CN1524853A - Environmental protection Method for synthesizing room temperature ion liquid - Google Patents
Environmental protection Method for synthesizing room temperature ion liquid Download PDFInfo
- Publication number
- CN1524853A CN1524853A CNA031040950A CN03104095A CN1524853A CN 1524853 A CN1524853 A CN 1524853A CN A031040950 A CNA031040950 A CN A031040950A CN 03104095 A CN03104095 A CN 03104095A CN 1524853 A CN1524853 A CN 1524853A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- room temperature
- pyridine
- reaction
- dialkylimidazolium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an environmental friendly method for synthesizing ambient temperature ionic liquid, wherein corresponding destination product is utilized as reaction agent, and pyridine or N-alkyl glyoxaline or 1,2-dialkyl glyoxaline, alkylogen and fluorine containing salt are used as raw material to synthesizing ambient temperature ionic liquid at normal atmosphere by continuation method or one step method, which comprises alkyl pyridine positive ions or 1,3-dialkyl glyoxaline positive ions, or 1,2,3-trialkyl glyoxaline positive ions and negative ions containing fluorine.
Description
Technical field
The present invention relates to a kind of green synthesis method of ionic liquid at room temperature.Present method is applicable to pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane are raw material with containing villiaumite, and be synthetic by alkyl pyridine positively charged ion or 1,3-dialkylimidazolium positively charged ion or 1,2, the occasion of the ionic liquid at room temperature that 3-trialkyl glyoxaline cation and fluo anion are formed.
Background technology
Ionic liquid at room temperature is called " planner's solvent " again, is meant the material that is made of ion that is in a liquid state under near temperature room temperature or the room temperature.Liquid wide ranges, soluble end are wide because ionic liquid at room temperature has, vapour pressure is zero, good stability, acid-basicity is adjustable, electrochemical window is wide and be easy to peculiar property such as recycle, in the applied research of aspects such as sepn process, chemical reaction (especially catalyzed reaction) and electrochemistry to obtain many gratifying results, therefore, be considered to have in the synthetic and cleaner production of a kind of green the novel environmental close friend's of broad prospect of application green solvent.
The ionic liquid that positively charged ion is made up of alkyl pyridine ion and alkyl imidazole ion respectively is the two big class ionic liquid at room temperature that are widely used under study for action at present, its preparation method normally carries out in two steps: at first, with pyridine (or N-alkyl imidazole or 1, the 2-dialkylimidazolium) and haloalkane be starting raw material, adopting acetone, toluene, acetonitrile, trichloroethane or excessive haloalkane is solvent, obtain N-alkyl pyridine ammonium halide (or 1 through stirring reaction, separation and purification, 3-dialkylimidazolium ammonium halide or 1,2,3-trialkyl imidazoles ammonium halide); Then, with the ammonium halide that makes with contain villiaumite and in organic solvent such as acetonitrile, acetone, trichloroethane or water, react, make the target chamber temperature ionic liquid.The shortcoming of this method maximum is exactly to need to use a large amount of volatile organic solvents, easily causes the pollution to environment.For fear of the pollution of organic solvent to environment, Namboodiri and Varma have successively studied with the promoted non-solvent method of microwave technology synthetic 1,3-dialkyl group ammonium halide and 1, method (Chem.Commun.2001, the 643-644 of 3-dialkyl group a tetrafluoro borate ionic liquid at room temperature; Tetrahedron Lett.2002,43,5381-5383), yet this method requires specific installation, should not realize that mass-producing synthesizes ionic liquid at room temperature; In addition, the reaction conditions of microwave method is wayward, and the thermal effect of microwave and electric field action easily cause reaction mass overheated and influence quality product.
Summary of the invention
The objective of the invention is to overcome the shortcoming of existing synthetic method, a kind of efficient, environmental friendliness is provided, both was suitable for the synthetic green synthesis method that also is suitable for the ionic liquid at room temperature of large-scale industrial production in laboratory.
The method of the synthetic ionic liquid at room temperature that we are bright, it is characterized in that adopting target product is that ionic liquid at room temperature is a reaction medium, with pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane are raw material with containing villiaumite, continuous processing or one kettle way are synthetic by N-alkyl pyridine positively charged ion or 1 under normal pressure, 3-dialkylimidazolium positively charged ion or 1,2, the ionic liquid at room temperature that 3-trialkyl glyoxaline cation and fluo anion are formed, the molar mass ratio of used reaction raw materials is: pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium: haloalkane: contain villiaumite=1～2: 1～3: 1, temperature of reaction is 30～150 ℃, the chemical structural formula of ionic liquid at room temperature is:
Wherein, R, R ' and R " to represent carbonatoms respectively be 1～12 alkyl, comprises straight-chain alkyl or branched hydrocarbyl, reaction principle is shown below.
Continuous processing:
One kettle way:
Described haloalkane is RX, X=Cl or Br or I.
The described villiaumite that contains is M
+Y
-, M
+=Li
+Or Na
+Or K
+Or Ag
+Or NH
4 +Y
-=BF
4 -Or PF
6 -Or AsF
6 -Or SbF
6 -Or CF
3COO
-Or C
3F
7COO
-Or CF
3SO
2 -Or C
4F
9SO
3 -Or (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N
-
Described reaction medium is that the consumption of target product ionic liquid at room temperature is that 100～500g/mol contains villiaumite.
The operation steps of described continuous processing is: with pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane are blended in the room-temperature ion liquid body medium, stirring reaction makes alkyl pyridine ammonium halide or 1,3-dialkylimidazolium ammonium halide or 1,2,3-trialkyl imidazoles ammonium halide then, adds and contains villiaumite, stirring reaction makes the target product ionic liquid at room temperature.
The operation steps of described one kettle way is: with pyridine or N-alkyl imidazole or 1, and 2-dialkylimidazolium and haloalkane and contain villiaumite and be mixed together in the ionic liquid at room temperature, stirring reaction, the directly synthetic target product ionic liquid at room temperature that makes.
The method of the bright synthetic ionic liquid at room temperature of we, its key problem in technology be with target product as reaction medium, the synthetic ionic liquid at room temperature of continuous processing or one kettle way under normal pressure.Its advantage is: 1) reaction medium environmental friendliness, cause the pollution to environment when having avoided with an organic solvent.2) operation is easy, no matter be continuous processing or one kettle way, has all removed the separation and the purification step of loaded down with trivial details intermediate ammonium halide from.3) product separation is simple, because used reaction medium is target product, has removed the separating step of product and reaction medium from.In addition, the reaction conditions gentleness of present method, reaction yield height, good product quality are a kind of methods of efficient, eco-friendly synthetic ionic liquid at room temperature, both have been suitable for that the laboratory is synthetic also to be suitable for large-scale industry and to be combined to ionic liquid at room temperature.
Embodiment
Embodiment 1
In the there-necked flask of 100mL, add 18.4g Potassium Hexafluorophosphate, 19.3g 1-bromooctane, 8.2g N-Methylimidazole and 20.0g 1-n-octyl-3-Methylimidazole hexafluorophosphate ionic liquid successively, 135 ℃ of stirring reactions 5 hours.Reaction finishes, add 25mL water, fully stir the back standing separation and go out water, ionic liquid is used the water washing 3 times of 20mL * 3 mutually respectively, then, decompression removes residual water, obtains 48.4g 1-n-octyl-3-methyl hexafluorophosphate ionic liquid, the newly-generated 28.4g ionic liquid of real reaction, yield 83.5%.
Embodiment 2
In the there-necked flask of 50mL, add 11.0g Sodium tetrafluoroborate, 14.0g 1-chlorobutane, 9.6g 1,2 dimethylimidazole and 20.0g 1-normal-butyl-2 successively, 3-methylimidazole tetrafluoroborate ion liquid was 80 ℃ of stirring reactions 35 hours.Reaction finishes, reaction solution is transferred in the 150mL flask, adds 40mL water, fully stir, then, with the ionic liquid of the dichloromethane extraction aqueous phase of 30mL * 55 times, combined dichloromethane extraction liquid, distillation removes solvent, obtain 39.5g 1-normal-butyl-2,3-methylimidazole tetrafluoroborate ion liquid, the newly-generated 19.5g ionic liquid of real reaction, yield 81.3%.
Embodiment 3
In the there-necked flask of 100mL, add 9.4g lithium-fluoroborate, 17.9g 2-heptyl bromide, 8.2g N-Methylimidazole and 25.0g 1-(1-methyl hexyl)-3-methyl imidazolium tetrafluoroborate ionic liquid successively, 100 ℃ of stirring reactions 12 hours.Reaction finishes, add 25mL water, fully stir the back standing separation and go out water, ionic liquid is mutually successively with 20mL * 3 water washings 3 times, then, decompression removes residual water, obtains 48.3g 1-(1-methyl hexyl)-3-methyl imidazolium tetrafluoroborate ionic liquid, the newly-generated 23.3g ionic liquid of real reaction, yield 86.9%.
Embodiment 4
In the there-necked flask of 100mL, add 16.3g ammonium hexafluorophosphate, 16.5g hexyl bromide 1 bromohexane, 15.8g pyridine and 30.0g N-n-hexyl pyridine hexafluorophosphate ionic liquid successively, 100 ℃ of stirring reactions 5 hours.Reaction finishes, and adds 20mL water, fully stirs the back standing separation and goes out water, mutually successively with 20mL * 3 water washings 3 times, then, decompression removes residual water to ionic liquid, obtain 53.6g N-n-hexyl pyridine hexafluorophosphate ionic liquid, the newly-generated 23.6g ionic liquid of real reaction, yield 76.4%.
Embodiment 5
In the there-necked flask of 50mL, add 16.3g monobromethane, 4.1g N-Methylimidazole and 15.0g 1-ethyl-3-Methylimidazole trifluoromethyl sulfonic acid ionic liquid successively, 40 ℃ of stirring reactions 24 hours, after unreacted monobromethane is reclaimed in distillation, add the 8.6g trifluoromethyl sulfonate, again 30 ℃ of stirring reactions 24 hours.Reaction finishes, reaction solution is transferred in the 100mL flask, add 20mL water, fully stir, use the dichloromethane extraction 5 times of 30mL * 5 then successively, the combined dichloromethane extraction liquid, distillation removes solvent, obtain 25.8g 1-ethyl-3-Methylimidazole trifluoromethyl sulfonic acid ionic liquid, the newly-generated 10.8g ionic liquid of real reaction, yield 83.1%.
Embodiment 6
In the there-necked flask of 50mL, add 15.6g iodoethane, 4.1g N-Methylimidazole and 20.0g 1-ethyl-3-Methylimidazole trifluoroacetate ionic liquid successively, at N
2Protection down in 70 ℃ of stirring reactions 18 hours, after unreacted iodoethane is reclaimed in distillation, adds 11.0g trifluoroacetic acid silver, again 30 ℃ of stirring reactions 2 hours.Reaction finishes, reaction mixture is transferred in the 100mL flask, add 30mL water, fully stir, remove by filter Silver iodide, use the dichloromethane extraction 5 times of 30mL * 5 then successively, the combined dichloromethane extraction liquid, distillation removes solvent, obtains 30.1g 1-ethyl-3-Methylimidazole trifluoroacetate ionic liquid, the newly-generated 10.1g ionic liquid of real reaction, yield 90.2%.
Embodiment 7
In the there-necked flask of 50mL, add 6.9g 1-n-butyl bromide, 4.1g N-Methylimidazole and 10.0g 1-normal-butyl-3-Methylimidazole perfluoro butyl sulfosalt ionic liquid successively, at 70 ℃ of stirring reactions after 24 hours, add 16.9g perfluoro butyl potassium sulfonate, again 70 ℃ of stirring reactions 24 hours.Reaction finishes, add 15mL water, fully stir the back standing separation and go out water, ionic liquid is mutually successively with 15mL * 3 water washings 3 times, then, decompression removes residual water, obtains 29.2g 1-normal-butyl-3-Methylimidazole perfluoro butyl sulfosalt ionic liquid, the newly-generated 19.2g ionic liquid of real reaction, yield 87.7%.
Embodiment 8
In the there-necked flask of 100mL, add 18.4g Potassium Hexafluorophosphate, 13.7g 1-n-butyl bromide, 8.2g N-Methylimidazole and 20.0g 1-normal-butyl-3-Methylimidazole hexafluorophosphate ionic liquid successively, 70 ℃ of stirring reactions 24 hours.Reaction finishes, add 25mL water, fully stir the back standing separation and go out water, ionic liquid is used the water washing 3 times of 20mL * 3 mutually respectively, then, decompression removes residual water, obtains 43.9g 1-normal-butyl-3-methyl hexafluorophosphate ionic liquid, the newly-generated 23.9g ionic liquid of real reaction, yield 84.2%.
Embodiment 9
Concrete operations are with embodiment 8, but 15.1g 1-bromo pentane silane and 20.0g 1-n-pentyl-3-Methylimidazole hexafluorophosphate ionic liquid are replaced 13.7g 1-n-butyl bromide and 20.0g 1-normal-butyl-3-Methylimidazole hexafluorophosphate ionic liquid respectively, react newly-generated 25.3g 1-n-pentyl-3-methyl hexafluorophosphate ionic liquid, yield 84.9%.
Embodiment 10
Concrete operations are with embodiment 8, but 16.5g hexyl bromide 1 bromohexane and 20.0g 1-n-hexyl-3-Methylimidazole hexafluorophosphate ionic liquid are replaced 13.7g 1-n-butyl bromide and 20.0g 1-normal-butyl-3-Methylimidazole hexafluorophosphate ionic liquid respectively, react newly-generated 26.6g 1-n-hexyl-3-methyl hexafluorophosphate ionic liquid, yield 85.3%.
Claims (6)
1. the green synthesis method of ionic liquid at room temperature, it is characterized in that adopting target product is that ionic liquid at room temperature is a reaction medium, with pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane are raw material with containing villiaumite, continuous processing or one kettle way are synthetic by alkyl pyridine positively charged ion or 1 under normal pressure, 3-dialkylimidazolium positively charged ion or 1,2, the ionic liquid at room temperature that 3-trialkyl glyoxaline cation and fluo anion are formed, wherein the molar mass of used reaction raw materials ratio is: pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium: haloalkane: contain villiaumite=1～2: 1～3: 1, temperature of reaction is 30～150 ℃, the chemical structural formula of ionic liquid at room temperature is:
Wherein, R, R ' and R " to represent carbonatoms respectively be 1～12 alkyl, comprises straight-chain alkyl or branched hydrocarbyl.
2. synthetic method according to claim 1 is characterized in that haloalkane is RX, X=Cl or Br or I.
3. synthetic method according to claim 1, it is characterized in that containing villiaumite is M
+Y
-, M
+=Li
+Or Na
+Or K
+Or Ag
+Or NH
4 +Y
-=BF
4 -Or PF
6 -Or AsF
6 -Or SbF
6 -Or CF
3COO
-Or C
3F
7COO
-Or CF
3SO
2 -Or C
4F
9SO
3 -Or (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N
-
4. synthetic method according to claim 1 is characterized in that reaction medium is that the consumption of target product ionic liquid at room temperature is that 100～500g/mol contains villiaumite.
5. synthetic method according to claim 1, when it is characterized in that adopting continuous processing: with pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane are blended in the room-temperature ion liquid body medium, stirring reaction, make alkyl pyridine ammonium halide or 1 earlier, 3-dialkylimidazolium ammonium halide or 1,2,3-trialkyl imidazoles ammonium halide, then, add and contain villiaumite, stirring reaction makes the target product ionic liquid at room temperature.
6. synthetic method according to claim 1, when it is characterized in that employing-pot method: with pyridine or N-alkyl imidazole or 1,2-dialkylimidazolium and haloalkane and contain villiaumite and be mixed together in the room-temperature ion liquid body medium, stirring reaction, the directly synthetic target product ionic liquid at room temperature that makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03104095 CN1266137C (en) | 2003-02-24 | 2003-02-24 | Environmental protection Method for synthesizing room temperature ion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03104095 CN1266137C (en) | 2003-02-24 | 2003-02-24 | Environmental protection Method for synthesizing room temperature ion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1524853A true CN1524853A (en) | 2004-09-01 |
| CN1266137C CN1266137C (en) | 2006-07-26 |
Family
ID=34282184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03104095 Expired - Lifetime CN1266137C (en) | 2003-02-24 | 2003-02-24 | Environmental protection Method for synthesizing room temperature ion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1266137C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008043309A1 (en) * | 2006-09-29 | 2008-04-17 | Accelergy Shanghai R & D Center Co., Ltd. | Process and system of preparing ultra pure ionic liquids |
| CN101831053A (en) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | Aqueous ultraviolet cured epoxy acrylic resin and preparation method thereof |
| WO2011000490A3 (en) * | 2009-06-30 | 2011-02-24 | Merck Patent Gmbh | Synthesis of ionic liquids |
| CN109867622A (en) * | 2017-12-01 | 2019-06-11 | 武汉软件工程职业学院 | It prepares the method for ionic liquid and prepares the device of ionic liquid |
| CN111001438A (en) * | 2019-11-27 | 2020-04-14 | 屈强好 | Catalyst for synthesizing dimethyl carbonate by ester exchange method and application thereof |
-
2003
- 2003-02-24 CN CN 03104095 patent/CN1266137C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008043309A1 (en) * | 2006-09-29 | 2008-04-17 | Accelergy Shanghai R & D Center Co., Ltd. | Process and system of preparing ultra pure ionic liquids |
| WO2011000490A3 (en) * | 2009-06-30 | 2011-02-24 | Merck Patent Gmbh | Synthesis of ionic liquids |
| CN101831053A (en) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | Aqueous ultraviolet cured epoxy acrylic resin and preparation method thereof |
| CN109867622A (en) * | 2017-12-01 | 2019-06-11 | 武汉软件工程职业学院 | It prepares the method for ionic liquid and prepares the device of ionic liquid |
| CN109867622B (en) * | 2017-12-01 | 2023-05-05 | 武汉软件工程职业学院 | Method for preparing ionic liquid and device for preparing ionic liquid |
| CN111001438A (en) * | 2019-11-27 | 2020-04-14 | 屈强好 | Catalyst for synthesizing dimethyl carbonate by ester exchange method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1266137C (en) | 2006-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bonhote et al. | Hydrophobic, highly conductive ambient-temperature molten salts | |
| US7972492B2 (en) | Electrosynthesis of organic compounds | |
| CA2537587C (en) | Superhigh purity ionic liquid | |
| CN101058559A (en) | Method of continuously synthesizing ionic liquid at room temperature | |
| Raiguel et al. | Stability of ionic liquids in Brønsted-basic media | |
| US20030100761A1 (en) | Process for synthesizing ionic metal complex | |
| CN1944439A (en) | Ionic liquid and its preparing method | |
| CN1266137C (en) | Environmental protection Method for synthesizing room temperature ion liquid | |
| JP2004529956A (en) | Use of ionic compositions as replacement reagents, compositions comprising fluorinated reagents and methods of using the same | |
| KR20100042264A (en) | Method for production of purified ammonium salt of fluorinated bis-sulfonylimide | |
| CN1235879C (en) | Process for preparing room temperature ionic liquid | |
| CN103172479B (en) | Preparation method for biaryl through palladium catalysis | |
| CN101054362A (en) | Method of synthesizing ion liquid at room temperature | |
| CN1850759A (en) | Environment-friendly method for synthesizing tetrabromo bisphenol A diene propyl ether | |
| JP2009046429A (en) | Method for producing ether | |
| JP6051757B2 (en) | Ionic liquid | |
| KR101316971B1 (en) | Fluorine-containing n-alkyl sulfonyl imide compound, manufacturing method therefor, and method of manufacturing an ionic compound | |
| CN1696088A (en) | Method for synthesizing fluoro-polypxylene | |
| JPH11322760A (en) | Production of organic onium salt | |
| CN1304376C (en) | Method for preparing ion liquid in halogenated alkyl imidazole type | |
| JP2005298375A (en) | Method for purifying salt molten at normal temperature | |
| CN114395770B (en) | Method for electrochemically synthesizing 5-trifluoromethyl uracil compound | |
| JP2009292728A (en) | New chlorofluorosulfonimide compound and method for producing the same | |
| JP6228862B2 (en) | Process for producing ionic compounds | |
| CN102887827A (en) | Ionic liquid of quaternary ammonium salt, preparation method thereof and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060726 |
|
| CX01 | Expiry of patent term |