Condensation of 2-methyl-4-amino (or hydroxy)-5-aminomethyl-pyrimidine hydrochloride and γ-aceto-γ-rhodanpropyl-acetate results in acetyl-thiochrome which gives thiochrome by hydrolysis with HCl. Three new kinds of thiochromine derivatives were synthesized by the utilization of this reaction.
Extraction by AoOEt of NH3-alkalized human urine obtained from men given p-aminomethylbenzene sulfonamide hydrochloride gives p-acetylaminomethylbenzene sulfonamide, m.p. 171-2°. Evaporation of the residual urine under reduced pressure and subsequent digestion of the residue with EtOH gives p-sulfonamido-benzylurea, m.p. 192-3°. This compound is believed to be the result of the condensation with urea during evaporation of p-aminomethylbenzene sulfonamide excreted into urine in its free form although the latter was not obtained as such.
Various conditions were observed of the synthetic process for lepidine from acetoacetic anilide through 2-hydroxylepidine and chlorolepidine. Some facts were made clear as to the simplification of synthetic procedure and improvement in the yield of lepidine.
On the assumption made earlier by the author that neostibosan was composed of antimonic acid and Hyden 693, condensation of diethylamine salts of p-aminophenylstibonic acid and that of antimonic acid was experimented resulting in a new complex compound. Contrary to the author's expectations, this compound was found not to be neostibosan although resembling it in several respects The new compound is very stable in its solution and contains, curiously, no diethylamine. The author, therefore, proposes a betain-like constitutional formula composed of 1mol. tri-acid of p-aminophenylstibonic acid and 4mol. antimonic acid for the compound obtained. It is assumed that the substance of unknown structure obtained by Dyson by the heating of p-aminophenylstibonic acid with HCl is identical with the complex compound obtained by the author.
For the purpose of obtaining neostibosan, diethlyamine salt of p-aminophenylstibonic acid and that of antimonic acid was condensed and a new complex compound was obtained. This new compound was composed of 1mol. each of the tri-acid of p-aminophenylstibonic acid, antimonic acid and diethylamine, and contained almost the same quantity of antimony as that in neostibosan. The carbon content of this compound was 3% less than that in neostibosan but in other properties, the two compounds resembled one another. The toxicity of the new complex comdound was higher than that of neostibosan but the addition of glucose lowered its toxicity.
Supersonic waves, when played on compounds of higher molecules, give rise to colloidal and chemical changes in their solutions. Supersonic waves were applied, while measuring intensities, on the solutions of viscose and methylcellulose and Schweizer reagent solution of cotton cellulose and the decrease in their viscosity was measured by Ostwald's viscosimeter. All three solutions showed greater decrease in viscosity by the increase in the intensity of supersonic waves but viscose solution showed greatest decrease in a concentration around 1.5%. No change in the decrease rate of viscosity was seen in the methylcellulose solution due to intensity in concentrations under 0.5%. The average rate of polymerization reached 30 when supersonic waves of 0.5g weight intensity (radiation pressure bearing on a disc 1.5cm in diameter equal to ca. 277erg/cm3 when converted to energy density in the solution) was radiated for 30 minutes. Cotton cellulose dissolved in Schweizer reagent showed remarkable decrease in viscosity by 3-minutes radiation of 0.5g weight density but the decrease become gradual after that, the solution decomposing completely with radiation over 30 minntes, precipitating cellulose.
Condensation of 2-aryloxylepidine methiodide and aromatic aldehydes even with the use of amines having active hydrogen as a catalyst, will not give styryl dyes, as in the formation of 2-amino- or 2-methylaminolepidine methiodide by the use of ammonia and methylamine, respectively. Syntheses of 2-aminostyryl dyes were tried by the condensation of 2-aminolepidine methiodide and aromatic aldehydes. However, styryl dyes could only be obtained when the amino radicals were phenylamino or benzylamino and no such compounds could be obtained in the cases of -NH2, -NH⋅CH3 or -N(C2H5)2. These facts, compared with the facts that 4-aryloxy and 4-amino-quinaldine methiodide give 4-aminostyryl dyes under the same conditions, seem to point out that the activities of both the methyl radical at C4 and the phenoxy radical at C2 have decreased greatly in the 2-aryloxylepidine and that it easily forms 1, 2-quinolone.
Condensation of 4-methoxyquinaldine methiodide and piperonal, if performed in EtOH with triethylamine as a catalyst, gives 4-ethoxyquinaldine methiodide when the amount of the amine is kept under 1/8mol. but 4-ethoxypiperonylidene-quinaldine methiodide as well is obtained if the amount is around 1/2mol. If piperidine is used as a catalyst, the methoxyl radical at C4 changes to ethoxyl, resulting in 4-ethoxypiperonylidene-quinaldine methiodide. Absence of piperonal results in a condensation to isocyanine to 1, 1′, 2′-trimethyl-4-ethoxy-2, 4′-monomethine-quinocyanine iodide possessing λ (max) of 5390Å. From these results, it was assumed that the methoxyl radical in 4-methoxyquinaldine methiodide, under the presense of amine as a catalyst, was substituted by the solvent alcohol. Therefore, the same reactions were experimented with n-butyl and n-propyl alcohol by which compounds substituted with these alcohols were obtained. At the same time, it was found that these reactions were reversible. From these facts, the author assumed ionic reactions, the direction of which being decided by the slight move in the equilibrium.
Studies were made on the preparatory method for 6-chloro-4-n-octyl-resorcinol. This compound, possessing very weak irritability and extremely weak toxicity, is the most powerful anthelmintics among alkyl-resorcinol and chloralkyl-resorcinol compounds.
Condensation of 6-chloro-resorcinol and cyclohexanol under the presence of phosphoric acid or chlorination of 4-cyclohexyl-resorcinol by sulfuryl chloride results in synthesis of 6-chloro-4-cyclohexyl-resorcinol, m.p. 89-90°. The latter method gives a better yield. Although the compound has less irritability and weaker toxicity than hexyl-resorcinol, it was found to be a powerful anthelmintic agent.