Synthesis and Density Functional Theory Study of [1,2,3]Triazolo[4,5-D][1,2,4] Triazolo[4,3-a]Pyrimidine Derivatives: A Novel Heterocyclic System

Several 3H-[1,2,3]triazolo[4,5-d][1,2,4]triazolo[4,3-a]pyrimidine derivatives of a novel ring system have been synthesised. The initial substitution of the 4-Cl function of 2,4-dichloro-6-methylpyrimidin-5-amine with benzylamine followed by treatment with sodium nitrite generated 3-benzyl-5-chloro-7-methyl-3H-[1,2,3]triazolo[4,5-d]pyrimidine. Nucleophilic substitution of the 5-Cl moiety of the latter compound with hydrazine hydrate and subsequent treatment with carbon disulfide in boiling pyridine gave, quantitatively, the corresponding [1,2,3]triazolo[4,5-d][1,2,4]triazolo[4,3-a]pyrimidine derivatives. Density functional theory (DFT) studies were also performed to reveal regioselectivity of the ring closure via Gauge-Independent Atomic Orbital (GIAO) 1 H NMR calculations. The WP04 method was used as the DFT code to yield accurate chemical shift values. Theoretical results correlated well with the expected regioisomer and aided assignment of the final structure.