Designing a novel tetradentate polyoxometalate eco-catalyst for the synthesis of β-aminocyclohexanone derivatives in water

Abstract

The synthesis of a series of known β-aminocyclohexanones has been accomplished using pentaerythrityl tetramethyl imidazolium phosphotungstate (C(MIM-PTA)₄) as a new tetradentate acidic catalyst. It was prepared via condensation of pentaerythrityl tetrabromide with methyl imidazole. Then, bulky anion H₂PW₁₂O₄₀¹⁻ was substituted with Br⁻ in the structure. This tetradentate catalyst provides designable cations and anions. Anions have two types of acids, acidic protons, and metals with Lewis acidity. In order to test the efficient catalytic behavior of the tetradentate catalyst, a controlled reaction was performed using benzaldehyde, aniline and cyclohexanone. Imine from the condensation of benzaldehyde and aniline was observed in the absence of ionic catalyst instead of desired products. Thus, this reaction would be attractive because of the time, energy, and raw material saving considerations because of the absence of isolation of intermediates and stereospecificity. The catalyst shows high catalytic activity such that after four recycles the product was obtained with high yield and purity. This reaction was performed at room temperature. Although high temperature could improve the reaction rate, it contributes to side reactions and oxidation of aldehyde and amine. The catalyst was characterized by elemental analysis, FT-IR spectroscopy, ¹H NMR, ¹³C NMR, and TGA.