Control of selectivity in the preparation of 2-substituted benzoazoles by adjusting the surface hydrophobicity in two solid-based sulfonic acid catalysts.

A series of metal-free tandem reactions for the synthesis of pharmaceutically important 2-substituted benzoazoles from isothiocyanates and 2-aminothiophenol under catalyst-free conditions in the presence of Et-PMO-Me-PrSO3H (1a) and SBA-15-PrSO3H (1b) as solid acids were carried out in a highly selective way under solvent free conditions. A significant selectivity changeover toward either 2-mercaptobenzoxazole or 2-aminobenzoazole derivatives could be achieved by changing the employed catalyst from the relatively hydrophobic material 1a to the more hydrophilic catalyst 1b. This simple experimental procedure with a novel selective approach toward benzoazoles accompanied by green and reusable catalysts could be considered as an alternative to the existing methods for the synthesis of 2-substituted benzoazole derivatives.

Novel Ordered Mesoporous Carbon Based Sulfonic Acid as an Efficient Catalyst in the Selective Dehydration of Fructose into 5-HMF: the Role of Solvent and Surface Chemistry.

Novel ionic liquid derived ordered mesoporous carbons functionalized with sulfonic acid groups IOMC-ArSO3H and GIOMC-ArSO3H were prepared, characterized, and examined in the dehydration reaction of fructose into 5-hydroxymethylfurfural (5-HMF) both in aqueous and nonaqueous systems. To study and correlate the surface properties of these carbocatalysts and some other SBA-15 typed solid acids with 5-HMF yield, hydrophilicity index (H-index) were employed in the fructose dehydration. Our study systematically declared that almost a criterion may be expected for application of solid acids in which by increasing H-index value up to 0.8 the HMF yield enhances accordingly. More increase in H-index up to 1.3 did not change the HMF yield profoundly. Although, it has been shown that the catalyst with larger H-index (∼1.3) resulted in higher activity both in aqueous and 2-propanol systems, during the recycling process deactivation occurs because of more water uptake and the catalysts with optimum amount of H-index (∼0.8) is more robust in the dehydration of fructose.