1.2.4.5- Tetrazine 3- phenyl-, amination

Under similar conditions, 5-phenyltetrazole is converted to a complex mixture containing amine 164 (42%), 3,5-diphenyl triazole, and different phenyl-substituted triazines and tetrazines (62LA146). Electrophilic amination of 1,2,4-triazole by HOSA [80JCR(M)514] or by DNPH (89S269) leads to l-amino- and 4-aminotriazole with the great dominance of the first. This is the only method to synthesize unsubstituted 1-amino-s-triazole. It is known as the nitrene amination of 1,2,4-triazoles [Eq. (46)] [74AHC (17)213]. 

The examples shown are illustrative of the many easy nucleophilic additions to the polyaza-azines both 3-phenyl-l,2,4,5-tetrazine and 1,3,5-triazine itself add ammonia and simple amines (contrast the requirement for hot sodamide (Chichibabin reaction) for pyridine (8.3.1.2)) and thus amino and alkyamino derivatives can be obtained via oxidative trapping with permanganate. 

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