In the previous paper, authors reported the condensation of octadecene-1 with formaldehyde in acetic acid under the presence of some acids as the catalyst, and recognized the products which were considered as 3-pentadecyltetrahydropyranol-4, nonadecadiol-1, 3 and octadecanol. The formation of dioxane derivative was presumed from IR spectrum. In this paper, authors investigated above reaction in detail. In the first, nonadecadiol-1, 3 was correctly prepared by hydrolysis of alkyl-1, 3-dioxane in methanol under the presence of sulfuric acid as the catalyst, therefore, one of the product in this reaction is presumably confirmed to be 4-hexadecyl-1, 3-dioxane. To next, 3-pentadecyltetrahydropyranol-4 was obtained by disposition of nonadecadiol-1, 3 with paraformaldehyde in acetic acid under the presence of sulfuric acid as the catalyst, therefore, 3-pentadecyltetrahydropyranol-4 will be produced from nonadecadiol-1, 3 through 3-nonadecenol-1 as the intermediate. Oxydation of this alkyl-pyranol-4 with chromium trioxide gives alkyl-γ-pyron and still more oxydation with nitric acid under the presence of ammoniume vanadate gives corresponding dicarboxylic acid.
Methyl 8-oxycaprylate was prepared by means of Brown-Walker electrolytic oxidation of methyl hydrogen azelate. The free acid was separated from the product using maleic anhydride as a reagent. On the other hand, 8-oxycaprylic acid was prepared from methyl hydrogen azelate by the following method; the ester was transformed into the Ag salt, brominated, acetylated and hydrolized. As it was confirmed identical for the separated acid in comparison with the synthesized hydroxylic acid, the above electrolytic reaction was found as a new process for producing it. For the acid, authors measured the solubility for water and benzene, the velocity of the formation of the polyester at different temperatures. Ethyl-, isopropyl-, isobutyl- and isoamyl 8-oxycaprylate were synthesized. These compounds are new derivatives of 8-oxycaprylic acid. By the trans-esterification of the monoglyceride of the acid, it was found that the dimeric lactone of 8-oxycaprylic acid was obtained.
Study was made on selectiveness of reaction of hydrogenation and stability to oxidation of the resultant oil referred to in the previous report with IR and UV absorption spectra with the following result. 1. Catalyst consisting of reduced nickel and MPS produced less trans acid than the catalyst of reduced nickel alone. The effect of MPS is affected by its viscosity and the higher viscosity shows the higher effect than the low viscosity. 2. When the resultant oil is hydrogenated with catalyst of nickel alone until its iodine value reaches 86, conjugated diene acid disappeares. But with catalyst having MPS added, it disappeares at iodine value 81. On the other hand formation of trans acid has a tendency to increase sharply at about the iodine value at which conjugated diene acid disappeares. 3. Disappearance of triene acid occures at iodine value 90 or so with catalyst of nickel alone against 88 in the case of catalyst having an addition of MPS. 4. There is no difference in stability to oxidation between catalyst of nickel and that of nickel and MPS in the AOM and oven tests. And it has a tendency to rise sharply at about the iodine value at which triene acid disappeares. In hydrogenation for iodine value more than 90, reversion of fish flavor is recognized before rancid flavor is produced.
This paper deals with the reaction of hexamethylene diamine with acrylonitrile and synthesis of tetracyanoethylate at a high yield. In this experiment, the same method of cyanoethylation of primary fatty amine was used as reported in previous papers. As a result, it was found that the reaction carried out in polar solvent was effective in the tetra-cyanoethylation of hexamethylene diamine. N, N, N', N'-tetra (β-cyanoethyl) -hexamethylene diamine was obtained in stoichiometric quantity under the optimum condition that mixture of 6 mols of acrylonitrile per mol of the amine and 2 parts of methanol per part of the amine was refluxed at the reaction temperature of 70°C in atmospheric pressure and maintained for 24hrs. Furthermore, it was found possible to pursue for the primary, secondary and tertiary amino radical respectively by measuring T.A.V. and P.A.V. of the reaction mixture.
In this paper, the synthesis of tetracyanoethylate in the reaction of ethylene diamine or nonamethylene diamine with acrylonitrile were studied. Molratio of acrylonitril to amine, solvents, weight ratio of solvent to amine, reaction temperature and reaction time were investigated. As a result, it was found that the reaction carried out in methanol containing water was effective in the tetra-cyanoethylation of ethylene diamine, that the reaction carried out in methanol or methanol containing water were very effective in the tetra-cyanoethylation of nonamethylene diamine, and that the reactivity in cyanoethylation varied with the length of carbon chain of diamines, but nonamethylene diamine indicated approximately the same reactivity as that of hexamethylene diamine which was reported in previous papers. N, N, N', N'-tetra (β-cyanoethyl) -alkylene diamine was obtained in stoichiometric quantity under the optimum condition that twice methanol or methanol containing water by weight for the amine and six moles of acrylonitrile to one mol of amine was refluxed at the reaction temperature of 70°C for 24hrs or 48hrs.
Oxyrane oxygen of non-terminal epoxy compounds was determined with each method of hydrogen chloride-ether, dioxane and acetic acid solutions, and hydrogen bromide-acetic acid solution. It was found that water contained in the sample solution lowers the accuracy of determination. Hydrogen bromide-acetic acid solution method (Durbetaki's method) showed better accuracy among the above methods. Anhydrous hydrogen bromide-acetic acid solution was prepared easily by means of a procedure that hydrobromic acid was dissolved with acetic acid, and then equivalent amount of acetic anhydride to water was added into the solution. To increase the accuracy of determination, Durbetaki's method was modified as follows : In case standardization of hydrogen bromide-acetic acid solution, sodium carbonate was dissolved with 10ml of acetic acid, and then 10ml of benzene was added into the solution. The sample was dissolved with mixture of 10ml of benzene and 5ml of acetic acid. Interference for the determination was also investigated.
In the previous paper, the soysteryl acetate bromide was oxidized by chromic anhydride under suitable condition and stigmasterol was recovered. In this paper the reactivities of sitosteryl acetate dibromide to chromic anhydride and of stigmasteryl acetate tetrabromide were compared. Stigmasteryl acetate tetrabromide was oxidized but chromic anhydride consumption of the tetrabromide was less than that of sitosteryl acetate dibromide. Diatomous earth adsorbed chromic anhydride and concentration of chromic anhydride in the reaction mixture was there by lowered.