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Hexafluorophosphate
Selected AbstractsHomogeneous Hydrogenation of Tri- and Tetrasubstituted Olefins: Comparison of Iridium-Phospinooxazoline [Ir-PHOX] Complexes and Crabtree Catalysts with Hexafluorophosphate (PF6) and Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF) as CounterionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2008Bettina Wüstenberg Abstract Four iridium complexes with achiral phosphino-oxazoline (PHOX) ligands were readily prepared in two steps starting from commercially available phenyloxazolines. The air-stable complexes with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF) as counterion showed high reactivity in the hydrogenation of a range of tri- and tetrasubstituted olefins. The best results were obtained with an iridium complex (11) derived from a dicyclohexylphosphino-oxazoline ligand bearing no additional substituents in the oxazoline ring. With several substrates, which gave only low conversion with the Crabtree catalyst, [Ir(Py)(PCy3)(COD)]PF6, full conversion was observed. The productivity of the Crabtree catalyst could be strongly increased by replacing the hexafluorophosphate anion with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. In one case, in the hydrogenation of a tetraalkyl-substituted CC bond, [Ir(Py)(PCy3)(COD)]BArF gave higher conversion than catalyst 11. However, with several other substrates complex 11 proved to be superior. [source] 2,6-Diisopropyl-4-methylpyrylium Hexafluorophosphate.CHEMINFORM, Issue 39 2007T. S. Balaban Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Alkaline Earth Metal Poly(hydrogen fluorides) Hexafluoroarsenates(V) and Hexafluorophosphate(V): M2(H2F3)(HF2)2 (AF6) (M: Ca, A: As; M: Sr, A: As, P).CHEMINFORM, Issue 42 2005Melita Tramsek Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: Bis(sym-collidine)bromine(I) Hexafluorophosphate as Oxidant.CHEMINFORM, Issue 9 2001Gerard Rousseau Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] CH-Directed Anion,, Interactions in the Crystals of Pentafluorobenzyl-Substituted Ammonium and Pyridinium SaltsCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2010Markus Albrecht Prof. Abstract Simple pentafluorobenzyl-substituted ammonium and pyridinium salts with different anions can be easily obtained by treatment of the parent amine or pyridine with the respective pentafluorobenzyl halide. Hexafluorophosphate is introduced as the anion by salt metathesis. In the case of the ammonium salt 4, water co-crystallisation seems to suppress effective anion,, interactions of bromide with the electron-deficient aromatic system, whereas with salts 5 and 6 such interactions are observed despite the presence of water. However, due to asymmetric hydrogen-bonding interactions with ammonium side chains, the anion of 5 is located close to the rim of the pentafluorophenyl group (,1 interaction). In 6 the CH,anion hydrogen bonding is more symmetric and fixes the anion on top of the ring (,6). A similar structure-controlling effect is observed in case of the 1,4-diazabicyclo[2.2.2]octane derivatives 7. Here the position of the anion (Cl, Br, I) is shifted according to the length of the weak CH,halide interaction. The hexafluorophosphate 7,d reveals that this "non-coordinating" anion can be located on top of an aromatic , system. In the methyl-substituted pyridinium salts 9 and 10 different locations of the bromide anions with respect to the , system are observed. This is due to different conformations of the mono- versus disubstituted pyridine, which leads to different directions of the weak, but structurally important, HMeBr bonds. [source] Electrogenerated Chemiluminescence Sensor Based on Tris(2,2,-bipyridine)ruthenium(II)-Immobilized Natural Clay and Ionic LiquidELECTROANALYSIS, Issue 2 2010Ping Jiang Abstract A novel electrogenerated chemiluminescence (ECL) sensor based on natural clay and ionic liquid was fabricated. Tris(2,2,-bipyridine)ruthenium(II) (Ru(bpy)32+) was immobilized on natural clay surface through simple adsorption. An ECL sensor was prepared by mixing Ru(bpy)32+ -incorporated clay, graphite powder and an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) as the binder. The electrochemical behavior and ECL of the immobilized Ru(bpy)32+ was investigated. It was observed that the ECL of immobilized Ru(bpy)32+ was activated by the ionic liquid. The proposed ECL sensor showed high sensitivity to tri- n -propylamine (TPrA) and the detection limit was found to be 20,pM. In addition, the ECL sensor displayed good stability for TPrA detection and long-term storage stability. [source] Direct Electrochemistry and Electrocatalysis of Hemoglobin in Lipid Film Incorporated with Room-Temperature Ionic LiquidELECTROANALYSIS, Issue 20 2008Gaiping Li Abstract A facile phospholipid/room-temperature ionic liquid (RTIL) composite material based on dimyristoylphosphatidylcholine (DMPC) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6) was exploited as a new matrix for immobilizing protein. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were adopted to characterize this composite film. Hemoglobin (Hb) was chosen as a model protein to investigate the composite system. UV-vis absorbance spectra showed that Hb still maintained its heme crevice integrity in this composite film. By virtue of the Hb/DMPC/[bmim]PF6 composite film-modified glassy carbon electrode (GCE), a pair of well-defined redox peaks of Hb was obtained through the direct electron transfer between protein and underlying GCE. Moreover, the reduction of O2 and H2O2 at the Hb/DMPC/[bmim]PF6 composite film-modified GCE was dramatically enhanced. [source] Improved Voltammetric Response of L -Tyrosine on Multiwalled Carbon Nanotubes-Ionic Liquid Composite Coated Glassy Electrodes in the Presence of Cupric IonELECTROANALYSIS, Issue 19 2008Liqin Liu Abstract L -Tyrosine can exhibit a small anodic peak on multiwalled carbon nanotubes (MWCNTs) coated glassy carbon electrodes (GCE). At pH,5.5 its peak potential is 0.70,V (vs. SCE). When an ionic liquid (i.e., 1-octyl-3-methylimidazolium hexafluorophosphate, [omim][PF6]) is introduced on the MWCNT coat, the peak becomes bigger. Furthermore, in the presence of Cu2+ ion the anodic peak of L -tyrosine increases further due to the formation of Cu2+ - L -tyrosine complex, while the peak potential keeps unchanged. Therefore, a sensitive voltammetry based on the oxidation of Cu2+ - L -tyrosine complex on MWCNTs-[omim][PF6] composite coated electrode is developed for L -tyrosine. Under the optimized conditions, the anodic peak current is linear to L -tyrosine concentration in the range of 1×10,8,5×10,6 M, and the detection limit is 8×10,9 M. The modified electrode shows good reproducibility and stability. In addition, the voltammetric behavior of other amino acids is explored. It is found that among them tryptophan (Trp) and histidine (His) can also produce sensitive anodic peak under same experimental conditions, and their detection limits are 4×10,9 M and 4×10,6 M, respectively. [source] Fabrication, Characterization, and Application of ,Sandwich-Type' Electrode Based on Single-Walled Carbon Nanotubes and Room Temperature Ionic LiquidELECTROANALYSIS, Issue 17 2008Xuzhi Zhang Abstract The much-enhanced electrochemical responses of potassium ferricyanide and methylene blue (MB) were firstly explored at the glassy carbon electrode modified with single-walled carbon nanotubes (SWNT/GCE), indicating the distinct electrochemical activity of SWNTs towards electroactive molecules. A hydrophobic room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), was used as electrode modification material, which presented wide electrochemical windows, proton permeation and selective extraction ability. In consideration with the advantages of SWNTs and RTIL in detecting target molecules (TMs), a novel strategy of ,sandwich,type' electrode was established with TMs confined by RTIL between the SWNT/GCE and the RTIL membrane. The strategy was used for electrochemical detection of ascorbic acid (AA) and dopamine (DA), and detection limits of 400 and 80 fmol could be obtained, respectively. The selective detection of DA in the presence of high amount of AA could also be realized. This protocol presented many attractive advantages towards voltammetric detection of TMs, such as low sample demand, low cost, high sensitivity, and good stability. [source] Paste Electrode Based on Short Single-Walled Carbon Nanotubes and Room Temperature Ionic Liquid: Preparation, Characterization and Application in DNA DetectionELECTROANALYSIS, Issue 12 2008Xuzhi Zhang Abstract A paste electrode (SWNT&RTIL PE) has been prepared using carboxylic group-functionalized short single-walled carbon nanotubes (SWNTs) mixed with 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6, one kind of room temperature ionic liquid, RTIL). Its electrochemical behavior was investigated by cyclic voltammetry and electrochemical impedance spectroscopy in comparison with the paste electrode using mineral oil as a binder. Results highlighted the advantages of the paste electrode: not only higher conductivity, but also lower potential separation (,Ep), higher peak current (ip) and better reversibility towards dopamine (DA), methylene blue (MB) and K3[Fe(CN)6]. The SWNT&RTIL PE could be used to detect the number of guanine bases and adenine bases contents in per mol oligonucleotides according to the current response in the range of 0.05,2.0,nM. Based on the current response of guanine bases, oligonucleotides could be detected sensitively in the B,R buffer solution with a detection limit of 9.9,pM. The heterogeneous electron transfer rate constant (ks) of guanine bases contents in the oligonucleotides was investigated and its value was 0.90,s,1. In essence the SWNT&RTIL PE showed high sensitivity, reliability, stability and reproducibility for the detection of DNA. [source] Properties of Poly(sodium 4-styrenesulfonate)-Ionic Liquid Composite Film and Its Application in the Determination of Trace Metals Combined with Bismuth Film ElectrodeELECTROANALYSIS, Issue 5 2008Jianbo Jia Abstract A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)64,/Fe(CN)63, can be effectively improved at the PSS-BMIMPF6 modified GC. The bismuth modified PSS-BMIMPF6 composite film electrodes (GC/PSS-BMIMPF6/BiFEs) displayed high mechanical stability and sensitive stripping voltammetric performances for the determination of trace metal cations. The GC/PSS-BMIMPF6/BiFE exhibited well linear response to both Cd(II) and Pb(II) over a concentration range from 1.0 to 50,,g L,1. And the detection limits were 0.07,,g L,1 for Cd(II) and 0.09,,g L,1 for Pb(II) based on three times the standard deviation of the baseline with a preconcentration time of 120,s, respectively. Finally, the GC/PSS-BMIMPF6/BiFEs were successfully applied to the determination of Cd(II) and Pb(II) in real sample, and the results of present method agreed well with those of atomic absorption spectroscopy. [source] Investigation of the Role of Ionic Liquids in Imparting Electrocatalytic Behavior to Carbon Paste ElectrodeELECTROANALYSIS, Issue 21 2007Norouz Maleki Abstract In this paper, a survey has been undertaken to clarify the possible reasons for the electrocatalytic activity obtained by the presence of ionic liquid in carbon paste electrode (CPE). For this purpose, the effect of the addition of traces of ionic liquid to conventional CPE was investigated. Fe(CN)63,/4, was used as a probe and two ionic liquids, namely n -octylpyridinum hexafluorophosphate and 1-octyl-3-methylimidazolium hexaflourophosphate were tested for their electrocatalytic activity. The reasons for this electrocatalytic behavior were evaluated and it was found that different factors such as increase in the ionic conduction of the binder, decrease in the resistance of the modified electrode, increase in ion exchange properties of the electrode and the inherent catalytic activity of ionic liquids are responsible for the considerable improved electrochemical response obtained in the presence of traces of ionic liquid. [source] Dramatic Effects of Ionic Liquid on Platinum Electrode Surface and Electron-Transfer Rates of meso -TetraphenylporphyrinsELECTROANALYSIS, Issue 12 2006Afsaneh Safavi Abstract The effect of addition of a room temperature ionic liquid, 1-butyl-3-methyl imidazolium hexafluorophosphate [bmim][PF6], on the electrochemical behavior of different free-base para-substituted meso -tetraphenylporphyrins in dichloromethane solution has been studied using cyclic voltammetric technique. It has been found that the ionic liquid has the ability to regenerate platinum electrode surface and improves the reversibility of electrode processes. This has been true for the case of all the porphyrins studied. [source] A Reference Electrode for Electrochemical and Cryoelectrochemical Use in Tetrahydrofuran SolventELECTROANALYSIS, Issue 21 2005Christopher Abstract We report a reference electrode for direct use in tetrahydrofuran (THF) at low temperatures. A reference solution containing equimolar amounts of ferrocene/ferrocenium hexafluorophosphate (Fc/Fc+) are prepared to give a 4,mM solution in THF that contains tetrabutylammonium hexafluorophosphate (TBAF) supporting electrolyte thus, minimizing liquid junction potentials. The reference solution is added to a sealed glass tube with a porous frit at one end, and a platinum wire is inserted into the tube. The reference electrode assembly is then inserted into a THF test solution. Potentiometric measurements show that the system responds in the expected Nernstian fashion over the concentration and temperature ranges, 4,mM to 40,,M and 20,°C to ,45,°C respectively. In addition, it is shown by steady,state cyclic voltammetry at a platinum microelectrode that the chemical reactivity of ferrocenium hexafluorophosphate (Fc+) otherwise seen in THF is suppressed by ion-pairing with PF using tetrabutylammonium hexafluorophosphate (TBAF) as the supporting electrolyte. [source] Improved simultaneous enantioseparation of ,-agonists in CE using ,-CD and ionic liquidsELECTROPHORESIS, Issue 6 2009Lu Huang Abstract In this study, approaches to improve chiral resolutions in simultaneous enantioseparation of ,-agonists by CE via a CD inclusion complexation modified with ionic liquids (ILs) are described. Different types of ILs, including tetraalkylammonium-based ILs, alkylimidazolium-based ILs and alkylpyridinium-based ILs, were examined and compared for controlling the EOF in order to improve resolutions of ,-agonists enantiomers. In this regard, tetraalkylammonium-based ILs were more effective because they could be used at much higher concentrations than other types of ILs. N -octylpyridinium hexafluorophosphate gave poor resolutions of ,-agonists enantiomers. In addition, when different ILs were mixed to use, they would present particular properties of their own. Moreover, the presence of ILs was essential in the chiral separations of (±) salbutamol, (±) cimaterol and (±) formoterol, which were reportedly not enantioseparated by using the buffer electrolytes containing only ,-CD as a chiral selector. [source] The Variable Binding Modes of Phenylbis(pyrid-2-ylmethyl)phosphane and Bis(pyrid-2-ylmethyl) Phenylphosphonite with AgI and CuIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2009Fernando Hung-Low Abstract A series of new bridging phosphane and phosphonite structures forming three- and six-membered rings with the metal centers were synthesized and characterized. The resulting compounds of phenylbis(pyrid-2-ylmethyl)phosphane (1) with the silver(I) salts of trifluoroacetate (tfa,), tetrafluoroborate (BF4,), and trifluoromethanesulfonate (OTf,), and copper tetrakis(acetonitrile) hexafluorophosphate (PF6,) shows the flexibility of the ligand by displaying different coordination modes associated with the electronic and structural characteristics of the corresponding anion. Accordingly, ligand 1 in these complexes displays two different binding modes. With Agtfa and AgBF4 compounds 3 and 4 are obtained where the ligand chelates to two silver atoms that exhibit normalAg,Ag contacts in the range of 2.9 Ĺ. When AgOTf or Cu(NCCH3)4PF6 are used, one molecule of 1 bridges the metal centers through a phosphorus atom while another is terminally bound. This induces short M,M distances of 2.6871 and 2.568 Ĺ for 5 and 6, respectively. Similarly, the coordination behavior of the heterofunctional bis(pyrid-2-ylmethyl) phenylphosphonite ligand (2) is reported with Cu(NCCH3)4PF6 (7) and AgBF4 (8) to form two novel discrete molecules. In these complexes 2 coordinates through the P and N atoms, with the difference that in 7 the O atom of one of the carbinol arms is also bound to the Cu. Elemental analysis, variable-temperature multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and low-temperature luminescence studies were carried out to fully characterize the compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Solid-State Anion,Guest Encapsulation by Metallosupramolecular Capsules Made from Two Tetranuclear Copper(II) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2007Emilio Pardo Abstract A new cationic tetranuclear copper(II) complex self-assembles from one 1,3-phenylenebis(oxamato) (mpba) bridging ligand and four CuII ions partially blocked with N,N,N,,N, -tetramethylethylenediamine (tmen) terminal ligands. In the solid state, two of these tetracopper(II) oxamato complexes of bowl-like shape and helical conformation then serve as a building block for the generation of either hetero- (MP) or homochiral (MM/PP) dimeric capsules depending on the nature of the encapsulated anion guest, perchlorate or hexafluorophosphate. The overall magnetic behaviour of these metallosupramolecular capsules does not depend on the nature of the encapsulated anion guest, but it is consistent with the dimer-of-dimer structure of the tetracopper(II) cation host, where the interdimer magnetic coupling through the meta -phenylenediamidate bridge is negligibly smallrelative to the reasonably strong intradimer one across the oxamato bridge.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Structure, and Reactivity of Novel Intramolecularly Coordinated Organolead(II) CompoundsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2003Klaus Jurkschat Abstract The intramolecularly coordinated heteroleptic organolead(II) compounds {4- tBu-2,6-[P(O)(OEt)2]2C6H2}PbX (2, X = Cl; 3, X = SPh) have been synthesized. Single-crystal X-ray analyses reveal that both compounds adopt polymeric chain structures by intermolecular Pb,X···Pb bridges, a structural motif previously unknown for organolead(II) derivatives. Compound 2 reacts with lithium diisopropylamide, iPr2NLi, and lithium bis(trimethylsilyl)methane, (Me3Si)2CHLi, respectively, to provide in situ the corresponding organolead(II) compounds {4- tBu-2,6-[P(O)(OEt)2]2C6H2}PbX (4, X = iPr2N; 5, X = (Me3Si)2CH], which were identified by NMR spectroscopy but could not be obtained as analytically pure substances. Attempts to isolate the intramolecularly coordinated organolead(II) hexafluorophosphate {4- tBu-2,6-[P(O)(OEt)2]2C6H2}Pb+PF6, from the reaction of 2 with TlPF6 also failed. Instead, the unprecedented salt [{5- tBu-1,3-[P(O)(OEt)2]2C6H3}4·(Pb2F)] [PF6]3·4THF (6) was obtained, in which the [(Pb,F,Pb)]3+ cation is stabilized by eight intermolecular P=O,Pb interactions. Compound 6 was characterized by single-crystal X-ray analysis and electrospray mass spectrometry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Pseudorotaxanes and Rotaxanes Formed by Viologen DerivativesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 8 2006Adam B. Braunschweig Abstract Dibenzyl-4,4,-bipyridinium (BIPY2+) bis(hexafluorophosphate) and three of its derivatives , disubstituted at the para positions of the benzyl groups with CO2Me, F, and Me in turn , have been shown to form 1:1 complexes that are [2]pseudorotaxanes with dibenzo[24]crown-8 (DB24C8), benzometaphenylene[25]crown-8 (BMP25C8), and dipyrido[24]crown-8 (DP24C8) in CD3CN solution by 1H NMR spectroscopy and in one case in the solid state by X-ray crystallography. Binding constants (Ka) for all of these 1:1 complexes, which were determined both (1) by isothermal titration calorimetry in MeCN solution and (2) by the 1H NMR spectroscopic single-point method in CD3CN solution, were found to be, on the average, an order of magnitude less than the Ka values obtained for DB24C8 and DP24C8 with dibenzylammonium (DBA+) hexafluorophosphate and three of its derivatives, also disubstituted at the para positions of the benzyl groups with CO2Me, F and Me. In the case of BMP25C8, however, the Ka values with both categories (BIPY2+ and DBA+) of guests are much of a muchness, being both small and error prone. The equilibrium thermodynamics for these small libraries of [2]pseudorotaxanes indicate that the best bistable [2]rotaxanes incorporating both DBA+ and BIPY2+ recognition sites are going to involve ester functions in their dumbbell components and will employ DP24C8 or, failing that, DB24C8 as the ring component. The BIPY2+threads also directed the templated assembly of [2]rotaxanes incorporating the crown ethers (DB24C8, DP24C8, and BMP25C8) and triphenylphosphonium stoppers using the threading followed by stoppering approach. The rotaxanes were characterized in solution by 1H NMR spectroscopy, and in one case, in the solid state by X-ray crystallography.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Electron-Transfer-Initiated Cascade Cyclizations of Terpenoid Polyalkenes in a Low-Polarity Solvent: One-Step Synthesis of Mono- and Polycylic Terpenoids with Various FunctionalitiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2004Mustafa E. Ozser Abstract A methodology for the one-step synthesis of cyclic polyalkene terpenoids in a low-polarity solvent (dichloromethane) by photoinduced electron transfer (PET) is described. For the efficiency of such processes in low-polarity solvents, the use of the cationic electron acceptor N -methylquinolinium hexafluorophosphate is vital. The first direct cyclizations of farnesol and geranylgeraniol to the corresponding all- trans -fused 6,6- and 6,6,6-cyclic products are also reported. The mechanism of the termination of the cyclizations is also discussed, isotope-labeling experiments having shown that it proceeds through reduction of the final radical to the corresponding anion, followed by protonation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Ruthenium(II)-Catalyzed Regioselective Synthesis of Allyl Ketones from Alkynes and their Silver(I)-Catalyzed Hydroarylation into ,-Functionalized KetonesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009Min Zhang Abstract The regioselective synthesis of ,,,-unsaturated ketones from terminal alkynes is achieved by cooperative action of tris(acetonitrile)pentamethylcyclopentadieneruthenium hexafluorophosphate [Cp*Ru(NCMe)3+ PF6,] and para -toluenesulfonic acid catalysts. These allyl ketones undergo direct regioselective hydroarylation/Friedel,Crafts reaction to introduce an electron-rich aryl group at the ,-position in the presence of ligand-free silver triflate (AgOTf) catalyst. Both catalytic reactions take place with atom economy and provide an alternative to the synthesis of a variety of allyl ketones and , -arylated ketones. [source] Activation of Elemental Sulfur by Electrogenerated Cyanomethyl Anion: Synthesis of Substituted 2-Aminothiophenes by the Gewald ReactionADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17 2008Marta Feroci Abstract The activation of elemental sulfur (S8) has been achieved by means of electrogenerated cyanomethyl anion [easily obtained by galvanostatic reduction from acetonitrile/tetraethylammonium hexafluorophosphate (MeCN-Et4NPF6)]. The "activated" sulfur reacted with ylidenemalononitriles to give substituted 2-aminothiophenes in very high yields. This variation of the Gewald reaction has been carried out using only catalytic amounts of electricity and supporting electrolyte. A proposed mechanism for the interaction between S8 and cyanomethyl anion is described. [source] Novel [Ruthenium(substituted-tetramethylcyclopentadiene) (2-quinolinecarboxylato)(allyl)] Hexafluorophosphate Complexes as Efficient Catalysts for Highly Regioselective Nucleophilic Substitution of Aliphatic Allylic SubstratesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2008Hui-Jun Zhang Abstract Stable [ruthenium(R-substituted-tetramethylcyclopentadiene)(2-quinolinecarboxylato)(1-R,-substituted-allyl) hexafluorophosphate (R=Me, R,=H, Me, n- Pr, Ph; R=t- Bu, R,=Me) and [ruthenium(pentamethylcyclopentadiene)(2-quinolinecarboxylato)(1- n -propylallyl)] tetrafluoroborate (4,a), as allylruthenium(IV) complexes, have been synthesized in one step, starting from [ruthenium(R-substituted-tetramethylcyclopentadiene)tris(acetonitrile) hexafluorophosphate or tetrafluoroborate complexes, quinaldic acid, and allylic alcohols. Single stereoisomers are obtained and the X-ray single crystal structure determinations of 3b (R=t- Bu, R,=Me) and 4,a allow one to specify the preferred arrangement. Complexes 3a (R=R,=Me) and 3b are involved as precatalysts favoring the formation of branched products in regioselective nucleophilic allylic substitution reactions, starting from ethyl 2- (E) -hexen-1-yl carbonate and chlorohexene as unsymmetrical aliphatic allylic substrates. Phenols, dimethyl malonate, and primary (aniline) and secondary (pyrrolidine, piperidine) amines have been used as nucleophiles under mild basic conditions. For the first time, the regioselectivity in favor of the branched product obtained from purely aliphatic allylic substrates is close to the high regioselectivity previously reached starting from cinnamyl-type substrates in the presence of ruthenium catalysts. [source] Enhancement of activity and selectivity in lipase-catalyzed transesterification in ionic liquids by the use of additivesJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 10 2007Francisco J Hernández-Fernández Abstract BACKGROUND: Seven ionic liquids (ILs) based on 1-alkyl-3-methylimidazolium cation in combination with hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions were tested as reaction media for lipase-catalyzed transesterification in low water conditions. With the aim of improving the activity and/or selectivity of the lipase, various treatments were applied to ionic liquid media such as equilibration with aqueous solutions of salts, NaHCO3 or Na2CO3, or the addition of a catalytic amount of a non-reactive organic base to the reaction mixture, triethylamine. RESULTS: The treated ionic liquids were shown to be excellent media for lipase-catalyzed ester synthesis by transesterification compared with conventional organic solvents, such as n -hexane. All treatments were found to enhance the synthetic activity of the enzyme, the best results being achieved with the addition of triethylamine. The addition of a catalytic amount of this base to the ILs resulted in a significant increase in both the synthetic activity and selectivity values. For instance, the synthetic activity in [emim+][TfN2,] was enhanced more than 12 times and the selectivity increased from 86% to 95% when triethylamine was used. CONCLUSION: These treatments could be easy-to-use approaches to improve the efficiency of enzymatic reactions in ionic liquids when the reaction does not proceed smoothly. Copyright © 2007 Society of Chemical Industry [source] Global phase behavior of imidazolium ionic liquids and compressed 1,1,1,2-tetrafluoroethane (R-134a)AICHE JOURNAL, Issue 2 2009Wei Ren Abstract Novel processes involving ionic liquids with refrigerant gases have recently been developed. Here, the complete global phase behavior has been measured for the refrigerant gas, 1,1,1,2-tetrafluoroethane (R-134a) and 1- n -alkyl-3-methyl-imidazolium ionic liquids with the anions hexafluorophosphate [PF6], tetrafluoroborate [BF4] and bis(trifluoromethylsulfonyl)imide [Tf2N] from ,0°C to 105°C and to 33 MPa. All of the systems studied were Type V from the classification scheme of Scott-van Konynenburg with regions of vapor-liquid equilibrium, miscible/critical regions, vapor-liquid-liquid equilibrium, and upper and lower critical endpoints (UCEP and LCEP). The effect of the alkyl chain length has been investigated, for ethyl-([EMIm]), n -butyl-([BMIm]), and n -hexyl-([HMIm]). With increasing chain length, the temperature of the lower critical end points increases and pressure at the mixture critical points decrease. With a common cation, the temperature of the LCEP increased and the mixture critical point pressures decreased in the order of [BF4], [PF6], and [Tf2N]. © 2008 American Institute of Chemical Engineers AIChE J, 2009 [source] Solvent effects on chemical processes: new solvents designed on the basis of the molecular,microscopic properties of (molecular solvent,+,1,3-dialkylimidazolium) binary mixturesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 2 2008P. M. Mancini Abstract The purpose of this work was to analyze the microscopic feature of binary solvent systems formed by a molecular solvent (acetonitrile or dimethylformamide or methanol) and an ionic liquid (IL) cosolvent [1-(1-butyl)-3-methylimidazolium tetrafluoroborate or 1-(1-butyl)-3-methylimidazolium hexafluorophosphate]. The empirical solvatochromic solvent parameters ET(30), ,*, ,, and , were determined from the solvatochromic shifts of adequate indicators. The behavior of the solvent systems was analyzed according to their deviation from ideality. The study focused on the identification of solvent mixtures with relevant solvating properties in order to select mixed solvents with particular characteristics. The comparison of the molecular,microscopic solvent parameters corresponding to the selected binary mixtures with both ILs considered at similar mixed-solvent composition revealed that the difference is centered on the basic character of them. A kinetic study of a nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene (FDNB) and 1-butylamine (BU) developed in (acetonitrile or dimethylformamide,+,IL) solvent mixtures is presented in order to investigate and compare the solvent effects on a chemical process. For the explored reactive systems the solvation behavior is dominated by both the dipolarity/polarizability and the basicity of the media, contributing these solvent properties to accelerating the chemical process. Copyright © 2007 John Wiley & Sons, Ltd. [source] Self-assembly of daisy chain oligomers from heteroditopic molecules containing secondary ammonium ion and crown ether moietiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2010Harry W. Gibson Abstract MALDI-TOF MS of the heteroditopic compound 2 -(benzylammoniomethyl)dibenzo-24-crown-8 hexafluorophosphate (4) revealed oligomeric "daisy chain" species up to the hexamer. Similar results were obtained for 2-(6,-hydroxyhexylammoniomethyl)dibenzo-24-crown-8 hexafluorophosphate (8). The complexations of two substituted dibenzylammonium salts, 2,2,-dimethyldibenzylammonium hexaflurophosphate (9a) and 2,2,,5-trimethoxydibenzylammonium hexafluorophosphate (9b), with dibenzo-24-crown-8 were examined as models for slippage systems; association constants are reported for these systems. A crystal structure is reported for the new dimethylbenzylammonoium pseudorotaxane. The trimethoxy analog is shown to be capable of slippage formation of a rotaxane, albeit in low yield. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 975,985, 2010 [source] Electrochemical synthesis of PEDOT derivatives bearing imidazolium-ionic liquid moietiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2009Markus Döbbelin Abstract Novel poly(3,4-ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium-ionic liquid moieties were synthesized by electrochemical polymerizations. For this purpose, new functional monomers were synthesized having an 3,4-ethylenedioxythiophene (EDOT) unit and an imidazolium-ionic liquid with different anions such as tetrafluoroborate (BF), bis(trifluoromethane)sulfonimide ((CF3SO2)2N,), and hexafluorophosphate (PF). Next, polymer films were obtained by electrochemical synthesis in dicholoromethane solutions. Obtained polymers were characterized, revealing the characteristics of PEDOT in terms of electrochemical and spectroelectrochemical properties, FTIR, 1H NMR, and AFM microscopy. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PF > (CF3SO2)2N, > BF > pure PEDOT as determined by water contact angle measurements. Furthermore, the polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making these polymers interesting candidates for wet processing methods. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3010,3021, 2009 [source] Atom transfer radical polymerization of styrenic ionic liquid monomers and carbon dioxide absorption of the polymerized ionic liquidsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2005Huadong Tang Abstract Polymeric forms of ionic liquids have many potential applications because of their high thermal stability and ionic nature. Two ionic liquid monomers, 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate (VBIT) and 1-(4-vinylbenzyl)-3- butyl imidazolium hexafluorophosphate (VBIH), were synthesized through the quaternization of N -butylimidazole with 4-vinylbenzylchloride and a subsequent anion- exchange reaction with sodium tetrafluoroborate or potassium hexafluorophosphate. Copper-mediated atom transfer radical polymerization was used to polymerize VBIT and VBIH. The effects of various initiator/catalyst systems, monomer concentrations, solvent polarities, and reaction temperatures on the polymerization were examined. The polymerization was well controlled and exhibited living characteristics when CuBr/1,1,4,7,10,10-hexamethyltriethylenetetramine or CuBr/2,2,-bipyridine was used as the catalyst and ethyl 2-bromoisobutyrate was used as the initiator. Characterizations by thermogravimetric analysis, differential scanning calorimetry, and X-ray diffraction showed that the resulting VBIT polymer, poly[1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate] (PVBIT), was amorphous and had excellent thermal stability, with a glass-transition temperature of 84 °C. The polymerized ionic liquids could absorb CO2 as ionic liquids: PVBIT absorbed 0.30% (w/w) CO2 at room temperature and 0.78 atm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1432,1443, 2005 [source] Conductivity modification of proton conducting polymer gel electrolytes with the addition of fumed silicaPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 8 2006Jitender Paul Sharma Abstract The addition of nano size fumed silica to non aqueous proton conducting polymer gel electrolytes containing ammonium hexafluorophosphate (NH4PF6) has been found to modify the conductivity and viscosity behavior. Two maxima observed in the conductivity vs. fumed silica plot at very low concentrations have been explained to be due to an increase in free ion concentration with the dissociation of ion aggregates, and the formation of a high conducting interfacial layer between the particles of fumed silica and polymer gel electrolytes respectively. The change in free ion concentration has been monitored by pH measurements whereas change in mobility has been checked from viscosity measurements. The dissociation of ion aggregates with the addition of fumed silica has also been supported by FTIR results. The variation of conductivity and viscosity with temperature has also been studied and conductivity of nano dispersed gels does not show any change with time. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] | |||||||||||||||||||||||||||||||