The characterization of the esters obtained from acetylenedicarboxylic acid monopotassium salt upon treatment with methanol in the presence of sulfuric acid and their characteristic behavior in the amidation with methanolic and aqueous ammonia are described. Under ordinary conditions, the mono-potassium salt gives dimethyl acetylenedicarboxylate(1a) together with an appreciable amount of higher boiling substances consisting of dimethyl α, α-dimethoxysuccinate (5a), dimethyl methoxymaleate (2b), and dimethyl methoxyfumarate (3b), in which the latter two predominate.The evidence most partinent in establishing the structure of the esters obtained above has been presented. Amidation of la with excess ammonia gives generally a mixture of acetylenedicarboxamide (1b), aminofumaramide (3d) and methyl α-aminofumaraminate (3e), and the composition is variable depending on the reac tion conditions applied, of which the reaction temperature governs the relative amounts of 1b and 3e, and that of 1b and 3d are affected essentially by the reac tion time. Since 1b is transformed quantitatively after prolonged contact with ammonia into 3d, it is clear that 3d is produced from the initially formed 1b .2b yields in methanolic ammonia methoxymaleamide (2d) and aminomaleimide (6). With aqueous ammonia, 3b affords methyl α-methoxyfumaramate (3c), which is converted on further amidation into 3e and 6 . The mechanism of formation of the products has been discussed on the bases of above results.
Polymethyl acrylate and styrene-methyl acrylate copolymer have been treated with hydrazine hydrate to obtain the corresponding polyhydrazides. When the styrene content in the copolymer is increased, longer reaction time is required to complete the reaction. The polyhydrazides have been found to serve as positive polyelectrolytes;especially the polyhydrazides of styrene-methyl acrylate copolymer exhibits the properties of polysoap. The polyacrylic hydrazides are capable of reacting with carbonyl compounds and thus macromolecular glucohydrazones are formed upon treatment with glucose. An attempt to prepare polyhydrazides from methyl methacrylate polymers has also been made without success.
In the oxidation of carbazole, two isomers of dicarbazyl are formed as main reaction products. 3, 3'-Dicarbazyl is formed by bichromate or permanganate oxidation in acetic acid, whereas 9, 9'-dicarbazyl is formed by permanganate oxida tion in acetone. It has thus been clarified that the formation of the two different isomers depends on the type of solvent rather than that of oxidant. The possibility that 3, 3'-dicarbazyl might be formed from the 9, 9'-isomer in glacial acetic acid through rearrangement has been eliminated. The results also indicate the absence of the N-acylation reaction on carbazole which impair the formation of 9, 9'-dicarbazyl. The ultraviolet spectra of carbazole solutions in hexane, ethanol, acetic acid, and dioxane indicated thot proton acceptors such as dioxane or acetone affected the electronic distribution on the carbazole molecule. The formation of 9, 9'-dicarbazyl may be explained by the induced changes in electronic distribution on the carba zole molecule.The structure of the 9, 9'-dimer has now been confirmed spectroscopically.