Abstract:

2-Amino-3,5-dinitropyridine(1) and 2-amino-3,5-dinitropyridine-1-oxide(3) have been aminated by various nucleophilic substitution reaction, using hydroxylamine hydrochloride, 4-amino-1,2,4-triazole and 1,1,1-trimethylhydrazinium iodide as aminating agents. Based on amination via vicarious nucleophilic substitution(VNS) of hydrogen, the stereo-electronic effects of aminating agents and reactants on the composition and yield of target compounds were discussed. Reactants 1 and 3 were aminated at the 6-osition and 4-position using hydroxylamine with a yield in the range of 64%~89%. Reactions of 1 and 3 respectively with 4-amino-1,2,4-triazole or 1,1,1-trimethylhydrazinium generated compounds which were aminated at the 6-position, with a yield over 90%. Under the same conditions, the yields for the target compounds were improved with the increase of the activities of aminating agents.

Key words: amino-dinitropyridine, amino-dinitropyridine-oxide, VNS amination, amination reagent