Trifluoromethyl Sulfone Research Articles

Solubility Thermodynamics of CyMe_{4}-BTBP in Various Diluents Mixed with TBP

The two organic ligands 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[1,2,4]triazin-3-yl)[2,2′]bipyridine (CyMe_{4}-BTBP) and tri-butyl phosphate (TBP) have previously been investigated in different diluents for use within recycling of used nuclear fuel through solvent extraction. The thermodynamic parameters, K_{mathrm{S}}, Delta C_{p}, Delta H^{0} and Delta S^{0}, of the CyMe_{4}-BTBP solubility in three diluents (cyclohexanone, octanol and phenyl trifluoromethyl sulfone) mixed with TBP have been studied at 288, 298 and 308 K, both as pristine solutions and pre-equilibrated with 4 molcdot L^{-1} nitric acid. In addition, the amount of acid in the organic phase and density change after pre-equilibration have been measured. The solubility of CyMe_{4}-BTBP increases with an increased temperature in all systems, especially after acid pre-equilibration. This increased CyMe_{4}-BTBP solubility after pre-equilibration could be explained by acid dissolution into the solvent. Comparing the Delta H^{0} and Delta S^{0} calculated using Delta C_{p} with the same parameters derived from a linear fit indicates temperature independence of all three thermodynamic systems. The change in enthalpy is positive in all solutions.

Poly(benzyl methacrylate)-poly[(oligo ethylene glycol) methyl ether methacrylate] triblock-copolymers as solid electrolyte for lithium batteries

A triblock copolymer of benzyl methacrylate and oligo(ethylene glycol) methyl ether methacrylate was polymerized to form the general structure PBnMA-POEGMA-PBnMA, using atom transfer radical polymerization (ATRP). The block copolymer (BCP) was blended with lithium bis(trifluoro methylsulfonate) (LiTFSI) to form solid polymer electrolytes (SPEs). AC impedance spectroscopy was used to study the ionic conductivity of the SPE series in the temperature interval 30 °C to 90 °C. Small-angle X-ray scattering (SAXS) was used to study the morphology of the electrolytes in the temperature interval 30 °C to 150 °C. By using benzyl methacrylate as a mechanical block it was possible to tune the microphase separation by the addition of LiTFSI, as proven by SAXS. By doing so the ionic conductivity increased to values higher than ones measured on a methyl methacrylate triblock copolymer-based electrolyte in the mixed state, which was investigated in an earlier paper by our group. A Li|SPE|LiFePO4 half-cell was constructed and cycled at 60 °C. The cell produced a discharge capacity of about 100 mAh g−1 of LiFePO4 at C/10, and the half-cell cycled for more than 140 cycles.

D8-poly(methyl methacrylate)-poly[(oligo ethylene glycol) methyl ether methacrylate] tri-block-copolymer electrolytes: Morphology, conductivity and battery performance

A series of deuterated tri-block copolymers with the general structure d8-PMMA-POEGMA-d8-PMMA, with variation in d8-PMMA chain length, were synthesized using sequential controlled radical polymerization (ATRP). Solid polymer electrolytes (SPEs) were produced by blending tri-block copolymers and lithium bis(trifluoro methylsulfonate) (LiTFSI). Small-angle neutron scattering (SANS) was used to study the bulk morphology of the deuterated tri-block copolymer electrolyte series at 25 °C, 60 °C and 95 °C. The lack of a second Tg in DSC analysis together with modelling with the random phase approximation model (RPA) confirmed that the electrolytes are in the mixed state, with negative Flory-Huggins interaction parameters. AC impedance spectroscopy was used to study the ionic conductivity of the SPE series in the temperature interval 30 °C–90 °C, and a battery device was constructed to evaluate a 25 wt% d8-PMMA electrolyte. The Li | SPE | LiFePO4 cell cycled at 60 °C, giving a discharge capacity of 120 mAh g−1, while cyclic voltammetry showed that the SPE was stable at 60 °C.

Anomalous temperature dependence in the structural organization of charge alternation in imidazolium-based ionic liquids of various alkyl chain lengths

We report on trends observed in the X-ray static structure factor obtained for four homologous imidazolium-based ionic liquids. In a series of low-energy (laboratory) and high-energy synchrotron X-ray diffraction experiments, the temperature dependent structure was investigated in 1-alkyl-3-methylimidazolium cations, with chain lengths of n=4, 6, 8, and 10, paired with the trifluoromethylsulfonate (TF) anion. Interestingly, the charge alternation peak in the liquids displays an anomalous temperature evolution, increasing in amplitude as the temperature is raised. Analysis of the pair distribution function (PDF) evolution with temperature for all compositions attributes the observed anomalous behavior to a specific distance in the liquid. Extensive peak modelling of the structure factors confirms the anomaly for all compositions, which combined with the analysis of the temperature of the PDFs, suggests that the entropic tendency to decohere strict charge alternation overcomes enthalpic tendencies in these liquids.

Cycloadducts of phenylethynyl trifluoromethyl sulfone with diphenyldiazomethane and 9-diazofluorene and their transformations under conditions of van Alphen–Hüttel rearrangement

Diphenyldiazomethane and 9-diazofluorene react with phenylethynyl trifluoromethyl sulfone in diethyl ether at 20°C to give 1,3-dipolar cycloaddition products according to the von Auwers rule, the corresponding 3H-pyrazoles. The adduct with diphenyldiazomethane undergoes thermal van Alphen–Huttel rearrangement to 4,4,5-triphenyl-3-(trifluoromethanesulfonyl)-4H-pyrazole on heating in boiling benzene. Under analogous conditions, the adduct with 9-diazofluorene is converted into 3′-phenylspiro[fluorene-9,4′-pyrazol]-5′(1′H)-one, whereas 3a-phenyl-2,3a-dihydro-3H-dibenzo[e,g]indazol-3-one is formed in boiling methanol. The structure of 3′-phenylspiro[fluorene-9,4′-pyrazol]-5′(1′H)-one was determined by X-ray analysis.

Mathematical modeling of extraction of nitric acid, actinides, and fission products into 30% TBP in halogenated diluents using A.M. Rozen’s model

The effect of a series of halogenated diluents [bis(octafluoroamyloxy)methane, phenyl trifluoromethyl sulfone, methyl dodecafluoroheptyl ether, m-nitrobenzotrifluoride, hexachlorobutadiene, CHCl3, CCl4] on the extraction of spent nuclear fuel solution components [HNO3, U(VI), An(IV), Zr, and Tc] into 30% TBP was studied and mathematically described using improved A.M. Rozen’s model. Comparison with the TBP–paraffins extraction system was made.

Efficent Synthesis of 5-(4-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl))benzylidene-2,2-dimethyl-1,3-dioxane-4,6-dione Derivatives

Objective Synthesis of gastrodin intermediate 4-formylphenyl(2,3,4,6-O-tetraacetyl)-β-D-glucoside analogues. Methods 5-(4-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)) benzylidene-2,2-dimethyl-1,3-dioxane-4,6-dione derivatives were synthesized by the Knoevenagel reaction of self-made 4-formylphenyl(2,3,4,6-O-tetraacetyl)-β-D-glucoside and 2,2-dimethyl-1,3-dioxane -4,6-dione in the presence of N-methylimidazole trifluoromethyl sulfonate. Results and conclusions five products of gastrodin intermediate analogues characterized by NMR and MS(ESI). The reaction has the advantages of high yields(76%～84%), mild conditions, simple operation and environmental friendliness. N-methylimidazole trifluoromethyl sulfonate could be recycled and reused several times without significant loss of its efficiency.

Radiation Influencing of the Extraction Properties of the CyMe4-BTBP and CyMe4-BTPhen Solvents with FS-13

The radiolytic stability of two ligands, CyMe4-BTBP and CyMe4-BTPhen in system with the FS-13 (phenyl trifluoromethyl sulfone) diluent was investigated under irradiation by accelerated electrons to study impact of the degradation products on the separation process efficiency and safety. Irradiation experiments were carried out up to the absorbed dose of 200 kGy. The irradiated samples were analysed by HPLC for the degree of extractant degradation. In addition, the effect of the presence of HNO3 during the irradiation was studied. Extraction properties of the irradiated solvents were evaluated and compared with the extraction properties of non-irradiated solvents to assess the impact of the degradation products on extractions properties.The results obtained show that the stabilities of these ligands are higher in FS-13 than in the cyclohexanone-type solvents. The extraction properties are significantly influenced by degradation products contained in these systems. Surprisingly, both the distribution ratios for americium and europium, and the Am/Eu separation factor increase with the absorbed dose for the system withCyMe4-BTPhen in FS-13. Obviously, the degradation products of this ligand are efficient extractants too. In the next phase, an attempt will be done to identify the main degradation products, synthesise them and study their extraction properties.

Development of the Chalmers Grouped Actinide Extraction Process

Abstract Several solvents for Grouped ActiNide EXtraction (GANEX) processes have been investigated at Chalmers University of Technology in recent years. Four different GANEX solvents; cyclo-GANEX (CyMe4- -BTBP, 30 vol.% tri-butyl phosphate (TBP) and cyclohexanone), DEHBA-GANEX (CyMe4-BTBP, 20 vol.% N,N-di-2(ethylhexyl) butyramide (DEHBA) and cyclohexanone), hexanol-GANEX (CyMe4-BTBP, 30 vol.% TBP and hexanol) and FS-13-GANEX (CyMe4-BTBP, 30 vol.% TBP and phenyl trifluoromethyl sulfone (FS-13)) have been studied and the results are discussed and compared in this work. The cyclohexanone based solvents show fast and high extraction of the actinides but a somewhat poor diluent stability in contact with the acidic aqueous phase. FS-13-GANEX display high separation factors between the actinides and lanthanides and a good radiolytic and hydrolytic stability. However, the distribution ratios of the actinides are lower, compared to the cyclohexanone based solvents. The hexanol-GANEX is a cheap solvent system using a rather stable diluent but the actinide extraction is, however, comparatively low.

Phenyl trifluoromethyl sulfone as diluent in a grouped actinide extraction process: extraction properties of the solvent components TBP and CyMe4-BTBP

The grouped actinide extraction (GANEX) process combines two extractants CyMe4-BTBP and TBP in a diluent, in this study phenyl trifluoromethyl sulfone (FS-13). The extraction of U-235, Np-239, Pu-238, Am-241, Cm-244 and Eu-152 has been investigated in four different systems. System 1: 70 %vol FS-13, 30 %vol TBP and 10 mM CyMe4-BTBP, system 2: 70 %vol FS-13 and 30 %vol TBP, system 3: 100 %vol FS-13 and 10 mM CyMe4-BTBP and system 4: pure FS-13. In all cases 4 M HNO3 was used as aqueous phase. In system 1 all actinides were extracted and separated from the lanthanides. In both system 2 and 3 mainly U and Pu were extracted. In system 4 none of the metals were extracted.

Stability of phenyl trifluoromethyl sulfone as diluent in a grouped actinide extraction process

In this work, stability experiments have been performed on a phenyl trifluoromethyl sulfone based solvent containing 6,6′-bis(5,6-dialkyl-[1,2,4-]triazin-3-yl)-2,2′-bipyridine and tri-butyl phosphate. This solvent is intended to be used in a grouped actinide extraction process for partitioning and transmutation purposes. The distribution ratio for americium was determined to approximately 20 and for europium approximately 0.26 giving a separation factor of 77. The solvent maintain good distribution ratios and separation factors during both gamma irradiation of 6.6 kGy h−1 for up to 24 h and acid contact for up to 6 weeks at room temperature.

Thermosensitive Ionic Microgels via Surfactant-Free Emulsion Copolymerization and in Situ Quaternization Cross-Linking

A type of thermosensitive ionic microgel was successfully prepared via the simultaneous quaternized cross-linking reaction during the surfactant-free emulsion copolymerization of N-isopropylacrylamide (NIPAm) as the main monomer and 1-vinylimidazole or 4-vinylpyridine as the comonomer. 1,4-Dibromobutane and 1,6-dibromohexane were used as the halogenated compounds to quaternize the tertiary amine in the comonomer, leading to the formation of a cross-linking network and thermosensitive ionic microgels. The sizes, morphologies, and properties of the obtained ionic microgels were systematically investigated by using transmission electron microscopy (TEM), dynamic and static light scattering (DLS and SLS), electrophoretic light scattering (ELS), thermogravimetric analyses (TGA), and UV-visible spectroscopy. The obtained ionic microgels were spherical in shape with narrow size distribution. These ionic microgels exhibited thermosensitive behavior and a unique feature of poly(ionic liquid) in aqueous solutions, of which the counteranions of the microgels could be changed by anion exchange reaction with BF4K or lithium trifluoromethyl sulfonate (PFM-Li). After the anion exchange reaction, the ionic microgels were stable in aqueous solution and could be well dispersed in the solvents with different polarities, depending on the type of counteranion. The sizes and thermosensitive behavior of the ionic microgels could be well tuned by controlling the quaternization extent, the type of comonomer, halogenated compounds, and counteranions. The ionic microgels showed superior swelling properties in aqueous solution. Furthermore, these ionic microgels also showed capabilities to encapsulate and release the anionic dyes, like methyl orange, in aqueous solutions.

ChemInform Abstract: Nucleophilic Trifluoromethylation of Conjugated Acceptors via Phenyl Trifluoromethyl Sulfone.

AbstractThe title reaction can be also applied to the synthesis of compound (IX), a useful precursor for the preparation of befloxatone, which is a reversible and selective monoamine oxidase A inhibitor.

Acetalization Catalyzed by ReusableN-Methylimidazole Trifluoromethyl Sulfonate

Acetalization Catalyzed by Reusable<i>N</i>-Methylimidazole Trifluoromethyl Sulfonate

Nucleophilic trifluoromethylation of conjugate acceptors via phenyl trifluoromethyl sulfone

A mild procedure for the conjugate addition of the trifluoromethyl anion to activated Michael acceptors such as arylidenemalononitriles (15 examples) and arylidene Meldrum’s acids (9 examples) using phenyl trifluoromethyl sulfone through a reductive magnesium metal mediated procedure is described. The new methodology is used to prepare befloxatone, a reversible and selective monoamine oxidase A inhibitor.

Preparation and utilization of poly(methacryloylsilatrane) as a salt‐dissociation enhancer in PEO‐based polymer electrolytes

Polymers containing silatrane units were prepared by the free radical polymerization of methacryloylsilatrane (MPS), and their conductivities were evaluated. We confirmed that MPS can be polymerized without excessive decomposition of the silatrane units by the radical polymerization initiated by azobisisobutyronitrile. The chemical structure of the polymerized MPS (pMPS) was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. The pMPS formed a homogeneous complex with lithium trifluoromethyl sulfonate (LiOTf), although the obtained pMPS/LiOTf complex did not show conductivity. The negligible conductivity was caused by the high glass transition temperature (Tg) of the pMPS matrix, which exceeded 70°C. The pMPS was subsequently utilized as a salt‐dissociation enhancer for the poly(ethylene oxide)‐based polymer electrolyte. MPS was copolymerized with poly[methacryloyl oligo(ethylene oxide)] (pMEO) by free radical polymerization. When the pMEO incorporated a small amount of MPS units (i.e. lower than 15 mol%), the elevation in Tg was not observed, and the conductivity markedly improved. Among the series of copolymers and when compared with pristine pMEO, the copolymer containing 6.3% of MPS units had the maximum conductivity (3.1 × 10−4 S cm−1 at 80°C). The Vogel–Fulcher–Tammann fitting parameters showed that the conductivity was improved by the increase in the number of carrier ions. The enhancement in salt dissociation was presumably due to the homogeneous incorporation of polar MPS units. However, when the MPS unit content exceeded 15 mol%, the conductivity was lowered because of the increase in Tg. Copyright © 2013 John Wiley &amp; Sons, Ltd.

Evaluation of two calix-crown-6 ligands for the recovery of radio cesium from nuclear waste solutions: Solvent extraction and liquid membrane studies

Recovery of radio-cesium from high level radioactive waste is one of the major challenges in the back end of fuel cycle. Calix-crown ligands have been found to be highly selective for the recovery of Cs(I) from acidic feed solutions. The present work deals with the evaluation of the bis-(octyloxy)calix[4]arene-mono-crown-6 (BOCMC) as a selective extractant for radiocesium from nuclear waste solution. BOCMC was evaluated for Cs uptake using several diluents such as NPOE (2-nitro phenyl octyl ether), 1-octanol, hexone, nitrobenzene, PTMS (phenyl trifluoromethyl sulfone) and chloroform. Feed acidity variation studies revealed more favorable extraction at 2–3M HNO3 and inefficient stripping due to H+ ion extraction was countered by the addition of Alamine-336 to the organic phase. Batch co-current extraction studies revealed quantitative extraction of Cs in four successive contacts which was not affected significantly even when the solvent system was exposed to 100MRad gamma ray dose. Results obtained was compared with the previously studied commercially available extractant, calix[4]-bis-2,3-naptho-crown-6 (CNC).Supported liquid membrane studies were also carried out using BOCMC using 2.0×10−3M of the extractant in a mixture of 80% NPOE and 20% n-dodecane containing 0.4% Alamine-336. Diffusion coefficient values calculated from Wilke–Chang equation were compared with those obtained by Danesi's method and time lag method. The stability of membrane, studied over a period of 20 days was found to be reasonably good.

Thermal stability of UNEX/HCCD-PEG diluent FS-13

Phenyl trifluoromethyl sulfone (FS-13) is an inert diluent used in HCCD/PEG process for isolation and recovery of cesium and strontium from highly radioactive raffinate waste. There is no experimental data available in open literature describing pressurization due to the thermal decomposition of FS-13 at elevated temperatures. Experiments were conducted for determination of flash point and heating of FS-13 under pressurized closed-vent conditions in an adiabatic calorimeter. During adiabatic experiments, negligible pressurization was observed.

PVT properties of UNEX/HCCD-PEG diluent phenyl trifluoromethyl sulfone (FS-13) and experimental measurement of vapour pressure in 283.15–363.15 K range

Phenyl trifluoromethyl sulfone (FS-13) is a polar diluent, proposed in literature as an alternate to nitrobenzene, in UNEX/HCCD-PEG processes for better physical properties. Its PVT properties and accurate expression for estimation of its vapour pressure are not available in the literature. Recently PVT properties of FS-13 were estimated by authors and its vapour pressure was experimentally measured at temperatures ranging from 263.15 to 363.15 K. In this paper, results of these studies are presented.

A regioselective synthesis of poly-substituted aryl triflones through self-promoting three component reaction

In the absence of any additional catalysts, the reactions of (CF(3)SO)(2)CH(2), aldehydes, and 1,3-dienes gave gem-bis(triflyl)cyclohexenes in excellent yields with high regioselectivity. gem-Bis(triflyl)cyclohexene products can be easily converted to the corresponding aryl trifluoromethyl sulfones.