The characteristic absorption bonds of free water, structural water and unsymmetrically hydrogen bonded water were recorded in the range from 5, 040 to 5, 360cm-1 for dissolved water in methyldecanoate (172, 455ppm) and safflower oil (301, 780ppm). The sum of the intensities of three characteristic absorption bonds increased in proportion to the amount of dissolved water determined by the Karl Fisher method in methyldecanoate and safflower oil. Each intensity increased in proportion to the amount of dissolved water in the range from 364 to 2, 455ppm in methyldecanoate and from 30 to 1, 780ppm in safflower oil. In methyldecanoate the dissolved water was almost in the form of unsymmetrically hydrogen bonded water from 17 to 53ppm, but was 67% structural water at 176ppm. In the case of safflower oil, the dissolved water from 30 to 64ppm contained about 10% of the unsymmetrically hydrogen bonded water. These findings may be explained on the basis of the steric hindrance of the molecular structure.
Alkyloxy- and alkylthiomethyleneiminium salts were derived from dimethylformamide (DMF) or N, N, N', N'-tetramethylurea (TMU). The reaction of each iminium salt with methanol gave methoxymethyleneiminium salts. The reaction of benzyloxymethyleneiminium salts (2) with hydrogen chloride, thiophenol, and aniline in the presence of pyridine gave benzylchloride, benzylphenylsulfide, and N-benzylaniline, respectively. The reaction of sodium benzyloxide with (8) and (10) gave dibenzyl ether and benzyl methyl sulfide, respectively. The iminium salts (12) derived from TMU was used for the esterification of sterically hindered alcohols and carboxylic acids.
Polyoxyethylene (POE) fatty acid ester (1), POE glycerol fatty acid ester (2), POE hardened castor oil (3) and POE sorbitan fatty acid ester (4), all classsifyable as POE ester type nonionic surfactants, show similar IR and NMR spectra. For this reason, identification of these surfactants by means of spectroscopy has been difficult. But, from a detailed analysis of the NMR spectar of these nonionics, it was found that each has a characteristic signal specific for its structure. From the study of 1H-NMR, (3) was identified by the appearance of signals at 4.9 and 1.5ppm along with those of the alkyl, POE, and the ester groups. Similarly, (4) was identified by the signals at 4.5 and 4.7ppm. (1) and (2) could not be identified by 1H-NMR measurements since they have no characteristic signal. But by 13C-NMR spectroscopy, (1) and (2) were identified. The appearance of a signal at 78.9ppm indicates that the spectrum belongs to (2) and its disappearance to (1). These data show that either 1H-NMR or 13C-NMR spectroscopy is effective for identifying POE ester type nonionic surfactants.
The binary phase diagrams of certain diglycerol alkyl ethers (DGE) and water systems were determined and the solution behavior of these surfactants was studied. These surfactants form liquid crystalline phases with lamellar structures even at low concentrations at which ordinary nonionic surfactants with ethylene oxide chain give micellar solution. Aqueous solutions of 1% to 2% of DGE showed coloration which changed according to surfactant concentration. Furthermore, the color of these solutions observed by reflected light differed from that observed by transmitted light. On the basis of the phase diagram study and scanning electron micrographic determination, the structure of these colored solutions was concluded to be a dispersion of multi-lamellar liquid crystals containing large amounts of water within the interlayers. The coloration was thus considered to arise from the interference of light reflected at the interface of lamellar layers whose thickness was comparable to that of the wave length of visible light.
Refined commercially available vegetable oils (soybean, corn, rapeseed and rice bran oils) were heated in glass tubes for AOM test at 200°C for 30h (6h/d), and the changes in the unsaponifiables and desmethylsterol content in these oils were investigated. Individual sterol groups were separated as 4-desmethylsterol, 4-monomethylsterol and 4, 4'-dimethylsterol by TLC, and their components were determined by GLC. The percentage of unsaponifiable matter in the oils was fairly constant during heating, but that of 4-desmethylsterol decreased considerably. In general, the percentage of sitosterol in the 4-desmethylsterol, cycloeucalenol in the 4-monomethylsterol and β-amyrin in the 4, 4'-dimethylsterol, increased with heating. However, the percentage of campesterol and stigmasterol in the 4-desmethylsterol as well as that of obtusifoliol and citrostadienol in the 4-monomethylsterol decreased steadily.
Optically active thiomalic acid and N, N'-dimethylcystine were synthesized by a reaction of thioacetic acid with fumarylbis [(2S) -2-prolinanilide] (1) and (6S) -4-methyl-3-methylene-2, 5-dioxo-1, 4-azabicyclo [4.3.0] nonane (2), respectively.
Three color reactions for detecting tung oil, a maleic anhydride reaction (Reaction with maleic anhydride in chloroform), the Storch & Morawsky reaction (Reaction with sulfuric acid in acetic anhydride) and an antimony trichloride reaction (Reaction with 10% antimony trichloride-chloroform solution) were examined for the detection of tung oil. These reactions were applied to various vegetable oils present with tung oil as a mixture and to oils containing conjugated trienoic fatty acids prepared from linseed oil. The maleic anhydride reaction was observed to be stable with no change in the specific yellow color following the reaction period. However, this reaction was not suitable for deep colored oils. The Storch & Morawsky reaction soon showed a strong purplish red color which changed to a different color after 2030 s. The color resulting from the antimony trichloride reaction was very deep, but nearly 1h was required for this reaction to sufficiently take place. These reactions can be used to detect tung oil when present at a 5% concentration in vegetable oils. The color noted deeping the course of the above reactions was due to the presence of conjugated trienoic fatty acids in tung oil. Thus conjugated fatty acids prepared from linseed oil showed the same color reaction as tung oil. In the case of oil mixtures containing more than 5% tung oil, the above simple reactions should be used for tung oil detection instead of the rather complicated methods of gaschromatography or ultraviolet spectrophotometry. However, care must be taken since other oils containing conjugated trienoic fatty acids will show the same color reaction.