There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.
Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic
USD 100+
Accessible (Haz class 3, 4, 5 or 8), International
USD 200+
Structure of 79917-90-1 * Storage: {[proInfo.prStorage]}
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
To a 50ml Schleck tube was added 1-methyl-1H-imidazole (4.1g, 0.05 mol), 1-chlorobutane (9.2g, 0.1 mol, 2 equiv) and distilled toluene (20 ml), the mixture were heated and stirred at 90 °C oil bath for overnight, after reaction, all the versitile were removed under vacuo. the residue were washed with 2-methoxy-2-methylpropane (3* 20 ml), dried under vacuo, which afforded 3-butyl-1-methyl-1H-imidazol-3-ium chloride (NHC precursor E) as white solid (92percent, 8g)
90%
at 40℃; for 24 h;
1) N-Methylimidazole (4 g, 48.7 mmol)In a single-necked flask,And then weighed1-Chloromethane6.68 g (72.2 mmol)(The molar ratio of 1-methyl chloride to N-methyl imidazole was about 1.48: 1). After the dropwise addition, the reaction was carried out at 40 ° C for 24 hours. The reaction was monitored by thin layer chromatography , The excess of 1-methyl chloride distillation, the white solid is chlorinated 1-butyl-3-methyl imidazole, the yield of 90percent;
90%
at 150℃; Microwave irradiation
In a MW vial, 4 mL of 1-methylimidazole(0.0484 mol) and 7.6 mL of 1-chlorobutane (0.0726 mol) were consecutively added; then, the mixturewas irradiated (200 W) at 150 °C for 25 min. Then, the supernatant 1-chlorobutane was removedand the mixture was then washed with hexane and diluted with CH2Cl2 to be transferred in a roundbottom flask for the removal of solvent under vacuum. The desired product 5 was obtained in 90percentyield. 1H-NMR (200 MHz, CDCl3, ppm): δ = 9.71 (s, 1H), 7.99 (m, 1H), 7.89 (m, 1H), 4.24 (t, 2H,J = 7.0 Hz), 3.91 (s, 3H), 1.77 (m, 2H), 1.30 (m, 2H), 0.88 (t, 3H, J = 7.2 Hz).
88.6%
for 48 h; Reflux
Synthesis of 1-butyl-3-methylimidazolium chloride: A mixture of 1-methylimidazole (70.0 g, 0.853 mol), ethanenitrile (50 mL) and 1-chlorobutane (102 g, 1.10 mol) are heated under reflux with vigorous stirring for 48 hrs. 1-chlorobutane (99.5percent) is sourced from a commercial supplier (Sigma-Aldrich). Volatile substances are removed in a first step under reduced pressure (ca. 50° C., 20 mbar), and finally, in vacuo (ca. 80° C., 0.01 mbar) during 16 hrs, yielding 1-butyl-3-methylimidazolium chloride ([C4mim]Cl, 131.8 g, 88.6percent) as a pale yellow viscous liquid which crystallizes upon cooling to room temperature.
88%
at 60 - 65℃; for 24 h;
An amount of 1-methylimidazole (10 mmol, 1.745 g) and n-butylchloride (11 mmol, 1.018 g) were sequentially added into a 25 mL round-bottom flask assembled with the condenser. The reaction mixture was stirred magnetically with 250 rpm speed at 60–65 °C for 24 h. After cooling down to room temperature, the reaction mixture was washed with diethyl ether(5 x 10 mL) until no trace of n-butyl chloride, as well as 1-methylimidazole in a solution of diethylether were detected by thin layer chromatography (TLC) and gas chromatography (GC). The othersolution containing recyclable [Bmim]Cl was evaporated under reduced pressure at 80 °C for 30 minto afford a light yellow liquid in high yield (88percent). The identity and purity of [Bmim]Cl obtainedwere analyzed by 1H-NMR, 13C-NMR and LC/MS spectroscopy. In continuation of the preparationof [Bmim]Cl*2AlCl3, an amount of aluminum chloride (4 mmol, 0.534 g) was added slowly into a10 mL round-bottom flask containing [Bmim]Cl (2 mmol, 0.349 g). After that, the reaction mixturewere stirred magnetically at room temperature for 12 h. The identity and purity of acidic catalyst,[Bmim]Cl*2AlCl3, were checked by 1H-NMR and integrated as follows: 1H-NMR (500 MHz, D2O): δ (ppm) 8.65 (s, 1H), 7.43 (s,1H), 7.38 (s, 1H), 4.14 (t, J = 7.0 Hz, 2H), 3.84 (s, 3H), 1.77–1.82 (m, 2H),1.23–1.30 (m, 2H), 0.87 (t, J = 7.5 Hz, 3H).
86%
at 110℃; for 24 h;
To a vigorously stirred solution of 1-methylimidazole (1.25 mol) in toluene (125 mL) at 0 °C, 1-chlorobutane (1.38 mol) was added. The solution was heated to reflux at 110 °C for 24 h, after which it was placed in a freezer at - 20 °C for 12 h. The toluene was decanted and the remaining viscous oil/semi-solid was recrystallized from acetonitrile. Again it was repeatedly recrystallized from ethyl acetate to yield a white crystalline solid, which was further dried under reduced pressure to give [Bmim]Cl in approximately 86percent yield. 1H NMR (400 MHz, DMSO-d6): δ = 10.54 (1H, s), 7.55 (1H, m), 7.40 (1H, m), 4.26 (2H, t, J = 7.3 Hz), 4.11 (3H, s), 1.82 (2H, m), 1.30 (2H, m), 0.89 (3H, t, J = 7.3 Hz). Chloride ion is 21.10 wtpercent
85%
at 80℃;
1-Butyl-3-methylimidazolium chloride was prepared from the reaction of N-methylimidazole with n-butylchloride at 80 °C under neat conditions.
82%
at 75℃; for 48 h; Inert atmosphere
1-butyl-3-methylimidazolium chloride [bmim][Cl] synthesized accordingto organic synthesis [39]. A mixture of 1-methylimidazole(1 eq) and 1-chlorobutane (1.3 eq) in dry acetonitrile was stirred at75 °C for 48 h under nitrogen.The mixture was cooled to room temperature.The volatile material was removed under reduced pressure andthe remaining light-yellow oil dissolved in appropriate acetonitrileand added dropwise to a flask containing dry ethyl acetate dry ethyl acetatecontaining flask to give [bmim][Cl] as a white crystal in approximately82percent yeild.
80%
Reflux; Inert atmosphere
Two chloride-based ionic liquids, [BMIM]Cl and [AMIM]Cl, were synthesized according to the literature methods [10,11], respectively. Reactions were carried out under nitrogen atmosphere and followed by ESI-MS and 1H NMR. Produced ILs were dried overnight in a high vacuum at 50–70 °C and stored in a desiccator. Water content of the IL determined by the Mettler Toledo DL36 Karl Fischer coulometer was <0.1percent (w/w). (0012) [BMIM]Cl was prepared from butyl chloride (159.5 g, 1.72 mol) and N-methylimidazole (103.0 g, 1.25 mol) in a 500 ml flask by mixing and refluxing until all methylimidazole had reacted (24–48 h). The crude product was then recrystallized from an ethyl acetate–acetonitrile mixture (55:45). The yield of white [BMIM]Cl was 174.8 g (80percent). 1H NMR (200 MHz, CDCl3): δ 0.96 (3H, t, JHH = 7.3 Hz), 1.41 (2H, m), 1.89 (2H, m), 4.13 (3H, s), 4.34 (2H, t, JHH = 7.3 Hz), 7.47 (1H, t, JHH = 1.8 Hz), 7.62 (1H, t, JHH = 1.8 Hz),10.67 (1H,s). MS(ESI+) [m/z (rel. int. (percent))]: 139 (100, [BMIM]). MS(ESI−) [m/z (rel. int. (percent))]: 210 (100, Cl[BMIM]Cl)
72%
at 70℃; for 24 h;
General procedure: C4mimBr was synthesized according to the reported literatures.1 In a 100 mL round-bottom flask, 1-methylimidazole (8.21 g, 0.1 mol) was mixed with n-butyl bromide (16.44 g, 0.12 mol) and allowed to reflux for 24 h at 70 °C. The excess n-butyl bromide was distilled off under reduced pressure and the residue was finally extracted thoroughly 2-3 times (50 mL each) with diethyl ether to remove the traces of unreacted starting materials. A white solid of 1-n-butyl-3-methylimidazolium bromide was obtained in 87percent yield.
72.4%
at 75℃; for 48 h;
Equipped with a blender,Reflux condenser and a thermometer 500mL three-necked flask was added 68.60g N-methyl imidazole and 85.65g chlorobutane,And were added 80mL cyclohexane and toluene as the reaction medium,Control the temperature inside the bottle is 70 ,After stirring for 48h, the upper solvent and the unreacted raw materials were removed by pouring,The lower oily liquid was hot with ethyl acetate 4 times (each time the amount of 20mL)Remove the liquid transfer to a single mouth flask,Rotate under reduced pressure (water bath temperature was controlled at 70 ) to remove part of the solvent and raw materials unreacted raw materials.Turn the steam transfer to the vacuum drying oven,The temperature is 70 ,Vacuum dried 36h,That is to obtain the intermediate l-butyl-3-methylimidazolium chloride [Bmim] Cl,Yield 68.6percent.
70.2%
at 80℃; for 36 h;
500 mL equipped with a stirrer, reflux condenser and thermometerThree-necked flask was added 68.60gN-methylimidazole and85.65g chlorobutane, and were added 80mL cyclohexane and toluene as the reaction medium,Control the temperature inside the bottle is 80 ,After stirring for 36h, the upper solvent and the unreacted raw materials were removed by pouring,The lower oily liquid was hot with ethyl acetate 4 times (each time the amount of 20mL)Remove the liquid transfer to a single mouth flask,Rotate under reduced pressure (water bath temperature was controlled at 70 ) to remove part of the solvent and raw materials unreacted raw materials. Turn the steam transfer to a vacuum oven, the temperature is 70 ,Drying in vacuo for 36 h gave the intermediate productL-butyl-3-methylimidazolium chloride[Bmim] Cl, yield 70.2percent.
68.2%
at 70℃; for 48 h;
In the presence of a stirrer,Reflux condenser and a thermometer was charged 68.60 g of N-methylimidazole in a 500 mL three-necked flaskAnd 85.65 g of chlorobutane,And adding 80mL of cyclohexane and toluene as reaction intermediates,The temperature in the control bottle is 70 ° C,After stirring for 48 h, the upper layer solvent and the unreacted starting material were removed by the pouring method,The lower oily liquid was washed 4 times with ethyl acetate (20 mL each)Remove the liquid from the lower layer to the vial,Vacuum distillation (water bath temperature control at 70 ° C) to remove part of the solvent and raw materials in the unreacted raw materials.Steaming finished transferred to a vacuum oven,The temperature is 70 ° C, vacuum drying 36h,To give the intermediate 1-butyl-3-methylimidazolium chloride[Bmim] C1, yield 68.2percent.
61%
at 65℃; for 11 h;
9.27g (0.1mol) 1-chlorobutane was added dropwise to 11.50g (0.14mol) 1-methylimidazole. The mixture was heated at 65°C under stirring for 11h. Phase separation occurred and the viscous yellow liquid obtained was washed with ethyl acetate (60 mL for three times). Then the product was filtered and dried in vacuum dryness case until constant weigh. 10.80g [bmim]Cl was obtained, and the yield of colorless liquid was 61percent.
Reference:
[1] Journal fuer Praktische Chemie - Practical Applications and Applied Chemistry (Germany), 2000, vol. 342, # 4, p. 348 - 354
[2] Chemistry - A European Journal, 2006, vol. 12, # 20, p. 5328 - 5333
[3] Journal of Materials Chemistry, 2008, vol. 18, # 43, p. 5267 - 5273
[4] European Journal of Organic Chemistry, 2003, # 9, p. 1681 - 1686
[5] Molecules, 2008, vol. 13, # 1, p. 149 - 156
[6] Organic and Biomolecular Chemistry, 2018, vol. 16, # 18, p. 3453 - 3463
[7] Dalton Transactions, 2017, vol. 46, # 36, p. 12185 - 12200
[8] Analytical Chemistry, 2007, vol. 79, # 2, p. 758 - 764
[9] Journal of Chemistry, 2014, vol. 2014,
[10] Zeitschrift fur Anorganische und Allgemeine Chemie, 2017, vol. 643, # 1, p. 60 - 68
[11] Tetrahedron, 2010, vol. 66, # 6, p. 1352 - 1356
[12] Analytical Chemistry, 2005, vol. 77, # 2, p. 702 - 705
[13] New Journal of Chemistry, 2012, vol. 36, # 3, p. 650 - 655
[14] Chinese Journal of Catalysis, 2013, vol. 34, # 4, p. 769 - 780
[15] New Journal of Chemistry, 2015, vol. 39, # 6, p. 4994 - 5002
[16] RSC Advances, 2017, vol. 7, # 26, p. 15952 - 15963
[17] Journal of Chemical and Engineering Data, 2006, vol. 51, # 2, p. 696 - 701
[18] Small, 2016, vol. 12, # 14, p. 1935 - 1944
[19] Tetrahedron Letters, 2009, vol. 50, # 38, p. 5403 - 5405
[20] Organic and Biomolecular Chemistry, 2013, vol. 11, # 43, p. 7516 - 7521
[21] Synthesis (Germany), 2018, vol. 50, # 6, p. 1315 - 1322
[22] Organic Process Research and Development, 2002, vol. 6, # 6, p. 826 - 828
[23] Tetrahedron Letters, 2014, vol. 55, # 4, p. 826 - 829
[24] European Journal of Organic Chemistry, 2017, vol. 2017, # 42, p. 6319 - 6326
[25] Journal of the Chemical Society, Dalton Transactions, 2002, # 5, p. 680 - 685
[26] Australian Journal of Chemistry, 2006, vol. 59, # 4, p. 273 - 276
[27] Patent: CN105418511, 2016, A, . Location in patent: Paragraph 0055
[28] Molecules, 2018, vol. 23, # 11,
[29] Tetrahedron, 2009, vol. 65, # 41, p. 8507 - 8512
[30] Journal of Molecular Liquids, 2012, vol. 170, p. 66 - 71
[31] RSC Advances, 2014, vol. 4, # 39, p. 20308 - 20316
[32] Organic Syntheses, 2002, vol. 79, p. 236 - 236
[33] Patent: US2017/121633, 2017, A1, . Location in patent: Paragraph 0237
[34] Molecules, 2017, vol. 22, # 9,
[35] Green Chemistry, 2011, vol. 13, # 7, p. 1694 - 1707
[36] Science China Chemistry, 2012, vol. 55, # 8, p. 1587 - 1597
[37] Angewandte Chemie - International Edition, 2018, vol. 57, # 36, p. 11613 - 11617[38] Angew. Chem., 2018, vol. 130, # 36, p. 11787 - 11791,5
[39] Mendeleev Communications, 2004, vol. 14, # 2, p. 59 - 61
[40] Russian Chemical Bulletin, 2004, vol. 53, # 10, p. 2187 - 2191
[41] Petroleum Chemistry, 2005, vol. 45, # 1, p. 21 - 25
[42] Physical Chemistry Chemical Physics, 2003, vol. 5, # 13, p. 2790 - 2794
[43] Organic letters, 2002, vol. 4, # 18, p. 3161 - 3163
[44] Mendeleev Communications, 2011, vol. 21, # 6, p. 329 - 330
[45] Molecules, 2012, vol. 17, # 12, p. 13727 - 13739
[46] Thermochimica Acta, 2014, vol. 579, p. 15 - 21
[47] Organic and Biomolecular Chemistry, 2008, vol. 6, # 14, p. 2522 - 2529
[48] Russian Journal of Applied Chemistry, 2011, vol. 84, # 7, p. 1158 - 1164
[49] Comptes Rendus Chimie, 2012, vol. 15, # 11-12, p. 1077 - 1080
[50] Journal of Physical Chemistry B, 2003, vol. 107, # 42, p. 11749 - 11756
[51] Journal of Fluorine Chemistry, 2007, vol. 128, # 6, p. 612 - 618
[52] Synlett, 2003, # 10, p. 1447 - 1450
[53] Journal of Molecular Liquids, 2017, vol. 232, p. 462 - 470
[54] Tetrahedron, 2003, vol. 59, # 13, p. 2253 - 2258
[55] Asian Journal of Chemistry, 2010, vol. 22, # 8, p. 6026 - 6030
[56] ChemPhysChem, 2010, vol. 11, # 10, p. 2182 - 2190
[57] Catalysis Letters, 2011, vol. 141, # 9, p. 1254 - 1261
[58] Catalysis Today, 2012, vol. 196, # 1, p. 11 - 15
[59] Journal of the American Chemical Society, 2003, vol. 125, # 18, p. 5264 - 5265
[60] Chemical Communications, 2010, vol. 46, # 4, p. 571 - 573
[61] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2004, vol. 59, # 7, p. 763 - 770
[62] Chemical Communications, 2001, # 7, p. 643 - 644
[63] Journal of Organic Chemistry, 2007, vol. 72, # 20, p. 7790 - 7793
[64] Green Chemistry, 2011, vol. 13, # 5, p. 1182 - 1186
[65] Tetrahedron, 2012, vol. 68, # 20, p. 3835 - 3842
[66] Green Chemistry, 2012, vol. 14, # 10, p. 2752 - 2758,7
[67] Green Chemistry, 2012, vol. 14, # 10, p. 2752 - 2758
[68] Patent: CN106588778, 2017, A, . Location in patent: Paragraph 0034
[69] Bulletin of the Chemical Society of Japan, 2007, vol. 80, # 12, p. 2365 - 2374
[70] Patent: CN106632051, 2017, A, . Location in patent: Paragraph 0026
[71] Dalton Transactions, 2010, vol. 39, # 37, p. 8679 - 8687
[72] Dalton Transactions, 2015, vol. 44, # 42, p. 18576 - 18584
[73] Patent: CN106632052, 2017, A, . Location in patent: Paragraph 0032
[74] Physical Chemistry Chemical Physics, 2010, vol. 12, # 16, p. 4005 - 4011
[75] Journal of the Chemical Society - Dalton Transactions, 1997, # 19, p. 3465 - 3469
[76] Synthesis, 2003, # 17, p. 2626 - 2628
[77] Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 2, p. 259 - 261
[78] Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics, 1997, vol. 101, # 7, p. 1075 - 1077
[79] Journal of Physical Chemistry B, 1998, vol. 102, # 50, p. 10229 - 10233
[80] Analytical Chemistry, 1999, vol. 71, # 17, p. 3873 - 3876
[81] Analytical Chemistry, 2001, vol. 73, # 16, p. 3838 - 3844
[82] European Journal of Organic Chemistry, 2003, # 24, p. 4804 - 4809
[83] Journal of Chemical Thermodynamics, 2003, vol. 35, # 11, p. 1855 - 1860
[84] Tetrahedron Letters, 2001, vol. 42, # 48, p. 8445 - 8446
[85] Chemistry Letters, 2003, vol. 32, # 7, p. 654 - 655
[86] Journal of Physical Chemistry B, 2004, vol. 108, # 16, p. 5113 - 5119
[87] Journal of Physical Chemistry B, 2005, vol. 109, # 7, p. 2942 - 2948
[88] Analytical Chemistry, 2006, vol. 78, # 18, p. 6384 - 6390
[89] Physical Chemistry Chemical Physics, 2001, vol. 3, # 23, p. 5192 - 5200
[90] Journal of the American Chemical Society, 2003, vol. 125, # 22, p. 6632 - 6633
[91] Journal of the American Chemical Society, 2003, vol. 125, # 50, p. 15577 - 15588
[92] Chemistry Letters, 2003, vol. 32, # 8, p. 740 - 741
[93] Chemical Communications, 1998, # 16, p. 1765 - 1766
[94] Journal of Physical Chemistry B, 2003, vol. 107, # 48, p. 13532 - 13539
[95] Journal of the American Chemical Society, 2005, vol. 127, # 15, p. 5316 - 5317
[96] Journal of Chemical and Engineering Data, 2004, vol. 49, # 5, p. 1422 - 1424
[97] Journal of Catalysis, 2006, vol. 242, # 2, p. 357 - 364
[98] Advanced Synthesis and Catalysis, 2005, vol. 347, # 1, p. 137 - 142
[99] Journal of Chemical and Engineering Data, 2004, vol. 49, # 6, p. 1550 - 1553
[100] Journal of Physical Chemistry B, 2004, vol. 108, # 29, p. 10245 - 10255
[101] Tetrahedron Asymmetry, 2006, vol. 17, # 1, p. 7 - 11
[102] Journal of Physical Chemistry B, 2004, vol. 108, # 39, p. 15133 - 15140
[103] Tetrahedron, 2006, vol. 62, # 13, p. 3137 - 3145
[104] Journal of Physical Chemistry B, 2004, vol. 108, # 42, p. 16593 - 16600
[105] Australian Journal of Chemistry, 2004, vol. 57, # 2, p. 151 - 155
[106] Physical Chemistry Chemical Physics, 2004, vol. 6, # 12, p. 3106 - 3110
[107] Australian Journal of Chemistry, 2006, vol. 59, # 7, p. 463 - 467
[108] Analytical Chemistry, 2007, vol. 79, # 2, p. 620 - 625
[109] Nucleosides, Nucleotides and Nucleic Acids, 2005, vol. 24, # 5-7, p. 819 - 822
[110] Chemistry - A European Journal, 2006, vol. 12, # 35, p. 9036 - 9045
[111] Organic Letters, 2001, vol. 3, # 2, p. 233 - 236
[112] Chemistry - A European Journal, 2007, vol. 13, # 7, p. 2130 - 2137
[113] Synthesis, 2006, # 15, p. 2543 - 2550
[114] Journal of Solution Chemistry, 2006, vol. 35, # 3, p. 297 - 309
[115] Analytical Chemistry, 2006, vol. 78, # 14, p. 4909 - 4917
[116] Chemistry - A European Journal, 2007, vol. 13, # 19, p. 5642 - 5648
2
[ 109-69-3 ]
[ 79917-90-1 ]
Reference:
[1] Patent: US2003/50507, 2003, A1,
3
[ 284049-75-8 ]
[ 79917-90-1 ]
Yield
Reaction Conditions
Operation in experiment
93.5%
With hydrogenchloride In water at 50℃; Cooling
Comparative examples C1 to C3198 g (1 mol) of BMIM OAc (1-butyl-3-methylimidazolium acetate) are placed in a round-bottom flask which has been made inert and is provided with a dropping funnel and reflux condenser. The amount of acid indicated in the appended table is added slowly while stirring, with the temperature being kept below 50° C. (an exothermic reaction is observed during the addition; the temperature is kept down either by appropriately slow addition with air cooling or by cooling with water).After cooling to room temperature, the major part of the volatile constituents is taken off at a pressure of 0.1 mbar, with the internal temperature being increased to 120° C. When no more low boilers are given off from the mixture under these conditions, the mixture is cooled and nitrogen is admitted. The residue is transferred to the reservoir of the short-path distillation and fed in at a rate of 100 ml/h at the evaporator temperature indicated below. The pressure in the short-path distillation is set to 0.05 mbar. The product is obtained as bottom output, so that the short-path distillation here functions as a very efficient form of low boiler stripping.The condensed low boilers comprise water (when an aqueous reagent is added) and acetic acid. BMIM Evaporator Product OAc:acid temp. (salt having Yield No. Acid mol:mol ° C. the new anion) percent Purity* C1 HCl; 35percent in water 1:1.033 170 BMIM Cl 93.5 comprises 20 mol percent of HOAc after first passage comprises 3 mol percent of HOAc after second passage C2 CF3COOH 1:1.017 150 BMIM TFA 90.9 comprises 13 mol percent of HOAc after first passage (trifluoroacetic acid) comprises 4 mol percent of HOAc after second passage C3 CH3SO3H 1:1.005 170/190 BMIM 92.3 comprises 9 mol percent of HOAc after first passage (methanesulfonic CH3SO3 no HOAc after the second passage acid) *Analysis by H-NMR
General procedure: 1-butyl-imidazole and acid source were mixed at 0 °C, after removing the water under reduced pressure by using phosphorus pentoxide, after the addition of trimethyl ortho formate is reacted at a given temperature for a predetermined time to remove the triisopropyl ortho formate remaining in the reduced pressure the ionic liquid 13 to 22 respectively was produced.The yield of the ionic liquid 13 to 22 prepared each ion of the acid source, the reaction temperature and reaction time used in the production and accordingly liquids is shown in Table 1.
Reference:
[1] Green Chemistry, 2014, vol. 16, # 9, p. 4098 - 4101
[2] Patent: KR2015/79403, 2015, A, . Location in patent: Paragraph 0108-0112
Reference:
[1] Patent: CN106699551, 2017, A, . Location in patent: Paragraph 0020; 0021
10
[ 616-47-7 ]
[ 109-65-9 ]
[ 79917-90-1 ]
Reference:
[1] European Journal of Inorganic Chemistry, 2004, # 6, p. 1190 - 1197
[2] Chemistry - A European Journal, 2014, vol. 20, # 23, p. 6909 - 6914
Reference:
[1] Journal of Chemical and Engineering Data, 2010, vol. 55, # 4, p. 1679 - 1683
15
[ 79917-90-1 ]
[ 174501-64-5 ]
Yield
Reaction Conditions
Operation in experiment
27%
With lithium hexafluorophosphate In dichloromethane at 20℃; for 72 h; Inert atmosphere
Lithium hexafluorophosphate was mixed with 1-butyl-3-methylimidazolium chloride, [Bmim][Cl] in a two-neck round bottom flask. The reaction mixture was stirred in dry dichloromethane at room temperature for 72 h under an inert atmosphere. The reaction mixture was filtered and the excess lithium chloride was washed with dichloromethane. The combined organic extraction was washed with distilled water until the aqueous layer was free from halide, determined using the silver nitrate test. The dichloromethane layer was concentrated to give a yellow liquid. The yellow liquid was treated with activated charcoal and filtered through acidic alumina to give 1-butyl-3-methylimidazolium hexafluorophosphate (27percent) as a colorless liquid 28. IR (KBr) 3392.27 (OH), 1649.54 (C=C), 1008.56 (CN) cm–1; 1H NMR (400 MHz, DMSO-d6) δ 9.00 (1H, s, CH-2), 7.67 (1H, s, CH-4), 7.61 (1H, s, CH-5), 4.14 (2H, t, J= 7.32 Hz, NCH2CH2CH2CH3), 3.83 (3H, s, NCH3), 1.76 (2H, m, NCH2CH2CH2CH3), 1.26 (2H, m, NCH2CH2CH2CH3), 0.89 (3H, t, J= 7.32 Hz, NCH2CH2CH2CH3); 13C NMR (100 MHz,DMSO-d6) 136.9 (NCN), 124.0 (C-4), 122.6 (C-5), 49.1 (NCH2CH2CH2CH3), 36.1 (NCH3), 31.8 (NCH2CH2CH2CH3), 19.2 (NCH2CH2CH2CH3), 13.5 (NCH2CH2CH2CH3); MS (ESI+) m/z 423.21 [2(C4C1im) + PF6] and 139.12, [C4C1im], MS (ESI-) m/z 429.05 [2(PF6) + (C4C1im)] and 144.96 [PF6].
Reference:
[1] Molecules, 2012, vol. 17, # 4, p. 4007 - 4027
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2004, vol. 59, # 7, p. 763 - 770
[3] New Journal of Chemistry, 2012, vol. 36, # 3, p. 650 - 655
[4] Synthesis, 2003, # 17, p. 2626 - 2628
[5] Organic and Biomolecular Chemistry, 2008, vol. 6, # 14, p. 2522 - 2529
[6] Dalton Transactions, 2017, vol. 46, # 36, p. 12185 - 12200
[7] Organic Syntheses, 2002, vol. 79, p. 236 - 236
[8] Analytical Chemistry, 1999, vol. 71, # 17, p. 3873 - 3876
[9] Organic and Biomolecular Chemistry, 2013, vol. 11, # 43, p. 7516 - 7521
[10] Molecules, 2009, vol. 14, # 12, p. 5001 - 5016
[11] RSC Advances, 2018, vol. 8, # 46, p. 26237 - 26242
[12] Oriental Journal of Chemistry, 2014, vol. 30, # 3, p. 1191 - 1196
[13] Journal de Chimie Physique et de Physico-Chimie Biologique, 1998, vol. 95, # 7, p. 1626 - 1639
[14] Journal fuer Praktische Chemie - Practical Applications and Applied Chemistry (Germany), 2000, vol. 342, # 4, p. 348 - 354
[15] Analytical Chemistry, 2001, vol. 73, # 16, p. 3838 - 3844
[16] Journal of Physical Chemistry B, 2003, vol. 107, # 48, p. 13532 - 13539
[17] Journal of Physical Chemistry B, 2004, vol. 108, # 29, p. 10245 - 10255
[18] Journal of Physical Chemistry B, 2004, vol. 108, # 39, p. 15133 - 15140
[19] Physical Chemistry Chemical Physics, 2003, vol. 5, # 13, p. 2790 - 2794
[20] Journal of Physical Chemistry B, 2004, vol. 108, # 42, p. 16593 - 16600
[21] Journal of Physical Chemistry B, 2004, vol. 108, # 52, p. 20355 - 20365
[22] Synthesis, 2006, # 15, p. 2543 - 2550
[23] Chemical Communications, 2006, # 17, p. 1828 - 1830
[24] Journal of the American Chemical Society, 2009, vol. 131, # 4, p. 1390 - 1391
[25] Tetrahedron Letters, 2009, vol. 50, # 29, p. 4286 - 4288
[26] Journal of Chemical and Engineering Data, 2009, vol. 54, # 2, p. 472 - 479
[27] Journal of Physical Chemistry B, 2010, vol. 114, # 24, p. 8118 - 8125
[28] Journal of Thermal Analysis and Calorimetry, 2010, vol. 101, # 3, p. 1143 - 1148
[29] Journal of Physical Chemistry A, 2010, vol. 114, # 43, p. 11471 - 11476
[30] Journal of Materials Chemistry, 2010, vol. 20, # 28, p. 5820 - 5822
[31] Asian Journal of Chemistry, 2012, vol. 24, # 1, p. 261 - 263
[32] Journal of Molecular Liquids, 2013, vol. 181, p. 142 - 151
[33] Journal of Solution Chemistry, 2013, vol. 42, # 4, p. 738 - 745
[34] RSC Advances, 2013, vol. 3, # 33, p. 13825 - 13834
[35] Chemical Physics Letters, 2013, vol. 584, p. 79 - 82
[36] Asian Journal of Chemistry, 2014, vol. 26, # 9, p. 2695 - 2698
[37] Journal of the Chinese Chemical Society, 2014, vol. 61, # 7, p. 737 - 742
[38] RSC Advances, 2014, vol. 4, # 73, p. 38630 - 38642
[39] Journal of Solution Chemistry, 2015, vol. 44, # 7, p. 1518 - 1528
[40] Russian Journal of Physical Chemistry A, 2018, vol. 92, # 11, p. 2337 - 2340
With sodium tetrafluoroborate; In acetone; at 70℃; for 168h;
Die im ersten Schritt hergestellten 80,2 g (0,46 mol) 1-Butyl-3-methylimidazolium chloride werden in ca. 200 ml absolutem Aceton geloest und mit 75,62 g (0,69 mol) Natriumtetrafluoroborat versetzt und fuer ca. 1 Woche bei 70C geruehrt. Der entstandene Feststoff wird ueber eine Schutzgasfritte abfiltriert und das Filtrat am Rotationsverdampfer vom Loesungsmittel befreit und ueber Nacht bei 60C im HV getrocknet. Man erhaelt 1-Butyl-3-methyl-imidazoliumtetrafluoroborat in 74 %iger Ausbeute. Zum qualitativen Nachweis auf Chloridreste, werden ca. 1 ml des Produktes mit ca. 5 ml Wasser versetzt 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. Ein weisser Niederschlag spricht fuer eine nicht vollstaendige Chloridfreiheit des Produktes. 1H-NMR (300 MHz, CDCl3):0,79 (3 H, tr, J=5,8 Hz, Ha); 1,22 (2 H, m, Hb); 1,74 (2 H, m, Hc); 3,86 (3 H, s, Hh); 4,17 (2 H, tr, J=5,8 Hz, Hd); 7,51; 7,57 (je 1 H, s, Hf,g); 8,7 (1 H, s, He). 13C-NMR (75 MHz, CDCl3):14,1 (a); 20,3-36,8 (b, c, d); 50,4 (h); 123,2-125,0 (f,g); 137,8 (e). 19F-NMR (281 MHz, CDCl3):148,5-150,8 (m)
74%
With sodium tetrafluoroborate; at 70℃; for 168h;
Die im ersten Schritt hergestellten 80,2 g (0,46 mol) 1-Butyl-3-methylimidazoliumchloride werden in ca. 200 ml Aceton geloest und mit 75,62 g (0,69 mol) Natriumtetrafluoroborat versetzt und fuer ca. 1 Woche bei 70C geruehrt. Der entstandene Feststoff wird ueber eine Schutzgasfritte abfiltriert und das Filtrat am Rotationsverdampfer vom Loesungsmittel befreit und ueber Nacht bei 60C am HV getrocknet. Man erhaelt 1-Butyl-3-methyl-imidazoliumtetrafluoroborat in 74 %iger Ausbeute. Zum qualitativen Nachweis auf Chloridreste, werden ca. 1 ml des Produktes mit ca. 5 ml Wasser versetzt 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. Ein weisser Niederschlag spricht fuer eine nicht vollstaendige Chloridfreiheit des Produktes. 1H-NMR (300 MHz, CDCl3):0,79 (3 H, tr, J=5,8 Hz, Ha); 1,22 (2 H, m, Hb); 1,74 (2 H, m, Hc); 3,86 (3 H, s, Hh); 4,17 (2 H, tr, J=5,8 Hz, Hd); 7,51; 7,57 (je 1 H, s, Hf,g); 8,7 (1 H, s, He).13C-NMR (75 MHz, CDCl3):14,1 (a); 20,3-36,8 (b, c, d); 50,4 (h); 123,2-125,0 (f,g); 137,8 (e).19F-NMR (281 MHz, CDCl3):148,5-150,8 (m)
With sodium tetrafluoroborate; In water; at 20℃; for 1h;Product distribution / selectivity;
In 4-necked flask of 500ml, 151.9 g (1.850mol) of 1-methylimidazole, 188.4 g (2.035mol) of 1-chlorobutane, and 80.00g of toluene were added and stirred for 25 hours under reflux (approximately 106C). After they were reacted in this way, a reaction solution was cooled (air-cooled) to 70C or below. Then, 100.00g 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), 80.00g 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 N-methyl-N'-butyl imidazolium chloride (hereinafter, referred to as [BMIm]Cl) being a cation portion of an ionic liquid was contained.(Anion-Exchange Reaction) After the separation, the water layer (lower layer) was transferred to a 4-necked flask of 1000ml, to which 223.4g (2.035mol) of sodium tetrafluoroborate and 250.0g of ultra pure water were then added. A resultant mixture was stirred for 1 hour at room temperature in order to carry out an anion-exchange reaction. After the reaction, a lower layer (water layer) was separated out by using a separating funnel. An upper layer was mixed with 50.0g of ultra pure water and stirred for 30min. The stirring emulsified a resultant reaction liquid. The emulsified reaction liquid was then filtered. With 50.0g of acetone, a resultant filtrate was transferred to an egg-plant-shaped flask of 500ml and evaporated under reduced pressure at 60C under 20mmHg for 3.5 hours, so as to distill off water and acetone. In this way, a light yellow slurry whose solvent was N-methyl-N'-butyl imidazolium Tetrafluoroborate ([BMIm]BF4) was obtained.(Salt Removal Step) After 100.0g of acetone was added thereto, the light yellow slurry thus obtained was cooled to a temperature in a range of approximately 0 to 5C, and then stirred for 30 min, thereby crystallizing out sodium chloride (by-product) and unreacted sodium tetrafluoroborate. The sodium chloride and unreacted sodium dicyanamide thus crystallized out was filtered out with a Buchner funnel having an internal diameter of 55mm. Crystals thus obtained were washed with acetone (70.0g). A solution thus obtained was filtered to get a filtrate. The filtrate was then transferred to an egg-plant-shaped flask of 500ml and evaporated under reduced pressure at 60C under 20mmHg for 3 hour. In this way, 379.8g of a concentrated solution containing the target [BMIm]BF4 was obtained. The concentrated solution had water content of 0.1284% (1284ppm).(Water Removing Step and Purifying Step) 30.0g of the concentrated solution was transferred to an egg-plant-shaped flask of 50ml and mixed with 0.45g (0.00428mol) of methyl orthoformate (OFM). A resultant mixture was stirred at 80C for 4 hours so as to react OFM with water not distilled off from an ionic liquid. The reaction caused hydrolysis of OFM with the water thereby giving methanol and methyl formate. The methanol and methyl formate thus obtained and unreacted OFM 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]BF4 was obtained as a light yellow liquid.(Water Content Analysis of [BMIm]BF4) Water content of [BMIm]BF4 was measured by the Karl Fishcer test. Water content after the addition of OFM was 0.0112% (112ppm). Water content after methanol, methyl formate and the unreacted OFM was evaporated off was 0.0066% (66ppm).
With tetrafluoroboric acid;
RTILs used were synthesized following a two step procedure [34] as reported earlier [35]. Briefly, in the first step 1-methylimidazole or 1,2-dimethylimidazole was refluxed with n-butyl chloride for 90 h under argon atmosphere for the synthesis of 1-butyl-3-methylimidazolium chloride and 1-butyl-2, 3-dimethylimidazolium chloride respectively. In the next step the halide anion was exchanged with [BF] 4- or [PF] 6- using HBF4 or HPF6. The RTILs were vacuum dried and stored in desiccators under inert atmosphere
With lithium hexafluorophosphate; In dichloromethane; at 20℃; for 72h;Inert atmosphere;
Lithium hexafluorophosphate was mixed with 1-butyl-3-methylimidazolium chloride, [Bmim][Cl] in a two-neck round bottom flask. The reaction mixture was stirred in dry dichloromethane at room temperature for 72 h under an inert atmosphere. The reaction mixture was filtered and the excess lithium chloride was washed with dichloromethane. The combined organic extraction was washed with distilled water until the aqueous layer was free from halide, determined using the silver nitrate test. The dichloromethane layer was concentrated to give a yellow liquid. The yellow liquid was treated with activated charcoal and filtered through acidic alumina to give 1-butyl-3-methylimidazolium hexafluorophosphate (27%) as a colorless liquid 28. IR (KBr) 3392.27 (OH), 1649.54 (C=C), 1008.56 (CN) cm-1; 1H NMR (400 MHz, DMSO-d6) delta 9.00 (1H, s, CH-2), 7.67 (1H, s, CH-4), 7.61 (1H, s, CH-5), 4.14 (2H, t, J= 7.32 Hz, NCH2CH2CH2CH3), 3.83 (3H, s, NCH3), 1.76 (2H, m, NCH2CH2CH2CH3), 1.26 (2H, m, NCH2CH2CH2CH3), 0.89 (3H, t, J= 7.32 Hz, NCH2CH2CH2CH3); 13C NMR (100 MHz,DMSO-d6) 136.9 (NCN), 124.0 (C-4), 122.6 (C-5), 49.1 (NCH2CH2CH2CH3), 36.1 (NCH3), 31.8 (NCH2CH2CH2CH3), 19.2 (NCH2CH2CH2CH3), 13.5 (NCH2CH2CH2CH3); MS (ESI+) m/z 423.21 [2(C4C1im) + PF6] and 139.12, [C4C1im], MS (ESI-) m/z 429.05 [2(PF6) + (C4C1im)] and 144.96 [PF6].
With hexafluorophosphoric acid;
RTILs used were synthesized following a two step procedure [34] as reported earlier [35]. Briefly, in the first step 1-methylimidazole or 1,2-dimethylimidazole was refluxed with n-butyl chloride for 90 h under argon atmosphere for the synthesis of 1-butyl-3-methylimidazolium chloride and 1-butyl-2, 3-dimethylimidazolium chloride respectively. In the next step the halide anion was exchanged with [BF] 4- or [PF] 6- using HBF4 or HPF6. The RTILs were vacuum dried and stored in desiccators under inert atmosphere
With hexafluorophosphoric acid;
Sodium azide and p-toluenesulfonyl chloride were obtained from E-Merck. p-Nitroanisole and p-nitroaniline were obtained from Sigma-Aldrich. 1-Methylimidazole and 1-chlorobutane used for the synthesis of ILs were obtained from Spectrochem (India). Acetonitrile (GR grade, 99.9 %), methanol (GR grade, 99.9 %), ethyl acetate (GR grade,99.5 %) and dichloromethane (GR grade, 99.5 %) procured from Merck-India were purified and dried as per the standard methods [30]. Spectroscopic grade ILs, viz. [C4C1im]Cl,[C4C1im][CH3COO] and [C4C1im][PF6], were synthesized as per literature procedures [23,31-33]. In the first step of the synthesis, 1-methylimidazole was refluxed with n-butyl chloride for 90 h under argon to get 1-butyl-3-methylimidazolium chloride as a white J Solution Chem (2015) 44:1518-1528 1519123 crystalline solid. In the next step, the halide ion Cl- was exchanged with PF6 or CH3COO-on treatment with HPF6 or CH3COONa to get [C4C1im][PF6] or [C4C1im][CH3COO] respectively. The ILs were dried and stored in a desiccator under inert atmosphere and were characterized through 1H and 13C NMR spectroscopy and mass spectrometry. The water content of these ILs was analyzed by Karl Fischer titration and were restricted to50 ppm.
With potassium hexafluorophosphate; In water; at 70℃; for 72h;
1-Methylimidazole was placed in a two neckedround-bottomed flask fitted with a water condensertopped with a blue silica tube. 1-Chlorobutane(1.2 molar equivalents) was added dropwise into theflask with stirring at 70C. The reaction was allowed to proceed for 48-72 h. The desired product, [C4C1Im]Cl, as firstly dried using a rotary evaporator and then under high vacuum at 60C for 12 h toyield a white solid [12]. [C4C1Im]Cl was then dissolved in deionized waterin a round bottomed flask. A water condenser was setup and the solution was stirred at 70C. KPF6(1.2 molar equivalents) dissolved in deionized H2Oand was added dropwise. After 72 h, the mixture wasseparated and the lower phase was washed with deionizedwater five times to remove KCl and unreactedKPF6. The desired [C4C1Im][PF6] was dried using arotary evaporator and then under high vacuum at 60Cfor 12 h to yield a colourless liquid [13].
In water; at 20℃; for 0.5h;Product distribution / selectivity;
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).
In acetonitrile byproducts: NaCl; onium chloride reacted with excess of Na orthoborate under refluxing for1-3 d; cooled; NaCl filtered off; solvent evapd. at reduced pressure; dried under vac. at 100°C for 1 d; dissolved (CH2Cl2); storage at room temp. overnight; filtered; solvent evapd.; dried in vac. oven at 90°C for 2 d;
1-butyl-3-methylimidazolium bis[oxalato(2-)]-borate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
In neat (no solvent) at 80℃; for 24h;
76.8%
In acetonitrile byproducts: LiCl; onium chloride reacted with excess of Li orthoborate under refluxing for1-3 d; cooled; LiCl filtered off; solvent evapd. at reduced pressure; dried under vac. at 100°C for 1 d; dissolved (CH2Cl2); storage at room temp. overnight; filtered; solvent evapd.; dried under vac. at 90°C (2 d); detn. by NMR (weak Li signal);
In acetone at 80℃; for 0.166667h; microwave irrradiation;
89.4%
In acetone for 24h;
85%
In dichloromethane at 70℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;
85%
In dichloromethane at 20℃; for 24h;
2 Synthesis of [bmim][NO3], [bmim][SCN] and [bmim][N(CN)2]
General procedure: According to literature procedures [40], NaNO3(1.1 eq), KSCN(1.2 eq) or NaN(CN)2 (1.1 eq) was added to a solution of [Bmim][Cl](1 eq) in dichloromethane and stirred for 24 h at room temperature.The suspension was filtered to remove the produced NaCl andunreacted NaNO3, KSCN and NaN(CN)2 salts. The organic phase was repeatedlywashed with small volume of water until no precipitation ofAgCl occurred in the aqueous phase on addition of AgNO3 solution.Then solvent was removed in vacuo and the synthesized IL was stirredwith activated charcoal for 6 h, removing the solvent gives[bmim][NO3], [bmim][SCN] and [bmim][N(CN)2] with 82%, 74% and85% yields, respectively.
54%
In acetone at 20℃; for 21h;
at 35℃;
In water at 20℃; for 3h;
2
In 4-necked flask of 200ml, 16.42 g (0.200mol) of 1-methylimidazole, 20.37 g (0.220mol) of 1-chlorobutane, and 10.00g of toluene were added and stirred for 17 hours under reflux (approximately 106°C). After they were reacted in this way, a reaction solution was cooled (air-cooled) to 70°C or below. Then, 30.00g 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), 20.00g 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 N-methyl-N'-butyl imidazolium chloride (hereinafter, referred to as [BMIm]Cl) being a cation portion of an ionic liquid was contained.; After the separation, 18.55g (0.200mol) of 96% sodium dicyanamide (NaDCA), and 70.00g of ultra pure water were added to the water layer thus remained. A resultant was stirred for 3 hours at room temperature in order to carry out an anion-exchange reaction. Evaporation under reduced pressure was carried out at 60°C under 20mmHg for 2 hours.(Salt Removing Step) After 60.00g of acetone was added thereto, the white slurry was cooled to approximately 0°C to 5°C and stirred for 30 min, thereby crystallizing out sodium chloride and unreacted sodium dicyanamide. The sodium chloride and unreacted sodium dicyanamide thus crystallized out was filtered out with a Buchner funnel having an internal diameter of 55mm. Crystals thus obtained were washed with acetone (30.00g). A solution thus obtained was filtered to get a filtrate. The filtrate was then transferred to an egg-plant-shaped flask of 200ml and evaporated under reduced pressure at 50°C under 20mmHg for 1 hour. The filtrate was then further evaporated under reduced pressure at 50°C under 1mmHg to 2mmHg for 1 hour.(Water Removing Step and Purifying Step) To a concentrated liquid thus obtained, 4.81g (0.040mol) methyl orthoacetate (MOA) was added. A resultant mixture was stirred at 80°C 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 50°C under 20mmHg for 30min. A concentrated liquid thus obtained was further evaporated under reduced pressure at 60°C under 1mmHg to 2mmHg for 2 hours. In this way, a target material, namely, N-methyl-N'-butyl imidazolium dicyanamide ([BMIm]DCA) was obtained with 97.2% yield (39.9g, 0.194mol). The resultant [BMIm]DCA was a light yellow liquid with chloride ion (Cl-) concentration of 0.16%.(Water Content Analysis of [BMIm]DCA) Water content of [BMIm]DCA was measured by the Karl Fishcer test. Water content before the addition of MOA was 0.39% (3900ppm), but water content after the addition of MOA was 0% (0ppm). Water content after methanol, methyl acetate and the unreacted MOA was evaporated off was 0.0019% (19ppm).
2 Synthesis of [bmim][NO3], [bmim][SCN] and [bmim][N(CN)2]
General procedure: According to literature procedures [40], NaNO3(1.1 eq), KSCN(1.2 eq) or NaN(CN)2 (1.1 eq) was added to a solution of [Bmim][Cl](1 eq) in dichloromethane and stirred for 24 h at room temperature.The suspension was filtered to remove the produced NaCl andunreacted NaNO3, KSCN and NaN(CN)2 salts. The organic phase was repeatedlywashed with small volume of water until no precipitation ofAgCl occurred in the aqueous phase on addition of AgNO3 solution.Then solvent was removed in vacuo and the synthesized IL was stirredwith activated charcoal for 6 h, removing the solvent gives[bmim][NO3], [bmim][SCN] and [bmim][N(CN)2] with 82%, 74% and85% yields, respectively.
at 20℃; for 48h;
In acetone at 20℃; for 48h;
In ethanol at 20℃; for 24h;
In acetone at 20℃; for 48h;
In dichloromethane at 20℃; for 48h;
2.3. Synthesis of thiocyanate functionalized ionic liquid
IL is synthesized according to a simple modified literature method [2,28]. Briefly, the procedure is- a mixture of 1-methylimidazole and slightly excess molar quantity of 1-chlorobutane was refluxed at 70 C for 48 h in acetone. Two layers were formed, upper solvent layer was decanted. The IL, [BMIm][Cl] (1-butyl-3-methyl imidazolium chloride) thus formed was purified by washing with ethyl acetate (10 ml3) followed by n-hexane. It was then dried in vacuum under reduced pressure. Infurther step a metathesis reaction of [BMIm][Cl] and potassium thiocyanate was carried out. A stoichiometric mixture of [BMIm][Cl] and KSCN in dichloromethane was stirred vigorously for 48 hat room temperature. Synthesized IL, [BMIm][SCN] (1-butyl-3-methyl imidazolium thiocyanate) was then dried in vacuumunder reduced pressure (Scheme 1). It was then characterized by 1HNMR spectroscopy.
With bis(trifluoromethane)sulfonimide lithium; In water; at 20℃; for 90h;
(BMI+TF2N-) 41.92 g (0.240 mol) of 1-butyl-3-methylimidazolium chloride are dissolved in 300 ml of distilled water. 69.46 g (0.242 mol) of lithium bis(trifluoromethylsulphonyl)amide are added and the mixture is stirred under argon for 90 hours at ambient temperature. A two-phase system is formed. After extraction with 250 ml of dichloromethane, the organic phase is washed with 800 ml of water and then concentrated. The compound exists in the form of a slightly pinkish liquid which is purified by chromatography on a neutral alumina column (eluent: dichloromethane). It is then concentrated, taken up in acetonitrile in the presence of active carbon and filtered. After drying for several hours at 60 C., the compound is obtained in the form of a colourless liquid (81.47 g). Its structure, C10H15N3S2O4F6, was confirmed by NMR analysis.
Stage #1: L-3-phenyllactic acid With boric acid; lithium carbonate In water at 55℃; for 1h;
Stage #2: 1-butyl-3-methylimidazolium chloride In water at 20℃; Further stages.;
The intermediate [Bmim] Cl50g withSodium borofluoride(According to the ratio of its mass is 1: 1.05)Join a three-necked flask with a stirring device,100mL acetone as the reaction medium,Mechanical stirring at room temperature 48h, suction filtration (acetone washing) to remove NaCl,Rotate to acetone, and then add CH2C12 wash,Swirl to remove CH2C12,The resulting ionic liquid was dried in a vacuum oven at 80 24hAfter the pale yellow transparent liquid 56.3g:which isl-Butyl-3-methylimidazolium tetrafluoroborateIonic Liquid ([Bmim]BF4) in a yield of 86.7%.
85.1%
In acetone; at 20℃; for 48h;
The intermediate product [Bmim] Cl 87g was mixed with sodium fluoroborate (1: 1.05 in terms of its mass ratio)Was added to a three-necked flask equipped with a stirrer,To l0mL acetone as the reaction medium, room temperature mechanical stirring 48h,Pumping (acetone wash) to remove NaCl,Steamed to acetone, then add CH2C12 washing,The CH2C12 was removed by steaming and the resulting ionic liquid was dried in a vacuum oven at 80 C for 24 hAfter the light yellow transparent liquid 96.2g:Namely 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid([Bmim] BF4) in a yield of 85.1%.
85.4%
In acetone; at 20℃; for 48h;
The intermediate [Bmim] Cl 50g and sodium borofluoride (according to the ratio of its mass of 1: 1.05) was added to a three-necked flask equipped with a stirring device,100mL acetone as the reaction medium,Mechanical stirring at room temperature 48h,Suction filtration (acetone wash) to remove NaCl,Rotate to acetone,Then add CH2C12 washing,Swirl to remove CH2C12,The resulting ionic liquid was dried in a vacuum oven at 80 C for 24 hours to obtain 55.5g of light yellow transparent liquid: l-butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([Bmim] BF4)Yield 85.4%.
80%
In water; at 25 - 80℃; under 0.000750075 Torr; for 10.5h;
(1) at room temperature about 25 o C lower, will 103g sodium four fluorine boron (NaBF 4) is added to 100 ml of deionized water, 500 ml flask, mechanical stirring 30 minutes, so as to form saturated NaBF 4 aqueous solution, with a small amount of solid remaining at the bottom of the; (2) in the above-mentioned saturated solution continue adding 0.5mol/55gNaBF 4 and 0.5mol/87 g1-butyl-3-methyl imidazole chlorine salt BMImCl; (3) mechanical stirring 30 minutes, the full reaction; (4) standstill after the reaction, the solution is divided into three layers: the upper layer is mainly ionic liquid BMImBF 4, the middle layer is a saturated aqueous solution, the bottom layer is mainly solid inorganic salt NaCl by-product, is transferred to the solution in the separatory funnel, the remaining bottom layer for NaCl solid non-polar by-products. (5) solution of layering in the separatory funnel, the upper layer of the ionic liquid solution, the lower is the saturated aqueous solution, with the liquid, in the ionic liquid remain in the separatory funnel, for collecting the lower saturated aqueous solution. (6) to the above-mentioned is the ionic liquid solution to add a new configuration of the separatory funnel in NaBF 4 saturated aqueous solution 20 ml, fully after shaking, static hierarchical. Separating processing, the ionic liquid solution in the separatory funnel, for collecting liquid, so repeat two; (7) of the above-mentioned ionic liquid solution after washing transferred to the 250 ml round-bottom flask in grinding port, the magnetic stirring, 80 o C and 0.1 Pa vacuum drying under the conditions of 10 hours, filtering after standing, shall be 90g nocolor ionic liquid BMImBF 4, the yield is 80%. (8) in the above-mentioned step (4) the resulting solid inorganic salt by-product filter NaCl, new configuration for NaCl saturated aqueous solution of washing 3 times, each time the amount of 50 ml; (9) the above-mentioned inorganic salt NaCl transfer to 50 ml beaker, in 80 o C and 0.1 Pa dried in vacuum oven for 10 hours, to obtain 20g white solid NaCl, for the recovery of by-products 70%; (10) of step (5) collection of the lower saturated aqueous solution and step (6) of the collected liquid to be mixed to be mixed, mixed solution is mainly containing anion precursor saturated aqueous solution of inorganic salts, can be used repeatedly, that is, repeating the above-mentioned step (2), (3), (4), (5), (6), (7), (8), (9).
In water; for 24h;
Preparation of 1-butyl-3-methylimidazolium tetrafluoroborate; Methylimidazole and excessive amount of chloro-n-butane (molar ratio: 1/1.05) were reacted at 70 C. with stirring for 48 hours. Excessive of reactants were removed by rotary evaporation, thereby 1-butyl-3-methylimidazolium chloride was obtained. The obtained 1-butyl-3-methylimidazolium chloride was further added into an aqueous solution with excessive amount of sodium tetrafluoroborate (molar ratio: 1/1.1) and stirred for 24 hours. Then, adequate amount of methylene dichloride was added to extract the product. A mixture of the product and the methylene dichloride was washed with water until no chlorine ion was detected by a silver nitrate solution (0.1 mol/L). A product of 1-butyl-3-methylimidazolium tetrafluoroborate was obtained after removing methylene dichloride in the product by rotary evaporation and drying.
In neat (no solvent) byproducts: H2O; under dry N2, equimolar amt. of reactants;
In ethanol ionic liquid prepd. by mixing hot ethanolic solns. of FeCl3*6H2O and imidazolium chloride; mixt. heated with stirring for 10-15 min; ethanol evapd. under vac.; ionic liquid washed with cold dry ether and dried under vac. over P2O5 for d; elem. anal.;
In solid under dry N2, equimolar amt. of reactants;
In not given
In not given organic compound reacted with equimolar FeCl3 at room temp. for 3 h;
In neat (no solvent) FeCl3 added slowly with stirring to equal molar amt. of 1-butyl-3-methylimidazolium chloride in glove-box filled with dry Ar according to M. S. Sitze et al., Inorg. Chem., 40 (2001) 2298;
1
Example 1 1-Butyl-3-methylimidazolium methylsulfite A mixture of 8.81 g (50.4 mmol) of 1-butyl-3-methylimidazolium chloride and 5.56 g (50.5 mmol) of dimethyl sulfite is stirred at room temperature for 72 hours under an inert-gas atmosphere (nitrogen) in a sealed 100 ml reaction vessel. The end of the reaction is determined by NMR measurement. The product is pumped off over the course of 1 hour in vacuo at 13.3 Pa and 60° C. (temperature of the oil bath), giving 11.8 g of liquid 1-butyl-3-methylimidazolium methylsulfite. The yield is virtually quantitative. The product is investigated by means of NMR spectroscopy. 1H NMR (reference: TMS; solvent: CD3CN), ppm: 0.88 t (CH3); 1.28 m (CH2); 1.79 m (CH2); 3.17 s (CH3O); 3.86 s (CH3); 4.19 t (CH2); 7.54 d,d (CH); 7.56 d,d (CH); 9.66 br. s. (CH); 3JH,H=7.1 Hz; JH,H=1.5 Hz.
With tri-n-hexylamine; In toluene; at 40℃; for 1h;
13.11 g of 1-butyl-3-methylimidazolium chloride (75 mmol), 7.247 g (75 mmol) of methanesulfonic acid and 42.11 g of trihexylamine (150 mmol) in 42.11 g of toluene were heated to 40 C. After stirring for about 1 hour, the mixture was cooled to room temperature and the phases which formed were separated. The lower phase is dried at 80 C. and a pressure of 10 mbar. This gave 14.4 g of butyl-3-methylimidazolium methylsulfonate (which comprised 3.3% by weight of chloride).
Stage #1: 1-butyl-3-methylimidazolium chloride With OH--saturated Amberlyst X resin
Stage #2: acetic acid
With tri-n-hexylamine In toluene at 40℃; for 1h;
2
8.74 g of 1-butyl-3-methylimidazolium chloride (50 mmol), 3.00 g (50 mmol) of acetic acid (99%) and 28.00 g of trihexylamine (100 mmol) in 28 g of toluene were heated to 40° C. After stirring for about 1 hour, the mixture was cooled to room temperature and the phases which formed were separated. The lower phase is dried at 80° C. and a pressure of 10 mbar. This gave 7.0 g of butyl-3-methylimidazolium acetate.
Stage #1: 1-butyl-3-methylimidazolium chloride With purolite SGA-550-OH resin In methanol
Stage #2: acetic acid In methanol
With sulfuric acid In dichloromethane for 48h; Reflux; Cooling with ice;
a (a) Synthesis of 1-butyl-3-methylimidazolium hydrogensulfate:
This preparation was adapted from the procedure by Fraga-Dubreuil et al. (Catal. Commun. 2002, 3, 185). To a solution of 1-butyl-3-methylimidazolium chloride ([C4mim]Cl, 87.8 g, 0.503 mol) in dichloromethane (50 mL), concentrated sulfuric acid (96%, 51.4 g, 0.503 mol) is added dropwise while keeping the mixture refrigerated in an ice/water bath. The resulting solution is heated under reflux with stirring for 48 hrs. Then, volatiles (mostly containing dichloromethane) are distilled off under reduced pressure (ca. 30° C., 50 mbar), and the hydrogen chloride by-product is similarly removed in vacuo (ca. 90° C., 0.01 mbar) for 16 hrs, yielding 1-butyl-3-methylimidazolium hydrogensulfate ([C4mim][HSO4], 118.1 g, 99.4%) as a pale yellow viscous liquid.
97%
With sodium hydrogen sulfate In acetonitrile at 25℃; for 96h; Inert atmosphere;
95%
With sulfuric acid In dichloromethane for 24h; Reflux;
Synthesis of [bmim][HSO4]
1-butyl-3-methylimidazolium hydrogen sulfate [bmim][HSO4] wassynthesized according to the reported procedures [41], by a dropwiseaddition of concentrated sulfuric acid (1 eq) to a cooled solution of 1-butyl-3-methylimidazolium chloride (1 eq) in anhydrous methylenechloride. The mixture was refluxed for 24 h and the produced HCl wasneutrilized by the aqueous solution of NaOH. Then, the solution wascooled to room temperature,consequently removing of solvent andthen drying under vacuum at 75 °C for 3 h gave yellow viscous liquidwith 95% yeild.
89%
With sodium hydrogen sulfate In acetone at 20℃; for 24h;
3.Synthesis of 1-butyl-3-methylimdazolium hydrosulfate ([bmim]HSO4)
8.73g (50mmol)[bmim]Cl and sodium bisulfate was stirred in 40mL acetone at room temperature for 24h. The system is filtered to obtain supernatant, which dried in vacuum dryness case at 80°C for 24h. 10.53g light yellow transparent liquid was obtained, and the yield of [bmim]HSO4 was 89%.
With sulfuric acid In dichloromethane
With sulfuric acid In dichloromethane Cooling; Reflux;
With sulfuric acid
1-butyl-3-methylimidazolium hydrogensulfate ([BMIm][HSO4])
1-Butyl-3-Methylimidazolium hydrogensulfate ([BMIm][HSO4])[BMIm][HSO4] was prepared from the anion exchange of [BMIm][Cl] with H2SO4 in solvent. The ionic liquid is then dried under vacuum. 1H NMR chemical shifts (relative to TMS internal standard) and coupling constants J/Hz: S=8.65 (s, 1H), 7.39 (d, 2H, J=4.19), 4.17 (q, 2H, J=7.4), 3.93 (s, 3H), 1.87 (m, 4H), 1.32 (m, 6H) 0.87 (t, 3H, J=6.53); water content is less than 100 ppm.
With sulfuric acid In dichloromethane at 70℃; for 24h;
2.3 Synthesis of DESs and acidic ionic liquids
In a typical reaction for the synthesis of 1-butyl-3-methylimidazolium hydrogen sulphate [(Bmim)HSO4], [(Bmim)]Cl (5 g, 0.0286 mol) was added into 20mL dichloromethane in a round-bottom flask followed by drop wise addition of one equivalent of sulphuric acid (98%) (1.5 mL, 0.0286 mol) for 10 min at room temperature. The reaction mixture was refluxed for 24 h at 70 °C and the resulting IL was separated out, washed with ethyl acetate two times and dried at 70 °C for 6 h under vacuum. Similar metathesis reaction was carried out for the synthesis of the other two ILs, viz., choline hydrogen sulphate [(Chol)HSO4], methyl imidazolium hydrogen sulphate [(Hmim)HSO4] and choline acrylate. The structures were confirmed by 1H NMR and mass spectrometry (ESI-MS).
With sulfuric acid In dichloromethane
With sulfuric acid In dichloromethane at 20℃; for 24h; Inert atmosphere;
Preparation of [Bmim]HSO4 and [Bmim]H2PO4
General procedure: [Bmim]HSO4 and [Bmim]H2PO4 derived fromimidazole chloride salts were obtained by a drop-wiseaddition of one equivalent of concentrated H2SO4(98%) or H2PO4 (85%) to solution of the corresponding1-butyl-3-methylimidazolium chloride in anhydrousmethylene chloride. The reaction proceeded at roomtemperature for 24 h with vigorous stirring under astream of dry nitrogen. Then, the mixture was dried invacuum by a rotary evaporator to remove the HCl andsolvent to obtain the viscous clear [Bmim]HSO4 and[Bmim]H2PO4.
Multi-step reaction with 2 steps
1: Dowex Monosphere 550 A UPW OH form resin / water
2: sulfuric acid / water
With sulfuric acid In water at 100℃; for 4h;
2.2 Synthesis and characterization of the ionic liquids
The 1-butyl-3-methylimidazolium hydrogen sulfate (BMI.HSO4) and 1-butyl-3-methylimidazolium trifluoromethane sulfonate (BMI.CF3SO3) ionic liquids were synthesized by ion exchange reaction from the 1-butyl-3-methylimidazolium chloride (BMI.Cl) IL according to the procedures reported in the literature [30-32]. H2SO4 was added to a solution of BMI.Cl dissolved in deionized water. The resulting solution was maintained under reflux for 4h at 100°C and then dried under vacuum at 90°C. The final compound is a colorless viscous liquid.
C1
Comparative examples C1 to C3198 g (1 mol) of BMIM OAc (1-butyl-3-methylimidazolium acetate) are placed in a round-bottom flask which has been made inert and is provided with a dropping funnel and reflux condenser. The amount of acid indicated in the appended table is added slowly while stirring, with the temperature being kept below 50° C. (an exothermic reaction is observed during the addition; the temperature is kept down either by appropriately slow addition with air cooling or by cooling with water).After cooling to room temperature, the major part of the volatile constituents is taken off at a pressure of 0.1 mbar, with the internal temperature being increased to 120° C. When no more low boilers are given off from the mixture under these conditions, the mixture is cooled and nitrogen is admitted. The residue is transferred to the reservoir of the short-path distillation and fed in at a rate of 100 ml/h at the evaporator temperature indicated below. The pressure in the short-path distillation is set to 0.05 mbar. The product is obtained as bottom output, so that the short-path distillation here functions as a very efficient form of low boiler stripping.The condensed low boilers comprise water (when an aqueous reagent is added) and acetic acid. BMIM Evaporator Product OAc:acid temp. (salt having Yield No. Acid mol:mol ° C. the new anion) % Purity* C1 HCl; 35% in water 1:1.033 170 BMIM Cl 93.5 comprises 20 mol % of HOAc after first passage comprises 3 mol % of HOAc after second passage C2 CF3COOH 1:1.017 150 BMIM TFA 90.9 comprises 13 mol % of HOAc after first passage (trifluoroacetic acid) comprises 4 mol % of HOAc after second passage C3 CH3SO3H 1:1.005 170/190 BMIM 92.3 comprises 9 mol % of HOAc after first passage (methanesulfonic CH3SO3 no HOAc after the second passage acid) *Analysis by H-NMR
Preparation of magnetic ionic liquids
General procedure: lIn the present study, the preparation of MAILs (shown inScheme 2), such as C4mim/FeCl4, was synthesized according to the following methods (Bourissou, Guerret, Gabbai, & Bertrand,2000). Firstly, N-butylpyridiumchloride intermediates were pre-pared by reacting of 0.2 mol N-methylpyrrolidine with 0.24 mol n-chlorobutane at 80C for 48 h with magnetic stirring. The reaction intermediate products were purified and recrystallized from acetonitrile repeatedly, subsequently washed with ethyl acetate for four times and dried in a vacuum oven at 60 °C for 24 h. Secondly, the intermediates Cnmim Cl were mixed with equimolar of FeCl3·6H2O under N2 atmosphere with magnetic stirring at room temperature (~25C). The final products were washed with ether and deionized water repeatedly, purified by reduced pressure distillation and dried in a vacuum oven at 60 °C for 24 h successively. The MAILs, Cnmim/FeCl4, were obtained for further experiments.
at 20℃; for 0.5h;
at 20℃; for 24h;
Preparation of [BMIM][FeCl4]
Equimolar [BMIM][Cl] and FeCl3·6H2O weremixed under vigorous stirring, and the mixture was stirred for 24 hat room temperature. Two distinct layers were formed, in whichthe darker layer contained [BMIM][FeCl4], and the upper layermostly consisted of water. The aqueous upper layer was separatedby centrifugation, and the [BMIM][FeCl4] layer was then dried at80 C in order to remove the remaining water.
In ethanol for 24h; Heating;
Preparation of Fe-containing ionic liquid
General procedure: Firstly, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl,0.1 mol) was added in an ethanol solution of iron chloride(0.1 mol) (Warnke et al. 2010). The mixture was stirred at 40 °C for 24 h in the oil bath and a yellow solution was obtained. Then, the solvent (ethanol) in the solution was evaporated. Finally, the residue was washed with ethanoland dried in vacuum at 80 °C for 24 h. Thus, the [Bmim]FeCl4 catalyst was prepared. According to the samemethod, [Cxmim]FeCl4 (x = 8, 12, 16) catalysts were prepared by replacing [Bmim]Cl with [Cxmim]Cl (x = 8, 12, 16), respectively. [Bmim]FeCl4, [Omim]FeCl4 and[C12mim]FeCl4 existed as liquids, whereas [C16mim]FeCl4 existed as solid at room temperature.
1 A method for synthesizing ionic liquid with two aqueous phases, including the following steps:
At 25, 0.10mol of cationic precursor [BMIm]+[Cl]- and 0.12mol of anion precursor [Na]+[CH3CO2]- were dissolved in 10mL of water and mixed, and then 0.123mol (ie 18g) of layering was added Reagent lysine (add lysine in batches, 1g each time, when the added amount of lysine reaches 6g, stratification occurs, and the added amount reaches 18g, and the volume of the ionic liquid enriched layer does not change), stir and react for 30 Minutes, after the reaction is over, let stand, liquid/liquid stratification appears (upper layer is [BMIm]+[CH3CO2]-ionic liquid, lower layer is a mixture of layering reagent lysine, water, [Na]+, [Cl]- ), and the by-product [Na]+[Cl]-precipitates were separated to prepare an ionic liquid [BMIm]+[CH3CO2]-; then an aqueous solution of lysine (2.0mL water+7.0g lysine Acid) wash the ionic liquid [BMIm]+[CH3CO2]-2 times, dry the washed ionic liquid [BMIm]+[CH3CO2]- under the conditions of 60 and 0.1Pa for 10 hours, and filter after standing. 11.5 g of colorless ionic liquid [BMIm]+[CH3CO2]- was obtained, and the yield was 58%.
FIL was prepared by mixing equimolar [BMIM]Cl with anhydrous FeCl3 in a dry glovebox according to the literature procedures described elsewhere [28].
In ethanol at 20℃;
Inert atmosphere;
In neat (no solvent) Sealed tube;
for 0.25h;
Synthesis of MIL [bmim][FeCl4]
The magnetic ionic liquid was synthesizedfollowing the same way remarked in literature[36].5 mmol [bmim]Cl (0.870g) and 5 mmol FeCl3(0.825g) were added to a round bottom flask andstirred with a magnet for 15 minutes. The resultingionic liquid was dissolved in ethyl acetate (10 mL)and the solution was centrifuged after filtration inorder to separate any possible residue of inorganicsalts. Afterwards, ethylacetate was evaporated andthe obtained dark brown liquid, butyl methylimidazolium tetrachloroferrate(III) was dried undervacuum at 80 C overnight.
at 20℃;
2.2 Synthesis of the ILs
General procedure: All the [FeCl4]-based ILs were synthesized according tothe procedures described in the literatures [27,28]. TheseILs are readily obtained by mixing equal molar iron trihalidewith corresponding cationic chloride ILs [29]. The mixtureswere stirred at room temperature, and a two-phasemixture consisting of a brown liquid and a water layer wasformed after a few minutes. The crude product was obtainedafter removal of the top water layer, and was then washedwith an excess of deionized water to remove un-reactedFeCl3 from the final product. Thus obtained magnetic ILswere dried under vacuum at 70 °C for 48 h.
for 0.25h;
Synthesis of MIL[bmim][FeCl4]
The magnetic ionic liquid was synthesized following the same way remarked in literature. 5 mmol [bmim]Cl (0.870g) and 5 mmol FeCl3(0.825g) were added to a round bottom flask and stirred with a magnet for 15 minutes. The resulting ionic liquid was dissolved in ethyl acetate (10 mL) and the solution was centrifuged after filtration in order to separate any possible residue of inorganic salts. Afterwards, ethylacetate was evaporated and the obtained dark brown liquid, butyl methyl imidazolium tetrachloro ferrate(III) was dried under vacuum at 80 C overnight.
at 80℃;
at 20℃; for 12h; Inert atmosphere;
Preparation of MILs [Bmim][FeCl4], [Hmim][FeCl4] and [Omim][FeCl4]
[Bmim][FeCl4] was prepared via two steps [2]. Firstly, the intermediate 1-butyl-3-methylimidazoliumchloride ([Bmim]Cl) was synthesized by reacting 1-methylimidazole (0.20 mol) with 1-chlorobutane (0.24 mol) at 343.15 K for 48 h. The product was then washed with acetone for three times and dried in vacuum. Subsequently, the purified [Bmim]Cl was mixed with equimolar of FeCl3 under N2 atmosphere and stirred at room temperature for 12 h, leading to a dark brown liquid product. [Hmim][FeCl4] and [Omim][FeCl4] were prepared similarly, but 1-chlorobutane was replaced by 1-chlorohexane and 1-chlorooctane, respectively.
at 30℃; for 5h; Inert atmosphere;
2.2 Synthesis of Lewis Acidic Ionic Liquid [Bmim]FeCl4
The ionic liquid, 1-methyl-3-butylimidazolium chloride([Bmim]Cl), was synthesized according to the proceduresdescribed in the literatures [31, 32]. A given amount ofanhydrous FeCl3was added into [Bmim]Cl and the resultingmixture was stirred at 30 °C under N2atmosphere for5h to obtain Lewis acidic ionic liquids [Bmim]FeCl4 withdifferent FeCl3molar fraction, and it was a brown greenviscous liquid.
at 20℃; for 3h; Inert atmosphere;
at 30℃; for 3h; Inert atmosphere;
2.3 Preparation of the ionic liquids
General procedure: The ionic liquids were prepared by direct reactions of metal halides with [Et3NH]+Cl-, [Et3DH]+Cl-, EMIM-Cl, or BMIM-Cl. A glass reactor (V=50mL) was charged under argon with [Et3NH]+Cl- ([Et3DH]+Cl-, EMIM-Cl, or BMIM-Cl) (10mmol) and metal chloride (Al (III), Fe (III), Zn (II), Sn (II), Cu (II)) (10-20mmol). The reaction was carried out with continuous stirring at 70 °C for 3h. In the case of reactions involving copper (II) sulfate, CuSO4 (0.05mmol) was added to the prepared ionic liquid, and the mixture was stirred for additional 1h at room temperature.
at 30℃; for 3h;
1.1 Preparation of halogen metal salt ionic liquid [C4mim] [FeCl4]
Mix 20 mmol of ferric chloride with 1-butyl-4-methylimidazole chloride salt C4mimCl of equivalent mass, stir at 30 ° C for 3 h, and extract with 5 mL of dichloromethane.The resulting solution was spin-evaporated to remove the solvent, and vacuum dried at 60 ° C for 12-24h,The metal salt halogen ionic liquid [C4mim] [FeCl4] is obtained.
at 30℃; for 3h;
1.1 A method for preparing p-hydroxycinnamate by using an ionic liquid to catalyze lignin was used, comprising the following steps:
(1) preparation of a halogen metal-based ionic liquid [C4mim][FeCl4]: mixing 20 mmol of ferric chloride with an equivalent amount of 1-butyl-4-methylimidazole chloride C4mimCl, stirring at 30° C. for 3 h, then extracting with 5 mL of dichloromethane, evaporating the solvent off the resulting solution, and drying in vacuum at 60° C. for 12-24 h to obtain the halogen metal-based ionic liquid [C4mim][FeCl4]
at 115℃; for 2h; Schlenk technique; Inert atmosphere;
at 70℃; for 3h; Inert atmosphere;
Synthesis of ionic liquids
General procedure: Ionic liquids were synthesized bythe direct reaction of metal halides with Et3N•HCl, EMIMCl,and BMIMCl. A 50-mL glass fl ask was charged with Et3N•HCl,EMIMCl or BMIMCl (10 mmol) and AlCl3, FeCl3, ZnCl2, SnCl2or CuCl2 (10-20 mmol) under argon. The mixture was stirredat 70 C for 3 h. If additive of copper(II) sulfate was required, the obtained ionic liquid was treated with CuSO4 (0.05 mmol) andthe mixture was stirred for 1 h at room temperature
at 70℃; for 3h; Inert atmosphere;
Synthesis of ionic liquids
General procedure: Ionic liquids were synthesized bythe direct reaction of metal halides with Et3N•HCl, EMIMCl,and BMIMCl. A 50-mL glass fl ask was charged with Et3N•HCl,EMIMCl or BMIMCl (10 mmol) and AlCl3, FeCl3, ZnCl2, SnCl2or CuCl2 (10-20 mmol) under argon. The mixture was stirredat 70 C for 3 h. If additive of copper(II) sulfate was required, the obtained ionic liquid was treated with CuSO4 (0.05 mmol) andthe mixture was stirred for 1 h at room temperature
1-butyl-3-methyl-3H-imidazolium salicylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In acetonitrile; at 20℃;
The ionic liquid, 1-butyl-3-methylimidazolium salicylate,[BMIM][SAL] was prepared from 1-butyl-3-methylimidazoliumchloride [BMIM][Cl] and <strong>[54-21-7]sodium salicylate</strong>. 1-Butyl-3-methylimidazolium chloride synthesized and purified accordingto standard procedures reported in the literature [23-26]. Inbrief [BMIM][Cl] was synthesized by direct alkylation of N-methylim idazole, 0.05 mol (freshl y distilled) with an excess of 1-chlorobutane (0.06 mol) which added dropwise over 1 h intopowerfully stirring of N-methylimidazole in a two-necked roundbottom flask in ice bath. Then mixture, already turbid, was refluxedfor 72 h under a nitrogen atmosphere and at 343 K. The crudeproduct was decanted from hot solution in a separator funnel,washed four times with 50 ml ethyl acetate. The product was driedin at 353 K using a rotary evaporator for at least 5 h at reducedpressure (0.7 kPa) which was used after high vacuum desiccated(0.1 Pa) for at least 12 h to remove trace amount of moisture.Water contents found by Karl Fischer method in ionic liquidswas less than 0.05% in mass fraction. Ionic liquid were analyzedby1H NMR and IR spectra to confirm the absence of any majorimpurities and they were detected to be in good agreement withthose reported in the literature [25]. The purity of obtained ionicliquid was 98% in mass fraction. The 1-butyl-3-methylimidazoliumsalicylate ionic liquid [BMIM][SAL] was subsequent prepared byfollowing the similar metathesis reaction used for the preparationof 1-butyl-3-methylimidazolium dicyanamide IL [BMIM][DCA][27,28]. However, dried acetonitrile was used as the solvent ratherthan acetone. For the synthesis of 1-butyl-3-methylimidazoliumsalicylate, (0.4 mol) <strong>[54-21-7]sodium salicylate</strong> salt dissolved in driedacetonitrile and added slowly to (0.4 mol) [BMIM][Cl] whichwas dissolved in a minimum amount of dried acetonitrile. Theresulting mixture was stirred overnight at the room temperature.The solution was concentrated under reduced pressure. Theresidue was dried in a vacuum oven and then dissolved in a largeamount of anhydrous dichloromethane. The organic solution wasallowed to stand at 253.15 K overnight until precipitate sodiumchloride and the excess of <strong>[54-21-7]sodium salicylate</strong> [26]. Addition of drieddichloromethane was renovated until no further precipitation ofNaCl could be found. After filtration and evaporation of the solventfrom the filtrate, the reminder (a yellowish solid) was further driedat 343.15 K [27]. The water content of the API-IL was determinedusing a coulometric Karl-Fischer titrator (Metrohm 756 KF) andthe value was approximately 0.1% in mass fraction. The synthesizedAPI-IL was characterized by1H,13C NMR (Brucker Av-400) and IR(Brucker, tensor27).1HNMR spectrum of [BMIm][SAL] can be seenin Supporting information as Fig. S1
In dichloromethane at -15℃; for 1h; Inert atmosphere;
Synthesis of the Complexes I-IV
General procedure: Me2AlCl (1 mmol),biaryl ligand (1 mmol), ionic liquid (1 mmol) and anhydCH2Cl2 (1 mL) were placed in a round-bottom flask under adry, inert atmosphere at -15 °C. The contents of the flaskwere stirred for 1 h. After this time, evaporation of thesolvent gave complexes I-IV in high yields (90-99%).
With sodium acetate In acetonitrile at 80℃; Sonication;
General procedure for the synthesis of the hydroxyquinolin-3-ylmethylimidazolium adducts 8-12.
General procedure: To a solution of the respective quinolones (16d,e; 17a-d and 19a) or the quinolines 15a,d,e and 18b-e (1 equiv) in acetonitrile (3 mL), 3-butyl-1-methylimidazolium chloride (1.3 equiv) and AcONa (1.0 equiv) were added. The mixture was subjected to ultrasound irradiation at 80 °C during 1-7 h. The completion of the reaction was monitored by TLC. After solvent was removed under reduced pressure, the resulting solid was dissolved in H2O and extracted with CH2Cl2 (3 x 2 mL). The combined organic layers were dried with MgSO4 and the solvent was removed under reduced pressure. The residue was washed with hexanes to afford products 8-12.
With sodium acetate In acetonitrile at 80℃; Sonication;
General procedure for the synthesis of the hydroxyquinolin-3-ylmethylimidazolium adducts 8-12.
General procedure: To a solution of the respective quinolones (16d,e; 17a-d and 19a) or the quinolines 15a,d,e and 18b-e (1 equiv) in acetonitrile (3 mL), 3-butyl-1-methylimidazolium chloride (1.3 equiv) and AcONa (1.0 equiv) were added. The mixture was subjected to ultrasound irradiation at 80 °C during 1-7 h. The completion of the reaction was monitored by TLC. After solvent was removed under reduced pressure, the resulting solid was dissolved in H2O and extracted with CH2Cl2 (3 x 2 mL). The combined organic layers were dried with MgSO4 and the solvent was removed under reduced pressure. The residue was washed with hexanes to afford products 8-12.
1.2 Synthesis of 1-butyl-3-methylimidazolium Tetrachloroferrate ([BMIM]FeCl4)
Step 2: In glass reactor that is equipped with a magnetic stirring mechanism 0.87 g (5 mmol) of 1-butyl-3-methylimidazolium chloride, obtained from step 1, was introduced and 1.22 g (7.5 mmol) of iron chloride (III) anhydrous was added. The mixture was stirred for 20 minutes at room temperature under an inert atmosphere. A dark red liquid was obtained. The spectroscopic characterizations (1H and 13C NMR) confirm the following chemical structure:
62
[ 563-63-3 ]
[ 79917-90-1 ]
[ 284049-75-8 ]
Yield
Reaction Conditions
Operation in experiment
95%
In methanol at 20℃; Darkness;
85%
In water at 20℃; for 4h; Inert atmosphere;
1-Butyl-3-methylimidazolium acetate [bmim][ CH3COO] (3d)
To a solution of [bmim][Cl] (0.700g, 4mmol) in water(10 mL), CH3COOAg(0.67 g, 4mmol) was added and reaction mixture was stirred at room temperature for 4 h. The suspension was filtered to remove silver chloride. The water was removed in vacuum to afford 0.69g (85%) of a colorless oily ionic liquid.Yield: 85%,
Tetrafluoroborate acid was added dropwise to a cold aqueous solution of 1-butyl-3-methylimidazolium chloride, [Bmim][Cl] in a two-neck round bottom flask. The reaction mixture was stirred at room temperature for 72 h under an inert atmosphere. The resulting ionic liquid was extracted from the aqueous phase using dichloromethane and the layers separated. The dichloromethane layer was washed using distilled water to the excess unreacted acid and chloride salt. The aqueous layer was tested with litmus paper and silver nitrate whilst the dichloromethane layer was concentrated to give a yellow liquid. The yellow liquid was directly treated with activated charcoal and filtered through basic alumina to give 1-butyl-3-methylimidazolium tetrafluoroborate (28 %) as a colorless liquid 28. IR (KBr) 3565.66 (OH), 1635.22 (C=C), 1064.73 (CN) cm-1; 1H NMR (400 MHz, DMSO-d6) delta 9.01 (1H, s, CH-2), 7.70 (1H, s, CH-4), 7.63 (1H, s, CH-5), 4.15 (2H, t, J= 7.32 Hz, NCH2CH2CH2CH3), 3.88 (3H, s, NCH3), 1.76 (2H, m, NCH2CH2CH2CH3), 1.25 (2H, m, NCH2CH2CH2CH3), 0.88 (3H, t, J= 7.32 Hz, NCH2CH2CH2CH3); 13C NMR (100 MHz, DMSO-d6) 136.9 (NCN), 124.0 (C-4), 122.7 (C-5), 49.0 (NCH2CH2CH2CH3), 36.1 (NCH3), 31.8 (NCH2CH2CH2CH3), 19.1 (NCH2CH2CH2CH3), 13.6 (NCH2CH2CH2CH3); MS (ESI+) m/z 365.25 [2(C4C1im) + BF4] and 139.12 [C4C1im]; MS (ESI-) m/z 313.12 [2(BF4) + C4C1im].
1-butyl-3-methylimidazolium dodecylsulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In dichloromethane; at 20℃; for 15.0h;
1-Butyl-3-methylimidazolium chloride ([C4mim]Cl) was freshly prepared according to the procedures reported previously [14].1-Butyl-3-methylimidazolum dodecanesulfonate ([C4mim][C12SO3]) was obtained by ion exchange reaction of [C4mim]Cl and sodiumdodecylsulfonate. [C4mim]Cl and sodium 1-dodecanesulfonate were stirred in dichloromethane at room temperature for 15 h, and the precipitation was removed by filtration. Then the organic phase was washed with water until the water was chloride-free (tested by titration with AgNO3 from an acidic aqueous solution). The final product was dried in vacuum for 48 h at 55 C.
[bmim]OTf adopts two-step synthesis and the specific operation process are as follows: (1) The synthesis of [bmim]Cl: Molar ratio of N-methyl imidazole to chlorobutane 1:1 were mixed in a dry 250 ml flask with condensing facility, then heated with stirring for 48 h under 70 C. After reaction, reactants were washed for three times using ethyl acetate, and then streamed to remove ethyl acetate at 80 C. Finally, the pale yellow viscous liquid [bmim]Cl was obtained. (2) The synthesis of [bmim]OTf: Molar ratio of potassium trifluoromethanesulfonate to [bmim]Cl 1:1 were mixed, using dichloromethane as solvent, reflux condensation for 48 h under 60 C. After removing the dichloromethane by reduced pressure distillation at 40 C, the milky viscous liquid [bmim]OTf is obtained finally.
In water; at 20℃; for 24h;
8.25 g of the above-mentioned ionic liquid,KCF3SO39.4g were dissolved in 20 mL of water, respectively,Room temperature reaction 24h,Adding dichloroethane to remove water,The dichloroethane was removed under reduced pressure,80 vacuum drying 12h,The ionic liquid [Bmim] CF3SO3.
8 Example 8: Synthesis of 1-butyl-3-methylimidazolium octanoate
0.2 g (0.001 mol) of 1-butyl-3-methylimidazolium chloride was dissolved in 10 g of water, and 150 μl / min of sodium octanoate (0.001 mole) was dissolved in 10 g of water to make a volume of 150 μl / min. A microreactor controlled at 70 ° C. was charged with a sealer pump I passed it through. The solution passed through the microreactor was collected and concentrated under reduced pressure to give a pale white solid 1- -3-methylimidazolium octanoate was obtained in an amount of 0.31 g (91%). The analysis results of the obtained ionic liquid are as follows.
1.2 (2) Preparation of [Bmim][OAc]
0.06 mol of solid potassium acetate was placed in a 100 mL single-necked flask. Add a volume of absolute ethanol, Stir and dissolve to form a transparent, homogeneous salt solution. Then 0.05 mol [Bmim] [Cl] was added to the single-mouth bottle. Under a nitrogen atmosphere, After vigorously stirring the reaction at room temperature for 24 h, Filter to remove the white precipitate, Then add 0.025 mol of potassium acetate to the filtrate. Stir the reaction for 6.0 h at room temperature. To react to the unexchanged [Bmim][Cl], The formation of potassium chloride and excess potassium acetate were removed by filtration. The filtrate was rotary evaporated at 55 ° C under reduced pressure to remove the ethanol solvent. Then, 10 mL of anhydrous diethyl ether was added thereto, and washed. Precipitating unreacted potassium acetate precipitation, After filtration, the filtrate was rotary evaporated at 55 ° C for 1.0 h under reduced pressure. After the residue was placed in the refrigerator and allowed to stand for 12 h, Filter again to remove the precipitated salt, 8.67 g of a colorless, fluid, liquid [Bmim][OAc], The yield was 87.5%.
In isopropyl alcohol at 25℃; for 10h;
3 Example 3
0.05 mol of ionic liquid intermediate [Bmim] Cl was dissolved in 50 ml of isopropanol,Adding 2.5 times the amount of KOAc,Stirred at 25 ° C for 10 h,Filter to remove insoluble matter.The filtrate was distilled to remove the solvent,A pale yellow oil.The crude product was dissolved in methylene chloride,The activated carbon powder was added thereto for 10 h,filter,The filtrate was distilled to remove the solvent,Dried in vacuo to give a colorless oil,As the target product [Bmim] OAc.
In isopropyl alcohol at 25℃; for 10h;
2 Example 2
Take 0.05mol ionic liquid intermediate [Bmim] Cl dissolved in 50ml isopropanol, added 2.5 times the amount of KOAc,The mixture was stirred at 25 ° C for 10 h, filtered to remove insolubles. The filtrate was evaporated to remove the solvent, pale yellow oil. The crude product is extracted with dichloromethaneDissolved, to which activated carbon powder was added and stirred for 10h, filtered, the filtrate was evaporated to remove the solvent, vacuum dried to give a colorless oil,As the target product [Bmim] OAc.
4 Example 4
Take 0.06mol solid potassium formate dissolved in 50ml of methanol, then add 0.05mol [Bmim] Cl, at room temperatureThe reaction mixture was stirred for 24h and filtered to remove the white precipitate. The filtrate was rotary evaporated under reduced pressure at 45 ° C to remove the methanol solvent,Diethyl ether to precipitate unreacted solid potassium formate, and the solvent was removed by rotary evaporation to give a colorless viscous liquid [Bmim] [HCOO].
Preparation of basic ionic liquids:N-Methylimidazole and excess chlorinated n-butane were refluxed in toluene for 48 hours to give the 1-butyl-3-methylimidazolium chloride salt.With this chloride salt and NH4OH, NH4HCO3 in acetonitrile solution after ion exchange reaction,Filtering, removing the solvent and drying under vacuum to obtain the corresponding basic ionic liquid 1 and basic ionic liquid 2 respectively, as shown in the following formula:
With potassium carbonate In tetrahydrofuran; acetonitrile at 50℃; for 24h;
2.3. Synthesis of palladium PEPPSI-type complexes with differentcarbene ligands [PdCl2(NHC)(imidazole)]. Method B
General procedure: Palladium (II) complex with 1-methylimidazole ligands[PdCl2(1-methylimidazole)2] (0.5 mmol, 0.17 g), K2CO3 (1.5 mmol,0.21 g), MgSO4 (0.2 g, for drying), an appropriate imidazoliumchloride (0.65 mmol) and finally a mixture of solvents CH3CN:THF(8 ml: 5 ml) were placed in a round-bottom flask equipped with astirring bar. The flask was capped with a rubber septum. Themixture was heated in the oil bath for 24 h at 50 °C in the air atmosphere.During that time, the color changed from yellow togreenish. After the reaction, the cooled down mixture was filtratedto remove inorganic salts. Then, the yellow solutionwas evaporatedunder vacuum and the resulting oily residue was dissolved in aminimum amount of acetone. Next, 10 ml of water was slowlyadded to the yellow solution and clouding of the mixture wasobserved. The mixture was left to evaporate acetone and to enablesedimentation of the formed precipitate. After that time, waterwith excess of the imidazolium chloride and 1-methylimidazolewas decanted. The obtained product was washed with the waterand dried under vacuum. The complexes 2f and 2 g were obtainedfrom the appropriate imidazole and the precipitated solids requiredadditional washing with ethyl alcohol and diethyl ether. One of theobtained complexes [PdCl2(IMes)(1-methylimidazole)] (2e) wasdescribed in the literature [7b].
bis(1-n-buthyl-3-methylimidazolium) hexachloroplatinate(IV)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
In acetonitrile; for 3h;Schlenk technique; Reflux;
To a 25 ml Schlenck tube equipped with a magneticstirring bar 0.5 g (2.9 mmol) of [BMIM]Cl and 0.5 g (1.5 mmol) of<strong>[13454-96-1]PtCl4</strong> in hot CH3CN (2 ml) were added. The mixture was stirredfor 3 h under reflux. The solution was cooled to room temperatureand the solvent was evaporated. The orange product was washedwith diethyl ether (3 5 ml) and dried under vacuum. Productyield: 95% anal. calcd.
1-butyl-3-methylimidazolium lauryl ether sulfate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In dichloromethane for 5h; Reflux;
General procedure: Synthesis of [Hmim][C12H25O(C2H4O)2SO3] followed the procedure: sodium lauryl ether sulfate (0.03 mol) and [Hmim][Cl](0.032 mol) were dissolved in dichloromethane (60 mL), then the solution was refluxed 5 h. The white solid (sodium chloride) was filtered and the solvent (dichloromethane) was removed under vacuum. The obtained crude product ([Hmim][C12H25O(C2H4O)2-SO3]) was recrystallized with petroleum ether (3 40 mL) and dried in vacuo at 60 °C for 24 h for further studies.
2.2. Synthesis of ionic liquids
General procedure: All ionic liquids were synthesized using the anion exchangemethod described by Alcalde et al. [36]. In short, a glass columnwas filled with anion exchange resin Amberlyst A-26 (OH-form)and consequently, the OH-ions were exchanged with the desiredanion by slowly passing a 1 % solution of ammonium acetate/formatein water or a 1 % solution of (S)-lactic acid in water:methanol(1:1 v:v) through the column, until the pH of the eluate reachedthe same value as the base solution (pH = 6 for ammoniumacetate/formate, pH = 4 for (S)-lactic acid). Subsequently, a 1 %solution of [EMIm]Br or [BMIm]Cl in water was slowly passedthrough the column to exchange the halide with the desired carboxylateanion. Afterwards, the solvent was removed by rotaryevaporation and the ionic liquids dried at 60 C under vacuumfor at least 16 h. All anion-exchanged ionic liquids were receivedin nearly quantitative yields. The purity of the ILs was establishedby 1H and 13C NMR (Section 3, SI) and by anion chromatography(Section 4, SI), the water content was determined after drying byKarl Fischer titration.