For identification and determination of 1, 2-epithioalkanes (EPA), total and thiirane sulfur of them were determined. Investigations by GLC, TLC, UV, IR, NMR and GC-MS of EPA were also carried out for the same purpose. The samples employed were 1, 2-epithio derivatives of octane, decane, dodecane, tetradecane, hexadecane and octadecane. The results of GLC with Silicone DC 430 columns were in fair agreement with the data of total sulful content. 1, 2-Epithiohexadecane and 1, 2-epithiooctadecane, however, were degraded during GLC. For such compounds, TLC with silica gel G and petroleum ether was preferable. Determination methed of thiirane sulfur with iodine-acetic acid solution gave unsatisfactory results. Molecular extinction coefficients of EPA were 40.143.2 at λmax 261262 nm in heptane solution. The IR spectra of EPA and 10, 11-epithioundecanoic acid showed four characteristic bands near 681, 646, 622, and 604 cm-1. By the application of these bands, the concentration of EPA in CCl4 solution was able to be determined, even if small amount of α-olefins or 1-thiols was present. The peaks of the protons of methylene and methyne of thiirane ring appeared at 7.75 τ (quartet) and 7.25τ (quintet) in CCl4 solution, respectively. In the mass spectrum of 1, 2-epithiodecane, parent peak did not exist, but M-32 peak due to elimination of sulfur from the compound appeared Base peak was a peak at m/e 41 due to C3H5+ .From the above results, following methods are suitable for the identification and determination of EPA : Combination of GLC and IR for the identification ; combination of GLC and total sulfur content for the determination. For the compounds degraded during GLC, following methods are recomended : Combination of TLC and IR for the identification ; combination of IR and total sulfur content for the determination.
The syntheses of dialkyl N-phosphonophosphoramidates by the reaction of higher dialkyl phosphoramidate with phosphorus pentachloride were investigated. The alkyl groups were amyl, heptyl, hexyl, and octyl. Unfavourably, the cleavage of C-O-P or P-N bonding took place owing to the large amount of hydrogen chloride liberated during the reaction. Therefore, the reaction mixture must be kept at a low temperature such as from 5 to 10°C and the reaction time must be shortened. On the hydrolysis, although two chlorine atoms out of three chlorine atoms combined with the phosphorous atom of the intermediate were released readily, it was difficult to release one remained chlorine completely and to remove the liberated hydrogen chloride from the product completely. It was found that the convenient hydrogen chloride scavenger in this synthesis is propylene oxide. Use of large exess of propylene oxide resulted to form the addition product of propylene oxide. Mono-and di-potassium salts of dialkyl N-phosphonophosphoramidates indicated excellent surface activities to give the lowest value of surface tension in aqueous solutions, as low as 26 dyne/cm. These compounds were found to possess the superior rust-preventive power against mild steel and aluminium in aqueous solutions in the range from pH 3 to 10.
Chlorophosphonation of 1-chloropropane and 1-chlorobutane was carried under condition of the reactant ratio of 1 : 5 of the chloride to PCl3, with oxygen gas flow rate of 200 ml/min at-150°C, for 3 hrs. The reaction products were analyzed by GLC using a 3 m ×3 mm φ column, packed with Ucon LB 550 X, with nitrogen gas carrier. In the case reaction of 1-chloropropane, the products obtained were as follows, 1-chloro-1- (13.7%), 1-chloro-2- (43.6%), 1-chloro-3-dichlorophosphinylpropane (32.7%), and 1-chloro-2-dichlorophosphinyloxypropane (10.0%). In the case reaction of 1-chlorobutane, the products obtained were as follows 1-chloro-1- (7.9%), 1-chloro-2- (17.0%), 1-chloro-3- (38.6%), 1-chloro-4- (23.1%), 3-chloro-1-dichlorophosphi-nylbutane (3.1%), and 1-chloro-2-dichlorophosphinyloxybutane (10.3%). The mechanisms of the formations of dichiorophosphinyloxyalkane and the chlorine-migrated isomers were discussed.
It was found that the low-temperature deterioration of hardened coconut oil series was due to strong adsorption of water on the active surface during crystal growing. It was expected that oxygen would also be adsorbed at the same time and, therefore, experiments were made on the addition of β-carotene which is relatively affected by oxidation. The oils added with β-carotene were stored at 5°, 15° or 30°C for 2 months, there by the A.V., P.O.V. and residual rate of β-carotene were measured. Color tone was examined by the Rovibond method and absorbance was measured at 450 mμ. 1) Coconut oil series stored at 5° or 15°C showed an increase in A.V., accompanied by green coloration but such coloration was not observed in the oil stored at 30°C, and in the control samples of hardened soybean oil and hardened whale oil which were stored at 15°C. 2) Measurement of the amount of β-carotene showed that the residual quantity decreesed in the order of increase in A.V. and green coloration. The decrease was especially marked in hardened palm kernel oil, the residual β-carotene being nil after 2 months of storage at 5° or 15°C. 3) Residual color estimated from absorbance at 450 mμ also showed the same tendency but the residual rate of β-carotene was rather large. It was therefore considered that changes in color were due to the formation of an oxidation intermediate. 4) Colored substance was separated from β-carotene by column chromatography and submitted to thin-layer chromatography. The chromatogram revealed yellow, greenish, orange and bluish green spots, which were considered to be oxidation products, other wise than the spot for β-carotene. 5) Absorption spectra in the visible range were measured with each of the fractions separated by thin-layer cnromatography. The spot at Rf 0.56 had large absorption maxima at 426 and 451 mμ, and a small absorption at 405 mμ. The spot at Rf 0.20 was labile and its spectral measurement could not be made. These spots were considered to be the main components of the green-colored substance.
The electrolytic reduction of 1, 5-cyclooctadiene was carried out in hexamethylphosphoric triamide (HMPA) -ethanol or 1-propanol in the presence of lithium chloride. The relative amounts of cyclooctene and cyclooctane obtained by the electrolytic reduction of cyclooctadiene at constant currents depend on the kind of alcohols and the concentration of HMPA. The investigation on the time change of the electrolytic reduction shows that the conversion increased with time, but the current efficiency increased firstly with time and decreased gradually after passing a maximum, followed by increases in the cathode potential. The experiment with various current densities under the constant total amount of electricity shows that, when the current density was relatively low, it scarcely affected the conversion, the selectivity, and the current efficiency. The use of 1-propanol afforded high amount of cyclooctene than that of ethanol, probably owing to its lower acidity. The selective reduction of 1, 5-cyclooctadiene into cyclooctene was performed nearly perfect by adopting the conditions of lower concentration of the proton donor with relatively low acidity, and of the higher current density.