Synthesis Of Ethers Research Articles

Facile Synthesis and Antitumor Activity of o-Iodoaromatic Ether

Abstract: In this study, an efficient method for the synthesis of one type of aromatic ether was introduced, and its antitumor activity was investigated. Specifically, (diacetoxyiodo)arene was prepared from 2-methyliodobenzene and used to oxidize the 4-nitrophenol to give the aromatic ether. Our study further found that aromatic ether has a strong apoptotic effect on U937 monocytes, suggesting that it might be developed as a new drug for the treatment of acute myeloid leukemia.

Diverse Synthesis of (Thio)ethers and (Thio)esters Using Halodiborylmethane as a Transformable C1 Building Block.

The development of effective strategies to forge C-O and C-S bonds in diverse chemical spaces is of considerable interest in synthetic organic chemistry. Herein we report a versatile approach for the modular synthesis of structurally diverse (thio)ethers and (thio)esters via homologative coupling of α-halodiborylmethane followed by transformation of the introduced diborylmethyl group. This method accommodates a wide array of oxygen- and sulfur-containing molecules, including biologically active compounds. The initial coupling exhibits a broad substrate scope, while subsequent diversification of the diborylmethyl moiety enables access to various structural motifs through deborylative alkylation, Zweifel olefination, and boron-Wittig reaction. This protocol efficiently generates diversely functionalized (thio)ethers and (thio)esters, expanding the toolkit for accessing biologically relevant scaffolds.

Preparation of chiral polyether dendrimer and its non-bonding immobilized CALB for high enantioselective synergy resolution of amines

Monodisperse polyethylene glycol monomethyl ether and chiral glycidyl tosylate were utilized as substrates in the synthesis of the chiral monomer unit epoxypropyl polyethylene glycol monomethyl ether (MPEGn-EPO). The initiator propargyl-terminated polyethylene glycol alkyne-PEG3-OH was employed, while the phosphazene base P4-t-Bu facilitated the controlled ROP of MPEGn-EPO, resulting in clickable dendritic P(MPEGn-EPO) with terminal alkyne. The chiral four-arm dendritic polymer 4-Arm-PEG3-Mn was synthesized through a click reaction between 4-Arm-PEG3-N3 and P(MPEGn-EPO) using Cu(PPh3)3Br/CuBr as a catalyst. Candida antarctica lipase B (CALB) was chosen as a model enzyme for the preparation of a non-covalently immobilized biocatalyst (CALB-M) via a simple adsorption process with magnesium silicate and 4-Arm-PEG3-M4-20. The immobilized lipase CALB-M16 demonstrated high enzyme activity in the resolution of racemic amines, yielding chiral amines with enantioselectivity up to 99 % ee. Circular dichroism (CD) analysis indicated the formation of helical conformation in the dendritic polyethers 4-Arm-PEG3-M16-20 in the presence of magnesium silicate at 5 °C. The polyethylene glycol side groups of 4-Arm-PEG3-M16-20 are suggested to potentially form a crown ether-like structure with magnesium ions, which could enhance steric hindrance and induce a right-handed helix. Furthermore, the helical structure of this dendritic polyether is thought to work in synergy with CALB, improving the enantioselective resolution of amines.

Photoinduced synthesis of polymer-coated covalent organic framework microspheres for highly efficient lithium recovery

The increasing demand for lithium-ion batteries has led to a surge in global lithium consumption, calling for efficient extraction and recovery methods. Adsorption-based lithium recovery has gained attention for its simplicity, selectivity, and low energy requirements. However, conventional adsorption materials for lithium-ion (Li+) suffer from low surface area and covered active sites, resulting in slow recovery and inefficient uptake. Herein, we present a facile photoinduced synthesis of crown ether (CE)-based polymer grafted covalent organic framework (COF) microspheres, termed COF-CE, as an efficient lithium adsorbent. The COF-CE hybrid material possesses abundant nanochannels and highly porous surfaces, enabling rapid ion diffusion and enhancing ion accessibility to functional groups with the exclusive selectivity imparted by the grafted CE polymer towards Li+ over other monovalent cations. Notably, COF-CE exhibits exceptional absorption capacity (7.4 mg/g), rapid adsorption rates (k2 = 0.137 g mg−1 min−1) and high selectivity towards Li+, outperforming existing adsorbents. Moreover, COF-CE demonstrates remarkable Li+ regeneration and recycling capabilities, achieving near-unity recovery of lithium during the desorption phase and retaining 97 % of its adsorption capacity after five cycles. These results highlight the potential of COF-CE as an advanced adsorbent for lithium recovery in various applications, including industrial wastewater treatment and environmental remediation efforts.

SEPS functionalized PEG copolymer for improved toughness without obvious plasticization in epoxy resin

AbstractThe effects of grafting level of polyethylene glycol (PEG) grafted styrene ethylene propylene styrene (SEPS) on the intrinsic brittleness of epoxy thermosets were studied. The SEPS‐g‐PEG block copolymer (BCP) was synthesized by grafting various grafting degree of PEG (i.e., 10%, 20%, 30%, and 40%) on polystyrene (PS) blocks of SEPS following Williamson ether synthesis method. A total of 10 wt% of the BCP modifiers were dispersed in epoxy thermosets. PEG side chains were miscible in the epoxy which formed a uniform BCP dispersion within the epoxy thermoset matrix. As the degree of PEG grafting was increased, the BCP phase was absorbed in the epoxy matrix. This absorption occurred because the increase in PEG grafting provided more miscible PEG chains to bind the BCP and epoxy nanostructures together. The differential scanning calorimeter and dynamic mechanical thermal analysis analyses indicated that BCP toughened epoxy exhibited an improved glass transition temperature (Tg). At a 40% PEG grafting degree in the BCP, the critical stress intensity factor (KIC) and critical strain energy release rate (GIC) increased up to 80% and 180%, respectively. This trend suggested that the energy associated with fractures could be absorbed through the deformation of the softer phases when a load was applied to them.

Kinetic and Thermodynamic Requirements for Polyoxymethylene Dimethyl Ether Synthesis Catalyzed by Ion-Exchange Resin

Kinetic and Thermodynamic Requirements for Polyoxymethylene Dimethyl Ether Synthesis Catalyzed by Ion-Exchange Resin

Behavioral and electrophysiological responses of the male medfly, Ceratitis capitata, to thymol and carvacrol ethers.

The Mediterranean fruit fly, Ceratitis capitata, is one of the most economically important insect pests attacking fruits and vegetables in tropical and subtropical areas of the world. Semiochemical-based pest management programs are being used to provide environmentally friendly control methods for medflies. The goals of the current study were to discover potential new, attractive, kairomones by designing, synthesizing, and testing simplified ethers of thymol and carvacrol along with their ether derivatives in short-range attraction assays and electroantennogram (EAG) assays with male C. capitata. To the best of our knowledge, this study represents the first investigation of thymol and carvacrol, and their respective ethers for attractancy to C. capitata, a major agricultural pest worldwide. In short-range attraction bioassays, parent compounds, thymol and carvacrol, along with their propyl, butyl, benzyl, and octyl ethers captured the most male C. capitata. The attraction patterns changed over time and captures were only significant if they were greater than the positive controltea tree oil (TTO) at 90 min. In EAG assays, thymol benzyl, octyl ethers, and carvacrol benzyl ether evoked significantly greater antennal responses than their parent compounds. The EAG responses did not correlate with short-range male attraction. The aliphatic side chains of thymol and carvacrol had a small effect on the activity. Future studies will investigate the long-range attraction of the ethers that elicited large EAG responses. This report provides new information for discovering potential kairomones through synthesis and structure-activity studies for sterile male medflies. Thymol, carvacrol, and several of their ether derivatives displayed improved longevity of attraction compared with TTO (a strong medfly attractant), with significantly higher captures than TTO observed at 90 min in laboratory bioassays. Further chemical synthesis of thymol and carvacrol ethers within this series may lead to the development of ethers that are more attractive or persistent than their parent compounds, thymol and carvacrol. © 2024 Society of Chemical Industry. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Multigram two-step synthesis of difluoromethyl ethers from aliphatic alcohols and glycols

A convenient method for synthesis of alkyl(difluoromethyl)ethers, including subsequent stages of chlorination and fluorination of the O-formyl derivatives was investigated on series of aliphatic alcohols and glycols. Primary and secondary alcohols are converted to the corresponding O-difluoromethyl derivatives in high yield, polydifluoromethyl derivatives of 1,3-propyleneglycol, diethyleneglycole and pentaerythritol can only be successfully obtained with this procedure.

Efficient Flow Synthesis of Glycidyl Ether Using BuSnCl3 as a Mild Lewis Acid

AbstractA ring-opening protocol of epichlorohydrin with 2-ethylhexanol was investigated for the synthesis of the corresponding chlorohydrin ether. BuSnCl3 proved to be an efficient mild Lewis acid catalyst, yielding the product with high selectivity. A scalable flow synthesis was achieved by modifying the flow setup. The flow synthesis of the corresponding glycidyl ether from the chlorohydrin ether was also carried out in an efficient manner by using the basic treatment.

Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones.

Acylsilanes are emerging bench-stable reagents for the generation of electron-rich oxycarbenes that are difficult to access with unstable diazo compounds. Herein, we report a siloxycarbene-mediated stereoselective synthesis of silyl enol ethers through visible-light-induced intermolecular reactions between acylsilanes and α,β-unsaturated ketones. Both the solvent and low temperature are important for the success of the reaction. This approach features atomic economics, exclusive stereocontrol, and broad substrate scope. The synthetic potential of this methodology is demonstrated by gram-scale reaction and various downstream transformations including that requiring configuration purity of the silyl enol ethers.

Effect of TiO2 on Acidity and Dispersion of H3PW12O40 in Bifunctional Cu-ZnO(Al)-H3PW12O40/TiO2 Catalysts for Direct Dimethyl Ether Synthesis

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.

Reducing Energy Consumption in the Synthesis of Dimethyl Ether (DME) from Methanol Dehydration by Modifying Heat Transfer Unit Using Aspen HYSYS

In the pursuit of a transport sector free from fossil fuels, the incorporation of Dimethyl ether (DME) emerges as a commendable ecological substitute. The DME is a synthetically produced serves as a viable alternative to conventional fuels such as diesel and liquified petroleum gas (LPG). The Dimethyl Ether (DME) production is carried out by catalytic dehydration of methanol over an acidic zeolite-based catalyst. The technological process for the DME synthesis was simulated using Aspen HYSYS based on the combined operating parameters of the reaction dynamic model for the methanol dehydration reaction. This paper attempts to evaluate a modification in dehydration of methanol process to reducing energy consumption by modifying heat transfer unit. The heater and cooler heat transfer units were converted into heat exchangers (HE) by utilizing the output of the process that can be used for other processes so that energy consumption is reduced. The temperature of reaction and the heat transfer unit are modified to reduce energy consumption from 11.850 MMBtu/h to 7.6291 MMBtu/h by changing one heater and one cooler with two heat exchangers. Copyright © 2024 by Authors, Published by Universitas Diponegoro and BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Improving Net Energy Efficiency of Dimethyl Ether Production Process by Methanol Dehydration

Dimethyl ether (DME) is a source of fuel that produces clean energy for the future. Methanol can be used as a raw material for the manufacture of DME as a natural gas that is treated for synthesis. This paper evaluates how to improve net energy efficiency in DME production and how to review the net energy efficiency calculations in DME production. Methods used for production of DME are methanol dehydration, thermodynamics examination, also improving the net energy efficiency of DME with the addition of the heat exchanger (E-100), the addition of a heater (E-104) before entering a column (T-102), and moved the mixer position before the heater (E-100). By modifying the addition of a heat exchanger (E-100), heater (E-104), and changing the position of the mixer in DME production, it has been proven that it can reduce energy requirements in the dimethyl ether synthesis process from methanol and increase net energy efficiency by up to 98.83%. The results of the case study indicate that the addition heat exchanger (E-100) able to reduce the heater load after the creation process and remove the cooler (E-101) that existed before creation, then the addition of the heater (E-104) serves to reduce the load of Qcond2 and Qreb2 on columns (T-102), also the position of the mixer for the methanol recycling flow is moved before the heater (E-100) is intended to remove the heaters (E-103). Copyright © 2024 by Authors, Published by Universitas Diponegoro and BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Novel side-reactor dividing wall column and reactive distillation process for enhanced electronic-grade propylene glycol monomethyl ether acetate production

The semiconductor industry is experiencing rapid growth and has become one of the largest sectors in the world. Propylene glycol monomethyl ether acetate (PGMEA) is prized for its exceptional properties and its ability to meet the stringent requirements as a solvent for electronic processing. This work aims to enhance the production of electronic-grade PGMEA through a practical and advanced intensified configuration. First, the kinetic reactor for propylene glycol monomethyl ether (PGME) synthesis has been modeled and pinpointed optimal operating conditions through sensitivity analysis. Subsequently, several process alternatives incorporating intensified techniques, such as the dividing wall column (DWC), pressure swing distillation (PSD), reactive DWC (RDWC), and side-reactor DWC (SR-DWC), have been investigated. These processes have been systematically designed and optimized through a sequential design procedure. Response surface methodology, a practical optimization method, has been employed to optimize the complex column's structure with the help of Aspen Plus and Minitab. Energy requirements and costs of all process alternatives were evaluated for a fair comparison. The SR-DWC-RD process has emerged as the most promising option, as it can save up to 11.5 % in energy requirements and 19.9 % in total annual costs. This practical design, complete with detailed optimal design parameters, presents significant opportunities for improving industrial PGMEA production.

Directional synthesis and application of long-chain ethers from biomass-derived carbonyls

The work introduced an innovative pathway for converting biomass-derived carbonyls into long-chain ethers, examining their low-temperature oxidation in a modified Cooperative Fuel Research (CFR) engine. The conversion of 2-butanone achieved 100 % and the selectivity of sec-butyl isopropyl ether reached the maximum of 83.13 % under optimal reaction conditions. Conversion of biomass-derived carbonyls increased from 31.77 % at 1 h to 36.28 % at 12 h, with the mass yield of long-chain ethers rising from 53.94 % to 62.86 %. At the same compression ratio, the maximum in-cylinder pressure and temperature increased as the long-chain ethers blending ratio increased. At the critical compression ratio, the net heat release rates (NHR) for blended fuels with 10 vol%, 20 vol% and 30 vol% long-chain ethers at the low-temperature heat release peak were 9.6 J/deg, 10.1 J/deg, and 10.0 J/deg better than that of n-heptane (6.3 J/deg), respectively. CO emissions from blended fuels before compression ignition were higher than n-heptane, while the value for the blended fuel with 30 vol.% long-chain ethers was reduced by 44.97 % compared to n-heptane after autoignition.

Does Direct Dimethyl Ether Synthesis from Carbon Dioxide and Hydrogen Yield More Valuable Products than the Equivalent Methanol Production? A Review on Recent Work

AbstractDimethyl ether (DME) has promising properties as e‐fuel and platform chemical. Its direct synthesis from CO2 and hydrogen, which is thermodynamically more favorable than the indirect route over methanol, is reviewed. Systematic thermodynamic equilibrium calculations are evaluated and compared to bifunctional catalysis experiments performed with Cu/ZnO/ZrO2 methanol catalyst and ferrierite or heteropolyacid‐coated dehydration catalysts under thermodynamic and kinetic conditions. In the thermodynamic region, the methyl yield of direct DME synthesis is superior over sole methanol synthesis. Significant differences among the solid acids used are absent. However, under kinetic conditions, the heteropolyacid‐coated catalysts show superior performance for dehydration over zeolites.

Preparation and catalytic evaluation of phosphated zirconia nanopowder for ethanol dehydration into diethyl ether

Research on renewable energy development is intensified nowadays, including the production of diethyl ether (DEE) as a high-value alternative fuel. This study explored the catalytic conversion of ethanol into diethyl ether using a phosphated zirconia catalyst. We examined different concentrations of phosphoric acid (1, 2, 3, and 4 M) and calcination temperatures (400, 500, and 600 °C) applied to zirconia nanopowder to evaluate their influence on the acidity of the resulting phosphated zirconia. The catalysts were characterized by FTIR, XRD, SAA, SEM-EDX Mapping, and TG-DTA. Among the catalysts tested, the PZ-2-400 catalyst, prepared with a 2 M H3PO4 concentration and calcined at 400 °C, exhibited the highest acidity value of 0.56 g/mol pyridine. When operated at the optimum temperature of 225 °C, this catalyst achieved an ethanol conversion of 80.04 % and a diethyl ether yield of 1.00 %. These findings suggest that modification of ZrO2 with phosphoric acid acts as a solid acid catalyst for diethyl ether synthesis with better activity and selectivity than unmodified ZrO2.

Synthesis and evaluation of phosphoric ester pyrogallic acid hexaglycidyl ether as a green corrosion protective agent in the gas and oil industries

Synthesis and evaluation of phosphoric ester pyrogallic acid hexaglycidyl ether as a green corrosion protective agent in the gas and oil industries

Electrochemical Deconstructive and Ring-Expansion Functionalization of Unstrained Cycloalkanols.

An efficient and sustainable electrochemical method for the synthesis of cyclic ethers and acyclic aldehydes from alkanols has been reported. This strategy has been successfully applied to cycloalkanols bearing different ring sizes and different types of nucleophiles. In addition, mechanistic investigations show that the reactions undergo sequential processes, including anodic oxidation, β-scission, and nucleophilic addition. This method provides a new synthetic approach to constructing cyclic ethers and terminal aldehydes from cycloalkanols and nucleophiles.

Pillared Bentonite Materials as Potential Solid Acid Catalyst for Diethyl Ether Synthesis: A Brief Review

Pillared Bentonite Materials as Potential Solid Acid Catalyst for Diethyl Ether Synthesis: A Brief Review