Diethyl Ether Research Articles

Linear Inverse Sandwich Complexes of Tetraanionic Benzene Stabilized by Covalent δ-Bonding with Late Lanthanides.

A series of dilanthanide benzene inverse sandwich complexes of the type (CpiPr5Ln)2(μ-η6:η6-C6H6) (1-Ln) (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpiPr52Ln2I4 (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bzcentroid distances of 1-Ln are the shortest distances observed to date, ranging from 1.943(1) Å for 1-Tm to 2.039(6) Å for 1-Gd. Structural, spectroscopic, and magnetic analyses together with density functional theory calculations support the presence of a rare, unsubstituted tetraanionic benzene in each compound, which is stabilized by strong covalent δ bonding interactions involving the filled π* orbitals of (C6H6)4- and vacant dxy and dx2-y2 orbitals of the Ln3+ ions. Notably, 1-Ln are the first examples of compounds of the later lanthanides to feature an unsubstituted tetraanionic benzene.

An Effective Synthesis of Phosphated Silica (PO<sub>4</sub>/SiO<sub>2</sub>) Catalyst and its Performance for Converting Ethanol into Diethyl Ether (DEE)

Research on phosphated silica (PO4/SiO2) as a heterogeneous acid catalyst in the dehydration reaction of ethanol into diethyl ether has been carried out. The PO4/SiO2 was prepared from TEOS by a wet impregnation method with various concentrations of H3PO4 (1, 2, 3, 4 M) and calcination temperatures (400, 500, and 600 °C) to obtain it with an optimum acidity. Afterward, the catalysts were characterized by FTIR, XRD, SEM-EDX, SAA, and TG-DTA. Ethanol dehydration was run using a fixed-batch reactor with a flow of N2 gas, and GC determined the selectivity of diethyl ether. The PS-4-400 catalyst had the highest activity and selectivity in the ethanol dehydration to diethyl ether at a temperature of 225 °C, with a conversion of 58.00% and a DEE selectivity of 3.71%.

Nickel Oxide-Impregnated Phosphated Silica Catalyst: Synthesis and Application for Ethanol Dehydration into Diethyl Ether (DEE)

The synthesis, characterization, and application of a NiO-PO4/SiO2 catalyst for ethanol dehydration to diethyl ether were successfully conducted. The sol-gel method utilized TEOS as the silica source, NaHCO3 as a template, and different phosphoric acid concentrations (1, 2, and 3 M). Calcination occurred at temperatures of 400, 500, and 600 °C. The catalyst with the highest acidity underwent impregnation with 1, 2, and 3% (w/w) nickel precursor proceeded by calcination with N2 gas. Characterization techniques included FTIR, XRD, SEM-EDX, and AAS. The application of SP 2-NiO 3% catalyst as the catalyst with the highest acidity demonstrated significant activity and selectivity in diethyl ether production at 175, 200, and 225 °C temperatures, yielding 88% conversion and 5.07% diethyl ether selectivity at its optimum temperature of 225 °C.

Qualitative Analysis of Daphnane Diterpenoids in Various Parts of Daphne pontica L. by UHPLC-Q-Exactive-Orbitrap MS.

Daphne pontica L. is an evergreen shrub that is recorded as an anti-diarrheic plant in Turkish folk medicine. Previous studies on D. pontica have reported, albeit slightly, the isolation of daphnane diterpenoids, but no systematic phytochemical analysis of daphnane diterpenoids has been conducted. This study aimed to comprehensively investigate daphnane diterpenoids in the extracts from the different parts (stems, leaves, and fruits) of D. pontica. An ultra-high-performance liquid chromatography coupled with Q-Exactive hybrid quadrupole Orbitrap mass spectrometer (UHPLC-Q-Exactive-Orbitrap MS) was used for the qualitative analysis of D. pontica. The stems, leaves, and fruits of D. pontica were extracted with diethyl ether. Each extract was then pretreated by a solid phase extraction cartridge and subjected to LC-MS/MS analysis. Detected daphnane diterpenoids were tentatively identified by comparison with an in-house daphnane library, and their chemical structures were estimated in detail by MS/MS fragmentation evaluation. A total of 33 kinds of daphnanes were identified from the different parts of D. pontica, and were classified into three subtypes: daphnane orthoester, polyhydroxy daphnane, and macrocyclic daphnane orthoester. Among them, six daphnanes were postulated to be previously unreported compounds based on MS/MS fragmentation elucidation. Furthermore, the three plant parts showed similar daphnane diterpenoid profiles, with the stems containing the most abundant daphnane diterpenoids. This is the first study to perform qualitative analysis of daphnane diterpenoids systematically and comprehensively in different parts of D. pontica. The results revealed that D. pontica is a plant resource rich in a variety of daphnane diterpenoids.

Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.

Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.

A Rare Example of a Gallium-Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF5)3.

The Lewis superacid Ga(OTeF5)3 has been synthesized and characterized, revealing a monomeric structure in solution and a dimeric structure in the solid state. Isolated adducts of Ga(OTeF5)3 with strong and weak Lewis bases have been characterized spectroscopically as well as by single-crystal X-ray diffractometry. The Lewis acidity of this new species has been evaluated by means of different experimental and theoretical methods, which has allowed to classify it as one of only a few examples of a gallium-based Lewis superacid. The high Lewis acidity of Ga(OTeF5)3 was used to amplify the strength of the Brønsted acid HOTeF5, leading to the protonation of diethyl ether. Furthermore, Ga(OTeF5)3 was utilized to access the strong oxidizing system Ga(OTeF5)3/Xe(OTeF5)2 in SO2ClF, which was successfully employed in the synthesis of the dimethyl chloronium salt [Cl(CH3)2][Ga(OTeF5)4], a strong electrophilic methylation reagent.

BF3 ⋅ OEt2 as a Versatile Reagent: Applications in Organic Synthesis

AbstractBoron trifluoride diethyl etherate, commonly referred to as BF3 ⋅ OEt2, plays a crucial role as a potent reagent in various organic transformations, particularly in the synthesis of heterocyclic systems through the establishment of carbon‐carbon & carbon‐heteroatom bonds. Its Lewis acid properties, reactivity, and stability at room temperature make it essential for a wide range of chemical reactions. BF3 ⋅ OEt2 demonstrates remarkable efficacy in processes such as hydroxylation of double bonds, epoxide cleavage, acid esterification, cyanation, coupling, and diverse cyclization reactions, surpassing other Lewis acids in performance. Its significant impact on organic synthesis extends to the formation of natural products, highlighting its profound significance in the realm of chemistry. The unique properties and versatility of boron trifluoride diethyl etherate make it a fundamental tool for a diverse array of chemical transformations. The numerous applications of this reagent in organic synthesis have prompted the development of a comprehensive review, focusing on its various roles and contributions in this field.

Low-cost green antisolvent with an ultrawide processing window for efficient and stable perovskite solar cells

Antisolvent engineering is one of the most useful strategies to get high-efficiency perovskite solar cells (PSCs). Nevertheless, the most present commonly used effective antisolvents, such as chlorobenzene and diethyl ether, are toxic and expensive. Moreover, these antisolvents applied in PSCs are rather restricted due to their narrow processing window. Herein, we report a low-cost green antisolvent isopropanol (IPA) that displays ultrawide processing window, which dramatically enhances the reproducibility of PSCs. The highest power conversation efficiency of PSCs treated by IPA can reach as high as 24.8%. The origin of IPA effects is further disclosed by the intermolecular hydrogen-bonding force between IPA and DMF/DMSO, and the force can effectively remove DMF/DMSO in the spinning perovskite precursor film and helpfully enhance perovskite crystal growth with less carrier recombination as demonstrated by using various techniques. Our results here demonstrate a cheap green antisolvent for reproducible, high-efficient, stable PSCs and also provide an in-depth understanding the significant role of antisolvent in the fabrication of PSCs.

Explosion limits of binary mixtures of ammonia and additives (hydrogen, natural gas, and diethyl ether)

This study investigates the explosion limits of ammonia (NH3) and the effect of three different active fuels, hydrogen (H2), natural gas (NG), and diethyl ether (C2H5OC2H5, DEE), on the explosive characteristics of NH3 through comprehensive chemical kinetics analysis. The results reveal that the explosion limits of NH3 exhibit the narrowest explosive range and display comparatively weakest explosive reactivity among the four fuels, presenting a monotonic changing trend. Reaction pathway analysis unveils that with increasing temperature, NH2 tends to oxidize more predominantly through the NH-N2H2-NNH-N2 pathway, while the conversion of NH2 to H2NO pathway decreases. Therefore, the introduction of active fuels significantly enhances the explosive reactivity of NH3. However, their impact under various temperature-pressure conditions presents nuanced and diversified characteristics. When a 0.5 % mole fraction of active fuel is added to NH3, DEE exhibits the most significant enhancement in medium to high-pressure conditions, while H2 predominates at low pressure, with NG consistently demonstrating the least pronounced enhancement. Upon the active fuel proportion being increased to 20 %, the promoting effect of DEE remains the most significant in the medium to high-pressure region, while NG has surpassed H2 as the secondary dominant fuel. In the low-pressure region, NH3-H2 still demonstrates the highest reactivity, followed by NH3-DEE, while NH3-NG exhibits the least reactivity. These findings provide valuable insights into the widespread utilization and scientific exploration of ammonia as a fuel source.

Effect of Solvent and Cholesterol on Liposome Production by the Reverse-Phase Evaporation (RPE) Method.

Liposomal drug delivery is a promising approach for delivering therapeutics effectively. While most liposomes are designed to be nanometer-sized for efficient cellular uptake, micron-sized liposomes are gaining interest due to their larger drug-loading capacity. When combined with macroscale structures, such as implants and hydrogels, they offer prolonged therapeutic delivery. This study investigates how solvents affect the production of micron-sized liposomes, with or without cholesterol, using the reverse-phase evaporation (RPE) method. Although the RPE method is established for producing micron-sized liposomes, the influence of solvents on liposome size and uniformity is not well understood. The study explores whether controlling the size of inverse micelles, an intermediate product, through the use of different organic solvents affects the final liposome size. Three solvents─diethyl ether, methanol, and acetone─were tested for their effect on the formation of inverse micelles and liposomes and their sizes. Results showed that without cholesterol, diethyl ether produced uniform inverse micelles, leading to mostly nanosized liposomes. Methanol and acetone resulted in phase separation, preventing uniform liposome formation, although some micron-sized liposomes appeared. The acetone sample yielded mostly oil droplets. The results showed that forming inverse micelles lead to nanosized liposomes. With cholesterol, phase separation was dominant in methanol, but micron-sized liposomes still formed. Across all cases, cholesterol reduced the liposome size. The findings reveal that inverse micelles are not always reliable predictors of the final liposome size and that the RPE method is highly sensitive to solvent polarity and lipid-solvent interactions. Overall, the findings of this study provide valuable insights into how the choice of solvent and lipid composition can influence the production of liposomes via the RPE method. These insights are critical for optimizing liposome production and influencing future designs of liposomal drug delivery systems.

Synthesis and Characterization of Extremely Bulky Aminopyridinate Ligands and a Series of Their Groups 1 and 2 Metal Complexes

High-yielding synthetic routes to five new extremely bulky aminopyridine pro-ligands were developed, viz. (C5H3N-6-Ar1)N(H)Ar2-2; Ar1 = Trip, Ar2 = TCHP (HAmPy1), Ar* (HAmPy2) or Ar† (HAmPy3); Ar1 = TCHP, Ar2 = Ar* (HAmPy4) or Ar† (HAmPy5) (Trip = 2,4,6-triisopropylphenyl, TCHP = 2,4,6-tricyclohexylphenyl, Ar* = C6H2(CHPh2)2Me-2,6,4, Ar† = C6H2(CHPh2)2Pri-2,6,4. Four of these were deprotonated with LiBun in diethyl ether to give lithium aminopyridinate complexes which were dimeric for the least bulky ligand, [{Li(AmPy1)}2] or monomeric for the bulkier aminopyridinates, i.e., in [Li(AmPy2−4)(OEt2)]. One aminopyridine was deprotonated with MeMgI to give monomeric [Mg(AmPy3)I(OEt2)2]. When treated with sodium or potassium mirrors or 5% w/w Na/NaCl, over-reduction occurred, leading to the alkali metal aminopyridinates, [M(AmPy3)(η6-toluene)] (M = Na or K) or [{Na(AmPy3)}∞]. An attempted reduction of [Mg(AmPy3)I(OEt2)2] with a dimagnesium(I) compound led only to partial loss of diethyl ether and the formation of [(AmPy3)Mg(μ-I)2Mg(AmPy3)(OEt2)]. All prepared complexes have potential as ligand transfer reagents in salt metathesis reactions with metal halide complexes.

Cost‐effective synthesis of unsymmetric tetrazines

Abstract1,2,4,5‐Tetrazines serve as versatile two‐carbon synthons, essential for synthesizing a variety of (hetero)aromatic compounds. Their specific reactivity with certain dienophiles, without interfering with biochemical processes, makes them ideal for bioorthogonal ligation. Despite their broad utility, current synthetic methods are costly and raise safety concerns, particularly during scale‐up. This study introduces safer and more cost‐effective synthetic strategies utilizing zinc chloride or boron trifluoride diethyl etherate as catalysts. These alternatives significantly reduce costs and enhance safety, potentially expanding the applicability of tetrazine synthesis across broader research domains.

Nosema ceranae infection reduces the fat body lipid reserves in the honeybee Apis mellifera

Nosema ceranae is an intestinal parasite frequently found in Apis mellifera colonies. This parasite belongs to Microsporidia, a group of obligate intracellular parasites known to be strongly dependent on their host for energy and resources. Previous studies have shown that N. ceranae could alter several metabolic pathways, including those involved in the nutrient storage. To explore the impact of N. ceranae on the fat body reserves, newly emerged summer bees were experimentally infected, and we measured (1) the lipid percentage of the abdominal fat body at 2-, 7- and 14-days post-inoculation (p.i.) using diethyl ether lipid extraction, (2) the triglyceride and protein concentrations by spectrophotometric assay methods, and (3) the amount of intracellular lipid droplets in trophocytes at 14- and 21-days p.i. using Nile Red staining. Comparing the three methods used to evaluate lipid stores, our data revealed that Nile Red staining seemed to be the simplest, fastest and reliable method. Our results first revealed that the percentage of fat body lipids significantly decreased in infected bees at D14 p.i. The protein stores did not seem to be affected by the infection, while triglyceride concentration was reduced by 30% and lipid droplet amount by 50% at D14 p.i. Finally, a similar decrease in lipid droplet reserves in response to N. ceranae infection was observed in bees collected in fall.

Half‐Sandwich Iron Chalcogenopropargylcarbonato Complexes as CO‐Releasing Molecules

ABSTRACTInteraction of iron chalcogenides (μ‐Ex)[CpFe(CO)2]2 (E = S; x = 2–4, E = Se, x = 1) with propargyl chloroformate (ClCO2CH2C≡CH) in diethyl ether yielded iron(II) chalcogenopropargylcarbonato complexes CpFe(CO)2ECO2CH2C≡CH (E = S (1), Se (2)). These complexes have been characterized by elemental analysis, UV–Vis, IR, and 1H‐ and 13C{1H}‐NMR spectroscopy and single‐crystal x‐ray diffraction techniques. Further, the suitability of complexes 1 and 2 as CO‐releasing molecules (CORMs) for the administration of carbon monoxide has been studied. CO gas is released upon irradiation of THF solution of these complexes in the presence of hemoglobin.

Development and Validation of a New HPLC Bio Analytical Internal Standard Method for the Analysis of Two Immunology Drugs (Lamivudine and Dolutegravir) in Human Plasma

Bioanalytical methods are useful for the quantitative analysis of drugs and their metabolites in biological fluids. Bio-analytical internal standards methods plays vital role in areas of human clinical pharmacology. The aim of this work is to development and validation of bio-analytical internal standard method for determination of two immunology drugs Lamivudine (LMVD) and Dolutegravir (DTGR) in plasma with Abacavir(ABVR) drug as internal standard (IS). Liquid-liquid extraction with Diethyl ether and methanol in the ratio of 50:50 (v/v) was used for the extraction of drugs from the biological matrix. The optimized chromatography conditions consist of Water, Acetonitrile and Methanol in the ratio of 40:25:35 (v/v) as a mobile phase with Ascentis, C18 Column (250 X 4.6 mm, 5μ) as stationery phase. Isocratic elution with 1.2 ml flow separates theLMVD at 3.5 min, DTGR at 9.8 min and ABVR at 6.8 min. The method was validated as per ICH guidelines. The relative standard deviation (%RSD) were found to be <5%for precision studies. Hence the method was found to be suitable fort the analysis of LMVD and DTGR in spiked human plasma.

A green and efficient synthesis of alkyl 2-((5-hydroxy-1H-pyrazole-4-carbonothioyl)thio)acetates via a one-pot, solvent-free reaction

A green and efficient synthesis of alkyl 2-((5-hydroxy-1H-pyrazole-4-carbonothioyl)thio)acetates is described. The method involves a one-pot, solvent-free reaction of pyrazolone derivatives, carbon disulfide, and alkyl bromoacetates in the presence of triethylamine. The crude products were readily purified by simple water washing followed by recrystallization from diethyl ether. The structures of the synthesized pyrazole-4-carbonothioyl-thio-acetate derivatives were confirmed by IR, 1H NMR, 13C NMR, and mass spectrometry.

DFT Study on Bucherer–Bergs multicomponent synthesis of hydantoins

ABSTRACT The Bucherer–Bergs multicomponent synthesis of hydantoins has been meticulously examined using density functional theory (DFT) at the B3LYP/6-311G level to scrutinise the reaction mechanism in diethyl ether as a solvent. This study explores all plausible pathways, optimises the structures of intermediates, and identifies corresponding transition states. Furthermore, a comprehensive computational analysis of molecular structures and their energy-structural correlations has been conducted.

Experimental study on the cerium oxide nanoparticles doped in diesel fuel improving the cold start performance of diesel engines at high-altitude and low-temperature environments

CeO2 nanoparticles are effective fuel additives that enhance fuel spray, atomization, and combustion characteristics due to their high catalytic activity and excellent thermal properties. When added to fuel, CeO2 nanoparticles significantly improve in-cylinder combustion, and engine performance, and reduce pollutant emissions under normal engine operating conditions. Diesel engines encounter persistent challenges during cold starts at low temperatures and high altitudes. However, there is limited research on the effects of CeO2 nanoparticles on ignition and combustion at low temperatures and cold start performance. This study aims to evaluate the impact of CeO2 nanoparticles doping in diesel fuel on the cold start performance of diesel engines in high-altitude and low-temperature environments. Diesel fuel doped with CeO2 nanoparticles at various concentrations was prepared using magnetic stirring and ultrasonication. The cold start performance of the test engine was assessed in an environmental chamber. This work investigated and evaluated the improvements of CeO2 nanoparticles on cold start performance from three perspectives: general low-temperature conditions, high-altitude environments, and extreme low-temperature scenarios with diethyl ether premixing. Experimental results indicate that incorporating CeO2 nanoparticles expanded the critical temperature required for a successful cold start from 0 °C to −5 °C. At high altitudes, the addition of CeO2 nanoparticles effectively increased the proportion of efficient combustion, evidenced by single peak and parent peak patterns during cold starts. CeO2 nanoparticles facilitated the transition from low-temperature to high-temperature reactions, promoting fuel ignition during the first injection cycle and reducing speed fluctuations during cold starts with diethyl ether premixing at −40 °C. Furthermore, adding CeO2 nanoparticles prevented detonation and rapid pressure surges during cold starts. Overall, doping diesel fuel with CeO2 nanoparticles proves to be an effective method for enhancing cold start performance in diesel engines. This study offers a novel approach for improving diesel engine cold start performance in high-altitude and low-temperature conditions.

Decreasing Electrical Resistivity of Ag Film by Low-Temperature Evaporation and Sintering through Azeotrope Application

In the temperature-sensitive components, such as perovskite solar cells, large-area electrical connections with high electrical conductivity are also required. To fulfill the requirements, low-temperature evaporation was realized by preparing binder-free pastes with Ag flakes and a solvent mixture, followed by sintering at 140 °C. The mixed solvent was based on viscous α-terpineol with the addition of an appropriate amount of dipropylene glycol methyl ether acetate or diethylene glycol diethyl ether to achieve an azeotrope composition, followed by the addition of a low-molecular-weight hydroxypropyl cellulose to increase the viscosity and thixotropy. During sintering at 140 °C in air for up to 30 min, the paste with 49.5 wt% α-terpineol, 49.5 wt% dipropylene glycol monomethyl ether acetate, and 1 wt% hydroxypropyl cellulose mixture exhibited an excellent electrical conductivity of 7.72 × 10−6 Ω·cm despite the implementation of low-temperature sintering. The excellent processability of the prepared Ag-based pastes at 140 °C demonstrated their potential for novel application areas.

Unraveling a novel biphasic CO2 capture process through rigorous modeling

Modification of the chemical absorbent is a crucial aspect in the field of CO2 capture. Nevertheless, the consequences arising from the utilization of modified solvents have not been thoroughly examined on a process scale. This study investigates a biphasic chemical absorption process for CO2 capture using a blended solvent composed of 2-ethylamino ethanol (EAE), diethylene glycol diethyl ether (DEGDEE), and water. The design was based on rigorous consideration of the physical properties of the pure components and the solution, as well as chemical equilibrium. Our results indicate that the proposed biphasic process reduces specific regeneration energy by 6.45 % compared to the conventional method using monoethanolamine (MEA) solution as a solvent (biphasic: 3.41 GJ/Ton; conventional: 3.63 GJ/Ton). Furthermore, it presents the advantage of utilizing low-temperature waste heat for solvent stripping, resulting in a notable 56 % decrease in indirect emissions (biphasic process: 0.119 Ton/Ton, conventional: 0.274 Ton/Ton). When processing flue gases that are more diluted in CO2, the CO2-e of the biphasic process was only slightly increased. Finally, the techno-economic analysis demonstrated that the biphasic process exhibits minimum required treatment prices (MRTPs) comparable to those of conventional methods for treating flue gases with CO2 concentrations ranging from 10 to 19 mol% (biphasic: 0.755 to 1.452 USD/kg, conventional: 0.756 to 1.455 USD/kg). This finding highlights the economic potential of the biphasic process. Overall, this investigation sheds light on the potential of intensifying the CO2 capture process in a biphasic environment.