Thermal reaction of safflower oil in the presence of manganese iodide was investigated under the following reaction conditions : 0.065 mol/kg, 220°C, 0.13 mol/kg, 220°C; 0.26 mol/kg, 200°C ; 0.26 mol/ kg, 220°C. The fatty acid compositions of reaction products were determined by means of GLC and UV methods. Conjugated dienes formed but monoenoic acid did not increase during the reaction. When safflower oil was heated in the presence of manganese iodide 0.26 mol/kg, at 220°Cfor 3h, remarkable amounts of residue were formed which contained mainly polymerization products, ca. 1.6% decomposition products and ca. 3.9% manganese soap. The GPC analysis of the polymerization product showed that it was composed of dimers, trimers, tetramers, and higher oligomers of fatty acids.
The Krafft points of some zwitter ionic or amphoteric surfactants have been measured in the presence and absence of inorganic salts. The zwitter ionic surfactants can be classified into two groups with respect to the Krafft point change upon the addition of salts. The Kraff t points of the surfactants in group I are depressed by added salts, whereas the surfactants in group II are not salted-in. It is found from the molecular structure of the zwitter ionic surfactants classified into group I and II that the distance between positive and negative charge of the surfactant molecule is the governing factor to distinguish between the salting-in type and the salting-out type of the surfactant. The zwitter ionic surfactants with the charge-charge distance longer than 0.40.5 nm may be salted-in, probably because the ions of the added salt can enter into the interior of the zwitter ions of the surfactant and interact electrostatically with them at the surface of the micelles.
Poly (ethylene glycol) (PEG) has widely been used as a nonionic surfactant for dispersion, solubilination, and dehydration of protein or lipid. Recently, PEG is used fordfsf purification or concentration of biological substances such as viral suspenlion. Sensitive method is required for the measurement of PEG in the presence of impurities since the biological substances are usually contained large amounts of proteins or lipids. By Stevenson's method which is widely used for the measurement of PEG, it was difficult to measure the PEG in the presence of protein or lipid because nonspecific color development occurred by impurities. In this paper, we determined the substances which caused the nonspecific color development and found the procedure which removed them from samples. We described also more sensitive procedure for the measurement of PEG by the modification of concentration of chemical reagents which are used in Stevenson's method.
2-Alkylcyclopentanones (4) were synthesized from cyclopentene oxide by the procedure described in Scheme-5. cis-1-Alkyl-2-chlorocyclopentanols (3) were produced selectively by the reaction of 2-chlorocyclopentanone (2) with various Grignard reagents. The reaction of (3) (alkyl group used ; -C6H13, -C5H11, -C4H9, -C3H7, -isoC3H, ) with aqueous alkali metal hydroxide (LiOH, NaOH, KOH, CsOH) was kinetically investigated. Rate constants (l·mol-1·h-1) for the reaction in aqueous KOH were 0.0197 (-C6H13), 0.0695 (-C5H11), 0.248 (-C4H9), 0.993 (-C3H7), and 0.398 (-isoC3H7), respectively. Apparent activation energies (2326 kcal·mol-1) varied depending an alkyl group. Compounds (4) were prepared in high yields from compounds (3). Either by the addition of dimethyl sulfoxide to aqueous alkali metal hydroxide or by the use of aqueous AgNO3 instead of alkali metal hydroxide, this reaction was accelerated remarkably without a significant change in apparent activation energies. These results suggest that the deprotonation from hydroxyl group of (3) is the first step to produce (4) from (3).
A method is described for the determination of ferulate in rice bran oils by high performance liquid chromatography using a detector set at 315 nm which is an absorption maximum of ferulate. Previously reported wave length of the detector was 254 nm. The sensitivity of response for cholesteryl ferulate at 315 nm was 1.7 times higher than the sensitivity for it at 254 nm. Operating conditions were Zipax-BOP column and the mixture of hexane and diethyl ether (85 : 15 vol/vol) as a mobile phase. Cholesteryl ferulate was used as an external standard. Though components of ferulate were not still separated from each other, newly presented method is useful for the determination of the ferulate contents in refined rice bran oils.
Esterified tocopherols and tocotrienols in rice bran oil, soybean oil, and sesame oil were separated from free tocopherols and tocotrienols by TLC. After saponif ication of the esters, free tocopherols and tocotrienols were determined by high performance liquid chromatography. Refined rice bran oil contained 40μg/g of α-tocopherol, 3μg/g of, β-tocopherol, 3μg/g of γ-tocopherol and 5μg/g of γ-tocotrienol, Refined soybean oil also contained 3μg/g of γ-tocopherol and 3μg/g of δ-tocopherol, α-Tocopherol (7 μg/g) occurred as an esterif ied form in commercial sesame oil.