The catalytic addition reaction of maleic anhydride to castor fatty acids or their methyl esters by flow method was investigated. It is found that the synthetic silica-alumina composed of 70% of SiO2 and 29% of Al2O3 has high catalytic activity for the addition reaction of maleic anhydride to castor fatty acid methyl esters and that the addition to castor fatty acids is also easily carrieds out by continuously passing the mixed solution of maleic anhydride and castor fatty acids over a catalyst having phosphoric acid deposited on the silica-alumina as a carrier. The adduct separated by column chromatography was known to be predominantly consisted of the fatty acids and maleic anhydride at a proportion of 1 : 1 and to have a cyclohexene ring structure by IR, NMR, and MS spectral analysis. Then, the addition reaction was considered to be based on the Diels-Alder addition reaction of maleic anhydride to conjugated octadecadienoic acids produced with the dehydration of ricinoleic acid by the catalyst.
The effect of aromatic hydroxycarboxylic acids as antioxidant and the influence of the metallic ion (Fe (II)) on the dissolved oxygen in O/W type emulsion was investigated by a polarographic Beckman Oxygen Analyzer, Model 777. Soybean oils with different POV (peroxide value) and water were emulsified into O/W type emulsion using Tween-40 as the emulsifier, and the variation of dissolved oxygen was measured in the presence of the Fe (II) ion. In order to evaluate the effect of aromatic hydroxycarboxylic acids, an acid solution was added to the emulsion, then, the metallic solution was added to the same emulsion, and the variation in the dissolved oxygen was measured. The results of these measurements revealed that the oxygen absorption increased in the presence of Fe (II) and, that the deteriorating effect was suppressed by the addition of these acids. When comparing the stabilizing effect of 2-hydroxybenzoic 2, 4-and 2, 6-dihydroxybenzoic acids with those of 2, 5-, 3, 4-, 3, 5-dihydroxybenzoic and gallic acids, the former are seen to function as the chelating agent, the latter are clearly seen to function as the radical inhibitor.
Autoxidized oils including peroxide have been generally known to cause certain diseases in animals. It has been also known that the erythrocytes of vitamin E deficient animals easily hemolyze in the presence of hydrogen peroxide or dilauric acid in vitro due to the peroxidation of lipids in thier membranes. However, very few observations have been reported whether the erythrocytes of rats hemolyze or not when autoxidized oil is given orally. In the present paper, the authors examined the relation between the H2O2-induced hemolysis of the erythrocytes and the vitamin E contents of the sera of the rats fed on autoxidized methyl linoleate (AOML) or a mixture of AOML and vitamin E. The diet shown in Table-2 was given to rats in each experimental group for 7 days, respectively. The following results were obtained; 1. The hemolysis of the erythrocytes in the rats fed on methyl linoleate appeared more frequently than in the rats fed on the basal diet. 2. Higher hemolysis was observed in the erythrocytes of the rats fed on AOML than in those of the rats fed on methyl linoleate. 3. Any hemolysis of the erythrocytes was hardly observed in the rats fed on the additional vitamin E with the basal diet containing methyl linoleate (fresh or autoxidized). 4. The serum vitamin E content of the rat in the AOML group was the lowest of all the groups tested. From these results, the authors presumed that the hemolysis of the erythrocytes of the rats fed on AOML might be caused by the following process; Some digestible and absorbable components from AOML decreased in vivo serum vitamin E content below a level susceptable of vitamin E deficiency.
N, N'-Bis (1-carboxyalkyl) alkanediamine (BDAC) was prepared by reaction of methyl ester of 2-bromofatty acid with 1, 2-ethylenediamine or 1, 4-tetramethylenediamine, where fatty acids used are lauric, palmitic, and myristic acids. The pH titration curves of BDAC were measured to determine cationic, zwitter ionic or anionic region of them. BDAC was employed as a chelating agent and heavy metallic ions such as Cu (II), Pb (II), Ca (II), and Cr (VI) were extracted from aqueous solution of pH 212 into isobutyl methyl ketone (IBMK) as BDAC-complex. The effects of pH of the solution, alkyl chain length and methylene numbers of alkanediamine on the extraction were determined by atomic absorption spectrophotometry. BDAC was found to have good chelating propertiy with respect to Cu (II) and Pb (II) in the pH range of 1012.
Nineteen samples of rapeseed were examined : 10 samples from Canada including 4 varieties of zero-erucic type, 6 samples in Japan, and other 3 samples from Formosa, France, and West Germany. The species identification for 7 samples of which species were obscure, was carried out by cultivation test and chromosome numbers. Properties of the seed samples were investigated, and physical and chemical constants of the oils extracted from them with n-hexane were determined. The fatty acid composition of the oils was determined by GLC. The results obtained are briefly summarized below. 1. The seeds of Brassica campestris except R·500 variety are generally reddish brown, whereas the seeds of Brassica napus are dark brown. The seed size is smaller for B. campestris except R·500 variety than for B. napus. On an average, the oil content of B. napus seeds is higher than that of B. campestris by about 3%. 2. The oil samples from both B. campestris and B. napus show some differences in their characteristics and in their fatty acid compositions. Comparing the ordinary rapeseed oil samples excluding low or zero erucic acid (Nos. 57 and 1719), however, the mean values of characteristics and major component fatty acids of B. campestris oils are found close to the corresponding values of B. napus oils. 3. Among the correlation coefficients between major component fatty acid pairs calculated from the data on all sample oils, the largest in absolute value is for erucic and oleic acids pair, -0.983. The following regression equation is given : Erucic acid %=-1.141 (oleic acid %) +61.59
In order to find the exact characteristics of cacao butter with regard to its purity judgment, general properties, especially chemical composition, fats extracted from 22 kinds of cacao beans and 20 kinds of cacao butter products were analyzed, and the following results were obtained. 1) In total fatty acid composition, the main components were C16, C18, and C18 : 1 acids, being present in 27, 34, and 35%, respectively. This composition is rather rare among other vegetable fats. 2) The total number of carbons in the acyl chains of the triglyceride was almost 50, 52, and 54, whereas it's distribution among samples was relatively similar, being approximately 18, 52 and 30%, respectively. 3) In the extracted fats, fatty acid composition in 2-position was C18 : 1 in more than 80%, and unsaturated fatty acids in more than 90% whereas saturated acids consisted of a small amount of C16 and C18 acids. Some products, however, clearly contained a larger amount of saturated acids and a smaller amount of C18 : 1 acid. 4) Sterol composition of the extracted fats showed a slight variation according to the locality of production but generally contained campesterol, stigmasterol, and sitosterol in approximately 1 : 4 : 9 ratio. Presence of a large amount of stigmasterol is the prominent feature of cacao butter and this is not found in other vegetable fats. It was also found that there was a definite negative correlation in the composition ratio of stigmasterol and sitosterol. 5) As an index for the judgement of purity of cacao butter, ratios of C16/C18, stigmasterol/campesterol, a few others were examined, and it was found that the factor based on the distribution of the total number of carbons in the acyl chains of the triglyceride showed little scatter and was found to be useful.
Thirteen lanthanoide shift reagents [Ln (DPM) 3, Ln (FOD) 3, Ln (PTA) 3, Ln (TBC) 3 and Ln (TFC) 3; Ln=Eu, Yb, Pr, Ho or Dy] in 1H-NMR spectroscopy were evaluated with regard to solubility, interference of the t-butyl signal of the ligands, line broadening effects, and shift strength relative to Eu (DPM) 3 reagent, using cholestanol and its oxo, acetoxy, and methyl ether derivatives as substrates. From the data obtained, it was concluded that Eu (FOD) 3 as well as Eu (DPM) 3 and Pr (FOD) 3 are the most satisfactory shift reagents, giving sizeable downfield and upfield shifts, respectively. Yb (FOD) 3 and Ho (FOD) 3 were also superior downfield and upfield shift reagents, respectively, in co-ordinating more effectively with weak Lewis bases such as ether, though the line broadening effect was somewhat serious. The complexing ability of the substrates with the shift reagents decreased in the order : alcohol >ketone>ester>ether.