The measurement of carbonyl value by 2, 4-dinitrophenylhydrazine (in alkaline solution) is generally practiced for the estimation of an oxidative stage of oil processing. This paper deals the estimation method of carbonyl compounds. 1) In the case of measurement of the total carbonyl value of an oxidized oil, an approximate value can be obtained by reading the extinction only at 440mμ and calculation is as follows; Total carbonyl value (m eq/kg) =E/0.584×W ×103 E : Extinction at 440mμ W : Weight of oil (mg) 2) When this method was applied to the high peroxide oil, the carbonyl value was biased to be overestimated. The peroxide may have a substantial influence on the carbonyl value, probably because hydroperoxide reacts with 2, 4-DNPH. 3) It is undesirable to dilute the sample with solvent after color developing, because there occurs the shift of absorption maximum and the subsequent change of extinction. 4) Some of carbonyl radicals that exist in oxidized glyceride molecules seem to be difficult to react with 2, 4-DNPH rather than hydroxylamine or hydrazine. 5) What ever kind of unit is applied as the total carbonyl value, it is reasonable to understand that the number obtained is not an accurate value of carbonyl contents, but a tentative measure indicating an oxidative stage of oil.
In the previous paper, authors reported that the antarctic sei whale blubber oil comprizes more than 45 fatty acids including minor constituents, some were not yet reported, such as polyunsaturated odd-numbered fatty acids (17 : 4, 19 : 5 and 21 : 5) and several branched-chain fatty acids. In the present investigation, a quantitative comparison was made by gas-liquid chromatography (GLC) of the fatty acid composition of the blubber, bone, and visceral oils from the antarctic fin whale, blue whale and sei whale. Each oil was converted directly into methyl esters by alkali-catalyzed methanolysis, then the resulting crude methyl esters were purified by preparative silica gel thin-layer chromatography, and the refined methyl esters were analyzed by GLC using hydrogen flame ionization detector as previously reported. The composition of these methyl esters was determined for the major constituents (about 30 fatty acids) by triangulation. As for the whales used in the present study, it was observed that the oil of sei whale was significantly different from those of fin and blue whales in the fatty acid composition, and that, in general, visceral oils contained more amounts of 20 : 5 and 22 : 6, and less quantities of monoenoic acids as contrasted with blubber or bone oils.
Hydroxycitric lactone was synthesized by the oxidation of trans-tri-methylaconitate with potassium permanganate, and the structures were presumed by means of infrared spectra and N. M. R. spectra. The lactone acid was added in cottonseed and soybean oils and the stabilizing effect to the oils was evaluated by the A. O. M. and oven tests (at 63°C). The A. O. M. data showed the effect of lactone acid to the oils as approximately equal in effectiveness of citric acid, but the oven test data was better than citric aicd.
In the previous paper, authors stated that there occurred the side reaction which is considered to be due to polymerisation of glycidol in the synthesis of glycerine by epichlorohydrin hydrolysis with sodium hydroxide, which makes it possible to consider to elevate the yield of glycerine by pH control of alkali solution, because hydroxide ion concentration has an important effect on polymerisation of glycidol. In this paper, the relation between pH of alkali solution and the yield of glycerine is studied, and it is found that the higher the pH, the lower the yield is as far as pH is more than 11.5, and the yield reaches more than 90% with pH less than 11.5. Moreover, the by-product in epichlorohydrin hydrolysis with strong alkali solution showed the same IR spectrum as polyglycidol. Therefore, it is concluded that our assumption-polymerisation of glycidol decreases the yield of glycerine-is correct.
1, 3-Butylene glycol diesters were synthesized and investigated as a plasticizer for PVC. 1) Following four type diesters were prepared : (a) esterified with fatty acid for pri-OH and with benzoic acid for sec-OH, (b) esterified with benzoic acid for pri-OH and with fatty acid for sec-OH, (c) esterified with fatty acid for pri-and sec-OH, (d) esterified with benzoic acid for pri-and sec- OH (fatty acid : C6C14) 2) Most of diesters showed a good compatibility and gave a elastic sheet except some long chain derivatives of (c) group, and for (c) group it seems that the total carbon number of two acyl groups must be less than 20. 3) Physical properties of prepared PVC sheets showed same or better properties than DOP-sheet. (a), (b) and (c) had favorable characteristic at low temperature (brittling temperature : -20-62°C; DOP : -22°C) and especially some of (c) had good thermal resistance.
The authors have studied about the properties and compositions of the above mentioned fish oils, and the results obtained were briefly given as follows : Both mugil and sciana schegellii fatty acids were composed of C12-C20 (chiefly C16, C14) saturated and C12-C20 (chiefly C16, C18) unsaturated fatty acids. Unsaponifiable matter had the following properties : mp (°C) I.V. Color Mugil body oil 107.0-123.3 79.8 Yellowish brown Mugil internal organs 110.6-116.5 116.5 Yellowish brown Sciana body oil 109.0-116.2 142.4 Yellowish red