Simultaneous activation of aldehydes and methylamine liberation by 4,4ʹ-trimethylenedipiperidine in the solid-state synthesis of N-methyl imines

摘要

Abstract The commercially available 4,4ʹ-trimethylenedipiperidine (TMDP) was used in the solid state to activate various aldehydes and controlled the libration of methyl amine for preparing the corresponding N-methyl imines. It was indicated that TMDP could play multiple roles simultaneously in this reaction, including (a) a bifunctional base with a predicted pKa ~ 11 and a good scavenger of acid, (b) a catalyst able to form strong hydrogen bonding and chemical interactions with aldehyde functional group through hemiaminal and/or iminium intermediate, and (c) liberating methyl amine from its salt viz. methylammonium chloride. TMDP could be regenerated by neutralization. It was also regenerated by heating at 70 °C, which is reported for the first time according to the best of our knowledge. The regenerated reagent was stable regarding its chemical structure, and there was no significant loss in the catalytic efficiency even after several runs. The mechanism was investigated by performing several control reactions and studying the FTIR and NMR spectra in the solid-state synthesis. The current work demonstrated TMDP as a safe and greener promoter-acid scavenger for organic transformations compared with toxic, flammable, volatile liquid secondary amines such as piperidine.Graphical abstract