Showing papers on "Ether published in 2011"

The Lithium–Oxygen Battery with Ether-Based Electrolytes

Abstract: The rechargeable Li–air (O2) battery is receiving a great deal of interest because theoretically it can store significantly more energy than lithium ion batteries, thus potentially transforming energy storage. Since it was first described, a number of aspects of the Li–O2 battery with a non-aqueous electrolyte have been investigated. The electrolyte is recognized as one of the greatest challenges. To date, organic carbonate-based electrolytes (e.g. LiPF6 in propylene carbonate) have been widely used. However, recently, it has been shown that instead of O2 being reduced in the porous cathode to form Li2O2, as desired, discharge in organic carbonate electrolytes is associated with severe electrolyte decomposition. As a result it is very important to investigate other solvents in the search for a suitable electrolyte. In this regard much attention is now focused on electrolytes based on ethers (e.g. tetraglyme (tetraethylene glycol dimethyl ether)). Ethers are attractive for the Li–O2 battery because they are one of the few solvents that combine the following attributes: capable of operating with a lithium metal anode, stable to oxidation potentials in excess of 4.5 V versus Li/Li, safe, of low cost and, in the case of higher molecular weights, such as tetraglyme, they are of low volatility. Crucially, they are also anticipated to show greater stability towards reduced O2 species compared with organic carbonates. Herein we show that although the ethers are more stable than the organic carbonates, the Li2O2 that forms on the first discharge is accompanied by electrolyte decomposition, to give a mixture of Li2CO3, HCO2Li, CH3CO2Li, polyethers/ esters, CO2, and H2O. The extent of electrolyte degradation compared with Li2O2 formation on discharge appears to increase rapidly with cycling (that is, charging and discharging), such that after only 5 cycles there is little or no evidence of Li2O2 from powder X-ray diffraction. We show that the same decomposition products occur for linear chain lengths other than tetraglyme. In the case of cyclic ethers, such as 1,3dioxolane and 2-methyltetrahydrofuran (2-Me-THF), decomposition also occurs. For 1,3-dioxolane, decomposition forms polyethers/esters, Li2CO3, HCO2Li, and C2H4(OCO2Li)2, and for 2-Me-THF the main products are HCO2Li, CH3CO2Li; in both cases CO2 and H2O evolve. The results presented herein demonstrate that ether-based electrolytes are not suitable for rechargeable Li–O2 cells. A Li–O2 cell consisting of a lithium metal anode, an electrolyte, comprising 1m LiPF6 in tetraglyme, and a porous cathode (Super P/Kynar) was constructed as described in the Experimental Section. The cell was discharged in 1 atm O2 to 2 V. The porous cathode was then removed, washed with CH3CN, and examined by powder X-ray diffraction (PXRD) and FTIR. The results are presented in Figure 1 and Figure 2. The PXRD data demonstrate the presence of Li2O2, consistent with previous PXRD data for a Li–O2 cell with a tetraglyme electrolyte at the end of the first discharge. However, examination of the FTIR spectra, Figure 2, reveals that, in addition to Li2O2, other products form. Although the FTIR spectra provide clear evidence of electrolyte decom-

Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers

Abstract: Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>>Ar-OMe>ArCH2-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.

Direct Sp3α-C-H activation and functionalization of alcohol and ether.

Abstract: Seven kinds of sp3 α-C–H activation/C–C formation reactions of alcohols and ethers have been reviewed in this tutorial review, from the viewpoint of both methodology and synthetic application, towards the efficiency, chemo-, regio- and stereoselectivity, catalytic system, substrate scope and mechanistic study. Section 2 describes radical-mediated α-C–H activation and addition/elimination of ethers with unsaturated (CC and CC) species. Sections 3–8 discuss the α-C–H activation and additions of alcohols and/or ethers with unsaturated (CC, CC, CO and CN) compounds, which involve the key processes of radical mediation, carbenoid insertion, 1,5-H-migration, oxidative dehydrogenation coupling, transfer hydrogenative coupling, and metal-mediated CC insertion into the C–H bond.

Theoretical Study of the Remarkably Diverse Linkages in Lignin

Abstract: Lignin in plant cell walls is a potential renewable source of biofuels, chemicals, and value-added products. It consists of various aryl ethers, irregularly connected by a variety of linkages creating a complex structural network; hence, it is difficult to identify selective bond breaking events. In this study, we predict dissociation tendencies of a diverse set of lignin linkages encompassing 65 lignin model compounds using the density functional theoretical (DFT) approach. The chosen 65 lignin model compounds represent the most prevalent carbon–oxygen (ether) and carbon–carbon (C–C) bond linkages. Results from our systematic study identify the weakest and strongest linkages connecting arene rings in different classes of lignin model compounds. Also, the dissociating linkages can have different adjacent substituents, such as the methoxy group on the arene ring and hydrocarbon, methyl, and hydroxyl group substitutions on aliphatic carbon atoms. These substituents affect the ease of dissociation of lignin ...

Bu4NI‐Catalyzed C ? O Bond Formation by Using a Cross‐Dehydrogenative Coupling (CDC) Reaction

Abstract: Title reaction proceeds in the absence of transition metal catalysts, is operationally simple and tolerates a wide variety of functional groups like cyano, amide, aromatic halide, ether, ketone groups and C—C double bonds.

Fluorene-Based Poly(arylene ether sulfone)s Containing Clustered Flexible Pendant Sulfonic Acids as Proton Exchange Membranes

Abstract: A new bisphenol monomer, 9,9-bis(3,5-dimethoxy-4-hydroxyphenyl) fluorene, was synthesized and polymerized to form fluorene-based poly(arylene ether sulfone) copolymers containing tetra-methoxy groups (MPAES). After converting the methoxy group to the reactive hydroxyl group, the respective side-chain type sulfonated copolymers (SPAES) were obtained by sulfobutylation. The polymers were characterized by 1H NMR, thermogravimetric analysis (TGA), water uptake, and proton and methanol transport for fuel cell applications. These SPAES copolymers had good overall properties as polymer electrolyte membrane (PEM) materials, having high proton conductivity in the range of 0.061–0.209 and 0.146–0.365 S/cm at 30 and 80 °C (under hydrated conditions), respectively. SPAES-39 (IEC = 1.93 mequiv/g) showed higher or comparable proton conductivity than that of Nafion 117 at 50–95% RH (relative humidity). The methanol permeabilities of these membranes were in the range of 3.22 to 13.1 × 10–7 cm2/s, which is lower than Nafi...

Guanidinium-Functionalized Anion Exchange Polymer Electrolytes via Activated Fluorophenyl-Amine Reaction

Abstract: Guanidinium-functionalized poly(arylene ether sulfone) anion exchange polymer electrolytes were synthesized via activated fluorophnyl-amine reaction, followed by the methylation with dimethyl sulfate. The activated fluorine-amine reaction gives precise control of cation functionality without the deleterious side reactions and allows the direct connection of guanidinium into stable phenyl rings.

Ether-functionalized ionic liquids as highly efficient SO2 absorbents

Abstract: Room temperature ionic liquids (RTILs), ether-functionalized imidazolium methanesulfonates, exhibit extremely high SO2 solubility, at least 2 moles of SO2 per mole of RTIL at 30 °C and at atmospheric pressure. The solubility of SO2 in these RTILs increases with increasing number of tethered ether oxygen atoms and also with the pressure rise. FT-IR spectroscopic and quantum mechanical calculation results show that such high SO2 solubility is originated from the combined interactions of SO2 with methanesulfonate anion and ether oxygen atom or atoms on the imidazolium ring. The absorbed SO2 gas can be readily and completely desorbed from the RTILs by heating at 100 °C in a N2 flow, thereby allowing the RTILs to be reused up to 5 cycles without loss of their initial capacity.

A General Method for Copper-Catalyzed Arene Cross-Dimerization

Abstract: A general method for a highly regioselective copper-catalyzed cross-coupling of two aromatic compounds using iodine as an oxidant has been developed. The reactions involve an initial iodination of one arene followed by arylation of the most acidic C-H bond of the other coupling component. Cross-coupling of electron-rich arenes, electron-poor arenes, and five- and six-membered heterocycles is possible in many combinations. Typically, a 1/1.5 to 1/3 ratio of coupling components is used, in contrast to existing methodology that often employs a large excess of one of the arenes. Common functionalities such as ester, ketone, aldehyde, ether, nitrile, nitro, and amine are well-tolerated.

Stereoconvergent Synthesis of Chiral Allylboronates from an E/Z Mixture of Allylic Aryl Ethers Using a 6-NHC−Cu(I) Catalyst

Abstract: We present a 6-NHC−Cu(I) complex that provides α-substituted allylboronates using allylic aryl ether substrates. The method was discovered by comparison of the chemoselectivities exhibited by complexes 1a, 1b, 2, and 3. We observed that 1a preferentially reacts with electron-rich alkenes over electron-deficient alkenes. Development of an asymmetric method revealed that 1b reacts with both the E and Z isomers to provide the same absolute configuration without showing E−Z isomerization. This stereoconvergent reaction occurs with high yields (av 86%), high SN2′ selectivity (>99:1), and high ee (av 94%) and exhibits wide functional-group tolerance using pure E or Z isomer or E/Z alkene mixtures. The stereoconvergent feature enables the use of many different olefination strategies for substrate production, including cross-metathesis. Chiral allylboronates could be purified by silica gel chromatography and stored in the freezer without decomposition.

Solubility of CO2 in Alcohols, Glycols, Ethers, and Ketones at High Pressures from (288.15 to 318.15) K

Abstract: The constant-volume method is used to determine the solubility of CO2 in methanol, ethanol, n-propanol, n-butanol, n-propanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether under the pressure of 6 MPa and the temperature variations from (288.15 to 318.15) K in this paper. It is found by contrast that ketones have a greater ability to dissolve CO2 than alcohols, ethers, and glycols, which also indicate that both the carbonyl group and the ether bond in solvents can promote the CO2 absorption, but hydroxyl group will inhibit the CO2 absorption.

Hydrolytic Cleavage of β-O-4 Ether Bonds of Lignin Model Compounds in an Ionic Liquid with Metal Chlorides

Abstract: The hydrolytic cleavage of β-O-4 ether bonds in lignin model compounds, guaiacylglycerol-β-guaiacyl ether (GG) and veratrylglycerol-β-guaiacyl ether (VG), was studied in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) with metal chlorides and water. FeCl3, CuCl2, and AlCl3 were found to be effective and functioned catalytically in cleaving the β-O-4 bond of GG, although a number of other metal chlorides are considerably less active. AlCl3 functioned more effectively in cleaving the β-O-4 bond of VG than did FeCl3 and CuCl2. After 120 min at 150 °C, GG conversion reached 100%, and about 70% of the β-O-4 bonds of GG were hydrolyzed, liberating guaiacol, in the presence of FeCl3 and CuCl2, while about 80% of the β-O-4 bonds of GG were hydrolyzed in the presence of AlCl3 with 100% GG conversion. About 75% of the β-O-4 bonds of VG were hydrolyzed in the presence of AlCl3 after 240 min at 150 °C. The catalytic activity is associated with the hydrochloric acid, working as the acid catalyst, formed in situ by the...

Poly(allyl glycidyl ether)-A versatile and functional polyether platform.

Abstract: Allyl glycidyl ether, polymerized from potassium alkoxide/naphthalenide initiators under both neat and solution conditions was shown to be a highly-controlled process. In both cases, molar masses (10-100 kg/mol) were determined by the reaction stoichiometry, and low polydispersity indices (1.05-1.33) could be obtained with a full understanding of the dominant side reaction, isomerization of the allyl side chain, being developed. The degree of isomerization of allyl to cis-prop-1-enyl ether groups (0 - 10 % mol.) was not correlated to the molar mass or polydispersity of the polymer but was dictated by the polymerization temperature. This allows the extent of isomerization to be reduced to essentially zero under either melt or solution conditions at polymerization temperatures of less than 40 °C.

UCST-type behavior of poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) in aliphatic alcohols: solvent, co-solvent, molecular weight, and end group dependences

Abstract: Poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) is shown to possess insoluble–soluble transitions (UCST-type phase behavior) in a large variety of aliphatic alcohols. Samples of different molecular weights ranging from 5 kg mol−1 to 23 kg mol−1 prepared by the RAFT process and featuring different end groups at each end were analyzed by cloud point measurements. Transitions occurred sharply and were fully reversible. The UCST was found to increase with an increasing molecular weight. Hydrophobic (alkyl chain) end groups were found to lower the critical temperature in isopropanol, while rigid aromatic end groups raised the transition temperature. In ternary mixtures of isopropanol/chloroform/POEGMA, the UCST decreased with an increasing chloroform concentration, with 10 vol% of chloroform accounting for a 30 °C drop. In mixtures of isopropanol/hexane/POEGMA, the cloud point increased significantly only with hexane concentrations above 30 vol%, at which level a 2 °C transition temperature increase was found. Addition of water to isopropanol solutions had a strong effect, with 1 vol% of water causing a decrease of the transition temperature of 12.5 °C. With an increasing chain length of the solvent, the cloud point increased, while a branching of the hydrocarbon chains lowered the cloud point. Samples of 23 kg mol−1POEGMA were for instance found to have cloud points of 22.0 °C in ethanol, 35.7 °C in isopentanol, and 75.4 °C in dodecanol.

Emissions from Ethers and Organic Carbonate Fuel Additives: A Review

Abstract: This paper is a review of the available literature on the main features of 11 of the most widely adopted oxygenated additives to base gasoline and diesel, focusing particularly on the emissions from the oxygenates considered as additives. The oxygenated additives studied are methyl tert-butyl ether, ethyl tertiary butyl ether, tert-amyl ethyl ether, tertiary amyl methyl ether, isopropyl ether, dimethyl carbonate, dimethoxymethane, dibutyl ether, diglycol methyl ether, diethyl carbonate, and 2-methoxyethyl acetate.

Formation and Stability of Prolinol and Prolinol Ether Enamines by NMR: Delicate Selectivity and Reactivity Balances and Parasitic Equilibria

Abstract: Enamine key intermediates in organocatalysis, derived from aldehydes and prolinol or Jorgensen−Hayashi-type prolinol ether catalysts, were generated in different solvents and investigated by NMR spectroscopy. Depending on the catalyst structure, trends for their formation and amounts are elucidated. For prolinol catalysts, the first enamine detection in situ is presented and the rapid cyclization of the enamine to the oxazolidine (“parasitic equilibrium”) is monitored. In the case of diphenylprolinol, this equilibrium is fully shifted to the endo-oxazolidine (“dead end”) by the two geminal phenyl rings, most probably because of the Thorpe−Ingold effect. With bulkier and electron-withdrawing aryl rings, however, the enamine is stabilized relative to the oxazolidine, allowing for the parallel detection of the enamine and the oxazolidine. In the case of prolinol ethers, the enamine amounts decrease with increasing sizes of the aryl meta-substituents and the O-protecting group. In addition, for small aldehyde...

Cross‐Coupling of Nonactivated Alkyl Halides with Alkynyl Grignard Reagents: A Nickel Pincer Complex as the Catalyst

Abstract: The nickel pincer complex 1 catalyzes the cross-coupling of the title compounds with remarkable substrate scope and functional group tolerance. A nickel/alkynyl species was isolated and shown to be catalytically competent. THF=tetrahydrofuran, O-TMEDA=bis[2-(N,N-dimethylaminoethyl)] ether.

Computational study of bond dissociation enthalpies for substituted β-O-4 lignin model compounds.

Abstract: The biopolymer lignin is a potential source of valuable chemicals. Phenethyl phenyl ether (PPE) is representative of the dominant β-O-4 ether linkage. DFT is used to calculate the Boltzmann-weighted carbon-oxygen and carbon-carbon bond dissociation enthalpies (BDEs) of substituted PPE. These values are important for understanding lignin decomposition. Exclusion of all conformers that have distributions of less than 5% at 298 K impacts the BDE by less than 1 kcal mol(-1). We find that aliphatic hydroxyl/methylhydroxyl substituents introduce only small changes to the BDEs (0-3 kcal mol(-1)). Substitution on the phenyl ring at the ortho position substantially lowers the C-O BDE, except in combination with the hydroxyl/methylhydroxyl substituents, for which the effect of methoxy substitution is reduced by hydrogen bonding. Hydrogen bonding between the aliphatic substituents and the ether oxygen in the PPE derivatives has a significant influence on the BDE. CCSD(T)-calculated BDEs and hydrogen-bond strengths of ortho-substituted anisoles, when compared with M06-2X values, confirm that the latter method is sufficient to describe the molecules studied and provide an important benchmark for lignin model compounds.

Synthesis and utility of fluorogenic acetoxymethyl ethers.

Abstract: Phenolic fluorophores such as fluorescein, Tokyo Green, resorufin, and their derivatives are workhorses of biological science. Acylating the phenolic hydroxyl group(s) in these fluorophores masks their fluorescence. The ensuing ester is a substrate for cellular esterases, which can restore fluorescence. These esters are, however, notoriously unstable to hydrolysis, severely compromising their utility. The acetoxymethyl (AM) group is an esterase-sensitive motif that can mask polar functionalities in small molecules. Here, we report on the use of AM ether groups to mask phenolic fluorophores. The resulting profluorophores have a desirable combination of low background fluorescence, high chemical stability, and high enzymatic reactivity, both in vitro and in cellulo. These simple phenyl ether-based profluorophores could supplement or supplant the use of phenyl esters for imaging biochemical and biological systems.

Distinct conformational preferences of prolinol and prolinol ether enamines in solution revealed by NMR

Abstract: Enamines, which are key intermediates in organocatalysis derived from aldehydes and prolinol or Jorgensen–Hayashi-type prolinol ether catalysts, were investigated conformationally in different solvents by means of NMR spectroscopy, in order to provide an experimental basis for a better understanding of the origin of stereoselection. For all of the enamines studied, surprisingly strong conformational preferences were observed. The enamines of the diarylprolinol (ether) catalysts were found to exclusively exist in the s-trans conformation due to the bulkiness of the pyrrolidine α-substituent. For prolinol enamines, however, a partial population of the s-cis conformation in solution was also evidenced for the first time. In addition, for all of the enamines studied, the pyrrolidine ring was found to adopt the down conformation. Concerning the exocyclic C–C bond, the sc-exo conformation, stabilized by CH/π interactions, is exclusively observed in the case of diarylprolinol ether enamines. In contrast, diarylprolinol enamines adopt the sc-endo conformation, allowing for an OH⋯N hydrogen bond and a CH/π interaction. A rapid screening approach for the different conformational enamine features is presented and this was applied to show their generality for various catalysts, aldehydes and solvents. Thus, by unexpectedly revealing the pronounced conformational preferences of prolinol and prolinol ether enamines in solution, our study provides the first experimental basis for discussing the previously controversial issues of s-cis/s-trans and sc-endo/sc-exo conformations. Moreover, our findings are in striking agreement with the experimental results from synthetic organic chemistry. They are therefore expected to also have a significant impact on future theoretical calculations and synthetic optimization of asymmetric prolinol (ether) enamine catalysis.