CN101633641B - Preparation method of imidazole type ionic liquid - Google Patents
Preparation method of imidazole type ionic liquid Download PDFInfo
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- CN101633641B CN101633641B CN200910041805XA CN200910041805A CN101633641B CN 101633641 B CN101633641 B CN 101633641B CN 200910041805X A CN200910041805X A CN 200910041805XA CN 200910041805 A CN200910041805 A CN 200910041805A CN 101633641 B CN101633641 B CN 101633641B
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Abstract
The present invention discloses a preparation method of imidazole type ionic liquid. The imidazole type ionic liquid has the following structural formula: Q<+>X<->, wherein Q<+> refers to an imidazole type onium cation, and X<-> refers to an anion. The preparation method comprises the following steps: a. carrying out reaction on imidazole or substituent imidazole to produce corresponding salt containing the imidazole onium cation and a carbonic ester anion; b. carrying out anion exchange on the imidazole type ionic liquid containing the carbonic ester anion, and inorganic or organic acid to produce the imidazole type ionic liquid containing the X<-> anion. The halogen-free high-purity ionic liquid can be conveniently obtained by using low-cost carbonic ester to salinize various tertiary amines and quaternary ammoniums and then carrying out ion exchange with a target anion.
Description
Technical field
The present invention relates to a kind of preparation method of imidazole type ion liquid.
Background technology
In recent years, ionic liquid at room temperature is subjected to the extensive concern of academia and industry member as a kind of " green solvent " and reaction medium.As the new green solvent of a class, ionic liquid at room temperature has the not available following characteristics of many conventional solvent: (1) low melting point and broad liquid scope.Alkyl imidazole ionic liquid particularly, its liquid scope even can reach more than 450 ℃.(2) inorganics and organism had good dissolving ability.The room-temperature ion liquid physical efficiency is dissolved many inorganicss, organism (comprising organometallic compound and macromolecular material), and has bigger solubleness.(3) " zero " vapour pressure can be used for high vacuum system and pollution-free, and this also is the important evidence that ionic liquid is considered to green.(4) high conductivity and wide electrochemical window (can be higher than 5V) can be used for the electrolytic solution of many materials, realize the electrolysis under the room temperature condition.(5) good thermal conductivity, high heat capacity and thermal energy storage density (, high 6.4 times) than the thermal energy storage density 9MJ/m of the heat accumulation oil that uses now.(6) good thermostability and oxidation-resistance.(7) designability.The ionic liquid that can have property by reasonably combined zwitterion design according to the needs of differential responses.The not available peculiar property of these other traditional sucroses makes ionic liquid become and has " solid " liquid of liquid and solid dual-use function and characteristic concurrently, thereby demonstrated great potential and application prospect in the greenization process of current chemical.
Although ionic liquid is used widely in the Green Chemistry process as novel dissolvent and catalyzer, but a lot of ionic liquids contain the halogen ion, these not exclusively are the ion liquid application of Halogen ionic and the research of " green ", bring detrimentally affect for the ionic liquid quality, preparing not, Halogen ionic high-purity ion liquid has great importance and actual application value.Glyoxaline ion liquid in the past is mainly by taking synthesizing cationic salt with alkyl halide to imidazoles or substituted imidazole quaternized, carries out anionic exchange by this Halogen ion as the cationic salts of counter ion and anionic acid again and comes synthetic.There is the problem of halogen ion residues in synthetic ionic liquid by this method.In order to remove the halogen ion, often use acid to form hydrogen halide so that its evaporable method, but this method can produce corrosive obnoxious flavour.In addition, use anionic an alkali metal salt to make the halogen ion form an alkali metal salt, also be widely used through the method that washing is removed again, but this method still is difficult to remove fully the halogen ion.Also have the patent introduction to adopt methyl-sulfate to prepare ionic liquid, but this method is used the methyl-sulfate of severe toxicity, causes environmental pollution easily as the methylating reagent of imidazoles.The synthetic method of research and development environmental protection and not halogen-containing ionic imidazole type ion liquid is extremely important.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of imidazole type ion liquid.
A kind of preparation method of imidazole type ion liquid, described imidazole type ion liquid has following general structure: Q
+X
-
Q wherein
+For having the imidazole type positively charged ion of following general formula
Wherein R1～R5 is identical or different, is selected from: be selected from: H, halogen or carbonatoms are 1～8 alkyl;
X
-Be negatively charged ion, be PF
6 -, BF
4 -, AsF
6 -, SbF
6 -, N (RfSO
3)
3 -, C (RfSO
3)
3 -, F
-, Cl
-, Br
-, I
-, ClO
4 -, AlF
4 -Or Si F
6 2-, Rf is the fluoro-alkyl of carbonatoms 1～6;
The preparation method comprises the steps:
A, imidazoles or substituted imidazole and carbonate reaction generate and contain glyoxaline cation and the anionic salt of carbonic ether accordingly;
B, the anionic imidazole type ion liquid of carbonate-containing and inorganic or organic acid carry out anionresin and generate and contain X
-Anionic imidazole type ion liquid.
Further, described carbonic ether is the chain dialkyl carbonate of carbonatoms 3～8.Further, described chain dialkyl carbonate is methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, carbonic acid di-n-propyl ester, carbonic acid diisopropyl ester or n-butyl carbonate.
Further, among the step a, in imidazoles or substituted imidazole and the carbonate reaction, add consisting of phase-transferring agent, under the effect of consisting of phase-transferring agent, the productive rate of above-mentioned imidazole type ion liquid significantly improves.Further, described consisting of phase-transferring agent is palmityl trimethyl ammonium chloride, Tetrabutyl amonium bromide or a polyoxyethylene glycol-400.
Adopt alkyl halide to prepare ion liquid method, be difficult to remove fully the halogen ion as quaternizing agent.Halogen high-purity ion liquid of the present invention can carry out ion-exchange with the target negatively charged ion and obtain easily by using inexpensive carbonic ether with various tertiary amine quaternary ammonium saltizations again.
With imidazoles or substituted imidazole and carbonic ether mixing, add suitable consisting of phase-transferring agent simultaneously, keep 80～180 ℃ of temperature of reaction, reaction times is 6～72 hours, add the equimolar functional group acid accordingly that contains then, keeping temperature of reaction is 30～100 ℃, and the reaction times is 1 hour to tens hours, underpressure distillation removes and desolvates, and just obtains the imidazole ion liquid that purity can satisfy general application requiring.
Prepare above-mentioned imidazole type ion liquid and can take to add continuously after the above-mentioned esterification acid and directly obtain ion liquid method, also can adopt the sectional two-step reaction to obtain.Promptly on the ion liquid basis of carbonates of preparation, can make the ionic liquid of other types by the reaction of second step.The preparation method of ionic liquid that for example contains tetrafluoroborate, acetate is as follows: under the room temperature, with equimolar carbonates ionic liquid and Tetrafluoroboric acid or acetic acid reaction, mechanical stirring is through ageing, after the filtration treatment, promptly obtain containing required anion ion liquid.
Generate at imidazoles or substituted imidazole and carbonate reaction and to contain accordingly in the reaction of glyoxaline cation and carbonate group anion salt, in order to add the speed of fast response, can select suitable protic polar solvent such as methyl alcohol, ethanol, the alcohols of carbonatomss 1～3 such as 1-propyl alcohol and 2-propyl alcohol or tetrahydrofuran (THF) are as reaction solvent, also can not add any solvent, directly imidazoles or substituted imidazole and carbonic ether be reacted under pressurized conditions.
Once had document to mention as alkylating reagent tertiary amine to be carried out quaterisation to prepare ionic liquid, but there is the too much shortcoming of byproduct of reaction in the method that in the past adopted with dialkyl carbonate.The present invention finds to adopt suitable consisting of phase-transferring agent can effectively reduce content of by-products, significantly increases the productive rate that needs the synthetic imidazole type ion liquid, provides a valid approach for preparing highly purified imidazole type ion liquid.
Consisting of phase-transferring agent used in the present invention mainly comprises various quaternary ammonium salt, quaternary alkylphosphonium salts, polyethers, crown ether etc.Quaternary ammonium salt phase transfer catalyst commonly used is benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate (TBAB), palmityl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride etc.Polyethers polyethylene glycols commonly used used in the present invention mainly contains PEG-400, PEG-600, PEG monoether, PEG bis ether and PEG monoether or monoesters etc.Crown ether-like comprises 18 hats, 6,15 hats 5, cyclodextrin etc.
The glyoxaline ion liquid of the present invention preparation all pass through infrared spectra (IR), proton nmr spectra (
1H-NMR), structural characterization and affirmation are carried out in mass spectrum (MS) and ultimate analysis.The solid fusing point is measured roughly with micro-fusing point instrument, and the fusing point of solid and liquid is accurately measured with differential scanning calorimeter DSC, and ion liquid density adopts the method for changing of observing volume under the weighing differing temps to measure.Also adopt high performance liquid chromatography (HPLC) that product is formed and carry out quantitative analysis.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment below, but should not be so limited.
Embodiment 1
Methylcarbonate, 100.5 gram tetrahydrofuran (THF)s (solvent), the 0.2 gram Tetrabutyl amonium bromide (consisting of phase-transferring agent) of 40.1 gram N-ethyl imidazol(e)s, 75.2 grams are added uniform dissolution in the reactor.Thereafter be warming up to 100 ℃, back flow reaction is 12 hours under stirring.Excess carbon dimethyl phthalate and tetrahydrofuran solvent are removed in distillation, can obtain 50.5 gram 1-ethyl-3-Methylimidazole methyl carbonic salt, productive rate 98.3%.Under 25 ℃ of stirrings, slowly in 1-ethyl-3-Methylimidazole methyl carbonic salt that 60.1 grams, 42% the fluoborate aqueous solution that drips obtains to aforesaid method, through ageing 3 hours, after the filtration treatment, promptly obtain lurid liquid, Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 89.5%.
The reaction product warp
1H-NMR, mass spectrum (MS) are confirmed EMIBF
4 1The H-NMR data are as follows:
1H-NMR(D
2O)，δ：ppm，9.41(s，1H)，8.24(t，1H)，8.17(t，1H)，4.95(m，2H)，4.64(s，3H)，2.23(t，3H)
Embodiment 2
With 100.2 gram N-ethyl imidazol(e)s, 200.5 gram methylcarbonates and 300.1 gram tetrahydrofuran (THF)s, join in the reactor, add 0.5 gram palmityl trimethyl ammonium chloride then, uniform dissolution.Be warming up to 100 ℃, stir reaction down 24 hours.After being cooled to room temperature, stir the fluoborate aqueous solution of 100.2 grams 42% that drip slowly down.Through ageing 3 hours, obtain lurid liquid after the filtration treatment, Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 91.5%.The reaction product warp
1H-NMR, mass spectrum (MS) are confirmed.
Embodiment 3
With 100.2 gram N-propyl imidazoles, 200.5 gram methylcarbonates and 300.1 gram tetrahydrofuran (THF)s, 0.2 gram Tetrabutyl amonium bromide joins uniform dissolution in the reactor.Be warming up to 150 ℃, stir reaction down 24 hours.After being cooled to room temperature, stir the fluoborate aqueous solution of 85.2 grams 42% that drip slowly down.Through ageing 3 hours, obtain 125.2 gram light yellow liquids after the filtration treatment.This liquid warp
1H-NMR, and mass spectroscopy confirms that the product that obtains is: Tetrafluoroboric acid 1-propyl group-3-Methylimidazole (PMIBF
4), productive rate is 93.2%.
PMIBF
4 1The H-NMR data are as follows:
1H-NMR(D
2O)，δ：ppm，8.54(s，1H)，7.33(t，1H)，7.29(t，1H)，4.02(m，2H)，3.75(s，3H)，1.75(m，2H)，0.77(t，3H)
Embodiment 4
With 100.2 gram N-butyl imidazole, 200.5 gram methylcarbonates and 300.1 gram tetrahydrofuran (THF)s, 0.4 gram Tetrabutyl amonium bromide joins uniform dissolution in the reactor.Be warming up to 150 ℃, stir reaction down 24 hours.After being cooled to room temperature, stir the fluoborate aqueous solution of 90.2 grams 42% that drip slowly down.Through ageing 3 hours, obtain 122.3 gram light yellow liquids after the filtration treatment.This liquid warp
1H-NMR, and mass spectroscopy confirms that the product that obtains is: Tetrafluoroboric acid 1-butyl-3-Methylimidazole (BMIBF
4), productive rate is 90.2%.
BMIBF
4 1The H-NMR data are as follows:
1H-NMR(D
2O)，δ：ppm，8.53(s，1H)，7.31(t，1H)，7.27(t，1H)，4.04(m，2H)，3.73(s，3H)，1.70(m，2H)，1.16(m，2H)，0.76(t，3H)
Embodiment 5
With 100.2 gram 1-butyl-glyoxal ethylines, 200.5 gram methylcarbonates and 300.1 gram tetrahydrofuran (THF)s, 0.4 gram Tetrabutyl amonium bromide joins uniform dissolution in the reactor.Be warming up to 150 ℃, stir reaction down 24 hours.After being cooled to room temperature, stir the fluoborate aqueous solution of 90.2 grams 40% that drip slowly down.Through ageing 3 hours, obtain 122.3 gram tawny liquid after the filtration treatment.This liquid warp
1H-NMR, and mass spectroscopy confirms that the product that obtains is: Tetrafluoroboric acid 1-butyl-2,3-methylimidazole (B2MIBF
4), productive rate is 90.2%.
B2MIBF
4 1The H-NMR data are as follows:
1H-NMR(D
2O)，δ：ppm，9.15(s，1H，CH)；7.19(s，1H，CH)；7.18(s，1H，CH)；4.14(t，2H，CH
2)；4.11(s，3H，CH
3)；1.19(m，2H，CH
2)；1.14(m，2H，CH
2)；0.19(t，3H，CH
3)。
Embodiment 6
With 100.2 gram 1-butyl-glyoxal ethylines, 200.5 gram methylcarbonates and 300.1 gram tetrahydrofuran (THF)s, 0.4 gram Tetrabutyl amonium bromide joins uniform dissolution in the reactor.Be warming up to 150 ℃, stir reaction down 24 hours.After being cooled to room temperature, stir the phosphofluoric acid aqueous solution of 100.2 grams 30% that drip slowly down.Through ageing 3 hours, obtain 120.2 gram tawny liquid after the filtration treatment.This liquid warp
1H-NMR, and mass spectroscopy confirms that the product that obtains is: phosphofluoric acid 1-butyl-2,3-methylimidazole (B2MIPF
6), productive rate is 88.1%.
B2MIPF
6 1The H-NMR data are as follows:
1H-NMR(D
2O)，δ：ppm，8.20(s，1H，CH)；7.18(s，1H，CH)；7.17(s，1H，CH)；4.13(t，2H，CH
2)；4.10(s，3H，CH
3)；1.19(m，2H，CH
2)；1.14(m，2H，CH
2)；0.19(t，3H，CH
3)。
Embodiment 7
With 100.2 gram N monomethyl imidazoles, 150.1 gram diethyl carbonates and 200.2 gram ethanol (solvent), 0.5 gram palmityl trimethyl ammonium chloride joins uniform dissolution in the reactor.Be warming up to 150 ℃, stir reaction down 48 hours.After being cooled to room temperature, stir the fluoborate aqueous solution of 100.1 grams 42% that drip slowly down.Through ageing 3 hours, obtain the lurid liquid of 111 grams after the filtration treatment,, this liquid warp
1H-NMR and mass spectroscopy confirm that the product that obtains is Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 84.5%.
Embodiment 8
Under 25 ℃ of stirrings, slowly drip 50.2 grams, 70% high chloro acid solution in 50.5 gram 1-ethyl-3-Methylimidazole methyl carbonic salt of embodiment 1 gained, through ageing 3 hours, after the filtration treatment, promptly obtain perchloric acid 1-ethyl-3-Methylimidazole, productive rate is 86.3%.
Embodiment 9
Under 25 ℃ of stirrings, slowly drip 70.2 grams, 50% aqueous acetic acid in 50.5 gram 1-ethyl-3-Methylimidazole methyl carbonic salt of experimental example 1 gained, through ageing 3 hours, after the filtration treatment, promptly obtain acetic acid 1-ethyl-3-Methylimidazole, productive rate is 84.3%.
Embodiment 10
Diethyl carbonate, 200.1 gram ethanol and 5 gram potassium hydroxide with 40.3 gram N monomethyl imidazoles, 75.5 grams add in the reactor, add 0.5 gram polyoxyethylene glycol-400 (PEG-400) (consisting of phase-transferring agent) uniform dissolution then.Be warming up to 120 ℃, stir reaction down 24 hours thereafter.Excess carbon diethyl phthalate and alcohol solvent are removed in distillation, can obtain 48.2 gram 1-ethyl-3-Methylimidazole methyl carbonic salt, the reaction product warp (
1H-NMR), mass spectrum (MS) is confirmed.
Under 25 ℃ of stirrings, slowly drip 50.1 grams, 42% fluoborate aqueous solution in 48.2 gram 1-methyl 3-ethyl imidazol(e) methyl carbonic salt of above-mentioned experiment gained, through ageing 3 hours, after the filtration treatment, promptly obtain Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 92.6%.
Comparative example
Comparative example 1
Except not adding consisting of phase-transferring agent 0.2 gram Tetrabutyl amonium bromide, other experiment condition is identical with embodiment 1, obtains 32.5 gram Tetrafluoroboric acid 1-ethyl-3-Methylimidazole and 22.8 other by products of gram, Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4) productive rate be 58.2%.
Comparative example 2
Except not adding consisting of phase-transferring agent 0.5 gram palmityl trimethyl ammonium chloride, other experiment condition is identical with embodiment 2, and reaction obtains Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF after finishing
4), productive rate only is 60.1%, other product is various by products.
Comparative example 3
Except not adding 0.4 gram Tetrabutyl amonium bromide, other experiment condition is identical with embodiment 3, and the product after reaction finishes is Tetrafluoroboric acid 1-propyl group-3-Methylimidazole (PMIBF
4), productive rate is 50.7%, all the other are by product.
Comparative example 4
Except not adding 0.4 gram Tetrabutyl amonium bromide, other experiment condition is identical with embodiment 4, and the product after reaction finishes is Tetrafluoroboric acid 1-butyl-3-Methylimidazole (BMIBF
4) productive rate is 48.3%, all the other are by product.
Comparative example 5
Except not adding 0.5 gram palmityl trimethyl ammonium chloride, other experiment condition is identical with embodiment 7, and the product after reaction finishes is Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 51.2%, all the other are by product.
Comparative example 6
Except not adding 0.5 gram PEG-400, other experiment condition is identical with embodiment 10, and the product after reaction finishes is Tetrafluoroboric acid 1-ethyl-3-Methylimidazole (EMIBF
4), productive rate is 68.6%, all the other are by product.
Claims (3)
1. the preparation method of an imidazole type ion liquid, described imidazole type ion liquid has following general structure: Q
+X
-Q wherein
+For having the imidazole type positively charged ion of following general formula
Wherein R1～R5 is identical or different, is selected from: H, halogen or carbonatoms are 1～8 alkyl;
X
-Be negatively charged ion, be PF
6 -, BF
4 -, AsF
6 -, SbF
6 -, C (RfSO
3)
3 -, F
-, Cl
-, Br
-, I
-, ClO
4 -Or AlF
4 -, Rf is the fluoro-alkyl of carbonatoms 1～6;
The preparation method comprises the steps:
A, imidazoles or substituted imidazole and carbonate reaction generate and contain glyoxaline cation and the anionic salt of carbonic ether accordingly;
B, the anionic imidazole type ion liquid of carbonate-containing and inorganic or organic acid carry out anionresin and generate and contain X
-Anionic imidazole type ion liquid;
Among the step a, in imidazoles or substituted imidazole and the carbonate reaction, add consisting of phase-transferring agent, described consisting of phase-transferring agent is palmityl trimethyl ammonium chloride, Tetrabutyl amonium bromide or a polyoxyethylene glycol-400.
2. preparation method according to claim 1 is characterized in that: described carbonic ether is the chain dialkyl carbonate of carbonatoms 3～8.
3. preparation method according to claim 2 is characterized in that: described chain dialkyl carbonate is methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, carbonic acid di-n-propyl ester or carbonic acid diisopropyl ester.
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| CN102863339B (en) * | 2012-09-18 | 2015-10-14 | 常州大学 | A kind of method of methylcarbonate and diethyl carbonate transesterify Catalysts of Preparing Methyl Ethyl Carbonate |
| CN103420915B (en) * | 2013-08-02 | 2015-11-18 | 西安工程大学 | The preparation method of 1-substituting group-3-Methylimidazole acetic acid salt form ionic liquid |
| CN103588730B (en) * | 2013-11-14 | 2016-01-20 | 江苏剑牌农化股份有限公司 | One prepares the synthetic method of triazole fungicide type (III) compound |
| CN106810499A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of ionic liquid and preparation method thereof |
| CN109309161A (en) * | 2018-09-13 | 2019-02-05 | 华南师范大学 | A kind of application of ionic liquid, solar cell device and preparation method thereof |
| CN112279846B (en) * | 2019-07-25 | 2022-05-06 | 上海医药工业研究院 | Method for preparing antifungal drug isaconazole sulfate |
| CN110294712B (en) * | 2019-08-06 | 2022-05-24 | 山东科技大学 | Preparation method of high-purity imidazole acetate ionic liquid |
| CN114591245B (en) * | 2022-03-17 | 2024-04-05 | 浙江肯特催化材料科技有限公司 | Method for preparing 1, 3-dialkyl imidazole ionic liquid |
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Non-Patent Citations (2)
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| JP特开2006-156728A 2006.06.15 |
| Zhi-Bin Zhou et al.New hydrophobic ionic liquids based on perfluoroalkyltrifluoroborate anions.《Journal of Fluorine Chemistry》.2004,第125卷(第3期),471-476. * |
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