butylene oxide the optimum conditions on the concentration of butylene oxide, effect of isomers and other factors have been decided.
Soysterol can be acetylated, brominated and then oxidized by using chromic anhydride ; water ; sulfuric acid; glacial acetic acid in carbon tetrachloride solution, and androstenolone is obtainable with stigmasetrol recovered. Yields of androstenolone and stigmasterol were investigated under various conditions. From 150 g of soysterol, iodine value 77.3 (pyridine bromide method), a 22 g of stigmasteryl acetate tetrabromide was recovered and 5.4 g of androstenolone acetate semicarbazone was obtained by using the oxidizing agent containing 228 g of chromic anhydride which was added during 7 hrs and then agitated for 15 hrs at 20°C. The yield of androstenolone acetate semicarbazone was slightly increased by the addition of cupric sulfate as catalyst.
Higher aliphatic amine or its mineral acid salt when treated with ethylene oxide reacts to produce the quaternary ammonium hydroxide or quaternary ammonium salt in the presence of water. The rate of the reaction depends on the steric effect more than the base strength of amine. The reaction of amine-salt and ethylene oxide involves two reaction mechanisms which depend on the steric effect of amine. In the reaction of HCl-salt, one course is (1); ethylene oxide reacts with amine, and the other is (2); ammonium hydroxide produced from ethylene oxide and amine reacts with ethylene chlorohydrin from ethylene oxide and HCl.
The foaming properties of mixtures of PEG-nonylphenylethers (p=6, 9, 12, 20) and saturated fatty acid sodium salts (C12, C14, C16) have been investigated. The combination ratios of nonylphenylethers and soaps, having the foaming power equal or superior to soaps, are limited between a narrow range. The foaming power decreases as the amount of nonylphenylether increases. The range of the above combination ratios becomes wider as the EO mol number of nonylphenylether increases and as the alkyl chain length of fatty acid soap increases. Soap A nonylphenylether=30 : 7010 : 90 have minimum foaming power.
For the direct analysis of cationics in binary or ternary surfactants mixtures, the determination of cationics in the mixtures by “Bromophenol Blue-Dichlorethane” method has been investigated. The anionics standard solution is titrated with the sample solution containing cationics by using Bromophenol blue (BPB) as an indicator. The end point is reached when the indicator shifts from the water to the solvent (DCE) phase. The experimental results with various binary or ternary mixtures showed that ampholytics and nonionics had no influence on the titration by adjusting pH at 9.812, and that cationics in the mixtures could be directly titrated with satisfactory accuracy by “BPB-DCE” method.