The thermal addition of formaldehyde to linear olefins such as octene-1, octene 2 and heptene-3 was studied. When mixtures of unsaturated hydrocarbons and paraformaldehyde were heated in an autoclave in the presence of acetic anhydride, acetate of unsaturated primary alcohols were produced. By saponification of these acetates the corresponding alcohols were obtained. From octene-1 a mixture of acetate of traps- and crs-3-nonene-1-ol, from octene-2 a mixture of acetate of 2-vinylheptanol-1 and 2-methyl-3-octene-1-ol were produced respectively. In these reactions acetic anhydride was a more effective solvent than acetic acid. No alcoholic compound was obtained from heptene-3.
Unsaturated acid and its esters can be polymerized by heating and with the use of proper catalysts. It was reported that oleic acid can be dimerized with BF3 or organoperoxide catalysts. The author found that oleic acid and its esters can be polymerized by the activated clay catalyst. This paper deals with the studies of polymerization of oleic acid and ethyl oleate with the catalyst. The effects of the amounts o catalyst and the reaction temperature on the yields of dimer and polymer, on the properties and structures of the products were studied. Besides the polymerization, such side reactions as decarboxylation, lactone formation, and isomerization were observed. Hydrogenation, accompanied with the dehydrogenetic dimerization, was also estimated from the formation of saturated acids. Under the reaction condition of 210°C and 2 hr, about 25% of dimer and 25% of polymers were formed from oleic acid with the use of 50 wt % of activated clay to oleic acid. The main diner was considered to have one double bond in its molecule, but the dimer which contains two double bonds was also formed by the selection of the reaction condition.
Sulfonation behaviors of commercial alkylbenzenes were determined by using gas chromatography according to the previous report. The relative sulfonation rates of all isomers, contained in soft type alkylbenzene (Nalkene ML-N 500), were obtained. These rates showed that in the sulfonation with 20% oleum there exist great selectivity owing to the benzene ring position and the alkyl chain length. But the change of the average molecular weight of the unsulfonated alkylbenzene was rather small. In the case of sulfur trioxide sulfonation, the selectivity is smaller than that of oleum. And it was suggested that this method, involved in the determination of change of the chromatogram by sulfonation, is also useful to estimate the components of impurities contained in commercial alkylbenzenes. Hard type alkylbenzene was not clearly separated by the gas chromatography using packed column, and the change of composition by sulfonation was not observed clearly, thus the selectivity was not clear.
Thin-layer chromatography technique using the plate coated with silica-calcium sulfate containing barium acetate or sodium carbonate and the solvent system consisting of methylethylketone-benzene ethanol-water was successfully applied to the analysis of various nonionic surfactants having polyoxyethylene chain. In the experiment carried on various fatty alcohol polyoxyethylene ethers, alkyl-phenol polyoxyethylene ethers, fatty acid monoethanolamide ethoxylates, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene glycols, many spots were recognized as corresponding to the distribution of ethylene oxide polymerization degree. R f value of these spot group becomes smaller according to the increase in polymerization degree.
Fatty amides (saturated, C6, 8, 10, 12, 14, 16, 18 and C22; cis and trans forms, Δ9-C18F, Δ11-C20F and Δ13-C22F) and N, N'-methylenebisamides (saturated, C6, 8, 10, 12, 14, 16, 18 and C22; cis-form, Δ9-C18F, Δ11-C20F and Δ13-C22F ; trans-form, Δ9-C18F) were prepared, and subjected to measure melting point and thermal stability. The stability was measured with thermobalance. Purity of each compound was more than 99% by gas chromatography. Saturated N, N'-methylenebisamides melt between 175.5°C(C6) and 141.9°C(C22), and the melting points go down according to increse of carbon number. On the other hand, saturated simple amides (C6 to C22) melt at various temperatures in the region from 100 to 110°C. Melting points of unsaturated simple amides are as follows : oleamide, 76.2°C; cis-11-eicosenamide, 79.3°C; erucamide, 83.5°C ; elaidamide, 91.2 °C ; trans-11-eicosenamide, 91.2°C ; and brassidamide, 95.0°C. Also, melting points of unsaturated N, N'-methylenebisamides are as follows : cis-form, C18F, 118.1°C ; C20F, 122.3°C ; C22F, 123.8°C ; trans-form, C18F, 131.2°C. Thermal stability of saturated simple amides (C12 to C22) increase with addition of methylene group, and the thermogravimetric curves are parallel to each other. Stability of unsaturated simple amides (cis-form, C18F to C22F) are somewhat larger than that of saturated simple amides (C18 to C22). Saturated (C10 to C22) and unsaturated N, N'-methylene bisamides have larger thermal stability than that of simple amides having the same carbon atoms because of higher molecular weight. Stability of C10 bisamide containing 21 carbon atoms is similar to that of C20 simple amide. However, the stability of C18 bisamide containing 37 carbon atoms is nearly equal to that of C22 simple amide. Thermal stability of unsaturated bisamides is similar to that of saturated bisamides.