"In-water" Dehydration Reaction of an Aromatic Diol on an Inorganic Surface.

ABSTRACT

The effect of a synthetic saponite surface on the "in-water" dehydration reaction of diol was examined using 4-formyl-1-methylquinolinium salt (MQu+) as a substrate. The equilibrium between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was affected by the surrounding environment. The equilibrium behavior was observed by 1H nuclear magnetic resonance (NMR) and UV-vis absorption measurements. Although MQu+ was completely in the form of MQu+-Diol in water, the equilibrium almost shifted to the MQu+-Aldehyde side when MQu+ was adsorbed on the saponite surface in water. In addition, the MQu+-Aldehyde ratio depended on the negative charge density of saponite. The factors that determine MQu+-Aldehyde MQu+-Diol ratio were discussed from the thermodynamic analysis of the system. These data indicate that the electrostatic interaction between the charged saponite surface and MQu+ stabilized the aldehyde side enthalpically and destabilized it entropically. The major reason for these results is considered to be the difference in adsorption stabilization between MQu+-Aldehyde and MQu+-Diol on saponite surfaces.