1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

In einen 5 I Reaktionsgefaess werden 620, 5 g (5 mol) 1-Butylimidazol vorgelegt und 630, 5g (5 mol) Dimethylsulfat portionsweise zugegeben. Der Ansatz wird danach 15 Minuten nachgeruehrt. Dazu gibt man eine Mischung von 1435, 3g (5 mol) Lithium-bis-trifluormethansulfonimid in 2 Liter Wasser. Sofort bildet sich das Produkt als eine zweite fluessige Phase. Nach einer Phasentrennung wird das Produkt bei 60°C am HV getrocknet. Man erhaelt 1-Butyl-3-methylimidazolium-bis(trifluormethylsulfon)imid in 98 percentiger Ausbeute. Zum qualitativen Nachweis auf Chloridreste, werden ca. 1 g des Produktes in ca. 5 ml Wasser geloest und mit 2 Tropfen konzentrierter Salpetersaeure angesaeuert. Zu dieser Loesung werden dann ca. 3-4 Tropfen Silbernitrat gegeben um etwaig vorhandenes Chlorid als Silberchlorid auszufaellen. Das Ausbleiben eines Silberchlorid-Niederschlags spricht fuer die komplette Abwesenheit von Halogenidionen. 1H-NMR (300 MHz, Aceton-d3):0, 95 (3 H, tr, J=9, 2 Hz, Hh); 1, 33-1, 39 (2 H, m, Hg); 1, 90-2, 00 (2 H, m, Hf); 4, 07 (3 H, s, Hb); 4, 37 (2 H, tr, J=9, 3 Hz, He); 7, 71;7, 76 (je 1 H, s, Hc, d); 9, 02 (1 H, s, Ha) ppm.First 0.02 mol imidazolium bromide salt was added to 50 mL of dichloromethane and mixed. Then 0.02 mol bis(trifluoromethanesulfonyl)imide salt of lithium was added to the stirring solution of imidazolium bromide salt. The mixture was left stirring for about 24 h at room temperature. Then the lithium bromide salt was filtered and the concentrated AgNO3 solution was added to the solution. The resulting solution was washed with pure water so that AgBr was allowed to pass into the water phase. Then dichloromethane was evaporated with a rotary evaporator. The yield was calculated as 60percent.1-butyl imidazole 1.28 mmol (0.168 mL) and bis (trifluoromethanesulfonyl) imide 1.28 mmol (360 mg) it was stirred for 30 minutes to put the schlenk tube. Then the reaction was refluxed trimethyl ortho formate 9.1mmol (0.7 mL) under N2 to the residue. Confirming that the protonated imidazole disappears then removed trimethyl ortho formate remaining in vacuo, and ethyl acetate and then dissolved in a small amount of methanol, deprotonate the small amount of the protonated imidazole was passed through a basic alumina It was. After having passed through this solution, putting them in a vacuum and the product was confirmed by NMR. Yield: 95percent35 g (0.16 mol) of [C4mim][Br] was diluted with 100 mL of deionized water and 45.7 g (0.16 mol)of Li(Tf2N) was added. After mixing, the reaction mixture was separated into two layers. Thebottom layer was [C4mim] [Tf2N] and the top layer was aqueous LiCl. After decanting the toplayer, 100 mL of fresh deionized water was added and the solution was thoroughly mixed. Thisprocedure was repeated twice. The ionic liquid was dried in vacuo (under 0.1mbar) at 60C for 24hours, producing a colorless liquid (yield: 61.5 g, 87.5%).First 0.02 mol imidazolium bromide salt was added to 50 mL of dichloromethane and mixed. Then 0.02 mol bis(trifluoromethanesulfonyl)imide salt of lithium was added to the stirring solution of imidazolium bromide salt. The mixture was left stirring for about 24 h at room temperature. Then the lithium bromide salt was filtered and the concentrated AgNO3 solution was added to the solution. The resulting solution was washed with pure water so that AgBr was allowed to pass into the water phase. Then dichloromethane was evaporated with a rotary evaporator. The yield was calculated as 60%.An embodiment of a reversible mirror of the invention was fabricated as follows: two electrodes were prepared using 6×8 cm single-side planar ITO coated glass plates having a sheet resistivity of 7 Omega/square. Each plate was provided with a bus bar by attaching a copper electrical contact approximately 1 cm wide along the entire edge of the 6 cm end of each plate. The electrodes were then washed with water, methanol and acetone, and dried in a stream of warm air to remove any dust or grease. An o-ring (2 cm internal diameter (ID) vycor rubber donut-shaped o-ring, 0.3 cm thick) was used as a gasket to seal one electrode to the other. A silver wire (5 cm long, 0.25 mm diameter, 99.9% metal purity) was inserted through the o-ring by first piercing a hollow needle through the o-ring, placing one end of the silver wire through the hollow needle, and then withdrawing the hollow needle from the o-ring. Approximately 0.4 mm of the silver wire protruded through the o-ring. The o-ring was then placed between the two electrodes with the conducting ITO coating in contact with the o-ring (see FIGS. 1 and 2) with the bus bars at opposite ends of the device. Two spring-loaded clips were used to hold the device together and provide a tight seal. A digital ohmmeter was used to ensure that the three electrodes (working, counter and pseudo-reference electrodes) were in electrical isolation of each other. Butylmethylimidazolium bis(trifluoromethylsulfonyl)imide was synthesized as follows: Butylmethylimidazolium bromide (50 g) was dissolved deionized water (100 mL). Decolorizing charcoal or activated carbon (3 g) was added to the solution, which was boiled for 3 minutes and filtered. The filtrate was added to a solution of lithium bis(trifluoromethylsulfonyl)imide (65.5 g) in 100 mL of deionized water. After stirring at room temperature for 3 hrs, two layers formed. The bottom layer containing butylmethylimidazolium bis(trifluoromethylsulfonyl)imide was separated, washed deionized water (3×50 mL), heated at 100 C. under vacuum (0.1 mbar) for 48 hrs, and then filtered through activated alumina to give anhydrous, highly pure, molten butylmethylimidazolium bis(trifluoromethylsulfonyl)imide. The purity of the molten salt was assayed by cyclic voltammetry, absorbance spectroscopy or fluorescence measurements. A solution of 3-butyl-1-methylimadazolium bis(trifluoromethylsulfonyl)imide containing less than 1 ppm water and 0.035 mol/L of bismuth (III) bis(trifluoromethylsulfonyl)imide was prepared in a helium atmosphere drybox. The solution was introduced into the chamber of the device by inserting two hollow needles through the o-ring (one needle for introducing the solution, the other needle for removing displaced gas). Afterward, the needles were removed and the o-ring was checked for leaks. Wire connectors were attached to the bus bars and to a potentiostat that provided the voltage for electrodeposition. A bismuth mirror was deposited at a potential of -0.65 Volts versus the silver reference electrode. The bismuth mirror was deplated at a potential of +0.1 Volts versus the silver reference electrode. Overall, this reversible mirror device exhibited good optical reflectance in the reflective state and good transparency in the non-mirrored state, and was switched repetitively between these two states without degradation of performance.General procedure: The respective halide IL was dissolved in deionized water (pH =6) and after an equimolar amount of LiNTf2 in water had been added dropwise, the reaction mixture was stirred for 1 day at 70 C. Then CH2Cl2 was added and the aqueous phase was removed. The organic phase was washed halide-free with deionized water (AgNO3 test). The solution was filtered over a column filled with neutral Al2O3 and activated charcoal. The organic solvent was removed under reduced pressure and the reaction product finally dried under dynamic vacuum for 1-2 days at 80-90 C.Ionic liquid [bmim]Br was heated gently at 80C. The lithiumsalt LiTFSI was added to the melt under N2and stirred for 24 h.Adding CH2Cl2, LiBr was precipitated and separated by filtration.The filtrate was evaporated to dryness then the [bmim][TFSI]obtained.Then, the dried precursor BmimBr (0. 05 mmol, 10.5 g) and equimolar LiN (S02) 2 (CF3) 2 (0. 05 mmol, 13.7 g) were each dissolved in 20 mL H20 and mixed at room temperature 24h, After adding 50mL CH2Cl2, the water was removed and the aqueous phase was removed. After 5 times, CH2C12 was removed and dried at 80 C for 12 h to obtain ionic liquid [Bmim] [Tf2N].In 4-necked flask of 500ml, 82.1 g (1.000mol) of 1-methylimidazole, 101.8 g (1.100mol) of 1-chlorobutane, and 50.0g of toluene were added and stirred for 15 hours under reflux (approximately 106C). After they were reacted in this way, a reaction solution was cooled (air-cooled) to 70C or below. Then, 100.0g of ultra pure water was added therein, the resultant solution was water-cooled to room temperature. After the cooling, an upper layer (toluene layer) of the solution was separated off from the solution by using a separating funnel. To a lower layer (water layer), 100.0g of toluene was further added. After the resultant solution was stirred for 30 min, an upper layer (toluene layer) was separated off from the solution by using a separating funnel, thereby remaining a water layer in which [BMIm]Cl being a cation portion of an ionic liquid was contained.(Anion-Exchange Reaction) After the separation, 53.8g of the water layer containing [BMIm]Cl (corresponding to 0.200mol of [BMIm]Cl) was transferred to a 300ml conical flask, and mixed with 63.2g (0.220mol) of lithium bis(trifluoromethanesulfonyl)imide and 50.0g of ultra pure water. A resultant mixture was stirred for 30min at room temperature in order to carry out an anion-exchange reaction. After the reaction, an upper layer (water layer) was separated out by using a separating funnel. A lower layer was mixed with 50.0g of ultra pure water and stirred for 30min at room temperature. Then, an upper layer (water layer) was separated out by using a separating funnel. A lower layer containing the cation portion of the ionic liquid was transferred to an egg-plant-shaped flask of 100ml and evaporated under reduced pressure at 60C under 20mmHg for 1 hour, so as to distill off water. In this way, a light yellow solution whose solvent was N-methyl-N'-butyl imidazolium bis(trifluoromethanesulfonyl)imide ([BMIm]NTf2) was obtained.(Salt Removal Step) After 50.0g of acetone was added thereto, the light yellow solution thus obtained was cooled to a temperature in a range of approximately 0 to 5C, and then stirred for 30 min, thereby trying to crystallize out lithium chloride (by-product) and unreacted lithium bis(trifluoromethanesulfonyl)imide. Even though the crystallization yielded no crystals, the resultant solution was filtered with a Buchner funnel having an internal diameter of 55mm, and then washed with 20.0g of acetone. A filtrate obtained from the filtration was then transferred to an egg-plant-shaped flask of 200ml and evaporated under reduced pressure at 60C under 20mmHg for 2 hours, and then further evaporated under reduced pressure at 60C under 1mmHg to 2mmHg for 1 hour. In this way, 73.8g of a concentrated solution containing the target [BMIm]NTf2 was obtained. The concentrated solution had water content of 0.0111% (111ppm).(Water Removing Step and Purifying Step) Then, 73.8g of the concentrated solution thus obtained was mixed with 0.20g (0.00166mol) of methyl orthoacetate (MOA). A resultant mixture was stirred at 80C for 3 hours so as to react MOA with water not distilled off from an ionic liquid. The reaction caused hydrolysis of MOA with the water thereby giving methanol and methyl acetate. The methanol and methyl acetate thus obtained and unreacted MOA were evaporated off under reduced pressure at 60C under 20mmHg for 1 hour. A concentrated liquid thus obtained was further evaporated under reduced pressure at 60C under 1mmHg to 2mmHg for 2 hours. In this way, a target material, [BMIm]NTf2 was obtained as a light yellow liquid.(Water Content Analysis of [BMIm]NTf2) Water content of [BMIm]NTf2 was measured by the Karl Fishcer test. Water content after the addition of MOA was 0.0032% (32ppm). Water content after methanol, methyl acetate and the unreacted MOA was evaporated off was 0.0037% (37ppm).General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.General procedure: The diazonium tetrafluoroborates (10-20 mg) were dissolved in ionic liquids (0.4 mL). The solution was heated using the conditions shown in Table 1. The ionic liquids were extracted with hexane. After removal of the solvent, the residues were analyzed by NMR, and the product distributions are summarized in Table 1. Compounds 2a, 22 2b, 23 2c, 24 2d, 23 2e, 22 3a, 25 3d, 26 3e, 27 and 3f27 were identified by comparing their NMR spectra with those reported in the literature. The isomers ArOSO(CF3)(NTf) (4a-4f) and ArNTf2 (5a-5f) were attempted to be purified with SiO2 column chromatography using hexane-CH2Cl2 or hexane-ether as an eluent. However, they could not be separated by chromatography.

Molecular Weight:419.4
Hydrogen Bond Acceptor Count:11
Rotatable Bond Count:5
Exact Mass:419.04081729
Monoisotopic Mass:419.04081729
Topological Polar Surface Area:94.8
Heavy Atom Count:25
Complexity:467
Covalently-Bonded Unit Count:2
Compound Is Canonicalized:Yes