Condition for the modified normal pressure Reppe's process under continuous operation have been established as follows. It is recommended to add an acid at an amount approximately equivalent to the nickel of the nickelcarbonyl for the formation of a nickelous salt. Hydrogen chloride proved most satisfactory. The presence of nickelcarbonyl at a level 10-20 mol % in excess of the acid prevents the formation of the β-chloropropionate and the corrosion of equipments. The use of 5-10% excess acetylene over the totol carbon monoxide (free carbon monoxide plus nickel carbonyl) ensures the product purity and stable operation. In continuous operation, the reaction is effectuated at 40°C in the presence of 2-ethylhexyl alcohol at an weight almost same as that of 2-ethylhexyl acrylate.
In the previous reports, we have suggested that the radiation-induced reaction of ethylene in a mixed solvent of cyclohexane and carbon tetrachloride may consist of two succeeding steps ; firstly, the formation of ethylene-carbon tetrtrachloride telomer, and secondly, the grafting reaction of ethylene onto the telomer. Therefore, when the telomer is used instead of carbon tetrachloride, it may be expected that only the second reaction occurs. In the system of ethylene, cyclohexane, and an ethylene-carbon tetrachloride telomer, the yield of solid products increased linearly with increasing dose. Results of the differential thermal analysis showed that the products contained two components corresponding to the products of high melting points obtained in ethylenecyclohexane-carbon tetrachloride systems. Results suggested that only grafting reactions occurred and that the grafted branch grew fairly long.
2-Chloromethylbenzimidazole failed to give the expected 2-styrylbenzimidazole by the Horner reaction. Since the N-ethyl derivative gives N-ethyl-2-styrylbenzimidazole, the imino-hydrogen of the imidazole ring seems to inhibit this reaction.
Several azo- and anthraquinone-dyes containing dimethylaminomethyl group were synthesized, and their dyeing properties were tested using several kinds of fibers. Azo dyes were obtained by coupling 2-dimethylaminomethyl-1-naphthol (obtained by the reaction of α-naphthol with N, N, N', N'-tetramethyldiaminomethane) with diazonium or tetrazonium salts derived from aromatic primary amines. Anthraquinone dyes were synthesized by the reaction of substituted or unsubstituted 1-amino-4-hydroxyanthraquinones with N, N, N', N'-tetramethyldiaminomethane in acetic acid in the presence of hydrochloric acid. The dyes containing no sulfonic group readily dissolve in diluted acetic acid and dye acrylic fibers of Orlon type, and the dyes containing sulfonic group dye cotton in the presence of alkali by chemical combination.