π-3H5 Fe (CO)3X (X=Cl, Br, and I) was decomposed with molecular oxygen in several solvents. It was found that the iron atom of the complex was oxidized, and oxygen molecule consequently was reduced and activated in every case regardless of the kind of solvents. The process for the coordination of oxygen molecule to the complex, however, depended much on the nature of solvents : in solvents such as alcohols or acetone, the direct substitution of oxygen molecule with the halogen atom of the complex took place, while in solvents such as dimethyl sulfoxide, the complex was decomposed by the solvent to form π-C3H5 Fe (CO)3, to which oxygen molecule was then coordinated. The resulting activated oxygen oxygenated the allyl ligand or abstracted the hydrogen atom from the substrate.
It was found that triphenylphosphine was catalytically oxidized with molecular oxygen in the presence of π-C3H5Fe (CO) 3Br to form triphenylphosphine oxide. The oxidation reaction included not only the oxidation of the phosphine, but also the oxidative decomposition of π-C3H5Fe (CO) 3Br. In the former reaction, the phosphine was coordinated to the complex by the equimolecular substitution with the carbonyl. The resulting complex, π-C3H5Fe (CO) 2 (PPh3) Br, reacted with oxygen molecule to form the binuclear peroxo complex having oxygen molecule in the form of O22-, which oxidized the phosphine to its oxide. The latter reaction, on the other hand, comprised the activation of molecular oxygen to superoxide ion O2- on the complex. This type of oxygen was considered not to take part in the oxidation of the phosphine, and decompose its dioxygen complex. The oxidation of some other phosphorus compounds, such as P (n-butyl) 3, PCl3 and P (OPh) 3 were also tried using π-C3H5Fe (CO) 3Br as catalyst.
Safflower oil was heated at 200°C with 0.065mol/kg of the following organoiodine compounds : methyl iodide, methylene iodide, iodoform, ethyl iodide, 1, 2-diiodoethane, iodoacetic acid, 3-iodopro pionic acid, and 1-iodopentane. It was found that iodoform, 1, 2-diiodoethane, and iodoacetic acid among those organoiodine compounds used promote conjugation reaction. Moreover, the thermal reaction of safflower oil in the presence of those three iodine compounds was studied under various reaction conditions. The fatty acid compositions of reaction products were determined by means of GLC and UV methods. The results show that other reactinos occur such as the formation of octadecenoic acids, polymerization, and decomposition besides isomerization. Also, it is clarified that 1, 2-diiodoethane promotes isomerization most rapidly and secondly iodoform does. The components formed by side reactions such as decomposition, polymerization, and so on were analyzed by means of GC-MS and GLC method. The presence of ω-phenyl fatty acids and 18- (o-alkylphenyl) C18 fatty acids was confirmed and that of η-alkanes, alkyl iodides, and alkylbenzenes was presumed. The similarity of the substances formed in the thermal reaction with organoiodine compounds mentioned above to those with iodine reported in our previous work suggests that free iodine liberated from organoiodine compounds in the thermal reaction will play mainly the role of catalyst.
The effects of temperature, length of alkyl chain, and counter ion on the interaction between alkyl sulfates and alkylbenzyldimethylammonium chlorides in aqueous solutions have been studied by means of the conductometric method. The equilibrium constants (K) and the standard affinities (-Δμ°) of the reactions between them have been found to decrease with an increase in the temperature, but they increased with an increase in the length of the alkyl chain. The standard heats of reaction (-ΔH°) and the standard entropies (-ΔS°) increased with an increase in the length of the alkyl chain. The equilibrium constants and the thermodynamic parameters of the reactions were appreciably affected by the counter ions of the alkyl sulfates. It is suggested that the reactions between them are dependent on not only the electrostatic interaction between the oppositely-charged organic ions, but also on the interaction between the hydrophobic groups of the surfactants.
Clear melting points of three kinds of monoglyceride, measured by the Mettler automatic melting point apparatus, Model FP-5/FP-51, under various conditions were compared with those measured by the AOCS method. Measurement of Bomer number, used for judging purity of lard, was comparatively examined by the Mettler method and JAS method. Results obtained were as follows : 1) The melting point of powdered monoglyceride by the Mettler method showed a higher value when the heating rate was rapid, and showed a good agreement with that measured by the AOCS method when the heating rate was 0.2 and 1°C/min. The dispersion of measured values tended to become greater with faster heating rate, but the values measured by the Mettler method were smaller than those by the AOCS method, σ being lower than 0.3. 2) The melting point of a sample, which had been aged at 50°C for 120h after solidifying rapidly, by the Mettler method was the same as that of the powdered sample, and the dispersion of measured values was smaller. The melting point, obtained from the melting curves by connecting with a recorder, showed a slightly higher value than the temperature indicated by a digital recorder. 3) The clear melting point of glycerides and fatty acids, prepared for the determination of Bomer number, was measured by the Mettler method. The values obtained for glycerides at the heating rate of 1 and 2°C/min were in approximation with the results obtained by the JAS method, but the values for fatty acids were slightly lower than those by the JAS method. However, the Bomer number calculated from these values was in good approximation with those obtained from the JAS method. Consequently, the Mettler method is simple in procedure and has better reproducibility, and is considered to be fully utilizable in practice.
With four kinds of solid edible fats and fats with different degree of hardening, melting curves were measured by the Mettler automatic melting point apparatus, Model FP-5/FP-51, and clear melting points (MCP) were calculated from the curves. Comparative examination with other methods of measurements was made, especially on the clear point (CP) and the open-capillary melting point (OMP), and the following results were obtained. 1) The observed values of MCP tended to be higher with higher heating rate but the values agreed with those of CP when the heating rate was 0.2 and 1°C/min, and the dispersion of observed values was smaller. Difference between MCP and OMP tended to become smaller as the melting curve at the end of melting became sharper. 2) Melting curve at the end of melting of soybean oil and fish oil, with low degree of hardening, showed a tailing, almost in parallel with the base line, and the difference of MCP from CP and OMP became slightly greater, and the dispersion of observed values was greater. Inversely, in the case of hardened coconut oil, this difference of MCP from CP and OMP, and the dispersion of observed values became greater as the degree of hardening became greater. 3) There was a high correlation between MCP and CP and OMP, and MCP seemed to be sufficiently practicable for use as the melting point of solid fats.
The anti-dandruff and anti-itching effects of zinc pyrithione were investigated in the clinical study in connection with the residual amount of the agent on the hair. The dandruff and the itch decreased significantly by using a zinc pyrithione-containing hair rinse. The residual amount of zinc pyrithione on the hair rose with the increase of the content in a hair rinse. The more the agent remained, the more the antidandruff and anti-itching effects were found. The fact that the shampoo containing 1% of zinc pyrithione had the effects equivalent to the hair rinse containing 0.3% was relevant to its residual amount on hair.