Melamine and stearic anhydride, palmitic anhydride, myristic anhydride, orlauric anhydride (molar ratio 1: 2.2) were reacted by boiling in pyridine andeach of them yielded two kinds of diacyl substituted products having lowermelting point and higher melting point. Similarly, capric anhydride or caprylicanhydride yielded two kinds of diacyl substituted product and monoacyl substitutedproduct, while using of butyric anhydride or acetic anhydride gave onekind of each of diacyl substituted product and monoacyl substituted product. Reaction of each diacyl substituted product of low melting point and a correspondingamount of saturated fatty acid anhydride in pyridine for 10 hrs. causedisomerization into corresponding diacyl substituted product having high meltingpoint. Fusion reaction of melamine and palmitic anhydride or myristicanhydride yielded N, N′, N″-tripalmitoyl-and N, N′, N″-trimyristoylmelamine, respectively, and these are new substances not found in literatures.
The determination, by means of isotope dilution analysis, of the molar ratio of p-methyl (14C)-biphenyl, 4-methyl (14C)-2′-nitrobiphenyl, 4-methyl (14C)-3′-nitrobiphenyl, 4-methyl (14C)-4′-nitrobiphenyl, 2-chloro-4′-methyl (14C)-biphenyl, 3-chloro-4′-methyl (14C)-biphenyl and 4-chloro-4′-methyl (14C)-biphenyl formed through the reaction of N-nitroso-p-methyl (14C)-acetanilide in an equimolar mixture of nitrobenzene, chlorobenzene and benzene, is described. From the results, the partial rate factors of the ortho, meta and para positions for the homolytic p-methylphenylation were found to be 10.73, 1.07 and 8.93 for nitrobenzene, and 3.10, 1.04 and 1.16 for chlorobenzene, respectively, the reactivity of the one position of benzene being taken as unity.
Catalytic reduction of cyanamide by use of palladium catalyst has been investigated and a process of obtaining of f ormamidine salt, which was difficult in its preparation heretofore, with high yield was found. The reductive reaction was proceeded smoothly at room temperature and normal pressure in the presence of ammoium salt or mineral acid. Since there wasno reductive side reaction during the progress of this reductive reaction, the procedure and the treatment of reaction product were very simple and obtaining the product with high purity was possible. Observation on the state of absorption of hydrogen indicated that the cyanamide itself had a strong action of catalyst poison. For this reason, a portionwise addition of cyanamide to well activated palladium catalyst was made during the progress of reaction and its poison effect was suppressed. By carrying the process of portionwise addition of cyanamide to effect the dilution of the catalyst, the amount of palladium required was able to decrease to 1.7% of the cyanamide. By this process, formamidine sulfate, was newly prepared and some properties of this compound were also studied Experimental results indicated that this process has a value for practical application in the preparation of formamidine salt by using easily obtainable commercial cyanamide as a raw material.
Polymerization of vinyl monomer was carried out by using peroxybenzoic acid as an initiator. Styrene showed almost no polymerization. This was due to rapid decomposition of peroxybenzoic acid in styrene. Methyl methacrylate showed good polymerization. Acrylonitrile showed very good polymerization while vinyl acetate showed almost no polymerization. The rate of decomposition of peroxybenzoic acid in methyl methacrylate at 20-30°C was proportional to its concentration. Polymerization of methyl methacrylate was carried out by using peroxybenzoic acid and benzoyl peroxide, respectively, as an initiator. Both gave higher polymerization degree at 30°C. A polymer of low degree of polymerization was prepared by using peroxybenzoic acid as an initiator and its ultraviolet absorption was estimated. The presence of benzoyloxy group as a terminal group seemed to be certain. Since the polymerization of methyl methacrylate by peroxybenzoic acid was completely inhibited by the presence of oxygen or p-benzoquinone, this was considerd to be a radical polymerization.