The Studies on The Tetrazotization of Aromatic Diamines (I). Tetrazotization of p-Phenylenediamine in Hydrochloric Acid and Perchloric Acid

p-Phenylenediamine was tetrazotized with sodium nitrite in an excess amount of concentrated hydrochloric acid media at -10C. It was also tetrazotized almost completely in 45% perchloric acid media. The two diazo groups in the tetrazonium salt were substituted by halogen, and the degree of tetrazotization reaction was observed by dihalobenzene yielded. The result of the tetrazotization was dependent upon the stability of the tetrazonium salt, and the stability was determined by concentration and quantity of the acid media. In dilute acid media the tetrazonium salt was unstable and completely decomposed. In concentrated acid media, though the tetrazonium salt was stable, tetrazotization reaction was retarded. To harmonize the two opposing tendencies it was advisable to find the optimum acidity of media at which the salt was fairly stable. About % of the acid media was suitable. The fact that the ion behaved as a negative catalyst supported the assumption that the diazotization reaction is primarily a reaction between the free amine and a nitroso group. The reaction of tetrazotization is expressed with respect to the kinetics and mechanism of diazotization.