ο-トルエンジアゾニウムスルファート, チオシアン酸イオンおよび各種金属イオンの反応によるο-トリルチオシアナートの生成

抄録

Catalytic effect of some kinds of metal ions on the reaction of o-toluenediazonium sulfate and thiocyanate ion was examined by determination of o-tolyl thiocyanate produced, using gas-liquid chromatography. The catalytic action of zinc, cupric, ferrous, mercuric, cuprous, and mercurous ions was effective but that of other metal ions, such as ferric, potassium, lead, silver, cobalt, cadmium, nickel, uranyl, chromium, molybdate, tungstate, manganease and stannous ions, was weak or negligible. The catalytic reaction was affected by pH of the solution and the molar ratio of the reactants. Good yield of o-tolyl thiocyanate was obtained with Zn²⁺ and Fe²⁺ at pH 1-3, and with Cu²⁺ at pH 8.5, and the yield was better, the larger the amount of thiocyanate ion added. As a catalyst, zinc ion was found to be the best. A new method of mixing one mol of o-toluenediazonium sulfate, 4 or more mol of potassium thiocyanate, and 1 mol of zinc sulfate solution at pH 1-3 and allowing them to react is recommended for the synthesis of o-tolyl thiocyanate, which is obtained in ca. 50% yield by this procedure.