CN103980224A - Preparation method of aza crown ether ionic liquid - Google Patents
Preparation method of aza crown ether ionic liquid Download PDFInfo
- Publication number
- CN103980224A CN103980224A CN201410125062.5A CN201410125062A CN103980224A CN 103980224 A CN103980224 A CN 103980224A CN 201410125062 A CN201410125062 A CN 201410125062A CN 103980224 A CN103980224 A CN 103980224A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- tetrahydrofuran
- 6mmol
- thf
- room temperature
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/01—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having one nitrogen atom
Abstract
The invention discloses a preparation method of a room temperature ionic liquid. The preparation method comprises the following steps: mixing and dissolving 0.006mol of a potassium salt or a sodium salt, acid and aza crown ether in 80ml of a water and tetrahydrofuran mixed solvent, stirring, carrying out rotary evaporation to remove the solvent, and drying to obtain the pure room temperature ionic liquid. The preparation method is simple and is easy to implement, and the aza crown ether ionic liquid prepared by using the method is a liquid at room temperature, and has a functionalization modification advantage.
Description
Technical field
This patent relates to a kind of preparation method of room temperature type ionic liquid.Method of the present invention is with Azacrown ether containing and salt and sour preparation room warm type ionic liquid.
Background technology
Ionic liquid is comprised of ion and the electronegative ion of positively charged, refers to be when lower than 100 degrees Celsius now the fused salt of liquid state more.In ionic liquid, there is no electroneutral molecule, the 100%th, negatively charged ion and positively charged ion, between negative 100 degrees Celsius to 200 degrees Celsius, be all liquid state, there is good thermostability (decomposition temperature reaches 300 degrees Celsius) and electroconductibility, allow to a great extent kinetic control; Concerning most of inorganicss, organism and macromolecular material, ionic liquid is a kind of good solvent; Show acidity and super acids character, make it not only can be used as solvent use, but also can be used as the catalyzer use of some reaction, the solvent of these catalytic activitys has avoided extra possible poisonous catalyzer maybe may produce the shortcoming of a large amount of wastes; Ionic liquid generally can not become steam (non-volatile or " zero " vapour pressure), so can not produce the obnoxious flavour that atmosphere is polluted in chemical experiment process, this is the important evidence that ionic liquid is considered to green solvent; Price is relatively cheap, and most ionic liquids have stability to glassware for drinking water, easily in water, prepare; Ionic liquid also has good designability, can obtain by molecular designing the ionic liquid of specific function.In a word, ionic liquid tasteless, ordorless, pollution-free, nonflammable, easily and product separation, easily reclaim, can repeated multiple timesly recycle, the advantage such as easy to use, it is the ideal substitute of traditional volatile solvent, it has avoided the use of conventional organic solvents to cause the problems such as serious environment, health, safety and equipment corrosion effectively, is genuine, eco-friendly green solvent.Be suitable for current advocated cleaning technique and the requirement of Sustainable development, more and more by the extensive recognition and acceptance of people.In addition, ionic liquid also has the following advantages: strong electrostatic field (this is the key character that is different from molecule-type medium and material); Wide electrochemical window (can reach 5V-7V), this means that electrochemical reaction can not occur ionic liquid in so wide scope, i.e. degraded, and this is the not available characteristic of common electrolytic solution; Good ionic conduction (25ms/cm) and thermal conductivity, high heat capacity and thermal energy storage density.
Ionic liquid epoxidation reaction, the electrochemical synthesis of the catalytic hydrogenation reaction under the rearrangement reaction such as polyreaction, selective alkylation and amination reaction, acylation reaction, esterification, chemical bond, room temperature and normal pressure, alkene, the aspects such as preparation of branched chain fatty acid be applied, and demonstrate that speed of reaction is fast, transformation efficiency is high, the selectivity of reaction is high, the catalyst system advantage such as reuse capable of circulation.In addition, ionic liquid in the separation of solvent extraction, material and recovery, fuel cell and the solar cell of purifying, spent high molecular compound, industrial gaseous waste the extraction of carbonic acid gas, the aspects such as separated and processing of the dissolving of geological sample, nuclear fuel and nuke rubbish also demonstrate potential application prospect.
Crown ether-like ionic liquid is different from traditional glyoxaline ion liquid, because crown ether and cationic effect make its negatively charged ion have patent and the Chinese invention patent application (200910252353.X) of stronger nucleophilicity or the existing published crown ether-like ionic liquid Jin You of the alkalescence U.S..Aforementioned two class crown ether-like ionic liquids, its fusing point is all higher, and this type of ionic liquid is published in European the Chemicals (Chem. Eur. J. 2011,17,8731 – 8738) in the application of catalyse organic reaction.
Summary of the invention
The invention provides a kind of preparation method of room temperature type Azacrown ether containing ionic liquid, this room temperature type Azacrown ether containing ionic liquid is provided simultaneously.
The preparation method of Azacrown ether containing ionic liquid of the present invention mixes the sylvite of 0.006 mole or sodium salt to be dissolved in the water of 80 mL and the mixed solvent of tetrahydrofuran (THF) with acid and Azacrown ether containing, under room temperature, fully stir, except desolventizing, drying obtains pure ionic liquid at room temperature after processing, wherein: Azacrown ether containing is a[18-C-6]-1 or a[18-C-6]-2 or a[15-C-5]-3 or a[15-C-5]-4; Described acid is protonic acid; Sylvite or sodium salt: Azacrown ether containing: the mol ratio=1:1:1 of protonic acid; Water: volume ratio=1 of tetrahydrofuran (THF): 3-3: 1.
Water in the preparation method of Azacrown ether containing ionic liquid of the present invention: tetrahydrofuran (THF)=1: 1, while adopting this optimum proportion, Azacrown ether containing and salt and protonic acid can dissolve well.
3. so claim 1 or 2 aforesaid methods can be prepared the Azacrown ether containing ionic liquid of room temperature type.
The structural formula of part Azacrown ether containing ionic liquid prepared by the present invention is shown in formula one.
The structure and composition of formula one Azacrown ether containing ionic liquid
Preparation method of the present invention is simple, and the Azacrown ether containing ionic liquid of preparing by method of the present invention is at room temperature liquid, and have advantages of and can carry out functional modification, be the improvement to crown ether ionic liquid.
Embodiment
Embodiments of the invention are below provided.
Embodiment 1
Get benzyl azepine a[18-C-6]-1(6mmol), Potassium Bromide (6mmol), Hydrogen bromide (6mmol, 40-48%) be mixed in 20mL distilled water and 60mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
1a, fusing point-11
oc, decomposition point 212
oc.
Embodiment 2
Get benzyl azepine a[18-C-6]-1(6mmol), potassium acetate (6mmol), glacial acetic acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
1b, fusing point-18
oc, decomposition point 198
oc.
Embodiment 3
Get benzyl azepine a[18-C-6]-1(6mmol), sal enixum (6mmol) is mixed in 60mL distilled water and 20mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolves and steams except anhydrating and tetrahydrofuran (THF), and 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
1c, fusing point-17
oc, decomposition point 220
oc.
Embodiment 4
Get benzyl azepine a[18-C-6]-1(6mmol), potassium primary phosphate (6mmol), phosphoric acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
1d, fusing point-10
oc, decomposition point 208
oc.
Embodiment 5
Get benzyl azepine a[18-C-6]-1(6mmol), sal enixum (6mmol), sulfuric acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
1d, fusing point-20
oc, decomposition point 216
oc.
Embodiment 6
Get benzyl azepine a[18-C-6]-2(6mmol), Potassium Bromide (6mmol), Hydrogen bromide (6mmol, 40-48%) be mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
2a, fusing point-10
oc, decomposition point 245
oc.
Embodiment 7
Get benzyl azepine a[18-C-6]-2(6mmol), potassium acetate (6mmol), glacial acetic acid (6mmol) is mixed in 30mL distilled water and 50mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
2b, fusing point-24
oc, decomposition point 211
oc.
Embodiment 8
Get benzyl azepine a[18-C-6]-2(6mmol), sal enixum (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolves and steams except anhydrating and tetrahydrofuran (THF), and 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
2c, fusing point-16
oc, decomposition point 266
oc.
Embodiment 9
Get benzyl azepine a[18-C-6]-2(6mmol), potassium primary phosphate (6mmol), phosphoric acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
2d, fusing point-8
oc, decomposition point 202
oc.
Embodiment 10
Get benzyl azepine a[15-C-5]-3(6mmol), Sodium Bromide (6mmol), Hydrogen bromide (6mmol, 40-48%) be mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
3a, fusing point-7
oc, decomposition point 221
oc.
Embodiment 11
Get benzyl azepine a[15-C-5]-3(6mmol), sodium acetate (6mmol), glacial acetic acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
3b, fusing point-12
oc, decomposition point 190
oc.
Embodiment 12
Get benzyl azepine a[15-C-5]-3(6mmol), sodium tetrafluoroborate (6mmol), Tetrafluoroboric acid (6mmol, 40%) be mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
3c, fusing point-4
oc, decomposition point 211
oc.
Embodiment 13
Get butyl azepine a[15-C-5]-4(6mmol), Sodium Bromide (6mmol), Hydrogen bromide (6mmol, 40-48%) be mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
4a, fusing point-9
oc, decomposition point 202
oc.
Embodiment 14
Get butyl azepine a[15-C-5]-4(6mmol), sodium acetate (6mmol), glacial acetic acid (6mmol) is mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stirs 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
4b, fusing point-17
oc, decomposes 186
oc.
Embodiment 15
Get butyl azepine a[15-C-5]-2(6mmol), sodium tetrafluoroborate (6mmol), Tetrafluoroboric acid (6mmol, 40%) be mixed in 40mL distilled water and 40mL tetrahydrofuran (THF), under room temperature, stir 24h, revolve and steam except anhydrating and tetrahydrofuran (THF), 70 ℃ of vacuum-drying 24h obtain pure faint yellow ionic liquid
4c, fusing point-8
oc, decomposition point 197
oc.
In sum, the present invention has obtained the novel crown ether-like ionic liquid that contains dication and dianion easily with simple butyl or benzyl Azacrown ether containing and salt and protonic acid, they have lower fusing point than crown ether ionic liquid, and stability is also fine, work based on before us, this novel ionic liquid can be for the different chemical reaction of catalysis, and has than conventional ion liquid and have the better advantage such as water-soluble.
Claims (3)
1. the preparation method of an Azacrown ether containing ionic liquid, it is characterized in that the sylvite of 0.006 mole or sodium salt to mix and be dissolved in the water of 80 mL and the mixed solvent of tetrahydrofuran (THF) with acid and Azacrown ether containing, fully stir, except desolventizing, drying obtains pure ionic liquid at room temperature after processing, wherein: Azacrown ether containing is a[18-C-6]-1 or a[18-C-6]-2 or a[15-C-5]-3 or a[15-C-5]-4; Described acid is protonic acid; Sylvite or sodium salt: Azacrown ether containing: the mol ratio=1:1:1 of protonic acid; Water: volume ratio=1 of tetrahydrofuran (THF): 3-3: 1.
2. the preparation method of a kind of Azacrown ether containing ionic liquid according to claim 1, is characterized in that water: tetrahydrofuran (THF)=1: 1.
3. the Azacrown ether containing ionic liquid that prepared by the method described in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410125062.5A CN103980224A (en) | 2014-03-31 | 2014-03-31 | Preparation method of aza crown ether ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410125062.5A CN103980224A (en) | 2014-03-31 | 2014-03-31 | Preparation method of aza crown ether ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103980224A true CN103980224A (en) | 2014-08-13 |
Family
ID=51272420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410125062.5A Pending CN103980224A (en) | 2014-03-31 | 2014-03-31 | Preparation method of aza crown ether ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980224A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173640A1 (en) * | 2006-01-24 | 2007-07-26 | Park Sang H | Ionic liquid type crown ether derivatives, method for preparing the same and method for isolating metal ions using the same |
| CN101723928A (en) * | 2009-11-28 | 2010-06-09 | 兰州大学 | Ion liquid and preparation technology thereof |
| CN102134237A (en) * | 2010-12-27 | 2011-07-27 | 西北师范大学 | Crown ether ring imidazole ionic liquid |
| CN102212042A (en) * | 2011-04-18 | 2011-10-12 | 北京师范大学 | Synthetic method of tetra-azacrown ether |
| CN102584739A (en) * | 2011-12-21 | 2012-07-18 | 北京师范大学 | Carboxyl benzyl replaced nitrogen dioxide crown ether derivative and synthesizing method thereof |
-
2014
- 2014-03-31 CN CN201410125062.5A patent/CN103980224A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173640A1 (en) * | 2006-01-24 | 2007-07-26 | Park Sang H | Ionic liquid type crown ether derivatives, method for preparing the same and method for isolating metal ions using the same |
| CN101723928A (en) * | 2009-11-28 | 2010-06-09 | 兰州大学 | Ion liquid and preparation technology thereof |
| CN102134237A (en) * | 2010-12-27 | 2011-07-27 | 西北师范大学 | Crown ether ring imidazole ionic liquid |
| CN102212042A (en) * | 2011-04-18 | 2011-10-12 | 北京师范大学 | Synthetic method of tetra-azacrown ether |
| CN102584739A (en) * | 2011-12-21 | 2012-07-18 | 北京师范大学 | Carboxyl benzyl replaced nitrogen dioxide crown ether derivative and synthesizing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102584602A (en) | Quaternary ammonium salt and preparation method thereof | |
| CN104923167B (en) | A kind of stable Nano-meter SiO_22the preparation method of/tributyl phosphate composite adsorbing material | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN104829481A (en) | Preparation method of N,N,N',N'-tetraoctyl-3-oxa pentanediamide | |
| CN102153443B (en) | Method for degrading polyethylene terephthalate | |
| CN104610192A (en) | Room-temperature ionic liquid based on polyoxometallate and preparation method of room-temperature ionic liquid | |
| CN102921281A (en) | Method for obviously improving carbon capture performance by utilizing multipoint synergistic effect | |
| CN103752137A (en) | Method for capturing acid gases by adopting ether-base pyridine ionic liquid | |
| CN103980224A (en) | Preparation method of aza crown ether ionic liquid | |
| CN107973771A (en) | A kind of method that cobalt-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate | |
| CN101773785A (en) | Method for concentrating ion liquid by electrodialysis | |
| CN102659572B (en) | Preparation method of dehydroabietic acid | |
| CN102728401A (en) | Post-processing modification method of Ti-Si molecular sieve | |
| CN103896868A (en) | Preparation method of acidic aza-crown ether ionic liquid | |
| CN102431994A (en) | Method using salt free zwitterion vesicle aqueous solution for extracting purified fullerene C60 | |
| CN107973772A (en) | A kind of method that ferrum-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate | |
| CN107827861A (en) | A kind of method that ferrum-based catalyst prepares cyclic carbonate | |
| CN114591181A (en) | Method for preparing high-purity ionic liquid | |
| CN105732695B (en) | A kind of tree-shaped skeleton ionic liquid and preparation method and application | |
| CN109824695A (en) | Crown ether type ionic liquid based on imidazoles, benzimidazole and its derivative | |
| CN106431844B (en) | A kind of method that ceria catalysis ecological oil prepares phenolic compound | |
| CN104831311A (en) | Method for preparation of methanol by electrolytic oxidation of coal mine gas | |
| CN109382142A (en) | A kind of regeneration method of acidic ion liquid | |
| CN107827859A (en) | A kind of method that aluminium-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate | |
| CN107721970A (en) | A kind of method that nickel-base catalyst prepares cyclic carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140813 |