GC-MS analysis permitted the determination of the fatty acid composition of triglycerides with the same carbon number. Then the most useful specific fragment ions are RCO+, and [RCO+128]+. Their intensities, however, are not always proportional to the amount of corresponding fatty acids present. Thirty diacid triglyceride (triglyceride molecules containing two different fatty acids) were synthesized, and investigated about the disproportionality. These samples comprise every possible diacid triglycerides of C8, C10, C12, C14, C16, and C18 saturated straight chain fatty acids. The intensity ratios of RCO+ were compared with the actual content ratio between two constitutive fatty acids. The intensity of RCO+ of longer chain fatty acid was always smaller than that of the shorter ones. This tendency was more significant increasing with the difference of carbon number between two constitutive fatty acids. The apparent intensity of [RCO+128]+ was influenced by [RCO+128+14n]+(n≥1).
Fluorinated surfactants with the general formula of CF3CF2CF2-O-[CF(CF3)CF2-O-]n-2-CF(CF3)-COONa [Rf-n, Rf: hydrophobic group, n: oligomerization degree, n=26] were synthesized from the corresponding hexafluoropropene oxide oligomer. The properties of these surfactant solutions such as surface tensions, Krafft points, foam capacities, and chemical stabilities were measured. With an increase of oligomerization degree cmc decreased and the minimum cmc was obtained for surfactant Rf-5. The secondary cmc was observed for surfactant Rf-4, 5, and 6. Unlike the conventional fluorinated surfactants, the Krafft points of all the present surfactants showed below 0°C. It may be attributed to flexibility of hydrophobic groups containing ether type oxygen and chain branching. The foam capacities of these surfactants were not excellent, but foam stability of surfactant Rf-4 was relatively high. The present surfactants were also stable against acidic and alkaline solutions as well as many other fluorinated surfactants. This investigation indicates that these materials are noted as an excellent surfactants.
The solubilization behavior of a series of dodecyl poly (oxyethylene) ethers (DPOE), C12H25O (CH2CH2O)nH, with oxyethylene units from 5 to 8 toward an oil-soluble dye, Oil Yellow OB, has been studied in relation to the chain length of polyoxyethylene of DPOE, the molecular weight, degree of saponification, and concentration of poly (vinyl alcohol) (PVA), and the temperature in polymer-surfactant mixed solutions. The solubilizing power (Sp) decreases with an increase in the chain length of polyoxyethylene of DPOE and the degree of saponification of PVA, but it increases with an increase in the molecular weight and concentration of partially-saponified PVA, and the temperature. The break points (Cb) in the curves of the amount of solubilized Oil Yellow OB vs. the concentration of DPOE varied in an opposite tendency from Sp. Completely-saponified PVA showed little solubilization effect. The absorption spectra of Oil Yellow OB in the solutions of n-dodecane, polyethylene glycol, and DPOE suggest that the portion of the dye solubilized in the polyoxyethylene region is larger than that in the hydrocarbon region.
2, 4-Dialkylphenols were synthesised by Friedel-Crafts reaction of monoalkylphenols with acyl chlorides, followed by Clemmensen reduction of acylalkylphenols. Dimers were prepared by the condensation of these 2, 4-dialkylphenols with formaldehyde and were allowed to react with ethylene oxide to yield dimeric surface active agents. Then formyl, nitro or amino group was introduced into these products according to the procedure reported in the previous paper. The surface tensions of aqueous solutions of each derivatives were determined and it was found that the surface tensions lowered to about 2936dyn/cm. These derivatives were screened for antimicrobial activity against gram-positive and gram-negative bacilli and fungi. Some of these showed the activity against both bacilli and fungi, but higher oxyethylated derivatives were not inhibitory for any organisms at the concentration tested (400μg/ml).
The autoxidation of Δ3-carene (1), camphene (2), cis-pinane (3), cyclofenchene (4), alloocimene (5), myrcene (6), and dihydromyrcene (7) in the presence of polar aprotic solvents [DMSO, DMF, sulfolane (SF) or ethylene carbonate (EC)] under O2 carrier gas have been investigated of various conditions. The results obtained are as follows: In DMSO, m-methyl acetophenone (10) (product ratio 58%) was obtained as the main product from (1). In DMF, fenchone (17) and pino-campheol (18) were obtained as two main products from (3) at the good selectivity (80% and 82%) among the oxidation products. In SF, camphor (13) was obtained as the main product from (4). In conditions, 2, 6-dimethyl-3, 7-octadien-2-ol (33) and 2, 6-dimethyl-1, 7-octadien-3-ol (34) were obtained as major two products from (7), amounting to 85% and 86% of the oxidation products under different temperatures. In EC, camphenilone (12) was obtained from (2) as the main product with high selectivity (91%). β-Methylcamphenilone (21) (product ratio 86%) was obtained from (4). 5-Isopropyl-2-methyl-2, 4-cyclohexadien-1-ol (25) was obtained from (5) as the main product, amounting to 80% of the oxidation products under the best conditions. Myrcenol (30) was obtained at the high selectivity (86%) in all converted products from (6). 2, 6-Dimethyl-7-octen-3-on (32) and (34) were obtained as two main products from (7) at the high selectivity (87% and 86%) among the oxidation products under different temperatures.
Alkoxyacetic acids and (2-alkoxyethoxy) acetic acids were prepared by the reaction of corresponding sodium alkoxide or 2-alkoxyethoxide with chloroacetic acid, and analyzed by GC using Gaskuropack 54 column. The retention time of these compounds was compared with that of fatty acids, and it was found that the additional one ether linkage for the former series corresponds to the increase of one methylene group for the latter. The MS, IR and 1H-NMR spectra and surface tension of these compounds were measured. The result of the surface tension of solution is summarized by Szyszkowski's equation and Gibbs equation, cross sectional area of a single molecule being 0.440.48nm2/molec, compared with fatty acid 0.30 nm2/molec.
On 237 samples for 17 kinds of crude vegetable oils and refined edible oils from them collected from 21 factories in 1980 and 1981, tocopherols in these oils were measured by high performance liquid chromatography under the same conditions as reported previously. Results obtained were as follows: 1) For crude oils, liquid oils at room temperature generally had a tendency to be higher contents of total tocopherols than solid ones. Also, the content and composition of tocopherols were found rather specific to the kind of oils, showing a slight dispersion among samples for same kind. In most samples, small amounts of β-tocopherol were detected. 2) For refined oils, contents of total tocopherols were generally found 6070% level of those in corresponding kinds of crude oils, while no significant difference of tocopherol compositions was observed between same kinds of refined oils and crude oils. 3) For all samples, a positive significant correlation was observed between the content of total tocopherols and the percentage of polyunsaturated fatty acids (C18:2+C18:3), and rapeseed oils showed that the low erucic type, showing higher percentage of polyunsaturated fatty acids, contained more total tocopherols than the high erucic type. However, sunflower and safflower oils, in which α-tocopherol occupied more than 90% of total tocopherols, contained less total tocopherols than soybean and rapeseed oils, although the former showed higher percentage of polyunsaturated fatty acids than the latter.