3-Dialkylamino-1,2,4-triazoles via Zn-Catalyzed Acyl Hydrazide-Dialkylcyanamide Coupling.

Zinc(II)-catalyzed (10 mol % ZnCl) coupling of acyl hydrazides and dialkylcyanamides in ethanol leads to 3-dialkylamino-1,2,4-triazoles (76-99%; 17 examples). This reaction represents a novel, straightforward, and high-yielding approach to practically important 3-NR-1,2,4-triazoles, which utilizes commercially available and/or easily generated substrates. Seventeen new 3-NR-1,2,4-triazoles were characterized by HRESI-MS and IR, H, and C{H} NMR spectroscopies and five species additionally by single-crystal X-ray diffraction (XRD). The Zn-catalyzed reaction proceeds via initial generation of the [Zn{RC(=O)NHNH}](ZnCl) complexes (exemplified by isolation of the complex with R = Ph, 76%; characterized by HRESI-MS, IR, CP-MAS TOSS C{H} NMR, and XRD). Electronic effects of substituents at the acyl hydrazide moiety do not significantly affect the reaction rate and the yield of the target triazoles, whereas the steric hindrances reduce the reaction rate without affecting the yield of the heterocycles.