Towards Efficient Acidic Catalysts via Optimization of SO3H-Organosilane Immobilization on SBA-15 under Increased Pressure: Potential Applications in Gas and Liquid Phase Reactions

In this paper, the optimization of the synthesis of catalysts based on acidic mesoporous silica of the SBA-15 type by post-synthesis immobilization of 3-(trihydroxysilyl)-1-propanesulfonic acid (TPS) under increased pressure up to 20 bar is reported. Sample structures and composition were examined by XRD measurement, low-temperature N2 adsorption/desorption and elemental analysis. The catalytic activities of the materials obtained were determined in both gas and liquid phase processes, i.e., by esterification of acetic acid and glycerol dehydration, respectively. The optimum pressure for modification leading to the highest number of acidic sites was found to be 10 bar. The final material was very active and stable in liquid phase processes; however, the stability in the gas-phase process was unsatisfactory due to the loss of sulphonic species from the catalyst surface.

Continuous synthesis of bromoalkyl glycosides by Fischer glycosylation in a microreactor

In this study, bromoalkyl glycosides were successfully synthesized in microreactor scale by Fischer glycosylation. Yields between 24 and 40% after purification were achieved using various acidic catalysts and conditions. In some experiments, yields 180% higher than with previously known methods could be achieved. This study showed also that reversed-phase flash chromatography is more successful than normal-phase flash chromatography for the purification of bromoalkyl glycosides. Furthermore, longer bromoalcohols were shown to be more compatible than shorter bromoalcohols under these reaction conditions.

Design and synthesis of a new magnetic metal organic framework as a versatile platform for immobilization of acidic catalysts and CO2 fixation reaction

The first report of the use of an acidic magnetic metal organic framework for the chemical fixation of CO2 as an environmentally friendly reaction.

N-triflylphosphoramides: Highly Acidic Catalysts for Asymmetric Transformations

N-triflylphosphoramides (NTPA), have become increasingly popular catalysts in the development of enantioselective transformations as they are stronger Brønsted acids than the corresponding phosphoric acids (PA). Their highly acidic, asymmetric active...

Homogenous Acidic and Basic Catalysts in Biodiesel Synthesis: A Review

Several techniques, in which different homogenous catalysts and procedures, that are in use for transesterification of a vegetable oil or an animal fat have been successful in synthesizing biodiesel, although with some certain limitations. For such a purpose, among the catalysts employed are acidic as well as basic catalysts. It has been found that acidic catalysts can be tolerant with a high content of free fatty acids found in those low value feedstock oils/fats to be transesterified, although some sort of pretreatment by means of esterification might be required in order to synthesize biodiesel. Moreover, with employing homogenous acidic catalysts, it seems that biodiesel purification procedures are simplified; thus, reducing synthesis cost. In fact, these features of homogenous acidic catalysts render them advantageous over basic ones. With basic homogenous catalysts this; however, has not been possible due to the development of saponification reaction. To effectively perform, such catalysts require that the content of free fatty acids in the feedstock oil/fat is minimal. This requirement is also applicable to the moisture level in the feedstock. In terms of corrosive effects; nevertheless, acidic catalysts are disadvantageous compared to basic ones.

A Hybrid Cellular-Heterogeneous Catalyst Strategy for the Production of Olefins from Glucose

Living systems provide a promising approach to chemical synthesis, having been optimized by evolution to convert renewable carbon sources such as glucose to an enormous range of small molecules. However, a large number of synthetic structures can still be difficult to obtain solely from cells, such as unsubstituted hydrocarbons. In this work, we demonstrate the use of a hybrid cellular-heterogeneous catalytic strategy to produce olefins from glucose, using a selective hydrolase to generate an activated intermediate that is readily deoxygenated. Using a new family of iterative thiolase enzymes, we have genetically engineered a microbial strain that produces 4.3 ± 0.4 g L−1 of fatty acid from glucose with 86% captured as 3-hydroxyoctanoic and 3-hydroxydecanoic acids. This 3-hydroxy substituent serves as a leaving group enabling heterogeneous tandem decarboxylation-dehydration routes to olefinic products on Lewis acidic catalysts without the additional redox input required for enzymatic or chemical deoxygenation of simple fatty acids.

Recent Advances in Continuous-Flow Reactions Using Metal-Free Homogeneous Catalysts

Developments that result in high-yielding, low-cost, safe, scalable, and less-wasteful processes are the most important goals in synthetic organic chemistry. Continuous-flow reactions have garnered much attention due to many advantages over conventional batch reactions that include precise control of short reaction times and temperatures, low risk in handling dangerous compounds, and ease in scaling up synthesis. Combinations of continuous-flow reactions with homogeneous, metal-free catalysts further enhances advantages that include low-cost and ready availability, low toxicity, higher stability in air and water, and increased synthetic efficiency due to the avoidance of the time-consuming removal of toxic metal traces. This review summarizes recently reported continuous-flow reactions using metal-free homogeneous catalysts and classifies them either as acidic catalysts, basic catalysts, or miscellaneous catalysts. In addition, we compare the results between continuous-flow conditions and conventional batch conditions to reveal the advantages of using flow reactions with metal-free homogeneous catalysts.