Many papers have ever been reported about cyclic monomers (mostly 6-membered ring compounds) formed from unsaturated fatty acids or their triglycerides during thermal treatment or by catalytic cyclization. But, existance of 5-membered ring compounds in such cyclic monomers has not been proved chemically. Therefore qualitative and quantitative condition of the color reaction of cyclopentadiene in a mixture of 1, 3-cyclohexadiene, benzene, cyclohexene, cyclohexane, cyclopentene and cyclopentane, was examined using sulfuric acid and ethyl alcohol in reference to our previous papers. On the other hand, purified ethyl linoleate, ethyl linolenate and photo-isomerized Lung oil were respectively heated to cyclize with sodium hydroxide and ethylene glycol under the condition of 295°C, 15min. in a stainless autoclave, then acidified, esterified and purified by silica gel column, yThe cyclized ethyl linoleate, ethyl linolenate and photo-isomerized tong oil fatty acid ethyl ester were separated by urea adduct and column chromatography obtained ethyl linoleate cyclic monomer (11CM), ethyl linolenate cyclic monomer (1nCM) and photo-isomerized tung oil fatty acid ethyl ester cyclic monomer (βCM) were analyzed by GLC, IR, TLC and the above mentioned color reaction. It was concluded that cyclopentadiene compounds were formed from ethyl linolenate, but not from ethyl linoleate and eleostearic acid, since 1nCM, βCM and 11CM contained 4.1%, 0.08% and 0% of cyclopentadiene compounds respectively.
The disproportionation reaction of rosin and tall oil with various kinds of metal iodides has been studied and iron (II) iodide was found to be an effective catalyst for the reaction. Compared with the reaction using iodine as the catalyst, the reaction rate of abietic acid was higher, other reactions than disproportionation were depressed, and dehydroabietic acid was obtained in a higher yield. The products obtained showed higher softening points.
Polyoxyethylene (POE) alkylether-assimilating bacteria were isolated from soils by enrichment culture technique. Four isolated strains were all identified as genus Pseudomonas and their substrate specificities for some compounds related to nonionics were discussed. Moreover, assimilating ability of other species of standard genus Pseudomonas were also studied. The biodegradability of nonionic surfactants by these isolated and standard strains decreased in the following order, POE acyl ester, POE sorbitan fatty acid ester, POE alkyl ether and POE alkyl phenyl ether. Ester-type nonionics were first hydrolyzed at ester linkage in a relatively short time and fatty acid parts were gradually degraded. Polyether parts, however, were found to be hardly degraded within several days.
Comparably large laboratory scale synthetic method of homogeneous POE nonylphenyl ethers was investigated by using williamson synthesis. Nonylphenol and dichloride of homogeneous polyethylenglycol were used as starting materials and the products with high purity were obtained by centrifugal molecular distillation or column chromatography. Their EO adducts of 4, 6, 8, 12 were prepared and some of their corresponding physical properties were determined.
Lithium naphthalenide reacts with carboxylic acids in the presence of diethylamine to give the dianions of carboxylic acids. Reactions of these dianions with various glycidyl ethers give the corresponding γ-hydroxy acids in good yield. The γ-hydroxy acids easily cyclize to give γ-butyrolactones containing ether group. In the case of α, β-unsaturated crotonic acid, the dianion of crotonic acid reacts with various epoxides to give unsaturated γ-butyrolactones.
Dielectric measurements of four linear long chain bromides, 1-bromodocosane (C22Br), 1-bromotetracosane (C24Br), 1-bromohexacosane (C26Br) and 1-bromooctacosane (C28Br), were carried out using a transformer bridge at 10 kHz. Phase transitions were observed on cooling in all the bromides studied here, and the transition points of C22Br, C24Br, C26Br and C28Br were 30, 35, 42 and 46°C respectively. These transitions were reversible except those of C22Br and C24Br. In the measurement with a high rate of temperature change, however, the transition point on heating of C24Br was observed also. Phase transition phenomena are affected by the rate of temperature change. Freezing points are on the smooth curve. Transition points are indicated as the linear function of carbon atoms of the samples. On the basis of this result, it is expected that the transition point of 1-bromooctadecane (C18Br) could be observed on cooling. Dielectric constants of high temperature phases of these compounds were higher than those of low temperature phases. In the high temperature phase, molecular rotations around the chain axes contribute to the srientation polarization which may be responsible for the high value of dielectric constant. Therefore, these high temperature phases are assumed to be a rotator phase. Dielectric constants of the high temperature phases on heating were gradually decreased by holding the samples at a constant temperature in these phases, so that the high temperature phase on heating may be metastable. However, the high temperature phase on cooling may be stable, considering the results of similar experiments. The difference between stable phase and metastable one can be explained as follows. The stable high temperature phases on cooling arise from the liquid state in which large degree of freedom of molecular motions are possessed, whereas the low temperature phases in which molecular motions are restricted in some measure change into the metastable high temperature phases on heating.
The steam volatile oil was obtained in 0.05% yield by steam distillation from the root of Saxifraga stolonifera Meerb.. The oil was treated successively with 5% sodium carbonate and 5% sodium hydroxide solution, and divided into neutral, sodium carbonate soluble and sodium hydroxide soluble fractions. Following compounds were identified or tentatively assumed ; α-pinene, cumene, terpinolene, p-cymene, linalool, α-terpineol, citronellol, geraniol, geranyl acetate, benzyl alcohol, β-phenyl ethyl alcohol, isovaleric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, p-cresol and alkane of C14 to C24.
This note describes a new preparative method of esters of geraniol from myrcene, diethylamine and sodium naphthalenide. N, N-Diethyl geranylamine was prepared from myrcene and diethylamine using sodium naphthalenide. By the reaction of N, N-diethylgeranylamine and propionic anhydride, geranyl propionate can be prepared.
The fatty acids of the seed oils of Neolitsea aciculata (Blume) Koidz. (Japanese name “Inugashi”) and Neolitsea Sericea (Blume) Koidz. (Japanese name “Shirodamo”) were analyzed by gas chromato graphy and mass spectrometry, and then each component was identified comparing with authentic compounds. Dodecanoic acid was the major component, while cis-4-decenoic, cis-4-dodecenoic and cis-4-tetradecenoic acid being present in smaller quantities in the seed oils of the above mentioned plants.
The biodegradability of secondary alcohol ethoxylate has been already proved by various test methods. This paper is provided to show that secondary alcohol ethoxylate is by far easily degradable than nonylphenol ethoxylate in continuous-flow activated sludge system. The tests were conducted at higher concentration of surfactants than any previous works through long periods. In the test, biodegradabilities were followed by measuring COD (Cr), COD (Mn), cobalt thiocyanate active substances (CT AS) and TOC.