CN103420915A - Preparation method of 1-substituent-3-methylimidazole acetate ionic liquid - Google Patents
Preparation method of 1-substituent-3-methylimidazole acetate ionic liquid Download PDFInfo
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Abstract
The invention discloses a preparation method of 1-substituent-3-methylimidazole acetate ionic liquid. The preparation method is specifically implemented according to the following steps: 1) weighing 1-substitutent imidazole, dimethyl carbonate and glacial acetic acid respectively; 2) adding the weighed 1-substitutent imidazole and the weighed dimethyl carbonate into an ionic liquid preparation device to obtain 1-substituent-3-methylimidazole methyl carbonate; 3) adding the weighed glacial acetic acid into a three-necked flask, and reacting the glacial acetic acid with the 1-substituent-3-methylimidazole methyl carbonate to obtain 1-substituent-3-methylimidazole acetate ionic liquid; 4) purifying the 1-substituent-3-methylimidazole acetate ionic liquid by using a high vacuum distillation device. The preparation method provided by the invention can prepare the 1-substituent-3-methylimidazole acetate ionic liquid under the conditions of normal pressure and low temperature without additional solvents, catalysts and reaction kettles.
Description
Technical field
The invention belongs to glyoxaline ion liquid preparation method technical field, relate to the preparation method of a kind of 1-substituting group-3-Methylimidazole acetate type ionic liquid.
Background technology
Imidazole type ion liquid is the room temperature melting salt by the negatively charged ion formation of glyoxaline cation and mineral acid (or organic acid), it is also maximum class of ionic liquid area research, be widely used in electrochemistry, catalyzed reaction, the energy, environment, material preparation, medicine and cellulosic dissolving regeneration field, and represented tempting application prospect.As: 1-allyl group-3-Methylimidazole villaumite ([amim] Cl) and 1-ethyl-3-methylimidazole acetate ([emim] Ac) have been proved to be cellulosic direct solvent, are expected to as green reproducible cellosolve and alternative traditional high pollution cellosolve.
Except the exploration of application facet, the scientific worker is also doing a large amount of research aspect the synthetic method of glyoxaline ion liquid and preparation technology.The preparation method of glyoxaline ion liquid conventionally is divided into single stage method and two-step approach.Wherein, in the ionic liquid that single stage method makes, negatively charged ion is generally halide-ions or sulfuric ester negatively charged ion; Two step method is mainly on the basis of single stage method, adopts suitable solvent or technique to carry out anionresin, with non-halide anion, substitutes halide anion, obtains target product.
Along with the development that application is explored, the needs that prepare non-halogen-type ionic liquid are more and more necessary, preparation method's exploitation also more and more low to cost, technique simple, carry out the aspect of energy-conserving and environment-protective.[emim] Ac of take is example, is the earliest with the N-Methylimidazole, with monobromethane, to react to make 1-ethyl-3-methylimidazole bromine salt ([emim] Br), and then [emim] Br reacts and makes [emim] Ac with Silver monoacetate (AgAc) in the water-methanol solvent system.Although [emim] Ac purity that the method is prepared is very high, owing to there being silver salt to participate in causing preparation cost too high; On the basis of this method, be to reduce preparation cost, developed with sodium-acetate (NaAc) or Potassium ethanoate (KAc) and replaced AgAc, the preparation method that the acetone (or methyl alcohol, ethanol) of take is solvent, but exist solid-liquid two phase reaction productive rate too low, purity is not high; Also have with plumbic acetate (PbAc) and replace AgAc, method prepared as solvent by the ethanol of take, although the productive rate of the method and purity are used the height of sodium salt or sylvite, fail widespread use owing to containing the lead salt that is difficult to separate.
Also have a kind of method for preparing the imidazoles ionic liquid of reacting with carbonic diester with the acidic ion liquid presoma, in the ionic liquid of preparing, not containing other metallic cation, with respect to ion exchange method, the object ion purity liquid obtained is very high; The negatively charged ion that the method relates to is a kind of in chlorion, bromide anion, iodide ion, nitrate ion, acetate ion, oxalate denominationby, sulfate ion, hydrogen sulfate ion, fluoro boron acid ion, phosphate anion, hydrogen phosphate, dihydrogen phosphate ions, reaction needed is carried out in reactor, 120 ℃～200 ℃ of reaction control temperature.The patent No. is ZL200910041805.X, patent name is: a kind of preparation method of imidazole type ion liquid, disclose with substituted imidazole and carbonate reaction and made the imidazoles carbonate salt, again imidazoles carbonate salt and corresponding inorganic or organic acid are carried out to anionresin and make object ion liquid, its negatively charged ion related to is:
F
-, Cl
-, Br
-, I
-,
Or
The fluoro-alkyl that Rf is carbonatoms l～6, this preparation method need to use solvent, as: tetrahydrofuran (THF), also need phase-transfer catalyst and reactor, temperature of reaction is 100 ℃～150 ℃, excess Temperature can make darkening of object ion liquid, and organic impurity content increases, and the introducing of catalyzer or phase-transfer catalyst also can make in target product to exist corresponding impurity.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of 1-substituting group-3-Methylimidazole acetate type ionic liquid, without additional solvent, catalyzer and reactor, just can under the atmospheric low-temperature condition, prepare 1-substituting group-3-Methylimidazole acetate type ionic liquid.
The technical solution adopted in the present invention is, the preparation method of 1-substituting group-3-Methylimidazole acetate type ionic liquid specifically implements according to following steps:
Step 4, the 1-substituting group-3-Methylimidazole acetate type ionic liquid that will prepare through step 3 carry out purifying with the molecular distillation device, obtain 1-substituting group after purifying-3-Methylimidazole acetate type ionic liquid.
Characteristics of the present invention also are,
By amount of substance than for 1:1～1.1:1～1.1, taking respectively 1-substituting group imidazoles, methylcarbonate and Glacial acetic acid.
Step 2.1, the 1-substituting group imidazoles taken in step 1 is poured in there-necked flask;
Step 2.2, constant pressure funnel, prolong and thermometer are connected respectively on three bottlenecks of there-necked flask, connect ion liquid preparation device;
Step 2.3, after step 2.2 connects prolong, first tap water is passed into to prolong as water of condensation, then there-necked flask is positioned on constant-temperature heating magnetic stirring apparatus, the temperature to 55 of regulating thermostatic heating magnetic stirring apparatus ℃～65 ℃;
Temperature in step 2.4, use thermometer Real-Time Monitoring there-necked flask, treat that the temperature in there-necked flask is 55 ℃～65 ℃, and the methylcarbonate taken in step 1 is poured in constant pressure funnel, and methylcarbonate splashes into there-necked flask in constant pressure funnel;
Step 2.5, through step 2.4, after methylcarbonate splashes in there-necked flask fully, keep motionless the treating in position of constant pressure funnel, 1-substituting group imidazoles and dimethyl carbonate 26h～28h in there-necked flask, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt.
Step 3.1, after step 2 obtains 1-substituting group-3-Methylimidazole methyl carbonate salt, take off the constant pressure funnel on the there-necked flask bottleneck, the Glacial acetic acid taken in step 1 is poured in there-necked flask, then is blocked bottleneck with ground glass stopper;
Step 3.2, by there-necked flask, continue to be positioned on constant-temperature heating magnetic stirring apparatus, under 55 ℃～65 ℃ conditions, 1-substituting group in there-necked flask-3-Methylimidazole methyl carbonate salt reacts 22h～26h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid.
The reactional equation of 1-substituting group in step 3.2-3-Methylimidazole methyl carbonate salt and Glacial acetic acid is:
Step 4 is specifically implemented in accordance with the following methods:
Step 4.1, get two mouthfuls of flask a, the 1-substituting group prepared in step 3-3-Methylimidazole acetate type ionic liquid is poured in two mouthfuls of flask a;
Step 4.2, the bottleneck of two mouthfuls of flask a is connected to condensation tower, the condensation tower upper end is provided with thermometer, condensation tower one side is connected with straight type water cooling tube, the tail end of straight type water cooling tube is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a, single port flask b and two mouthfuls of flask b, another bottleneck of two mouthfuls of flask b is connected with vacuum pump, connects and composes the molecular distillation device;
Step 4.3, nitrogen is passed into from another bottleneck of two mouthfuls of flask a, and the molecular distillation device that utilizes vacuum pump to connect step 4.2 vacuumized processing, keeping the vacuum tightness in the molecular distillation device is 5Pa;
Step 4.4, two mouthfuls of flask a after step 4.3 vacuumizes processing are positioned on constant-temperature heating magnetic stirring apparatus, the temperature of regulating thermostatic heating magnetic stirring apparatus, and utilize the temperature in thermometer Real-Time Monitoring molecular distillation device, start the 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid is carried out to vacuum distilling:
Single port flask a, under 5Pa, 110 ℃～130 ℃ conditions, collects the front-end volatiles of 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid;
Single port flask b, in 5Pa, under 140 ℃～150 ℃ conditions, collects the middle runnings of 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid, in single port flask b, obtains the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid.
Condensation tower in step 4 is thorn type condensation tower.
Beneficial effect of the present invention is:
The preparation method of 1-substituting group of the present invention-3-Methylimidazole acetate type ionic liquid, adopt 1-substituting group imidazoles, methylcarbonate and Glacial acetic acid as raw material, without high temperature and measuring body reactor, simple, the easy control of whole preparation process, environmental protection, efficient, the target product of finally collecting by vacuum distilling, purity is high, follow-up vacuum-drying that need not be conventional.
The accompanying drawing explanation
Fig. 1 is the structural representation of the ion liquid preparation device that adopts in the preparation method of 1-substituting group of the present invention-3-Methylimidazole acetate type ionic liquid;
Fig. 2 is the structural representation of the molecular distillation device that adopts in the preparation method of 1-substituting group of the present invention-3-Methylimidazole acetate type ionic liquid.
In figure, 1. constant-temperature heating magnetic stirring apparatus, 2. constant pressure funnel, 3. prolong, 4. thermometer, 5. there-necked flask, 6. two-mouth bottle a, 7. condensation tower, 8. straight type water cooling tube, 9. single port flask a, 10. single port flask b, 11. two mouthfuls of flask b.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of 1-substituting group of the present invention-3-Methylimidazole acetate type ionic liquid, specifically implement according to following steps:
Take respectively 1-substituting group imidazoles, methylcarbonate and Glacial acetic acid by amount of substance than for 1:1～1.1:1～1.1;
Step 2.1, the 1-substituting group imidazoles taken in step 1 is poured in there-necked flask 5;
Step 2.2, as shown in Figure 1, be connected respectively to constant pressure funnel 2, prolong 3 and thermometer 4 on three bottlenecks of there-necked flask 5 in step 2.1, connects ion liquid preparation device;
Step 2.3, after step 2.2 connects prolong 3, first using tap water as water of condensation, pass in prolong 3, then there-necked flask 5 be positioned on constant-temperature heating magnetic stirring apparatus 1, the temperature to 55 of regulating thermostatic heating magnetic stirring apparatus 1 ℃～65 ℃;
Temperature in step 2.4, use thermometer 4 Real-Time Monitoring there-necked flasks 5, treat that the temperature in there-necked flask 5 are 55 ℃～65 ℃, and the methylcarbonate taken in step 1 is poured in constant pressure funnel 2, and methylcarbonate splashes into there-necked flask 5 in constant pressure funnel 2;
Step 2.5, through step 2.4, methylcarbonate splash into fully there-necked flask 5 interior after, keep the position of constant pressure funnel 2 motionless, treat 1-substituting group imidazoles and dimethyl carbonate 26h～28h in there-necked flask 5, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt;
In the process of 1-substituting group imidazoles and dimethyl carbonate, detect the variation of 1-substituting group imidazoles and methylcarbonate mixed solution specific conductivity by conductivity detector, whether the judgement reaction reaches balance, until conductivity value no longer changes, illustrate that 1-substituting group imidazoles and dimethyl carbonate are complete, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt.
Step 3.1, after step 2 obtains 1-substituting group-3-Methylimidazole methyl carbonate salt, take off the constant pressure funnel 2 on there-necked flask 5 bottlenecks, the Glacial acetic acid taken in step 1 is poured in there-necked flask 5, then is blocked bottleneck with ground glass stopper;
Step 3.2, there-necked flask 5 is continued to be positioned on constant-temperature heating magnetic stirring apparatus 1, under 55 ℃～65 ℃ conditions, 1-substituting group in there-necked flask 5-3-Methylimidazole methyl carbonate salt reacts 22h～26h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid;
Wherein, the reactional equation of 1-substituting group-3-Methylimidazole methyl carbonate salt and Glacial acetic acid is:
Step 4, the 1-substituting group-3-Methylimidazole acetate type ionic liquid that will prepare through step 3 carry out purifying with the molecular distillation device, obtain 1-substituting group after purifying-3-Methylimidazole acetate type ionic liquid:
The 1-substituting group of preparing through step 3-3-Methylimidazole acetate type ionic liquid also needs to carry out purifying, to improve the purity of 1-substituting group-3-Methylimidazole acetate type ionic liquid.
Step 4.1, as shown in Figure 2, get two mouthfuls of flask a6, and the 1-substituting group prepared in step 3-3-Methylimidazole acetate type ionic liquid is poured in two mouthfuls of flask a6;
Step 4.2, the bottleneck of two mouthfuls of flask a6 is connected to condensation tower 7, condensation tower 7 upper ends are provided with thermometer 4, condensation tower 7 one sides are connected with straight type water cooling tube 8, the tail end of straight type water cooling tube 8 is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a9, single port flask b10 and two mouthfuls of flask b11, another bottleneck of two mouthfuls of flask b11 is connected with vacuum pump, connects and composes the molecular distillation device;
Wherein condensation tower 7 is thorn type condensation tower;
Step 4.3, nitrogen is passed into from another bottleneck of two mouthfuls of flask a6, and the molecular distillation device that utilizes vacuum pump to connect step 4.2 vacuumized processing, keeping the vacuum tightness in the molecular distillation device is 5Pa;
Step 4.4, two mouthfuls of flask a6 after step 4.3 vacuumizes processing are positioned on constant-temperature heating magnetic stirring apparatus 1, the temperature of regulating thermostatic heating magnetic stirring apparatus 1, and utilize the temperature in thermometer 4 Real-Time Monitoring molecular distillation devices, start the 1-substituting group in two mouthfuls of flask a6-3-Methylimidazole acetate type ionic liquid is carried out to vacuum distilling:
Single port flask a9, under 5Pa, 110 ℃～130 ℃ conditions, collects the front-end volatiles of 1-substituting group in two mouthfuls of flask a6-3-Methylimidazole acetate type ionic liquid;
Single port flask b10 is in 5Pa, under 140 ℃～150 ℃ conditions, collect the middle runnings of 1-substituting group in two mouthfuls of flask a6-3-Methylimidazole acetate type ionic liquid, in single port flask b10, obtain the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid;
Two mouthfuls of flask b11 are arranged between straight type water cooling tube 8 and vacuum pump, for adsorbed gas or trapping oil vapour, the function of serving as cold-trap and snubber.
Take respectively 1-substituting group imidazoles 0.2mol(19.220g), methylcarbonate 0.2mol(18.014g) and Glacial acetic acid 0.22mol(13.211g);
The 1-substituting group imidazoles taken is poured in there-necked flask, constant pressure funnel, prolong and thermometer are connected respectively on three bottlenecks of there-necked flask, first tap water is passed into to prolong as water of condensation, again there-necked flask is positioned on constant-temperature heating magnetic stirring apparatus to the temperature to 55 ℃ of regulating thermostatic heating magnetic stirring apparatus; By the temperature in thermometer Real-Time Monitoring there-necked flask, when the temperature in there-necked flask is 55 ℃, the methylcarbonate taken to be poured into during constant pressure funnel drips, methylcarbonate splashes in there-necked flask from constant pressure funnel; After methylcarbonate splashes into there-necked flask fully, keep the position of constant pressure funnel motionless, 1-substituting group imidazoles and dimethyl carbonate 26h in there-necked flask, detect the balance of the variation judgement reaction of specific conductivity in reaction process by conductivity detector, until specific conductivity does not change, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt;
After obtaining 1-substituting group-3-Methylimidazole methyl carbonate salt, take off constant pressure funnel, the Glacial acetic acid taken is poured in there-necked flask, with ground glass stopper, block bottleneck; Under 55 ℃ of conditions, the 1-substituting group in there-necked flask-3-Methylimidazole methyl carbonate salt reacts 22h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid;
First the 1-substituting group that makes-3-Methylimidazole acetate type ionic liquid is poured in two mouthfuls of flask a;
Nitrogen is passed into from the bottleneck of two mouthfuls of flask a, another bottleneck connects condensation tower, the condensation tower upper end is connected to thermometer, condensation tower one side is connected with straight type water cooling tube, the tail end of straight type water cooling tube is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a, single port flask b and two mouthfuls of flask b, and another bottleneck of two mouthfuls of flask b is connected with vacuum pump, connects and composes the molecular distillation device; Utilize vacuum pump to be vacuumized processing to the molecular distillation device, keeping the vacuum tightness in the molecular distillation device is 5Pa; Two mouthfuls of flask a that vacuumize after processing are arranged on constant-temperature heating magnetic stirring apparatus, 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid is carried out to vacuum distilling, single port flask a collects the front-end volatiles of 1-substituting group-3-Methylimidazole acetate under 5Pa, 110 ℃ of conditions, single port flask b is in 5Pa, under 140 ℃ of conditions, collect middle runnings, obtain the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid.
The 1-substituting group obtained after purified-3-Methylimidazole acetate type ionic liquid is colourless liquid, and the 1HNMR data presentation is 1,3-methylimidazole acetate, and quality is 28.6g, and the transformation efficiency of 1-Methylimidazole is 91.1%.
Corresponding reaction equation is as follows:
Tetramethylsilane for nuclear magnetic resonance experiment (TMS) is standard substance, and deuterochloroform is solvent.Experiment nuclear magnetic data: 1HNMR(CDCl3, TMS): δ=7.51(imidazole ring, H2), δ=7.04(imidazole ring, H4), δ=6.86(imidazole ring, H5), δ=3.68(2 NCH
3), δ=2.03(CH
3COO
-).
Take respectively 1-substituting group imidazoles 0.2mol(19.220g), methylcarbonate 0.22mol(19.8154g) and Glacial acetic acid 0.22mol(13.211g);
The 1-substituting group imidazoles taken is poured in there-necked flask, constant pressure funnel, prolong and thermometer are connected respectively on three bottlenecks of there-necked flask, first tap water is passed into to prolong as water of condensation, again there-necked flask is positioned on constant-temperature heating magnetic stirring apparatus, regulates the temperature to 60 ℃ of magnetic stirring apparatus; By the temperature in thermometer Real-Time Monitoring there-necked flask, when the temperature in there-necked flask is 60 ℃, the methylcarbonate taken to be poured into during constant pressure funnel drips, methylcarbonate splashes in there-necked flask from constant pressure funnel; After methylcarbonate splashes into there-necked flask fully, keep the constant pressure funnel position motionless, 1-substituting group imidazoles and dimethyl carbonate 27h in there-necked flask, detect the balance of the variation judgement reaction of specific conductivity in reaction process by conductivity detector, until specific conductivity does not change, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt;
After obtaining 1-substituting group-3-Methylimidazole methyl carbonate salt, take off constant pressure funnel, the Glacial acetic acid taken is poured in there-necked flask, with ground glass stopper, block bottleneck; Under 60 ℃ of conditions, the 1-substituting group in there-necked flask-3-Methylimidazole methyl carbonate salt reacts 24h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid;
First the 1-substituting group that makes-3-Methylimidazole acetate type ionic liquid is poured in two mouthfuls of flask a;
Nitrogen is passed into from the bottleneck of two mouthfuls of flask a, another bottleneck connects condensation tower, the condensation tower upper end is connected to thermometer, condensation tower one side is connected with straight type water cooling tube, the tail end of straight type water cooling tube is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a, single port flask b and two mouthfuls of flask b, and another bottleneck of two mouthfuls of flask b is connected with vacuum pump, connects and composes the molecular distillation device; Utilize vacuum pump to be vacuumized processing to the molecular distillation device, keeping the vacuum tightness in the molecular distillation device is 5Pa; Two mouthfuls of flask a that vacuumize after processing are arranged on constant-temperature heating magnetic stirring apparatus, 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate is carried out to vacuum distilling, single port flask a collects the front-end volatiles of 1-substituting group-3-Methylimidazole acetate type ionic liquid in two mouthfuls of flask a under 5Pa, 120 ℃ of conditions, single port flask b is in 5Pa, under 145 ℃ of conditions, collect 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid middle runnings, obtain the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid.
The 1-substituting group obtained-3-Methylimidazole acetate type ionic liquid is colourless liquid, and the 1HNMR data presentation is 1-ethyl-3-methylimidazole acetate, and quality is 31.5g, and the transformation efficiency of 1-ethyl imidazol(e) is 87.1%.
Corresponding reaction equation is as follows:
Tetramethylsilane for nuclear magnetic resonance experiment (TMS) is standard substance, and deuterochloroform is solvent.Experiment nuclear magnetic data: 1HNMR(CDCl3, TMS): δ=7.47(imidazole ring, H2), δ=7.25(imidazole ring, NCH
2), δ=6.99(imidazole ring, H4), δ=6.87(imidazole ring, H5), δ=3.96(NCH
3), δ=2.03(CH
3COO
-), δ=1.41(NCH
2CH
3).
Take respectively 1-substituting group imidazoles 0.2mol(19.220g), methylcarbonate 0.22mol(19.8154g) and Glacial acetic acid 0.2mol(12.01g);
The 1-substituting group imidazoles taken is poured in there-necked flask, constant pressure funnel, prolong and thermometer are connected respectively on three bottlenecks of there-necked flask, first tap water is passed into to prolong as water of condensation, again there-necked flask is positioned on constant-temperature heating magnetic stirring apparatus to the temperature to 65 ℃ of regulating thermostatic heating magnetic stirring apparatus; By the temperature in thermometer Real-Time Monitoring there-necked flask, treat that the temperature in there-necked flask is 65 ℃, the methylcarbonate taken to be poured into during constant pressure funnel drips, methylcarbonate splashes in there-necked flask from constant pressure funnel; After methylcarbonate splashes into there-necked flask fully, keep the constant pressure funnel position motionless, 1-substituting group imidazoles and dimethyl carbonate 28h in there-necked flask, detect the balance of the variation judgement reaction of specific conductivity in reaction process by conductivity detector, until specific conductivity does not change, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt;
After obtaining 1-substituting group-3-Methylimidazole methyl carbonate salt, take off constant pressure funnel, the Glacial acetic acid taken is poured in there-necked flask, with ground glass stopper, block bottleneck; Under 65 ℃ of conditions, the 1-substituting group in there-necked flask-3-Methylimidazole methyl carbonate salt reacts 26h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid;
First the 1-substituting group that makes-3-Methylimidazole acetate type ionic liquid is poured in two mouthfuls of flask a;
Nitrogen is passed into from the bottleneck of two mouthfuls of flask a, another bottleneck connects condensation tower, the condensation tower upper end is connected to thermometer, condensation tower one side is connected with straight type water cooling tube, the tail end of straight type water cooling tube is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a, single port flask b and two mouthfuls of flask b, and another bottleneck of two mouthfuls of flask b is connected with vacuum pump, connects and composes the molecular distillation device; Utilize vacuum pump to be vacuumized processing to the molecular distillation device, keeping the vacuum tightness in the molecular distillation device is 5Pa; Two mouthfuls of flask a that vacuumize after processing are arranged on constant-temperature heating magnetic stirring apparatus, 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate is carried out to vacuum distilling, single port flask a collects the front-end volatiles of 1-substituting group-3-Methylimidazole acetate type ionic liquid in two mouthfuls of flask a under 5Pa, 130 ℃ of conditions, single port flask b11 is in 5Pa, under 150 ℃ of conditions, collect the middle runnings of 1-substituting group in two mouthfuls of flask a-3-Methylimidazole acetate type ionic liquid, obtain the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid.
The 1-substituting group obtained-3-Methylimidazole acetate type ionic liquid is colourless liquid, and the 1HNMR data presentation is 1-butyl-3-Methylimidazole acetate, and quality is 36.3g, and the transformation efficiency of 1-butyl imidazole is 91.5%.
Corresponding reaction equation is as follows:
Tetramethylsilane for nuclear magnetic resonance experiment (TMS) is standard substance, and deuterochloroform is solvent.Experiment nuclear-magnetism: 1HNMR(CDCl3, TMS): δ=7.47(imidazole ring, H2), δ=7.27(imidazole ring, NCH
2), δ=7.01(imidazole ring, H4), δ=6.85(imidazole ring, H5), δ=3.88(NCH
3), δ=2.02(CH
3COO
-), δ=1.70(NCH
2CH
2), δ=1.26(NCH
2CH
2CH
2), δ=0.88(N CH
2CH
2CH
2CH
3).
Claims (7)
1.1-the preparation method of substituting group-3-Methylimidazole acetate type ionic liquid, is characterized in that, specifically implements according to following steps:
Step 1, take 1-substituting group imidazoles, methylcarbonate and Glacial acetic acid respectively;
Step 2, the 1-substituting group imidazoles and the methylcarbonate that take in step 1 are added in ion liquid preparation device, through reaction, obtain 1-substituting group-3-Methylimidazole methyl carbonate salt;
Step 3, the Glacial acetic acid taken in step 1 is added in there-necked flask (5), Glacial acetic acid and the 1-substituting group obtained through step 2-3-Methylimidazole methyl carbonate reactant salt, obtain 1-substituting group-3-Methylimidazole acetate type ionic liquid;
Step 4, the 1-substituting group-3-Methylimidazole acetate type ionic liquid that will prepare through step 3 carry out purifying with the molecular distillation device, obtain 1-substituting group after purifying-3-Methylimidazole acetate type ionic liquid.
2. the preparation method of 1-substituting group according to claim 1-3-Methylimidazole acetate type ionic liquid, is characterized in that, described step 1 is specifically implemented in accordance with the following methods:
By amount of substance than for 1:1～1.1:1～1.1, taking respectively 1-substituting group imidazoles, methylcarbonate and Glacial acetic acid.
3. the preparation method of 1-substituting group according to claim 1-3-Methylimidazole acetate type ionic liquid, is characterized in that, described step 2 is specifically implemented in accordance with the following methods:
Step 2.1, the 1-substituting group imidazoles taken in step 1 is poured in there-necked flask (5);
Step 2.2, constant pressure funnel (2), prolong (3) and thermometer (4) are connected respectively on three bottlenecks of there-necked flask (5), connect ion liquid preparation device;
Step 2.3, after step 2.2 connects prolong (3), first using tap water as water of condensation, pass in prolong (3), again there-necked flask (5) is positioned over to constant-temperature heating magnetic stirring apparatus (1) upper, the temperature to 55 of regulating thermostatic heating magnetic stirring apparatus (1) ℃～65 ℃;
Temperature in step 2.4, use thermometer (4) Real-Time Monitoring there-necked flask (5), treat that the temperature in there-necked flask (5) is 55 ℃～65 ℃, the methylcarbonate taken in step 1 is poured in constant pressure funnel (2), and methylcarbonate splashes into there-necked flask (5) in constant pressure funnel (2);
Step 2.5, through step 2.4, after methylcarbonate splashes in there-necked flask (5) fully, motionless the treating in position that keeps constant pressure funnel (2), 1-substituting group imidazoles and dimethyl carbonate 26h～28h in there-necked flask (5), obtain 1-substituting group-3-Methylimidazole methyl carbonate salt.
4. the preparation method of 1-substituting group according to claim 1-3-Methylimidazole acetate type ionic liquid, is characterized in that, described step 3 is specifically implemented in accordance with the following methods:
Step 3.1, after step 2 obtains 1-substituting group-3-Methylimidazole methyl carbonate salt, take off the constant pressure funnel (2) on there-necked flask (5) bottleneck, the Glacial acetic acid taken in step 1 is poured in there-necked flask (5), then is blocked bottleneck with ground glass stopper;
Step 3.2, there-necked flask (5) is continued to be positioned on constant-temperature heating magnetic stirring apparatus (1), under 55 ℃～65 ℃ conditions, 1-substituting group in there-necked flask (5)-3-Methylimidazole methyl carbonate salt reacts 22h～26h with Glacial acetic acid, obtains 1-substituting group-3-Methylimidazole acetate type ionic liquid.
5. the preparation method of 1-substituting group according to claim 4-3-Methylimidazole acetate type ionic liquid, is characterized in that, the reactional equation of 1-substituting group in described step 3.2-3-Methylimidazole methyl carbonate salt and Glacial acetic acid is:
6. the preparation method of 1-substituting group according to claim 1-3-Methylimidazole acetate type ionic liquid, is characterized in that, described step 4 is specifically implemented in accordance with the following methods:
Step 4.1, get two mouthfuls of flask a(6), pour the 1-substituting group prepared in step 3-3-Methylimidazole acetate type ionic liquid into two mouthfuls of flask a(6) in;
Step 4.2, by two mouthfuls of flask a(6) a bottleneck connect condensation tower (7), condensation tower (7) upper end is provided with thermometer (4), condensation tower (7) one sides are connected with straight type water cooling tube (8), the tail end of straight type water cooling tube (8) is provided with rotatable three interfaces, three interfaces are connected with respectively single port flask a(9), single port flask b(10) and two mouthfuls of flask b(11), two mouthfuls of flask b(11) another bottleneck is connected with vacuum pump, connects and composes the molecular distillation device;
Step 4.3, by nitrogen from two mouthfuls of flask a(6) another bottleneck pass into, and the molecular distillation device that utilizes vacuum pump to connect step 4.2 vacuumized processing, keeping the vacuum tightness in the molecular distillation device is 5Pa;
Step 4.4, by two mouthfuls of flask a(6 after step 4.3 vacuumizes processing) be positioned on constant-temperature heating magnetic stirring apparatus (1), the temperature of regulating thermostatic heating magnetic stirring apparatus (1), and utilize the temperature in thermometer (4) Real-Time Monitoring molecular distillation device, start two mouthfuls of flask a(6) in 1-substituting group-3-Methylimidazole acetate type ionic liquid carry out vacuum distilling:
Single port flask a(9) under 5Pa, 110 ℃～130 ℃ conditions, collect two mouthfuls of flask a(6) in the front-end volatiles of 1-substituting group-3-Methylimidazole acetate type ionic liquid;
Single port flask b(10) in 5Pa, under 140 ℃～150 ℃ conditions, collect two mouthfuls of flask a(6) in the middle runnings of 1-substituting group-3-Methylimidazole acetate type ionic liquid, i.e. single port flask b(10) in obtain the 1-substituting group of purifying-3-Methylimidazole acetate type ionic liquid.
7. the preparation method of 1-substituting group according to claim 6-3-Methylimidazole acetate type ionic liquid, is characterized in that, the condensation tower in described step 4 (7) is thorn type condensation tower.
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