Iodine catalysed disproportionation reactions between abietic acid and linolic acid have been studied. When the mixture of equimolecular amounts of abietic acid and linolic acid was treated with iodine (2mol% of abietic acid used) at 220°C, hydrogens were transferred from abietic acid to linolic acid to give dehydroabietic acid and octadecenoic acid mainly. The mixture of equimolecular amounts of abietic acid and conjugated linolic acid also gave the same products as well as the former in better yield. The ratios of homo-molecular reaction to hetero-molecular reaction were evaluated by the amounts of product in each reaction to give 1 : 4 in the former and 1 : 10 in the latter. Further dehydrogenation of abietic acid and hydrogenaton of linolic acid were investigated in detail. When equimolecular amount of iodine was added to abietic acid in the presence of water, the abietic acid changed into dehydroabietic acids in 89% by mole and the iodine was recovered as hydrogen iodide in 90% by mole. It was suggested that iodine catalysed disproportionation reaction between abietic acid and linolic acid consisted of the conjugation of linolic acid, the dehydrogenation of abietic acid, and the hydrogenation of conjugated linolic acid with hydrogen iodide formed in the reaction.
Soybean and hydrogenated soybean oils were treated by the water spraying and heating system as a model of deep fat frying in the presence or the absence of air. In the presence of air, the acid value of hydrogenated soybean oil increased very much as compared with that of soybean oil, but in the absence of air, the two oils showed almost the same increase of acid value (Fig.-1). These results give a suggestion that some factors to promote the hydrolysis were formed in the hydrogenated soybean oil by thermal oxidation. When these oils were thermally oxidized by bubbling dry air at 180°C, it was also recognized that increase of acid value in hydrogenated soybean oil was obviously greater than that in soybean oil (Table-4). The fact that saturated fatty acid esters are apt to produce acidic substances by thermal oxidation was further confirmed by the thermal oxidation of various fatty acid esters (Table-6, 7). Consequently, the reason why hydrogenated or saturated fats are very sensitive to the hydrolysis during deep fat frying, probably depends on a process that acidic substances which produced in these fats by thermal oxidation promote their hydrolysis in the presence of water.
Mass spectra of methyl α- and β-eleostearates were measured. Both spectra show that the relative intensity of fragment ions at m/e=91, 93 and 107 is much higher in comparison with that in mass spectrum of methyl linolenate in reference. It is observed that there is a slight difference in the mass spectra of α- and β-eleostearates and this is probably attributable to the difference of the geometrical configuration at 9-position. Further, the relation between electron accelerating voltage and the variation of relative intensity of predominant fragment ions in the mass spectra of both eleostearates was discussed.
Antioxidation activities of 15 amino acids and their benzyl esters (ethyl esters in the case of methionine and tryptophan) on the oxidation of lard or of lard containing natural tocopherol mixture (M-Toc), were examined by means of active oxygen method. All amino acid esters retarded the oxidation of lard containing M-Toc and especially the effects of esters of methionine, lysine, histidine and tryptophan were remarkable, whereas only methionine, phenylalanine, proline and tryptophan among the amino acids examined were fairly effective. Amino acids and their esters themselves, however, showed no antioxidative activities. It was recognized that sodium hydroxide which is strong inorganic base had an intense synergistic effect on M-Toc under conditions without water in this examination, as an incidental result.
By using polyoxyethylene nonylphenyl ethers as the stationary phase, the retention volume of some hydrocarbons was measured at varying temperature by gaschromatography. The activity coefficient and the excess thermodynamic functions of hydrocarbons were calculated from the retention values obtained. The results were available to interpret the interaction between hydrocarbons and polyoxyethylene nonylphenyl ethers on thermodynamic basis.
Tertiary ether amines were prepared and their surface active properties were discussed. The tertiary ether amines were synthesised as follows. N, N-di (alcoxy ethyl) ethanol amine (I) was prepared by N-alkylation of monoethanolamine with 1-chloro-polyoxaalkane. Tri-alcoxy ethyl amine (II) having the three same chaines of alcoxy ethyl group was prepared by the reaction of 1-chloropolyoxaalkane with the alcoholate of (I). Surface tension, foaming property, wetting, dispersing and emulsifying power of the aqueous and acidic solution of these tertiary amines were determined. It was observed that the aqueous solutions of the amines had very low foaming, good wetting and dispersing power.