* 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.
Examples 3 and 4: methylene diacetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 117.0 mmol), and 0.5 equivalents of dichloromethane (5.0 g, 58.7 mmol) were added at room temperature and the reaction was stirred at 50°C for 16h. After reaction the pure Product was distilled from the reaction mixture at 80°C under reduced pressure (85.0-percent). When dibromomethane was used as substrate the reaction was fast even at room temperature and highly exothermic. The reaction proceeds via homogeneous path way and the pure product distilled from the reaction mixture at 80°C under reduced pressure (86.0percent yield). Methylene diacetate: 1H NMR (CD3CN, 400.13 MHz): δ = 2.04 (s, 6H, CH3), 5.64 (s, 2H, CH2); 13C NMR: δ = 20.9 (CH3), 79.7 (CH2), 170.8 (CO); FTIR (ATR mode): v = 2996 (br), 1758 (s), 1190 (s), 1009 (s), 978 (s)
Example 1 and 2: ethylene glycol diacetate; A 100 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (50.0 g, 0.293 mol), and 0.5 equivalents of 1,2-dichloroethane (14.5 g, 0.146 mol) were added at room temperature and reaction was stirred at 70°C for 3h. After reaction two phases were obtained upper layer was decanted and the reaction mixture was extracted 3 times with diethyl ether, all fractions were combined and diethyl ether was removed under vacuum. The final pure product was obtained as color less liquid (90.0percent yield) When 1, 2-dibromoethane was used as substrate the reaction was very fast even at room temperature and was highly exothermic. The reaction proceeds via homogeneous pathway; the pure product was distilled from the reaction mixture at 100°C under reduced pressure (90.0percent yield). Ethylene glycol diacetate: 1H NMR (CDCl3, 400.13 MHz): δ = 2.02 (s, 6 H, CH3), 4.2 (s, 4H, CH2); 13C NMR: δ = 20.9 (CH3), 62.3 (CH2), 170.9 (CO); FTIR (ATR mode): v = 2961 (br), 1735 (s), 1371 (m), 1213 (s), 1048 (m).
Examples 6 and 7: sec-butyl acetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 0.117 mol), and 1.0 equivalents of 2-bromobutane (15.9 g, 0.116 mmol) were added at room temperature and the reaction was stirred at room temperature for 16h. After reaction two phases were obtained and the upper layer (product) was decanted (83.0percent yield). When 2-chlorobutane was used as substrate the reaction was stirred at 80°C for 16h. After reaction two phases were obtained. To get the pure product upper layer was decanted (82.0percent yield). 1H NMR (CD3CN, 400.13 MHz): δ = 0.87 (t, 3H, CH3), 1.15 (d, 3H, CH3), 1.53 (m, 2H, CH2), 4.75 (m, 1H, CH) 13C NMR: δ = 10.0 (CH3), 19.8 (CH3), 21.5 (CH3), 29.6 (CH2), 72.8 (CH), 171.3 (CO); FTIR (ATR mode): v = 2974 (br), 1733 (s), 1371 (m), 1238 (s), 1030 (m).
1-Ethyl-3-methylimidazolium bromine (0.2 mol) and lead (II) acetate trihydrate (0.1 mol) were dissolved in 30 mL of distilled water and 70 mL of distilled water, respectively. After they were completely dissolved, 1-ethyl-3-methylimidazolium bromine solution was poured into lead (II) acetate trihydrate solution under vigorous mechanical stirring. The reaction was carried out at 35 °C for 48 h under nitrogen atmosphere. Then the reaction system was refrigerated at 3 °C for 12 h and the precipitates were filtered off. The filtrates were distilled under reduced pressure to remove the water. The obtained EMIMAc (moisture content 0.02percent; bromide content 0.004percent) was light yellow viscous liquid and the yield was 93percent.
Reference：
[1] Carbohydrate Polymers, 2013, vol. 94, # 1, p. 505 - 510
[2] Journal of Molecular Structure, 2012, vol. 1015, p. 147 - 155
[3] Carbohydrate Polymers, 2012, vol. 89, # 1, p. 7 - 16
[4] Carbohydrate Polymers, 2012, vol. 90, # 2, p. 792 - 798
5
[ 563-63-3 ]
[ 65039-08-9 ]
[ 143314-17-4 ]
Reference：
[1] Chemical Communications, 2017, vol. 53, # 81, p. 11154 - 11156
[2] Physical Chemistry Chemical Physics, 2013, vol. 15, # 47, p. 20480 - 20495
[3] Carbohydrate Polymers, 2015, vol. 121, p. 348 - 354
6
[ 563-63-3 ]
[ 65039-09-0 ]
[ 143314-17-4 ]
Reference：
[1] Green Chemistry, 2012, vol. 14, # 10, p. 2738 - 2746,9
[2] Green Chemistry, 2012, vol. 14, # 10, p. 2738 - 2746
7
[ 127-08-2 ]
[ 65039-08-9 ]
[ 143314-17-4 ]
Yield
Reaction Conditions
Operation in experiment
10 g
at 20℃; for 36 h;
First, 1-ethyl-3-methyl-imidazole acetate ion was preparedliquid,In a 250 ml round bottom three-necked flask, 0.1 mol of 1-ethyl-3-methylimidazolium bromide was added(19.lg) and 2.5mol of potassium acetate (245.3g)160 ml of isopropanol was added to dissolve it,Stir at room temperature for 36 h. filter,Removal of insoluble material,The filtrate was steamed at 70 ° C for 8 h,To give a pale yellow oil,Dissolved in 80 ml of methylene chloride,And adding activated carbon powder at room temperature for 17h,Filtered, washed with carbon tetrachloride 3 times,The combined filtrates were evaporated in vacuo to remove the solvent,Yellow oil was obtained,The product was dried in vacuo at 70 ° C to give the desired product. 1-ethyl-3-methyl-imidazole acetate ion liquidLg,And 10 g of D-glucosamine hydrochloride having a molecular weight of 215. 5 was added,Adding equimolar amounts of boric acid with D-glucosamine hydrochloride,After mixing in 50 ml of dimethylsulfoxide, the reaction was carried out at 25 ° C for 48 hours. After completion of the reaction,At room temperature,20 ml of the reaction product solution,20 ml of acetonitrile were added,Extraction three times,Remove insoluble impurities,Concentrated by rotary evaporation,And allowed to stand for 10 hours to obtain deoxyfructose,Extraction agent recovery,Recovery and Reuse of Imidazole Ionic Liquids. The conversion rate of the reaction raw material D-glucosamine hydrochloride was 100percentCrystallization gave the product a purity of 97percent,The molar yield of deoxyfructose 60percent
Reference：
[1] Patent: CN105348205, 2016, A, . Location in patent: Paragraph 0032; 0033
[2] Patent: CN105294579, 2016, A, . Location in patent: Paragraph 0032
8
[ 616-47-7 ]
[ 74-96-4 ]
[ 301-04-2 ]
[ 143314-17-4 ]
Yield
Reaction Conditions
Operation in experiment
92 %Spectr.
at 50℃; for 0.5 h; Microwave irradiation
Synthesis of 1-ethyl-3-methylimidazolium acetate ([Emim] Ac) in one step To a 500 ml round bottom flask was added 1.2 mol of bromoethane and 0.5 mol of lead acetate, To the constant-pressure dropping funnel was added 1 mol of N-methylimidazole, The reaction was carried out in an ultrasonic microwave combined reactor, The knob of the constant-pressure dropping funnel was controlled so that 1 mol of N-methylimidazole was dropped in one minute, The left through the cooling water, Set the ultrasonic power to 1000W, Microwave heating power of 900W, The reaction was carried out at 50 ° C for 30 minutes. The content of the target product [Emim] Ac in the reaction mixture was determined to be 92percent by nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometry.
Reference：
[1] Journal of Molecular Liquids, 2012, vol. 165, p. 173 - 176
[2] Patent: CN105315215, 2016, A, . Location in patent: Paragraph 0013; 0014; 0015
9
[ 65039-08-9 ]
[ 143314-17-4 ]
Reference：
[1] Chinese Journal of Catalysis, 2017, vol. 38, # 5, p. 879 - 888
10
[ 616-47-7 ]
[ 64-17-5 ]
[ 64-19-7 ]
[ 143314-17-4 ]
Yield
Reaction Conditions
Operation in experiment
17%
at 165℃; for 72 h; Autoclave
Acetic acid 44 ml was added to a 250 ml Erlenmeyer flask containing 43 ml Ethanol. 6 ml 1-Methylimidazol was then added slowly to the stirred mixture. The mixture was then sealed inside a parr reactor whit continuous stirring for 72 hours at a temperature of 165 °C. The resulting dark liquid was placed in a rotary evaporator at 50 °C water bath. The mixture was then fed to a vacuum distillation equipment to remove the precursor and excess acetic acid. The still remaining liquid was then finally purified by Flash chromatography in a C18 pre-packet column with water as the eluent . The light yellow fractions were saved. This step was repeated 4 times. The final product was dissolved twice in 99,5percent ethyl alcohols and subjected to vacuum treatment. Yield 17percent. 13C-NMR (400HHz, DMSO) δ 175.0, 138.7, 124.6, 123.1, 44.9, 36.4, 26.4, 16.3.
Reference：
[1] Journal of Molecular Structure, 2012, vol. 1028, p. 156 - 163
Example 9 Preparation of 1-methyl-3-ethylimidazolium acetate 226.8 g (0.72 mol) of Ba(OH)2 (octahydrate) are suspended in 600 g of water. The suspension is heated to 80 C., resulting in the barium salt melting and forming an aqueous emulsion. 149.8 g (0.72 mol) of 1-methyl-3-ethylimidazolium hydrogensulfate are added dropwise to this emulsion, with the temperature rising to 100 C. Despite the barium sulfate which precipitates, the suspension remains readily stirrable. The reaction mixture is stirred for another 2 hours at 80 C., cooled and the precipitated BaSO4 is filtered off using Celite as filter aid. After addition of 43.5 g (0.72 mol) of glacial acetic acid, the water is removed on a rotary evaporator and the oil which remains is extracted with ethyl acetate. Drying under reduced pressure gives 113.3 g (0.67 mol) of 1-methyl-3-ethylimidazolium acetate (yield: 92%). The chloride content is 4 ppm.
88%
Example 8 Preparation of 1-methyl-3-ethylimidazolium acetate 149.8 g (0.72 mol) of 1-methyl-3-ethylimidazolium hydrogensulfate are dissolved in 600 ml of water, and 226.8 g (0.72 mol) of Ba(OH)2 (octahydrate) are subsequently added in portions over a period of 30 minutes. The temperature is increased to 60 C. and the reaction mixture is stirred for 2 hours at this temperature. It is allowed to cool overnight and the precipitated BaSO4 is filtered off using Celite as filter aid. After addition of 43.5 g (0.72 mol) of glacial acetic acid, the water is removed on a rotary evaporator and the oil which remains is extracted with ethyl acetate. To remove residual water, the oil is admixed with n-butanol and the n-butanol is subsequently distilled off under reduced pressure. This gives 108.3 g (0.636 mol) of 1-methyl-3-ethylimidazolium acetate (yield: 88% based on 1-methyl-3-ethylimidazolium hydrogensulfate).
, wherein said salt is selected from the group consisting of: ... 1,3-dimethylimidazolium methylsulphate, 1-methyl-3-butylimidazolium methylsulphate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium nitrite, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium sulphate, 1-ethyl-3-methylimidazolium bis(triflyl)amide, 1-butylpyridinium bromide, ...
1.02 g
General procedure: EXAMPLE 1-4 170 mL (102 mmol) of ion exchange resin (DOWEX (registered trademark), manufactured by The Dow Chemical Company) was admixed with ion exchanged water and filled in a column. Then, a solution in which 5.01 g (34.17 mmol) of 1-ethyl-3-methylimidazolium chloride was dissolved in 30.48 g of ion exchanged water was allowed to flow through it two times. Further, 19.99 g of ion exchanged water was divided to two portions and allowed to flow through the ion exchange resin to obtain 79.64 g of a reaction solution. From the obtained reaction solution, 13.66 g (5.85 mmol) was drawn and then added with 0.86 g (5.84 mmol) of 3-(2-methoxyethoxy)propanoic acid, which has been obtained in Preparation Example 1, followed by stirring for 24 hours at room temperature.The resulting reaction solution was concentrated and dried to obtain 1.38 g of 1-ethyl-3-methylimidazolium 3-(2-methoxyethoxy)propanoate (hereinbelow, abbreviated as [C2mim] [MEEPA]) (yield: 91%).
5
[ 79-20-9 ]
[ 108-24-7 ]
[ 143314-17-4 ]
[ 9004-34-6 ]
Cellulose acetate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Example 34; Immiscible Co-Solvent (Effect on IL Viscosity); To a 3-neck 50 mL round bottom flask equipped for mechanical stirring and with an N2/vacuum inlet added 20.03 g of <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong>. While stirring rapidly, added 1.05 g of dry cellulose powder (DP ca. 335). The flask was placed under vacuum (2 mm Hg) and placed in an oil bath preheated to 90 C. After 1 h 45 min, the oil bath temperature was increased to 100 C. and stirred an additional 55 min (2 h 40 min total contact time) before allowing the solution to cool to ambient temperature while under vacuum.To the cellulose solution was added 20 mL of methyl acetate resulting in a 2-phase reaction mixture. While stirring rapidly, a mixture of 131 mg of MSA and 4.63 g of Ac2O was added drop wise (10 min). The contact temperature increased from 23.3 C. to 35.4 C. and, at the end of the addition, the contact mixture was a single phase and the viscosity of the single phase was much less than that of the original cellulose-[EMIm]OAc solution. Twenty-five minutes after beginning the addition, the flask was placed in a preheated 50 C. oil bath. The contact mixture was stirred for 2 h at 50 C. before allowing the contact mixture to cool to ambient temperature over 50 min. The product was precipitated in 350 mL of MeOH and the slurry was stirred for ca. 1 h before the solids were isolated by filtration. The solids were washed by taking them up in 300 mL of MeOH and stirring the slurry for ca. 1 h before the solids were isolated by filtration. Twice, the solids were taken up in 300 mL of 12/1 MeOH/35% H2O2 and the slurry was stirred for ca. 1 h before the solids were isolated by filtration. The solids were then dried overnight at 50 C., ca. 20 mm Hg which gave 1.68 g of a white solid. Analysis by 1H NMR revealed that the solid was a cellulose acetate with a DS of 2.67. Analysis by GPC indicated that the cellulose acetate had a Mw of 51,428 and a Mw/Mn of 4.08.This example shows that a cellulose solution in an ionic liquid can be contacted with an immiscible or sparingly soluble co-solvent without causing precipitation of the cellulose. Upon contact with an acylating reagent, the cellulose is esterified changing the solubility of the now cellulose ester-ionic liquid solution with the formerly immiscible co-solvent so that the contact mixture becomes a single phase. The resulting single phase has much lower solution viscosity than the initial cellulose-ionic liquid solution. This discovery is significant in that highly viscous cellulose solutions can be used to make cellulose esters while still maintaining the ability to mix and process the solution. The discovery also provides a means to process highly viscous cellulose-ionic liquid solutions at lower contact temperatures. The cellulose ester product can be isolated from the new single phase by conventional means. The cellulose ester product has desirable degrees of substitution, molecular weights, and solubility in solvents such as acetone, and can be readily melt processed when plasticized with plasticizers such as diethyl phthalate and the like.
With methanesulfonic acid; at 80℃; for 2.66667h;Product distribution / selectivity;
Example 24; Acetylation of Cellulose in High Chloride [EMIm]OAc; Cellulose (1.19 g) was dissolved in 22.65 g of commercial [EMIm]OAc which, by XRF, contained 0.463 wt % chloride following the general procedure described in Example 8 with the exception that the mixture was not homogenized prior to heating to 80 C.To the mechanically stirred straw colored solution preheated to 80 C. was added a solution of MSA (141 mg) and acetic anhydride (3.76 g, 5 eq/AGU) dropwise (10 min). By the end of the addition, the contact mixture became dark brown-black. The contact solution was stirred for 2.5 h before pouring into H2O. The resulting solids were isolated by filtration, washed extensively with H2O, and dried overnight at 50 C., 5 mm Hg. This yielded 1.57 g of a brown-black CA powder. Analysis revealed that the CA had a DS of 2.21 and that the Mw was 42,206.This example shows that [EMIm]OAc containing high levels of halides is not a suitable solvent for esterification of cellulose.
Example 33; Production of Cellulose Triacetate; To a 3-neck 100 mL round bottom flask equipped for mechanical stirring and with an N2/vacuum inlet added 34.63 g of <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong>. While stirring rapidly, added 6.11 g (15 wt %) of dry cellulose powder (DP ca. 335). The flask was placed in a 90 C. oil bath and the mixture was stirred for 10 min before applying vacuum (2 mm Hg). After 50 min, the oil bath temperature was increased to 100 C. After 2 h 25 min, the oil bath was turned off and left the solution was left standing under vacuum overnight.To the cellulose solution was added a mixture of 731 mg of MSA and 19.24 g (5 eq) of Ac2O dropwise. Initially, the solution was stirred slowly so that the solution did not bunch around the stir shaft. As the Ac2O was added, the solution viscosity dropped; after adding ca. 5 mL, the solution stirred easily and the stir rate was increased. During the addition, the solution viscosity did not increase and no localized gels were observed until the last few drops of Ac2O were added (40 min addition). At this point the entire contact mixture suddenly gelled. The contact temperature rose from 24.1 C. to 47.5 C. by the end of addition. During the addition, there was little change in the color of the solution. After the reaction gelled, 11.54 g of the reaction mixture was removed with a spatula and solids were obtained by precipitation in MeOH (Sample 1). The flask containing the remaining reaction mixture was then placed in a preheated 50 C. oil bath. After 20 min at 50 C., there was no evidence of the gel softening. Hence, the gel was allowed to cool to room temperature and 50 mL of MeOH was added to the flask. The flask contents were then dumped into 400 mL of MeOH which gave a white precipitate (Sample 2). Both fractions were processed by stirring the initial slurry for ca. 1 h before isolating the solids by filtration. The solids were washed by taking them up in 300 mL of MeOH and stirring the slurry for ca. 1 h before the solids were isolated by filtration. The solids were twice taken up in 300 mL of 12/1 MeOH/35% H2O2 and the slurry was stirred for ca. 1 h before the solids were isolated by filtration. The solids were then dried overnight at 50 C., ca. 20 mm Hg.The combined yield for Sample 1 and 2 was 10.2 g of a white solid. Analysis by 1H NMR showed that Samples 1 and 2 were identical and that they were cellulose triacetates with a DS of 3.0. By GPC, both samples have a Mw of ca. 54,000.This example shows that cellulose triacetate can rapidly be prepared from cellulose dissolved in [EMIm]OAc. Cellulose triacetate can be used to prepare film useful in liquid crystalline displays and photographic film base.
Examples E8 and E9According to the Invention170 g (1 mol) EMIM OAc (<strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong>) are placed in a round-bottom flask which has been made inert and is provided with a dropping funnel and reflux condenser. The ammonium salt 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 3 mbar, with the internal temperature being increased to 130 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. EMIM Evaporator OAc:salt temp. Yield No. Salt mol:mol C. Product % Purity* E8 NH4SCN 1:1.011 160 EMIM SCN 93 >95% (H-NMR) E9 NH4 CF3COO 1:1.01 155 EMIM CF3COO 87 >95% (H-NMR) *H-NMR
Example 2; Approximately stoichiometric amounts of 1 -ethyl-3-methylimidazolium acetate (2.0205 g, 1 1.9 mmol) and sulfur (0.3740 g, 1.46 mmol, equivalent to 11.7 mmol of sulfur atoms) were placed in a two-neck round-bottomed flask. A reflux condenser was attached to the main neck, whereas the auxiliary neck was simply stoppered. The mixture was stirred at a controlled temperature of 25 0C. An evident change of colour of the mixture could be observed within the first minutes. Samples of the reaction medium were withdrawn for 1H NMR analysis at different times over a period of 5 days. The signals were consistent with the formation of 1 -ethyl-3-methylimidazole-2-thione, as reported in the literature (Tao et al., Syn. Commun. 2007, 37, 399-408). The integration of the spectra indicated that the reaction initially progresses fast, reaching a ca. 22 % conversion of ionic liquid to thione right after 15 minutes from the start; but then it slows down, reaching a maximum conversion of ca. 47 % within the first 24 h. For isolation of the thione formed, acetonitrile was added to the reacted medium. The unreacted sulfur did not dissolve, and it was filtered off. Then, the acetonitrile was removed, and water and dichloromethane were added. The organic phase was washed several times with fresh water, and finally the dichloromethane was removed under vacuum. The final sample was further purified under high vacuum, and it was characterised by gas chromatography mass spectroscopy (GC-MS), by ESI-MS and by 1H NMR and 13C NMR, all of the results indicating that the product was 1 -ethyl-3-methylimidazole-2-thione.
1 eq of ethylamine added dropwise to a suspension comprising 1 eq of paraformaldehyde in H2O at <31 C. (exothermic reaction, ice bath). Mixture stirred further for about 30 minutes. Mixture cooled to about 3 C. by means of an ice bath and 1 eq of methylamine run in at 3-5 C. 1 eq of glacial acetic acid added dropwise at <20 C. (exothermic reaction, ice bath), 2-phase mixture 1 eq of glyoxal solution added (exothermic reaction, ice bath, homogeneous) and mixture stirred at RT for 5 days. Mixture evaporated to dryness on a rotary evaporator (black-brown oil)
Synthesis of 1-ethyl-3-methylimidazolium acetate ([Emim] Ac) in one step To a 500 ml round bottom flask was added 1.2 mol of bromoethane and 0.5 mol of lead acetate, To the constant-pressure dropping funnel was added 1 mol of N-methylimidazole, The reaction was carried out in an ultrasonic microwave combined reactor, The knob of the constant-pressure dropping funnel was controlled so that 1 mol of N-methylimidazole was dropped in one minute, The left through the cooling water, Set the ultrasonic power to 1000W, Microwave heating power of 900W, The reaction was carried out at 50 C for 30 minutes. The content of the target product [Emim] Ac in the reaction mixture was determined to be 92% by nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometry.
Example 6 - Preparation of tert-butyl 2-[(4R,6S)-2,2-dimethyl-6-[(methyl- carbonyloxy)methyl]-1 ,3-dioxan-4-yl]acetate from BMI .OAc with three recycles of the ionic liquidRun 1In a "lOOmL round vessel was added crude tert-butyl 2-[(4R,6S)-6-(chloromethyl)- 2,2-dimethyl-1 ,3-dioxan-4-yl]acetate (5.0g) and 1-butyl-3-methyl imidazolium acetate (17.8g) and potassium acetate (1.8g). The mixture was heated at 100C for 4 hours.The mixture was extracted with heptane (3x25mL). The heptane extract was slowly cooled to -4C whereupon white needles of tert-butyl 2-[(4R,6S)-2,2- dimethyl-6-[(methyl-carbonyloxy)methyl]-1 ,3-dioxan-4-yl]acetate crystallised. Yield = 1.32g.Run 2
at 100℃; for 3h;Product distribution / selectivity;
Example 1 - Preparation of tert-butyl 2-[(4R,6S)-2,2-dimethyl-6-[(methyl- carbonyloxy)methyl]-1 ,3-dioxan-4-yl]acetate from EMIM.OAcIn a 100ml_ round vessel was added crude tert-butyl 2-[(4R,6S)-6~(chloromethyl)- 2,2-dimethyl-1 ,3-dioxan-4-yl]acetate (10, Og) and 1-ethyl-3-methyl imidazolium acetate (30.0g). The mixture was heated at 100C for 3 hours.Heptane (30mL) was then added to the reaction and the mixture stirred for 1 minute before decanting the heptane phase. The heptane extract was slowly cooled to -4C whereupon white needles of tert-butyl 2-[(4R,6S)-2,2-dimethyl-6- [(methyl-carbonyloxy)methyl]-1 ,3-dioxan-4-yl]acetate crystallised. Yield = 2.8g
1-Ethyl-3-methylimidazolium bromine (0.2 mol) and lead (II) acetate trihydrate (0.1 mol) were dissolved in 30 mL of distilled water and 70 mL of distilled water, respectively. After they were completely dissolved, 1-ethyl-3-methylimidazolium bromine solution was poured into lead (II) acetate trihydrate solution under vigorous mechanical stirring. The reaction was carried out at 35 C for 48 h under nitrogen atmosphere. Then the reaction system was refrigerated at 3 C for 12 h and the precipitates were filtered off. The filtrates were distilled under reduced pressure to remove the water. The obtained EMIMAc (moisture content 0.02%; bromide content 0.004%) was light yellow viscous liquid and the yield was 93%.
In methanol; water;
[emim]Ac was prepared following the reported procedures [14] and [15]. [emim]Br was synthesized by refluxing the N-methylimidazole with excess bromoethane at 50 C for 48 h. The excess bromoethane was removed by evaporation and the crude product was recrystallized twice by ethyl acetate. The resulting precipitate was brownish and was dried in vacuum for 24 h under reduced pressure. Then 0.2 mol [emim]Br and 0.1 mol Pb(Ac)2·3H2O were separately dissolved in solutions of methanol-water (4:1 v/v). Upon mixing the two solutions, a precipitate of PbBr2 was produced, which was removed by filtration after cooling at -20 C overnight. The solvent was removed from the filtrate by rotary evaporation, and the product [emim]Ac was gotted by drying in vacuum for 2 days at 80 C. The structure of [emim]Ac was confirmed by 1H NMR (400 MHz, D2O): deltaH = 1.46-1.52 (t, 3H; CH3), deltaH = 1.89-1.94 (t, 3H; CH3-COO-), deltaH = 3.89 (t, 3H; N-CH3), deltaH = 4.18-4.26 (t, 2H; CH2), deltaH = 7.4 (s, 1H; Ring-CH), deltaH = 7.5 (s, 1H; Ring-CH), deltaH = 8.7 (s, 1H; Ring-CH).
Acetic acid 44 ml was added to a 250 ml Erlenmeyer flask containing 43 ml Ethanol. 6 ml 1-Methylimidazol was then added slowly to the stirred mixture. The mixture was then sealed inside a parr reactor whit continuous stirring for 72 hours at a temperature of 165 C. The resulting dark liquid was placed in a rotary evaporator at 50 C water bath. The mixture was then fed to a vacuum distillation equipment to remove the precursor and excess acetic acid. The still remaining liquid was then finally purified by Flash chromatography in a C18 pre-packet column with water as the eluent . The light yellow fractions were saved. This step was repeated 4 times. The final product was dissolved twice in 99,5% ethyl alcohols and subjected to vacuum treatment. Yield 17%. 13C-NMR (400HHz, DMSO) delta 175.0, 138.7, 124.6, 123.1, 44.9, 36.4, 26.4, 16.3.
Examples 3 and 4: methylene diacetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 117.0 mmol), and 0.5 equivalents of dichloromethane (5.0 g, 58.7 mmol) were added at room temperature and the reaction was stirred at 50C for 16h. After reaction the pure Product was distilled from the reaction mixture at 80C under reduced pressure (85.0-%). When dibromomethane was used as substrate the reaction was fast even at room temperature and highly exothermic. The reaction proceeds via homogeneous path way and the pure product distilled from the reaction mixture at 80C under reduced pressure (86.0% yield). Methylene diacetate: 1H NMR (CD3CN, 400.13 MHz): delta = 2.04 (s, 6H, CH3), 5.64 (s, 2H, CH2); 13C NMR: delta = 20.9 (CH3), 79.7 (CH2), 170.8 (CO); FTIR (ATR mode): v = 2996 (br), 1758 (s), 1190 (s), 1009 (s), 978 (s)
Examples 3 and 4: methylene diacetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 117.0 mmol), and 0.5 equivalents of dichloromethane (5.0 g, 58.7 mmol) were added at room temperature and the reaction was stirred at 50C for 16h. After reaction the pure Product was distilled from the reaction mixture at 80C under reduced pressure (85.0-%). When dibromomethane was used as substrate the reaction was fast even at room temperature and highly exothermic. The reaction proceeds via homogeneous path way and the pure product distilled from the reaction mixture at 80C under reduced pressure (86.0% yield). Methylene diacetate: 1H NMR (CD3CN, 400.13 MHz): delta = 2.04 (s, 6H, CH3), 5.64 (s, 2H, CH2); 13C NMR: delta = 20.9 (CH3), 79.7 (CH2), 170.8 (CO); FTIR (ATR mode): v = 2996 (br), 1758 (s), 1190 (s), 1009 (s), 978 (s)
Example 5 benzyl acetate A 100 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (40.0 g, 0.235 mol), and benzyl chloride (28.0 g, 0.221 mol) were added at room temperature and reaction mixture was stirred for 2h at room temperature (rt), the reaction was fast and exothermic. After reaction two phases were obtained, the desired product formed the upper layer and was decanted (95.0% yield). 1H NMR (CDCl3, 400.13 MHz): delta = 2.09 (s, 3H, CH3), 5.1 (s, 2H, CH2), 7.35 (m, 5H, Ph); 13C NMR: delta = 21.2 (CH3), 66.5 (CH2), 122.4, 128.7, 136.1(Ph), 171.0 (CO); FTIR (ATR mode): v = 3034 (br), 1736 (s), 1222 (s), 1025 (s).
Example 1 and 2: ethylene glycol diacetate; A 100 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (50.0 g, 0.293 mol), and 0.5 equivalents of 1,2-dichloroethane (14.5 g, 0.146 mol) were added at room temperature and reaction was stirred at 70C for 3h. After reaction two phases were obtained upper layer was decanted and the reaction mixture was extracted 3 times with diethyl ether, all fractions were combined and diethyl ether was removed under vacuum. The final pure product was obtained as color less liquid (90.0% yield) When 1, 2-dibromoethane was used as substrate the reaction was very fast even at room temperature and was highly exothermic. The reaction proceeds via homogeneous pathway; the pure product was distilled from the reaction mixture at 100C under reduced pressure (90.0% yield). Ethylene glycol diacetate: 1H NMR (CDCl3, 400.13 MHz): delta = 2.02 (s, 6 H, CH3), 4.2 (s, 4H, CH2); 13C NMR: delta = 20.9 (CH3), 62.3 (CH2), 170.9 (CO); FTIR (ATR mode): v = 2961 (br), 1735 (s), 1371 (m), 1213 (s), 1048 (m).
Examples 6 and 7: sec-butyl acetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 0.117 mol), and 1.0 equivalents of 2-bromobutane (15.9 g, 0.116 mmol) were added at room temperature and the reaction was stirred at room temperature for 16h. After reaction two phases were obtained and the upper layer (product) was decanted (83.0% yield). When 2-chlorobutane was used as substrate the reaction was stirred at 80C for 16h. After reaction two phases were obtained. To get the pure product upper layer was decanted (82.0% yield). 1H NMR (CD3CN, 400.13 MHz): delta = 0.87 (t, 3H, CH3), 1.15 (d, 3H, CH3), 1.53 (m, 2H, CH2), 4.75 (m, 1H, CH) 13C NMR: delta = 10.0 (CH3), 19.8 (CH3), 21.5 (CH3), 29.6 (CH2), 72.8 (CH), 171.3 (CO); FTIR (ATR mode): v = 2974 (br), 1733 (s), 1371 (m), 1238 (s), 1030 (m).
Example 1 and 2: ethylene glycol diacetate; A 100 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (50.0 g, 0.293 mol), and 0.5 equivalents of 1,2-dichloroethane (14.5 g, 0.146 mol) were added at room temperature and reaction was stirred at 70C for 3h. After reaction two phases were obtained upper layer was decanted and the reaction mixture was extracted 3 times with diethyl ether, all fractions were combined and diethyl ether was removed under vacuum. The final pure product was obtained as color less liquid (90.0% yield) When 1, 2-dibromoethane was used as substrate the reaction was very fast even at room temperature and was highly exothermic. The reaction proceeds via homogeneous pathway; the pure product was distilled from the reaction mixture at 100C under reduced pressure (90.0% yield). Ethylene glycol diacetate: 1H NMR (CDCl3, 400.13 MHz): delta = 2.02 (s, 6 H, CH3), 4.2 (s, 4H, CH2); 13C NMR: delta = 20.9 (CH3), 62.3 (CH2), 170.9 (CO); FTIR (ATR mode): v = 2961 (br), 1735 (s), 1371 (m), 1213 (s), 1048 (m).
Examples 6 and 7: sec-butyl acetate A 50 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (20.0 g, 0.117 mol), and 1.0 equivalents of 2-bromobutane (15.9 g, 0.116 mmol) were added at room temperature and the reaction was stirred at room temperature for 16h. After reaction two phases were obtained and the upper layer (product) was decanted (83.0% yield). When 2-chlorobutane was used as substrate the reaction was stirred at 80C for 16h. After reaction two phases were obtained. To get the pure product upper layer was decanted (82.0% yield). 1H NMR (CD3CN, 400.13 MHz): delta = 0.87 (t, 3H, CH3), 1.15 (d, 3H, CH3), 1.53 (m, 2H, CH2), 4.75 (m, 1H, CH) 13C NMR: delta = 10.0 (CH3), 19.8 (CH3), 21.5 (CH3), 29.6 (CH2), 72.8 (CH), 171.3 (CO); FTIR (ATR mode): v = 2974 (br), 1733 (s), 1371 (m), 1238 (s), 1030 (m).
Example 9 Methyl (R)- (+)-2-acetoxy propionate An optically pure halide compound which is methyl-(R)-(+)-2- chloro propionate and EMIM-acetate were used as starting compounds (Scheme 3). A 25 mL Schlenk flask was equipped with a magnetic stirring bar, EMIM-acetate (1.0 g, 5.875 mmol), and 1.0 equivalents of methyl (R)- (+)-2-chloro propionate (0.72 g, 5.875mmol) were added at room temperature and reaction was stirred at room temperature for 2h. After the reaction, two phases were obtained upper layer was decanted which was contained pure compound (90.0% yield). 1H NMR (CDCl3, 400.13 MHz): delta = 1.46 (d, 3H, CH3), 1.12 (s, 3H, CH3), 3.74 (s, 3H, CH3), 5.06 (q, 1H, CH); FTIR (ATR mode): v = 1738 (s), 1372 (m), 1207 (m), 1097 (m). Optical activity: Optical activity of the starting material as well as product was measured with polarimeter. Sample was prepared in 20 mL heptane by dissolving 0.7g of methyl (R)- (+)-2-chloro propanate. The solution of 0.7 g of methyl (R)- (+)-2-acetoxy propionate was prepared in the same solvent. The specific rotation was found to be (alpha) = -3.20 at room temperature, whereas that of the starting material was 2.3.
In dimethylsulfoxide-d6; at 22℃; for 24h;Sealed tube;
The catalyst in this carbene catalysis is l-ethyl-3-methylimidazolin-2-ylidene carbene I (Figure 3), present in the [EMIMJOAc equilibrium that favors the ion pair form. The early steps of the proposed elementary reactions involved in the catalysis deviate somewhat from those put forth for the NHC-catalyzed umpolung of aldehydes and a, ?-unsaturated esters, due to the important role of HO Ac, which co-exists with carbene I in the [EMIMJOAc equilibrium. Specifically, nucleophilic addition of the carbene I to the carbonyl group of HMF generates a zwitterionic tetrahedral intermediate, which is protonated by HO Ac to afford a 2-(5-hydroxymethyl-2-a-hydroxyfuranyl) imidazolium acetate salt, the resting intermediate II.; Third, we obtained direct evidence for the formation of the resting intermediate II through NMR monitoring of the HMF reaction with [EMIMJOAc (1: 1 molar ratio) in DMSO-i4 at RT (-22 C) and 80 C with hexamethylbenzene as the internal standard. At RT, 17% HMF was consumed immediately upon mixing HMF with [EMIMJOAc, which approximately corresponds to the amount of the NHC catalyst accessible in [EMIMJOAc at this temperature for its reaction with HMF to form intermediate II. This intermediate is not converted into DHMF at RT, even after 24 h. With this valuable information, next we carried out the same reaction at RT but with a 1 :5 molar ratio of HMF: [EMIM]OAc to form the intermediate exclusively (i.e., devoid of HMF and DHMF), plus excess [EMIMJOAc; the reaction in this ratio at RT enabled conclusive spectroscopic characterization of intermediate II (Figures 4 and 5). Identification of Intermediate II from the Reaction of HMF with [EMIM]OAc. The 1:1 reaction of HMF with [EMIMJOAc at RT was monitored by NMR (DMSO-rf6) in a J. Young-type NMR tube using hexamethylbenzene as the internal standard. This study showed that 17% HMF was consumed immediately upon mixing HMF with [EMIMJOAc at RT, which approximately corresponds to the amount of the NHC catalyst accessible in [EMIMJOAc at this temperature for its reaction with HMF to form intermediate II. This intermediate is not converted into DHMF at RT, even after 24 hours, and the ]H NMR remained the same from the beginning of the reaction up to 24 hours at RT. To aid analysis of the spectra of the in situ reactions, the chemical shifts of the four species involved in the reaction of HMF with [EMIMJOAc were summarized as follows. All chemical shifts were reported in DMSO-i, and the NMR solvent residual signal was referenced at 2.54 ppm (not 2.50 ppm), based on the chemical shift of the hexamethylbenzene internal standard set at 2.15 ppm. ]H NMR for HMF (known compound): delta 9.56 (s, 1H, CHO), 7.51, 6.59 (d, 2Eta, furan ring Eta), 4.54 (s, 2Eta, CH2OH). ]H NMR for [EMIM]OAc (known compound): delta 9.60 (s, 1H, NCHN), 7.84, 7.76 (d, 2Eta, imidazolium ring Eta), 4.24 (q, 2Eta, NCH2CH3), 3.89 (s, 3H, NC), 1.65 (s, 3H, OAc), 1.44 (t, 3H, NCH2G).; ]H NMR for Intermediate II (new compound, see Figures 4 and 5): delta 7.98 (d, /H-H = 2.1 Hz, imidazol ring H), 7.93 (d, /H-H = 1-8 Hz, 1H, imidazol ring proton), 6.74 (s, 1H, CHOH), 6.38 (d, /H-H = 3.3, 1H, furan ring H), 6.24 (d, /H-H = 3.0 Hz, 1H, furan ring H), 4.41 (m, 2H, NCH2CH3), 4.36 (s, 2H, CH2OH), 3.96 (s, 3H, NC), 1.64 (s, 3H, OAc), 1.31 (t, /H-H = 7.2 Hz, 3H, NCH2C). 13C NMR: delta 175 (C=0), 158 (NCN), 151, 146, 109, 108 (4 resonances for the furan ring), 125, 122 (2 resonances for the imidazol ring), 60.4 (CH-OH), 56.3 (CH2OH), 44.2 (NCH2CH3), 36.2 (NCH3), 26.5 (0=C-CT), 16.3 (NCH2CH3).
The second stage was conversion to the acetate salt: [EMIM]Br (0.50 mol) was dissolved in water (150 mL) and added slowly into Ag(CH3COO) aqueous solution (0.50 mol in 250 mL). The mixture was stirred at room temperature for 6 h, followed by filtration to remove AgBr. Charcoal was added to the filtrate in order to remove any impurities (indicated by color), then refrigerated overnight. After filtering off the charcoal, water was removed from the filtrate through rotary evaporation under vacuum at 70 C. The obtained light yellow liquid was dried in a vacuum oven for 48 h at 80 C. The synthesized [EMIM]Ac (100 mg) dissolved in D2O (0.5 mL) for 1H NMR measurement. Multiplicities are reported as s (singlet), d (doublet), t (triplet) and m (multiplet). 1H NMR (400 MHz, D2O, delta ppm): 1.38 (t, 3H, -CH3), 1.77 (s, 3H, -CH2CH3), 3.78 (s, 3H, OOCH2CH3), 4.13 (m, 2H, OOCH2CH3), 7.33 (s, 1H, -N-CH = CH-), 7.39 (s, 1H, -N-CH = CH-), 8.63 (s, 1H, -N = CH-N-).
In acetonitrile; at 20℃; under 760.051 Torr; for 0.0833333h;
Example 3 In a round flask, 2 mL of methyl cyanide (acetonitrile) as an organic solvent was introduced, 0.145 g (1 mmol) of 5-chloromethylfurfural (CMF, compound I) was dissolved in the organic solvent, 0.170 g (1 mmol) of <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> was added to the solution, and then the mixed solution was reacted at normal pressure and room temperature for 5 minutes. After the reaction, the reaction product was extracted by the addition of a small amount of water (5 mL) and ethyl acetate (added twice by 20 mL) to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure to obtain light yellow liquid 5-acetoxymethylfurfural (AcHMF, compound II). The yield thereof is 36%. It was ascertained by 1H-NMR that the light yellow liquid is a target material. Analysis data is as follows. AcHMF: 1H NMR (400 MHz, CDCl3) 9.65 (s, 1H), 7.25 (d, J=3.6, 1H), 6.62 (d, J=3.6, 1H), 5.13 (s, 2H), 2.12 (s, 3H)
With dihydrogen peroxide; In water; dimethyl sulfoxide; at 20℃; for 240h;
(1) Preparation of 1-ethyl-3-methyl-imidazolium acetate ionic liquid. In a 250ml round bottom three-necked flask was added 0.1mol 1-ethyl-3-methylimidazolium bromide (19.1g)and potassium acetate 2.5mol (245.3g). Add 160ml of isopropyl alcohol to dissolve. At room temperature, stir for 36h. Filter to remove insolubles, the filtrate by rotary evaporation at 70 deg.C, 8h, pale yellow oil which was dissolved in 80ml of dichloromethane, and stirred at room temperature was added powdered activated carbon 17H, filtered, and washed three times with carbon tetrachloride, and the combined filtrate by rotary evaporation The solvent was removed to give a tan oil, 70 deg.C vacuum dried to yield the desired product. Take 1-ethyl-3-methyl - imidazole acetate ionic liquid 10g, add 20g 215.5 molecular weight of D- glucosamine hydrochloride. Add aqueous hydrogen peroxide solution that has a 30% mass fraction of D-glucosamine hydrochloride. After mixing in 80ml of dimethylsulfoxide, 20 deg.C reaction for 10 days.
2-deoxy-2-(sulfoamino)-D-glucopyranose sodium salt[ No CAS ]
[ 13185-73-4 ]
Yield
Reaction Conditions
Operation in experiment
With dihydrogen peroxide; In water; dimethyl sulfoxide; at 80℃; for 5h;
(1) Use the method as described in Example 1 to prepare <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> ionic liquid. Take <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> ionic liquid 20g. Add 15g sodium D-glucosamine 2-sulfate . Add 30% hydrogen peroxide aqueous solution that is 30 times the mass of raw material sodium D-glucosamine 2-sulfate. After mixing uniformly in 500ml dimethyl sulfoxide, react at 80 deg.C for 5 hours.
With sodium hypobromide; In dimethyl sulfoxide; at 150℃; for 5h;
(1)Use the method in Example 1 to prepare<strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> ionic liquid acetate. Take <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> ionic liquid 100g, add 1g of potassium D-glucosamine 2-sulfate. Add sodium hypobromite that is 45 times the mass of the potassium D-glucosamine 2-sulfate raw material. After uniformly mixing in 200ml dimethyl sulfoxide,react at 150 deg.C for 5 hours.
(1) Preparation of 1-ethyl-3-methyl-imidazolium acetate ionic liquid. In a 250ml round bottom three-necked flask was added 0.1mol 1-ethyl-3-methylimidazolium bromide (19.1g)and potassium acetate 2.5mol (245.3g). Add 160ml of isopropyl alcohol to dissolve. At room temperature, stir for 36h. Filter to remove insolubles, the filtrate by rotary evaporation at 70 deg.C, 8h, pale yellow oil which was dissolved in 80ml of dichloromethane, and stirred at room temperature was added powdered activated carbon 17H, filtered, and washed three times with carbon tetrachloride, and the combined filtrate by rotary evaporation The solvent was removed to give a tan oil, 70 deg.C vacuum dried to yield the desired product. Take 1-ethyl-3-methyl - imidazole acetate ionic liquid 10g, add 20g 215.5 molecular weight of D- glucosamine hydrochloride. Add aqueous hydrogen peroxide solution that has a 30% mass fraction of D-glucosamine hydrochloride. After mixing in 80ml of dimethylsulfoxide, 20 deg.C reaction for 10 days.
10 g
In isopropyl alcohol; at 20℃; for 36h;
First, 1-ethyl-3-methyl-imidazole acetate ion was preparedliquid,In a 250 ml round bottom three-necked flask, 0.1 mol of 1-ethyl-3-methylimidazolium bromide was added(19.lg) and 2.5mol of potassium acetate (245.3g)160 ml of isopropanol was added to dissolve it,Stir at room temperature for 36 h. filter,Removal of insoluble material,The filtrate was steamed at 70 C for 8 h,To give a pale yellow oil,Dissolved in 80 ml of methylene chloride,And adding activated carbon powder at room temperature for 17h,Filtered, washed with carbon tetrachloride 3 times,The combined filtrates were evaporated in vacuo to remove the solvent,Yellow oil was obtained,The product was dried in vacuo at 70 C to give the desired product. 1-ethyl-3-methyl-imidazole acetate ion liquidLg,And 10 g of D-glucosamine hydrochloride having a molecular weight of 215. 5 was added,Adding equimolar amounts of boric acid with D-glucosamine hydrochloride,After mixing in 50 ml of dimethylsulfoxide, the reaction was carried out at 25 C for 48 hours. After completion of the reaction,At room temperature,20 ml of the reaction product solution,20 ml of acetonitrile were added,Extraction three times,Remove insoluble impurities,Concentrated by rotary evaporation,And allowed to stand for 10 hours to obtain deoxyfructose,Extraction agent recovery,Recovery and Reuse of Imidazole Ionic Liquids. The conversion rate of the reaction raw material D-glucosamine hydrochloride was 100%Crystallization gave the product a purity of 97%,The molar yield of deoxyfructose 60%
EmimBr and lead acetate trihydrate were dissolved in deionized water at a molar ratio of about 2:1. The EmimBr solution was added dropwise to the lead acetate solution under stirring at room temperature for 4 h. After precipitation, the mixture was transferred to a refrigerator and left for 5 h for sedimentation. The filtrate was obtained by vacuum filtration while the mixture was still cool. The drying and purification procedure described above was used. Bright-yellow viscous EmimOAc was obtained and stored in a desiccator. 1H NMR (DMSO-d6): 1.31 (t, 3H), 1.59 (s, 3H), 3.86 (s, 3H), 4.18 (m, 2H), 7.74 (s, H), 7.83 (s, H), 9.73 (s, H); decomposed 180 C; purity: 98%.
Weigh 20g (NH4) 6Mo7O24.4H2O dissolved in 150ml deionized water, heated to 100 C under magnetic stirring, take18.22g ionic liquid [EMIM] OOCCH3, dropwise with a constant pressure dropping funnel, the solution was dried by blowing at 50 for 48h, the supernatantThe liquid crystallized at 50 C to give [EMIM] 6Mo7O24. Weigh 1.134g 5-hydroxymethylfurfural, 0.72g NaOH, 20ml deionized waterAnd 0.113g of catalyst, into a 250ml three-necked flask, magnetic stirring until the reaction reaches 98 , by constant pressure drop leakageTo the reaction mixture was dropped 5ml hydrogen peroxide, 1 hour after the reaction was completed. After testing, 5-hydroxymethyl furfural conversion reached98%, 2,5-furandicarboxylic acid selectivity at 95%.
1-ethyl-3-methylimidazolium triphenyl(p-tolyl)borate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
In 1,2-dichloro-ethane; for 1h;
As in Example 37 except that 3.4 g of triphenylsulfonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 1.7 g (10 mmol) of <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> (manufactured by Aldrich) To obtain 1-ethyl-3-methylimidazolium triphenyl (p-tolyl) borate (yield 92%, purity 99%).
[(4-hydroxy-1-methyl-7-phenoxy-isoquinoline-3-carbonyl)-amino]-acetic acid[ No CAS ]
[ 143314-17-4 ]
3-ethyl-1-methyl-1H-imidazol-3-ium (4-hydroxy-1-methyl-7-phenoxyisoquinoline-3-carbonyl)glycine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
51%
In tetrahydrofuran; at 25℃; for 22h;
1.0 g of roxadustat of form A was dosed into a flask and dissolved in 30 ml of THF. Subsequently, during 20 minutes, a solution of 3 -ethyl- 1 -methyl- lH-imidazol-3-ium acetate in dichloromethane (30 ml) was added by dripping and the mixture was stirred for 22 h at the room temperature (25C). After evaporation of approximately a half of the reaction mixture volume, the suspension was filtered and washed with a minimal quantity of THF. The product was obtained in the form of white powder in the yield of 0.59 g (51%) and with 99.8% purity (determined by means of UHPLC). An IR measurement confirmed formation of a salt. Ratio of roxadustate: 3 -ethyl- 1 -methyl- lH-imidazol-3-ium = 2:1, contents of solvents: 0.05 molar equivalents of THF and 0.05 molar equivalents of dichloromethane, determined by means of NMR. (0397) 1H-NMR (500 MHz, DMSO-d6): 9.16 (0.5H, s, AiH), 8.90 (1H, t, J= 4.8 Hz, NH), 8.29 (1H, d, J = 9.2 Hz, ArH), 7.77 (0.5 H, t, J = 1.8 Hz, ArH), 7.69 (0.5 Eta, t, J = 1.8 Hz, AiH), 7.61 (1H, d, J= 2.3 Hz, ArH), 7.52 (1Eta, dd, J= 9.0, 2.4 Hz, ArH), 7.48 (2Eta, -t, J = 7.4 Hz, ArH), 7.25 (1Eta, ~t, J= 7.4 Hz, ArH), 7.18 (2Eta, ~d, J= 8.6 Hz, ArH), 4.18 (1Eta, q, J= 7.2 Hz, CH2), 3.84 (1.5H, s, CH3), 3.81 (2Eta, d, J= 5.2 Hz, CH2), 2.69 (3Eta, s, CH3), 1.40 (1.5Eta, t, CH3). 13C NMR (125 MHz, DMSO-d6): 169.95, 169.06, 157.64, 155.60, 152.75, 146.67, 136.32, 131.30, 130.37, 125.21, 124.50, 123.64, 123.57, 122.40, 121.97, 119.71, 119.46, 112.18, 44.10, 42.13, 35.68, 21.53, 15.11. (0398) A TGA measurement confirmed the presence of 2,2% of water. (0399) The X-ray powder pattern of 3 -ethyl- 1 -methyl- lH-imidazol-3-ium roxadustat is shown in Fig. 62, the DSC record is shown in Fig. 63; this is a crystalline form with the melting point of 160C.
1.0 mol of 1-ethyl-3-methylimidazolium chloride was added to 880 g of ethanol with vigorous stirring.Slowly add a total of 90.1 g of potassium acetate in 4 batches, during the addition process,The solids were dissolved and precipitated continuously, and the reaction was stirred for 24 hours; the stirring was stopped, and the mixture was frozen to -15 C for 24 hours.Filtration, recovery of the cake, and evaporation of the filtrate at 80 degrees to obtain a total of 153.0 g of 1-ethyl-3-methylimidazolium acetate ionic liquid, the yield was 90.0%.The purity was determined by high performance liquid chromatography to be 97.0%, the K ion residue was about 8200 ppm, and the Cl ion residue was about 6400 ppm.
1.0 mol of 1-ethyl-3-methylimidazolium chloride was dissolved in 48 g of water.Solution A was obtained, and 1.2 mol of lithium perchlorate was dissolved in 254 g of water.Solution B was obtained; solution A was mixed with solution B, 575 g of dichloromethane was added, and the reaction was mechanically stirred for 12 hours;The aqueous phase is separated into waste liquid, recovered, and the organic phase is washed with 260 g of pure water each time.After washing 5 times, no precipitation was detected using AgNO3 solution; the organic phase was vacuum-screwed at 80 C.193 g of 1-ethyl-3-methylimidazolium perchlorate ionic liquid intermediate were obtained in a yield of 91.9%;Add 579g of ethanol and slowly add a total of 90.1g of potassium acetate in 4 batches with vigorous stirring.During the addition process, solids are dissolved and precipitated continuously, and the reaction is continuously stirred for 24 hours;Stirring was stopped, frozen to -15 C for 24 hours, filtered, and the filter cake was recovered. The filtrate was steamed at 80 C; cooled to room temperature.Add 4 volumes of a mixed solution of dichloromethane and 18-crown-6 (crown ether is mixed with dichloromethane in advance,1% of the mass of methylene chloride, frozen to -15 C for 24 hours, filtered, the filtrate was steamed at 60 C; 18-crown-6 liquid separation,A total of 154.0 g of 1-ethyl-3-methylimidazolium acetate ionic liquid was obtained, and the yield was 90.5%.The purity was 99.3% by high performance liquid chromatography, ?120ppm of K ion residue, and ?5ppm of Cl ion residue.
1.0 mol of 1-ethyl-3-methylimidazolium chloride was dissolved in 48 g of water.Solution A was obtained, and 1.2 mol of lithium perchlorate was dissolved in 254 g of water.Solution B was obtained; solution A was mixed with solution B, and 575 g of dichloromethane was added.Mechanically stir the reaction for 12 hours; dispense the liquid, separate the aqueous phase into waste liquid,Recycling, the organic phase is washed with 260g of pure water each time, and washed 5 times.No precipitation was detected using AgNO3 solution; the organic phase was vacuum-screwed at 80 C.Obtaining 193 g of 1-ethyl-3-methylimidazolium perchlorate ionic liquid intermediate in a yield of 91.9%; adding 579 g of ethanol with vigorous stirringSlowly added a total of 70.6 g of ammonium acetate in 4 batches, during the addition process,Solid solution and precipitation continued, stirring reaction continued for 24 hours; stirring was stopped.Freeze to -15 C for 24 hours, filter, filter cake recovery, the filtrate is steamed 80 degrees; cooled to room temperature,Add 4 volumes of a mixed solution of dichloromethane and 18-crown-6 (crown ether is mixed with dichloromethane in advance,1% by mass of methylene chloride, frozen to -15 C for 24 hours, filtered, and the filtrate was steamed at 60 degrees;The 18-crown-6 liquid was removed to obtain a total of 154.0 g of 1-ethyl-3-methylimidazolium acetate ionic liquid, and the yield was 90.5%.The purity was determined by high performance liquid chromatography to be 99.0%, the ammonium residue was ?120 ppm, and the Cl ion residue was ?5 ppm.
[Emim] Br (19.107 g, 0.1 mol) was placed in a 100 mL three-necked flask,Dissolve anhydrous sodium acetate (8.2g, 0.15mol) in anhydrous methanol (35mL) at 40 C.Slowly add the methanol solution of anhydrous sodium acetate to the three-necked flask using a constant pressure dropping funnel.After the dropwise addition, place it at 0 C or lower and vacuum filter.The filtrate was rotary evaporated to remove the solvent, and dried under vacuum at 80 C for 24h.The product was obtained as a pale yellow viscous liquid (14.46 g, 85%).
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