ATR-IR Spectroscopy of Pendant NH2 Groups on Silica Involved in the Knoevenagel Condensation

Abstract

The liquid-phase Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate catalyzed by aminopropyl-modified silica has been investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. The aim of the work was to demonstrate the different levels of information on the reaction mechanism that can be achieved by operating the spectroscopic cell in the absence and in the presence of a solvent, in flow-through and stop-flow modes and in combination with concentration modulation spectroscopy. The reaction mechanism involves the formation of an imine intermediate whose existence has been verified in situ by combining in one experiment continuous and stop-flow operations. Identical information has been gained more elegantly using concentration modulation spectroscopy, which additionally provided information on the possible origin of the solvent effect observed in the Knoevenagel reaction. Faster production and consumption of the imine intermediate was observed in cyclohexane solvent than in toluene. Identification of other species evolving on the catalyst surface and monitoring of the effluents of the spectroscopic cell provided some insight in possible catalyst deactivation.