Experimental and theoretical studies of the products of addition–elimination reactions between benzil dihydrazone and three isomeric chlorobenzaldehydes

Abstract

A series of mono- and di-Schiff bases formed between benzil dihydrazone {BDH; systematic name: (1Z)-[(2E)-2-hydrazinylidene-1,2-diphenylethylidene]hydrazine} and three isomeric chlorobenzaldehydes were designed and synthesized to be used as model compounds to help to explain the reaction mechanisms for the formation of Schiff bases. These compounds are 1-(2-chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine (BDHOCB), and the 3-chloro (BDHMCB) and 4-chloro (BDHPCB) analogues, all having the formula C28H20Cl2N4. Surprisingly, only di-Schiff bases were obtained; our attempts to push the reaction in favour of the mono-Schiff bases all failed. Density functional theory (DFT) calculations were performed to explain the trend in the experimental results. In the case of the systems studied, the type of Schiff base produced exhibits a clear dependence on the HOMO–LUMO energy gaps (ΔEHOMO–LUMO),i.e.the product is mainly governed by its stability. The compounds were characterized by single-crystal X-ray diffractometry, elemental analysis, melting point,1H NMR and13C NMR spectroscopy. The structural features of the three new Schiff bases are similar. For instance, they have the same chemical formula, all the molecules have a symmetrical double helix structure, with each Ph—C=N—N=C—Ph arm exhibiting ananticonformation, and their supramolecular interactions include intermolecular π–π and weak C—H...π stacking interactions. The crystal systems are different, however,viz.triclinic (space groupP\overline{1}) for BDHPCB, monoclinic (space groupP21/n) for BDHOCB and orthorhombic (space groupPnna) for BDHMCB.