Determination of total aromatic content in lubricating oil stocks by infrared absorption method was investigated. The following conclusions were obtained from the experimental results. 1) Four representative lubricating oil stocks A, B, C and D were separated into two main components, saturated hydrocarbons and aromatic hydrocarbons respectively by silica gel adsorption chromatography. Standard samples containing 1050wt% aromatics were prepared by adding aromatic hydrocarbons to saturated hydrocarbons obtained in chromatography. Linear calibration curves were obtained from the aromatic contents and the infrared absorbances at near 1, 613cm-1 of standard samples. And also, it was found that there are linear correlation between molecular weight of samples and gradient of their calibration curves. 2) Total aromatic contents in various lubricating oil stocks produced at the refinery in this country and foreign country from same crude oil were determined by chromatographic method and infrared absorption method. As a result, analytical values from these method agreeded with one another within ±3% by relative error. 3) As this procedure is simple and rapid (10min/one sample), this is considered as a very useful method for routine analysis.
It is advisable to use natural antioxidative substances instead of synthetic antioxidants for foodstuff. In the previous reports the authors dealt that the unsaponifiable matter obtained from the deodorizer sludge of soybean oil had an inhibiting effect against the autoxidation of partially hydrogenated or thermally polymerized whale oils. There are several reports which dealt the presence of antioxidative substances except tocopherols in the sludge unsaponifiable. Some of these substances are assumed to have the structures similar to those of tocopherols. However, their structures and properties have not yet been fully studied because of the difficulty of their isolation. In this paper, the concentration of these antioxidative substances from the unsaponifiable matter of the deodorizer sludge of soybean oil through silicagel column was investigated. Three antioxidative substances, one of them was new, were isolated from the concentrates by preparative thin layer chromatography. From the results of UV, IR, Mass and NMR spectra of these substances, it was found that these three antioxidative compounds were tocopherol dimers. The A.O.M. stabilities of partially hydrogenated whale oils containing the mixture of these tocopherol dimers or tocopherols were also determined. As a result it was observed that the mixture of tocopherol dimers had a strong inhibiting effect against the autoxidation of partially hydrogenated whale oil, although the potency was rather lower than that of the mixture of tocopherols.
The synthesis and reduction of acyloins, both symmetrical and mixed, were studied. A series of C8C36 symmetrical and mixed acyloins could be obtained by the condensation of methyl esters of fatty acids under presence of metallic sodium dispersion in inert solvent such as xylene. From mass spectra of the mixed acyloins obtained above, it was found that the reaction of different kinds of fatty esters usually gave the mixed acyloin, in which the long chain had a carbonyl radical and the short chain contained a hydroxyl group. For example methyl butyrate and methyl caprinate reacted as follows : These acyloins were reduced to the corresponding unsymmetrical ketone by the Clemmensen method. In this reduction the hydroxyl group changed into methylene group leaving the carbonyl group unreacted as shown in the following example : The yields were 94%. The Clemmensen reduction of long chain ketone didn't give the corresponding hydrocarbons, while Wolff-Kishner reduction gave hydrocarbon in rather good yields.
The reaction of 1-olefins with N-halo-N-tert-butyl and N-cyclohexyl-ethanesulfonamide was investigated. In this reaction, allylic hydrogen abstraction occurred and monohalogenated olefin was obtained in high yield, and no 1 : 1 adducts were formed because of the steric effect of N-tert-butyl or N-cyclohexyl group. Especially N-chloro derivative of N-tert-butyl or N-cyclohexylethanesulfonamide was effective for the allylic chlorinating reagent. The reaction of N-haloethanesulfonamide with excess of 1-olefin at 130°C in the presence of BPO was suitable to proceed allylic halogenation in high yield. The isomer ratio of 1-halo-2-olefin to 3-halo-1-olefin was determined, and its isomer ratio decreased with the increase of alkyl chain length of 1-olefin. The larger amounts of 1-halo-2-olefin was formed in the reaction of N-bromo-N-tert-butylethanesulfonamide with 1-olefin than that in the reaction of N-chloro-N-tert-butylethanesulfonamide.
Commercial α-olefins, used as a raw material for α-olefin sulfonates (AOS) which are new and promising active ingredient of synthetic detergents, may be furnished by thermal cracking of petroleum wax and Ziegler's ethylene polymerization. α-Olefins obtained from wax cracking contain impurities which give so intensively colored products that bleaching is required, in the sulfonation process with gaseous sulfur trioxide. An effective treatment was attained for removing impurities from the α-olefin feed by mixing with urea to form adduct followed by the separation from the impurities. The separated impurities were identified by chromatography as cyclic compounds composed of more than 140 components. When the cyclic compounds were treated with sulfuric acid, an intensive coloration was observed. As an another procedure for removing these impurities, the treatment with Friedel-Crafts catalyst such as anhydrous ferric chloride or boron trifluoride, was also promising.
In the previous paper, author reported on the constituents of the seed of kobushi (Magnolia kobus DC.), but there is no report on the constituents of the seed of tamushiba (Magnolia salicifolia Maxim.), which is the same family plant of kobushi, and which grows wild in all areas of Japan. In this report the author made clear the compositional difference between the two seeds. As a result, it was found that the constituents of the seed of tamushiba are similar to those of kobushi in their fatty acids, unsaponifiable matter, alkaloid, and lignan parts. However, a difference was observed in the essential oil.
Pour point reversions of various lubricating oils containing one of three different type pour point depressants (naphthalene-chlorinated paraffin condensation product, phenol-chlorinated paraffin condensation product and polyalkylmethacrylate) were measured by sudden cooling-heating cycle method and Federal test method. In the former test any pour point reversion was not recognized, but in the latter test a 2.57.5°C range of the pour point reversions was observed in all cases. Polyalkylmethacrylate gave the most effective pour point depressions and the most stable pour point reversions among the additives.
Chlorophosphonation of decane was carried out. After esterification of the product with ethanol the compositions were analyzed by GLC (PEG 6000, 200°C, N2 gas carrier), in comparison with authentic samples synthesized by other methods. The esterified product under conditions; 1 : 5 for the mol ratio of decane to PCl3, 200ml/min of the oxygen flow rate, -20 to 10°C for the temperature, and 5hrs for the time; was a mixture of 4.6% diethyl decane-1-, 16.8% diethyl decane-2-, 24.4% diethyl decane-3-, 29.4% diethyl decane-4-, and 24.6% diethyl decane-5-phosphonate, by GLC analysis.