Ring Transformations and Amination in Reactions of 3-Halogeno-5-phenyl-1,2,4-triazines with Potassium Amide in Liquid Ammonia

Article abstract of DOI:10.1021/jo01293a022

The reactions of 3-X-5-phenyl-1,2,4-triazines (X = fluoro, chloro, bromo, iodo) toward potassium amide/liquid ammonia were studied.Whereas the 3-fluoro compound gives only the 3-amino derivative, the 3-chloro, 3-bromo, and 3-iodo compounds yield a complex mixture containing, besides 3-amino-5-phenyl-1,2,4-triazine and 5-phenyl-1,2,4-triazine, ring transformation products, i.e., 3,5-diphenyl-1,2,4-triazine, 2,4-diphenyl-1,3,5-triazine, 6-amino-2,4-diphenyl-1,3,5-triazine, and 3-X-5-phenyl-1,2,4-triazole.Evidence is found that in the ring transformation of 3-X-5-phenyl-1,2,4-triazines into 2,4-diphenyl-1,3,5-triazines, benzamidine must be an intermediate.The mechanisms of the amination and ring transformation are extensively discussed.