Stable carbamate pathway towards organic–inorganic hybrid perovskites and aromatic imines

Methyl ammonium methyl carbamate (MAC), formulated as CH(3)NH(3)(+)CH(3)NHCO(2)(−), was synthesized by reacting liquid methylamine with supercritical CO(2), and its structure was refined by single-crystal X-ray diffraction. MAC is a white crystalline salt and is as reactive as methylamine, and is a very efficient alternative to toxic methylamine. We were able to produce hybrid perovskite MAPbI(3) (MA = methyl ammonium) by grinding MAC with PbI(2) and I(2) at room temperature, followed by storing the mixed powder. Moreover, this one-pot method is easily scalable for the large-scale synthesis of MAPbI(3) in a small vessel. We have also investigated the reactivity of MAC towards aromatic aldehydes in the absence of solvent. The solventless reactions afforded imines as exclusive products with over 97% yield, which show higher selectivity than the methylamine-based synthesis. Complete conversions were typically accomplished within 3 h at 25 °C. The results of this study emphasize the importance of solid carbamates such as MAC to develop an environmentally friendly process for the synthesis of various amine-based materials on the industrial scale.