The reaction of aliphatic primary and secondary amines with epoxypropane derivatives, such as epichlorohydrin and glycidolsulfonic acid esters in methanol as a solvent at a comparatively low temperature was investigated. At the reaction temperature of 20°c with an amine and epichlorohydrin, only a simple additive reaction such as aminochlorohydrin formation, occurred, sometimes trivial side reaction being followed. With amines and glycidolsulfonic acid. esters, a considerably strong side reaction always occurred. At a low temperature of 2-3°c, a simple additive reaction. (the formation of aminochlorohydrin by ring opening reaction of epoxy group) was sometimes taken. place with amines and glycidolsulfonic acid esters. So, in general there is a suppression of side reaction. It was considered from the tendency of reaction due to the kind of amines that the effect of steric hindrance was large.
By the reaction of several aliphatic secondary amines with epichlorohydrin, N-(γ-chloro-β-hydroxypropyl) amino compounds were isolated. These compounds were turned easily into quarternary ammoium compounds by standing for long period of time or by heating of their aqueous solution, but it was found that a complete quarternarisation was difficult in case of N, N'-bis(γ-chloro-β-hydroxypropyl) pipe-razine. However, N-(γ-chloro-β-hydroxypropyl) amino compounds or quarternary ammonium compounds were unable to be isolated from the reaction product of aliphatic primary amines with epichlorohydrin. Reactions of aliphatic amines and glycidolsulfonic acid esters gave products difficult for isolation of N-(γ-sulfonyloxy-β-hydroxypropyl) amino compounds but resulted in a directive formation of quarternary ammonium compounds, except for the reaction of piperazine and glycidol-p-toluenesulfonic acid esters. It was confirmed that these quarternary ammonium compounds were formed only as an intramolecular reaction resulting in the azetidinium ring.
Fusion of benzonaphthenone in methanol-potassium yielded a purple colored vat dye. The crude product was separated into methanol-soluble portion, chlorobenzene soluble portion, ο-dichlorobenzene-soluble portion, and its insoluble portions, in which the chlorobenzene-soluble portion (yield 5-10%) is considered to be composed mainly of peropyrenequinone type compound. Synthesis of peropyrene was made by the fusion of benzonaphthenone with zinc dust and oxidation of this gave peropyrenequinone soluble in chlorobenzene. The properties of above dyes were investigated. By fusion of a mixture of benzonaphthenone and benzanthrone in methanol-potassium a product considered to be benznaphthenonylbenzanthrone was obtained and further ethanol-potassium fusion of this compound gave the purple dye, which was considered to be a cyclized condensation product of benzonaphthenone and benzanthrone.
The condition for formation of tetramer of cyanogen chloride, kinds of solvent and catalyst used, the concentration of cyanogen chloride in the solution, the effect of moisture, the temperature and time required for polymerization and the reaction mechanism by use of bromine as a tracer were investigated. The results are summerized as follows: 1. The hydrogen chloride is an essential catalyst; 2. hydrogen chloride additive product of cyanogen chloride is related to the polymerization process; 3. this additive compound liberates hydrogen chloride in the formation of triazine nucleus, and 4. the tetramer (T.C.C.) is not obtainable from cyanulic chloride. These results indicated the reaction mechanism that the additive compound of cyanogen chloride with hydrogen chloride was formed at first, from which the dimer was formed, the reaction of the dimer with the additive compound gave a trimer and that the reaction of the two dimers gave a tetramer.