Effect and Mechanism of Aluminum(III) for Guaiacol–Glyoxylic Acid Condensation Reaction in Vanillin Production

Abstract

3-methoxy-4-hydroxymandelic acid (VMA) was the critical intermediate for the synthesis of vanillin by the glyoxylic acid method. Meanwhile, a valuable byproduct (2-hydroxy-3-methoxy-mandelic acid, <i>o</i>-VMA) was obtained during the reaction. Al³⁺ was found to be a helpful catalyst in increasing the selectivity for VMA and <i>o</i>-VMA. In the presence of Al³⁺, the selectivity for VMA and <i>o</i>-VMA increased from 83 to 88% and from 3 to 8%, respectively, while that of the helpless byproduct 2-hydroxy-3-methoxy-1,5-mandelic acid (di-VMA) decreased from 14% to less than 4%. The kinetics based on the kinetic equation of the condensation reaction was studied by the initial concentration method. The results indicated that the involvement of Al³⁺ could reduce the activation energy of the reaction on the basis of the Arrhenius equation. Combined with thermogravimetric analysis, <i>in situ</i> Fourier transform-infrared spectroscopy, and ¹H NMR research, Al³⁺ was found to interact with guaiacol through Al-O and Al···H, which further improved the selectivity of the VMA and <i>o</i>-VMA and reduced the selectivity of di-VMA by adding the electronegativity of the ortho- and para-positions of hydroxyl groups of guaiacol.