When polyunsaturated fatty acids are heated, cyclization occurs as well as decomposition and polymerization. J.A. MacDonald, R.B. Hutchson and J.C. Alexander et al. have reported that cyclic monomers from heated linseed oil contain cyclohexadiene compounds. N. Matsuo informed the presence of cyclohexadiene compounds as main components and ortho-substituted aromatic compounds in heated ethyl β-eleostearate. One double bond in polyunsaturated straight chain monomer disappears in intramolecular cyclization as a matter of course. But it is very interesting that aromatic compounds are present in the heated trienoic acid. In this paper, cyclic monomers were prepared from linseed oil under the condition of 295°C, 15min. in stainless autoclave with alkaline catalyst. Heated linseed oil fatty acid sodium salt was acidified and methyl esterified by the usual method, thus cyclic monomers were obtained by urea adduct separation. Nextly, the cyclic monomers were heated in 25ml ampoules under various conditions. These samples were analyzed by GLC, IR, and colorimetry of cyclohexadiene ring, etc. As a result, cyclohexadiene compounds gradually decreased, with inverse increase in the aromatic and cyclohexene compounds. The mechanism of formation of aromatic compounds in the cyclic monomers was explained by disproportionation reaction.
Reaction of vinylmagnesium chloride with aliphatic carboxylic acid methyl ester gives a mixture of vinylketone and divinylcarbinol. From methyl pentanoate, a mixture of n-butyl-3-hydroxyl-1, 4-pentadiene and 5-oxo-1-nonene is obtained. While reaction of linear α, β-unsaturated methyl esters with vinylmagnesium chloride yields vinylketones as the main product, the reaction of substituted α, β-unsaturated methyl esters yields triethylenic carbinols. Reaction of acid anhydrides and dibasic acid diesters with vinylmagnesium chloride yields mixtures of alkenones, hydroxy-alkenones and alkenols as the main products. Reaction of acid chloride with excess vinylmagnesium chloride at -40°C to -45°C gives 2-allyl-1, 3-diketones. From propanoyl chloride, a mixture of 4-allylheptane-3, 5-dione (33% yield), 6-heptene-3-one (0.5% yield) and 3-ethyl-1, 4-pentadiene-3-ol (2% yield) is obtained. Reaction of vinylmagnesium chloride with a fatty acid methyl ester in the presence of cuprous chloride gives a 1, 6-diketone. From methyl n-valerate, a mixture of n-tetradecane-5, l0-dione and 5-oxo-1-nonene is obtained.
In the previous paper of this series, the mass spectrometric characteristics of methyl sterols were discussed. The present report deals with an extended study on 14 kinds of methyl oxo-steroids with saturated, Δ4-, Δ5- and Δ7-3-oxo steroidal skeltons. Monomethyl oxo-steroids showed similar fragmentation pattern to the corresponding non-methylated oxo-steroids. On the other hand, fragmentation pattern of 4, 4-dimethyl oxo-steroids differed markedly from that of the non-methylated oxo-steroids. Several characteristic ions formed with rupture of ring AB were observed in the spectra of the former. It was suggested that the fragmentation process of molecule on 4, 4-dimethyl oxo-steroids was strongly controlled by 4, 4-dimethyl and 3-oxo groups.
The mass spectrometric fragmentations of 13 kinds of Δ22-steryl trimethylsilyl ether prepared from stigmasterol have been investigated. Steryl trimethylsilyl ethers containing a Δ22-bond gave 8 kinds of characteristic ion at m/e (M-side chain) +, (M-side chain-1) +, (M-side chain-2) +, (M-C8H16) +, (M-C8H17) +, (M-C6H13) +, (M-C3H7) + and (M-side chain-CH3-1) + which were formed with loss of the side chain or part of it from molecular ion. Eight ions derived with subsequent loss of trimethylsilanol from the ions as mentioned above also appeared. The formation of these ions serves to distinguish Δ22-sterols from other groups of sterol. Fragmentation patterns characterizing the position of double bonds in diunsaturated (Δ5, 22, Δ7, 22, Δ14, 22), triunsaturated (Δ5, 7, 22, Δ7, 14, 22, Δ8, 14, 22) and tetraunsaturated (Δ5, 7, 9 (11), 22) steryl trimethylsilyl ethers were observed.
The critical micelle concentration (cmc) of sodium sulfoalkyl alkanoates CnH2n+1COO (CH2) m SO3Na (n=9, 10 and 11; m=2, 3 and 4) in aqueous urea solution have been determined by the spectral change of pinacyanol chloride. The rate of increase in these cmc values due to the addition of urea increased with the number of carbon atoms inserted between the ester group and the sulfonate group, but decreased with increasing number of carbon atoms in the fatty acid portion of surfactant molecule. Accordingly, among the surfactants containing a given number of carbon atoms in the hydrocarbon chain, the farther the ester group mores from the terminal group to the center of the molecule, the increment in cmc value becomes larger.
Critical micelle concentration (cmc) of three kinds of sodium sulfoalkyl alkanoates, having linear alkyl chain with total of 14 carbon atoms, has been measured by electrical conductance of each aqueous solution at temperature ranging from 15° to 50°C. Variation of the cmc with the temperature exhibited a minimum for all the surfactants. The positions of minima in the cmc shifted toward lower temperature side with change of position of the ester group away from terminal to the center of hydrocarbon chain of the surfactant. The percentage deviation of the cmc values, obtained in different temperatures, from the value of the cmc at 30°C was plotted as a function of temperature for these surfactants. In the temperature range below the cmc minimum, the deviation of these surfactants decreased in accordance with the ester group position moved farther away from the terminal sulfonate group. But in the temperature range above the cmc minimum, the difference among the three deviation values became smaller and their magnitude were not in order. This phenomenon suggests that the hydration of the ester group is effected by a change in water structure with temperature and by the position of ester group in the alkyl chain of the surfactant. Also this proposal could be confirmed from the enthalpies and entropies of micelle formation.
In order to obtain information on the mode of solubilization of water-insoluble dyes into the micelles of nonionic surfactants, polyoxyethylene alkyiphenylethers, the solubilization ratios of dyes to the micelle and their flow dichroism have been investigated. Dyes used are Orange OT and 1, 4-diaminoanthraquinone. Experimental results showed that in every case one molecule of dye is solubilized per micelle at saturation. Above 100g/l of the surfactant concentration flow dichroism was clearly observed and constant differential dichroism was obtained. These facts suggest that above this concentration the shape of the surfactant micelles deviates markedly from sphere and the solubilized dyes orientate in the non-spherical micelles.
Solubilization of water by mixed nonionic and anionic or cationic surfactants in nonaqueous solutions was studied as a function of the temperature. Nonionic surfactants of hydrophobic property broadened the solubilization region of water at higher temperature by mixing with the anionic surfactant (Aerosol OT). On the other hand, by hydrophilic nonionic surfactants broadened the solubilization region at lower temperature by mixing. In the mixed cationic and nonionic surfactant solutions, the solubilization region in cationic surfactant solutions narrowed by addition of polyoxyethylated nonionics, whereas that broadened markedly by mixing with both glycerol and sorbitan mono-oleates.
In order to obtain a fundamental information on the emulsion and solubilization dyeings of fibers, the solubility behavior of aqueous dye solutions in nonaqueous surfactant solutions was studied as a function of the temperature. The solubility behavior of dye solutions in surfactant solutions is essentially similar to that of water or aqueous electrolyte solutions as previously reported by Shinoda et al. and present authors, that is, the solubilization region of dye solutions in surfactant solutions rapidly increased in a narrow temperature range. The W/O and O/W emulsion of dyes in anionic surfactant solutions appeared at lower and higher temperature of the solubilization region, but that of dyes in cationic and nonionic surfactant solutions reversed at lower and higher temperature. Particularly, the solubilization region of water in anionic surfactant solutions extended at higher temperature by the presence of acidic dyes. This effect was explained by the Derjauin-Landau-Verwey-Overbeek theory on the interaction of the double layers which were assumed to exist in the water-solubilizing lamellar micelle.