Correction to "Gravimetric and Thermal-Imaging Characterization of Water-Free Reflux Condensers for Laboratory Applications".

[This corrects the article DOI: 10.1021/acsomega.4c00411.].

Gravimetric and Thermal-Imaging Characterization of Water-Free Reflux Condensers for Laboratory Applications.

Water-free reflux condensers, which use convective cooling from the surrounding air to condense vapors, avoid the need for cooling water, which is more sustainable than water-cooled condensers, and eliminates the risk of flooding, but these devices are newer and less familiar to many chemists, who may never have used them before. To facilitate the shift to water-free condensers, several types of water-free condensers (simple glass tube, Vigreux column, Condensyn, Findenser, and air-cooled Dimroth) were characterized using three different solvents (ethyl acetate, acetone, and tetrahydrofuran) under both gentle and vigorous refluxing conditions to compare their relative performance and determine the condensing capacity/failure point. In addition to experimentally quantifying the performance of each condenser both gravimetrically and via infrared thermal imaging, energy-balance models were developed to gain insight into which factors were most important in driving their performance. Several of the water-free condensers, including the Findenser, Condensyn, and air-cooled Dimroth condenser, were shown to provide suitable performance for most refluxing operations.

Nanoscale organization of thiol and arylsulfonic acid on silica leads to a highly active and selective bifunctional, heterogeneous catalyst.

Ordered mesoporous silicas functionalized with alkylsulfonic acid and thiol group pairs have been shown to catalyze the synthesis of bisphenols from the condensation of phenol and various ketones, with activity and selectivity highly dependent on the distance between the acid and thiol. Here, a new route to thiol/sulfonic acid paired catalysts is reported. A bis-silane precursor molecule containing both a disulfide and a sulfonate ester bond is grafted onto the surface of ordered mesoporous silica, SBA-15, followed by simultaneous disulfide reduction and sulfonate ester hydrolysis. The resulting catalyst, containing organized pairs of arylsulfonic acid and thiol groups, is significantly more active than the alkylsulfonic acid/thiol paired catalyst in the synthesis of bisphenol A and Z, and this increase in activity does not lead to a loss of regioselectivity. The paired catalyst has activity similar to that of a randomly bifunctionalized arylsulfonic acid/thiol catalyst in the bisphenol A reaction but exhibits greater activity and selectivity than the randomly bifunctionalized catalyst in the bisphenol Z reaction.

Cooperative catalysis by silica-supported organic functional groups.

Hybrid inorganic-organic materials comprising organic functional groups tethered from silica surfaces are versatile, heterogeneous catalysts. Recent advances have led to the preparation of silica materials containing multiple, different functional groups that can show cooperative catalysis; that is, these functional groups can act together to provide catalytic activity and selectivity superior to what can be obtained from either monofunctional materials or homogeneous catalysts. This tutorial review discusses cooperative catalysis of silica-based catalytic materials, focusing on the cooperative action of acid-base, acid-thiol, amine-urea, and imidazole-alcohol-carboxylate groups. Particular attention is given to the effect of the spatial arrangement of these organic groups and recent developments in the spatial organization of multiple groups on the silica surface.

Organized surface functional groups: cooperative catalysis via thiol/sulfonic acid pairing.

The synthesis and characterization of heterogeneous catalysts containing surfaces functionalized with discrete pairs of sulfonic acid and thiol groups are reported. A catalyst having acid and thiol groups separated by three carbon atoms is ca. 3 times more active than a material containing randomly distributed acid and thiol groups in the condensation of acetone and phenol to bisphenol A and 14 times more active in the condensation of cyclohexanone and phenol to bisphenol Z. Increasing the acid/thiol distance in the paired materials decreases both the activity and selectivity. This work clearly reveals the importance of nanoscale organization of two disparate functional groups on the surface of heterogeneous catalysts.