The kinetics of the addition of iodine to cyclohexene, 3-methylcyclohexene, and 1-hexene in the liquid phase under the irradiation of light have been studied. The reaction rate was measured by following the decrease in the absorbance at 524 nm due to molecular iodine. It was observed that iodine concentration decreased very slowly in the dark according to the reaction C+I2→C·I2. The kinetic results of photoreaction show the occurence of the reaction C·I+I·→C·I2. In above reactions C·I and C·I2 denote iodine atom-olefin and iodine molecule-olefin charge-transfer complexes, respectively. It is possible to determine kinetically I2-olefin charge-transfer equilibrium constants.
Responses of sterol, fatty acid, sterol ester and triglyceride on a quantitative thin layer chrornato-graphic apparatus which was equipped with a flame ionization detector were determined using with six kinds of neutral lipid mixtures. These responses were represented as relative responses against to tri-glyceride response and converged within maximum error of 5-10% (S.D.) over a range of loads (2-10 μg lipid). All of the relative responses were in proportion to the weight ratio. It was found that the method is very superior and convenient means for the quantitative estimation of neutral lipid compositions.
Disproportionation of methyl abietate by metal complex catalysts was studied. The catalysts used were RhCI (PPh3) 3, PdCl2 (PPh3) 2, PtCl2 (PPh3) 2, Fe (CO) 5, Cr (CO) 5, Fe (acac) 3, Co (acac) 3, Pd/C, and I2. Among these Fe (CO) 5 was the most effective catalyst at 250°C. The effects of reaction temperature and catalyst amount on the product composition were investigated, and it was found that, with 10% Fe (CO) 5 at 250°C, almost all of methyl abietate entered into the reaction in 4 hr affording methyl dehydroabietate (66%) and methyl dihydroabietates (27%). Methyl dihydroabietates were separated by chromatography and their structures were determined by NMR and mass spectrometry. From the relative amounts of two isomers of methyl dihydroabietates, selectivity in hydrogenation was recognized. In the case of I2 catalyst, 13 α- (RtDeAb 0.46) and 13 β-abiet-8-enoate (RtDeAb 0.49) were obtained in 15.0% and 22.2% yield, respectively, while in the case of Fe (CO) 5 catalyst, the yields were 6.0% and 18.1%, respectively. Further, it was found that Fe (CO) 5 was effective for the disproportionation between methyl abietate and methyl linolate.
Methyl β-eleostearate was prepared by usual method from isomerized tung oil, and solutions with three different concentrations, 77.8, 44.9, and 4.5% of methyl β-eleostearate in methyl myristate were prepared. These samples with three different concentrations were heated at a settled temperature which ranged between 250°C to 500°C. As the results, since heat cyclization of methyl β-eleostearate resulted in formation of cyclic monomer and dimer as two main components, it was considerd that the reaction mechanism involved a competitive reaction which formed cyclic monomer and dimer. Moreover, the rate constants and activation energies at each reaction condition from the above mechanism were determined. Next, as the result of maximum conversions to the cyclic monomer from methyl β-eleostearate at each reaction condition were examined, the cyclic monomer was formed readily at a high reaction temperature in a low concentration of methyl β-eleostearate.
A rapid and precise method for the determination of microamounts of arsenic in fats and oils has been studied. The samples were decomposed by wet-digestion procedure using sulfuric acid and hydrogen peroxide (30%), then, arsenic in the decomposed solution were coprecipitated as the complexes with ferric hydroxide. The coprecipitations were reduced to gaseous arsine by zinc in an acid medium, then, arsine gases absorbed into solution of silver diethyldithio carbamate dissolved in pyridine. The absorbance of the arsine reacts solution were measured at about 530 nm. The most suitable pH for the coprecipitation of arsenic was about 9. The proposed method was evaluated with respect to recovery and reproducibility by earring out collaborative studies on the samples which were prepared by adding known amounts of arsenic to soybean oil. The results thus obtained showed good agreement with the theoretical values and satisfactory reproducibility.
Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several carboxylic acids as a catalyst in deuterium oxide. The reaction was carried out in a sealed pyrex tube at 120°C, and the contents of the product were determined by mass spectrometry. The exchange rate catalyzed by acids (DCl, RCO2H : R=CH3, ClCH2, Cl2CH, Cl3C, CF3, Ar) is larger than that by bases (NaOD, NaOAc). At lower acid concentrations, strong acids (DCl, RCO2H : R=CF3, Cl2CH, ClCH2) are more effective than acetic acid, while at higher acid concentrations vice versa. For the acetic acid catalyzed exchange, the rate increases with increasing the initial concentrations of the substrate and acid. For the reaction by the strong acids, the rate increases up to a maximum and then decreases with increasing the acid concentration, higher conversion being observed at higher concentration of the substrare. A possible reaction mechanism is proposed and discussed.
Polyoxyethylene fluoroethers, CF3 (CF2) mCH2O (C2H4O) pH and H (CF2CF2) n CH2O (C2H4O) pH (m=2, 6; n=2, 3, 4; p=3, 5, 10) were prepared by the addition of ethylene oxide (EO) to fluoroalcohols in the presence of a base catalyst and their physicochemical properties-cloud point, surface tension, foaming property, and emulsifying power-weremeasured. The effects of the number of EO moles added and the carbon chain length of starting alcohols onthe surface activities were clarified, and the following results were obtained. 1) Cloud points of aqueous solution of those adducts were found to be higher with an increase in the ni mber of oxyethylene units. 2) Aqueous surface tensions of those adducts decreased with increasing of the carbon chain length of starting alcohols. However, 5 moles EO adducts generally gave the lowest aqueous surface tension in each of the series other than H (CF2CF2) 2CH2O (C2H4O) pH. (p=3, 5, 10). 3) With the exception of ethylene glycol solutions of CF3 (CF2) 6CH2O (C2H4O) pH (p=0, 1, 3, 5, 10), the surface tensions of ethylene glycol solutions of those adducts decreased with increasing of the carbon chain length of starting alcohols and the number of oxyethylene units. 4) CF3 (CF2) 6CH2O (C2H4O) pH (p=5, 10) and H (CF2CF2) 4CH2O (C2H4O) 10H showed a good foaming property. 5) The adducts had strong emulsifying powers toward xylene but weak emulsifying powers toward liquid paraffin.
In this paper, the effect of ethylene glycol (E.G.) on solubilization of NaCI aqueous solution in perchloroethylene solution of Aerosol OT (A. OT) was investigated by means of turbidity method. It was shown that the maximum amount of solubilization of NaCI aqueous solution was less than that of non-NaCI aqueous solution in previous paper. As A. OT concentration was increased, solubilization ratio (S/So) of NaCI aqueous solution was decreased. But the maximum amount of solubilization of NaCl aqueous solution containing E.G increased more than in case of non-E.G. media, and this tendency was more remarkable when E.G. content in this solution increased. From these results, the mechanism of increase of maximum amount of solubilization of NaCI-E.G, aqueous solution was explained by the effect of common ion of Na from A.OT and NaCI in A.OT micell in perchloroethylene.
The fatty acids in the seed oil of Lindera citriodora (Sieb, et Zucc.) Hemsi. were investigated by means of gas chromatography, column chromatography, mass, infrared and nuclear magnetic resonance spectrum. The acids identified were octanoic, decanoic, cis-4-decenoic, undecanoic, dodecanoic, cis-4-dodecenoic, tetradecenoic, cis-4-tetradecenoic, hexadecanoic, hexadecenoic, octadecanoic, oleic, linoleic and eicosenoic acid. The content of cis-4-decenoic, cis-4-dodecenoic and cis-4-tetradecenoic acid obtained from the seed collected in July, decreased compared with that collected in September, but on the contrary the content of decanoic and dodecanoic acid increased.