Synthesis, ring transformations, IR-, NMR and DFT study of heterocycles with two ferrocenyl units

Cyclization of 1,5-bis(ferrocenylmethylidene)thiocarbonohydrazide with DMAD afforded diastereomeric dimethyl-thiazole-4,5-dicarboxylates. The cis-isomer undergoes ring opening and recyclization to a thiazolone derivative. A further thiazolone was obtained from this precursor with ethyl chloroacetate employing a bifunctional organocatalyst. Due to its propensity to dehydrogenation evidenced by DFT calculations, the studied thiocarbonohydrazide underwent oxidative cyclizations under different conditions to yield a 1,3,4-thiadiazole and a 1,2,4-triazole derivative, respectively. Thermal isomerisation of 1,3,4-thiadiazole into 1,2,4-triazole was also observed. The DMAD-mediated cyclizations of the S-metylated thiocarbonohydrazide and the 1,5-bis(ferrocenylmethylideneamino)guanidine gave 1,2,4-triazole derivatives and a 4-pyrimidone, respectively. The structure of the new compounds was established by IR and NMR spectroscopy, including HMQC, HMBC and DEPT measurements. The solid state structure of a triazole was revealed by single crystal X-ray analysis.