CN104803917A - Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid - Google Patents
Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid Download PDFInfo
- Publication number
- CN104803917A CN104803917A CN201410045298.8A CN201410045298A CN104803917A CN 104803917 A CN104803917 A CN 104803917A CN 201410045298 A CN201410045298 A CN 201410045298A CN 104803917 A CN104803917 A CN 104803917A
- Authority
- CN
- China
- Prior art keywords
- benzyl
- ionic liquid
- reaction
- alkyl
- ethyl imidazol
- 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
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the field of ionic liquid synthesis and relates to a preparation method of a 1-benzyl-3-alkyl-2-ethylimidazolium tetrafluoroborate ionic liquid. The preparation method comprises that benzyl chloride and 2-ethyl-imidazole undergo a reaction, the reaction product and bromoalkane undergo a reaction to produce quaternary ammonium salt, and the quaternary ammonium salt and sodium tetrafluoroborate undergo an anion exchange reaction to produce the 1-benzyl-3-alkyl-2-ethylimidazolium tetrafluoroborate ionic liquid. Compared with the prior art, the preparation method has the advantages of mild reaction conditions, green and environmentally friendly production process and good universality. The aryl-substituted imidazolium tetrafluoroborate has a molecular structure shown in the following description, wherein n is in a range of 3-7.
Description
One technical field
The invention belongs to ionic liquid synthesis field, particularly the preparation method of tetrafluoroborate ionic liquid that replaces of a kind of aryl.
Two background technologies
Ionic liquid is generally made up of organic cation and inorganic anion, the new medium of of closely growing up under the framework of Green Chemistry during the last ten years and functional materials, and develop in organic synthesis and catalysis, novel material, electrochemistry, environmental science, isolation technique etc. be applied in field, the research of ionic liquid is to scientific basis research or practical application all has very important meaning.Particularly the solubilized organic dye such as tetrafluoroborate ionic liquid, is applied in dyeing, printing technology significant.
With traditional solvent, as organic flux (VOC), water, supercutical fluid etc. are compared, it is 1. non-volatile that ionic liquid has more advantage, its vapour pressure is zero, can be used for high vacuum system, not easily loss and contaminate environment in use and storage, can be recycled, meet the requirement of Green Chemistry.2. wide, also non-volatile at relatively high temperatures with the temperature range of liquid state existence, some pyroreactions can be realized in ionic liquid.3. nonflammable, not exploding, be not oxidized, have good thermostability and chemical stability, is the fine solvent of many organic and inorganic things.4. solubility property is good, and scope is wide, all shows good dissolving power, be conducive to the carrying out of homogeneous reaction to many organic, electrodeless, organometallicss and macromolecular material.5. there is high ionic conductivity and wider decomposition voltage window, can be used as the electrolytic solution of electrochemical research, as the ionogen of fuel cell, electrical condenser etc.6. structure can modulation, is changed the composition of zwitterion by design, can the physicochemical property of modulation ionic liquid, and kind has hundreds of and even more, can be the reaction environment that chemical reaction provides new.
Increasing ionic liquid is commercially used now, novel ion liquid is constantly had to be born, the tetrafluoroborate ionic liquid that the present invention is intended to synthesize the replacement of a kind of aryl applies to textile printing processing technology, utilization has environmental protection ionic liquid and replaces the former paste of stamp, realizes ecological without slurry stamp cleanly production target.
Three summary of the invention
The object of the invention is the preparation method of the tetrafluoroborate ionic liquid providing a kind of aryl to replace, and dissolves poor universality or the high defect of cost with the ionic liquid overcoming at present preparation to dyestuff.
The technical scheme that this programme is taked is as follows:
(1) in two neck flasks, add DMF (DMF) and make solvent, after sodium hydride and 2-ethyl imidazol(e) slowly being added, keep-15 DEG C, under nitrogen atmosphere, stirred by reaction mixture, then Benzyl Chloride adds again.And the temperature of reaction is risen to-5 DEG C, stir 3 hours.After completing, reactant methyl alcohol process, obtains crude product, obtains 1-benzyl-2-ethyl imidazol(e), is designated as B.
(2) in two neck flasks with tetrahydrofuran (THF) (THF) for solvent, alkyl bromide and B are slowly added respectively, by reaction mixture 80 DEG C of stirrings.After reaction terminates, reaction mixture is under reduced pressure filtered, obtains 1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride.
(3) in the aqueous solution of 1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride, sodium tetrafluoroborate (NaBF is added
4), reaction mixture at room temperature stirs.After reaction terminates, mixture dichloromethane extraction, obtains 1-benzyl-3-alkyl-2-ethyl imidazol(e) tetrafluoroborate ion liquid.
The present invention, relative to prior art, has following advantage:
(1). have that synthetic method is simple, mild condition, environment amenable characteristic, belong to a kind of green method.(2). introduce benzyl and alkyl in ionic liquid, good to organism solvability, and ionic liquid purity is high, productive rate is high.(3). the thermally-stabilised scope of synthesized ionic liquid is all wider, stable in properties, highly versatile.This tetrafluoroborate ionic liquid, in textile printing processing technology, realizes the ecological application prospect without slurry stamp cleanly production field good.
Four accompanying drawing explanations
Fig. 1 is 1-benzyl-3-butyl-2-ethyl imidazol(e) hydrochloride
1hNMR schemes.
Fig. 2 is 1-benzyl-3-butyl-2-ethyl imidazol(e) hydrochloride
13cNMR schemes.
Fig. 3 is 1-benzyl-3-octyl group-2-ethyl imidazol(e) hydrochloride
1hNMR schemes.
Fig. 4 is 1-benzyl-3-octyl group-2-ethyl imidazol(e) hydrochloride
13cNMR schemes.
Five embodiments
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1 adds 2LN in two neck flasks, dinethylformamide (DMF) makes solvent, by sodium hydride (60% solution, 96g, 4mol) and 2-ethyl imidazol(e) (192.3g, after 2mol) slowly adding, keep-15 DEG C, under nitrogen atmosphere, reaction mixture is stirred 30 minutes again, then Benzyl Chloride (253g, 2mol) adds.And the temperature of reaction is risen to-5 DEG C, stir 3 hours.After completing, reactant 500mL methyl alcohol process, obtains crude product, obtains 1-benzyl-2-ethyl imidazol(e), is designated as B.
Embodiment 2 in two neck flasks with 2L tetrahydrofuran (THF) (THF) for solvent, alkyl bromide and B are slowly added respectively by the amount of the mol ratio of 2.5: 2, by reaction mixture 80 DEG C stir 4-6 hour.After reaction terminates, under reduced pressure filtered by reaction mixture, obtaining productive rate is 91%1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride.
Embodiment 3 adds NaBF in the aqueous solution of 1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride
4, dosage mol ratio is 2: 2.1, and reaction mixture at room temperature stirs 1.5 hours.After reaction terminates, mixture dichloromethane extraction, and revolve rotary evaporation by decompression, obtain 1-benzyl-3-alkyl-2-ethyl imidazol(e) tetrafluoroborate ion liquid, productive rate is more than 94%.
Embodiment 4 pairs of 1-benzyl-3-alkyl-2-ethyl imidazol(e) tetrafluoroborate ion liquids carry out nuclear-magnetism sign.
By reference to the accompanying drawings, with 1-benzyl-3-butyl-2-ethyl imidazol(e) hydrochloride and 1-benzyl-3-octyl group-2-ethyl imidazol(e) hydrochloride
1hNMR figure and
13cNMR is described.
1-benzyl-3-butyl-2-ethyl imidazol(e) hydrochloride:
1H NMR(500MHz，CDCl
3)：δ＝7.28-7.33(m，4H)，7.21-7.24(m，3H)，5.27(s，2H)，4.03(t，2H，J＝7.5Hz)，2.99(q，2H，J＝7.5Hz)，1.72-1.78(m，2H)，1.29-1.37(m，2H)，1.03(t，3H，J＝7.5Hz)，0.89(t，3H，J＝7.5Hz).
13C NMR(125MHz，CDCl
3)：δ＝147.64，129.38，129.10，128.04，122.05，121.31，51.84，48.11，31.99，19.53，16.92，13.49，11.36.
1-benzyl-3-octyl group-2-ethyl imidazol(e) hydrochloride:
1H NMR(500MHz，CDCl
3)：δ＝7.29-7.36(m，4H)，7.23-26(m，3H)，5.29(s，2H)，4.04(t，2H，J＝7.5Hz)，3.01(q，2H，J＝7.5Hz)，1.76-1.82(m，2H)，1.19-1.33(m，10H)，1.06(t，3H，J＝7.5Hz)，0.84(t，3H，J＝7.5Hz).
13C NMR(125MHz，CDCl
3)∶δ＝147.65，133.29，129.41，129.12，128.05，122.12，121.22，51.91，48.38，31.67，30.09，29.00，26.34，22.57，17.00，14.06，11.38.
Embodiment 5 makes differential thermal analysis record the stable range of 1-benzyl-3-alkyl-2-ethyl imidazol(e) tetrafluoroborate ion liquid at 160-200 degree.
Claims (3)
1. a functionalized ion liquid, is characterized by the structural formula of this ionic liquid:
wherein n=3-7
2. the preparation method of ionic liquid as claimed in claim 1, is characterized by following methods:
(1) in two neck flasks, add DMF (DMF) and make solvent, after sodium hydride and 2-ethyl imidazol(e) slowly being added, keep-15 DEG C, under nitrogen atmosphere, reaction mixture is stirred 30 minutes again, then Benzyl Chloride adds.And the temperature of reaction is risen to-5 DEG C, stir 3 hours.After completing, reactant methyl alcohol process, obtains 1-benzyl-2-ethyl imidazol(e), is designated as B.
(2) in two neck flasks with tetrahydrofuran (THF) (THF) for solvent, alkyl bromide and B are slowly added respectively, by reaction mixture 80 DEG C stir 4-6 hour.After reaction terminates, reaction mixture is under reduced pressure filtered, obtains 1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride.
(3) in the aqueous solution of 1-benzyl-3-alkyl-2-ethyl imidazol(e) hydrochloride, sodium tetrafluoroborate (NaBF is added
4), reaction mixture at room temperature stirs 1.5 hours.After reaction terminates, mixture methylene dichloride (3 × 10 milliliters) extraction, obtain 1-benzyl-3-alkyl-2-ethyl imidazol(e) tetrafluoroborate ion liquid, productive rate is more than 94%.
3. the ionic liquid prepared as claimed in claim 2, the thermally-stabilised scope of its feature is at 160-200 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410045298.8A CN104803917A (en) | 2014-01-26 | 2014-01-26 | Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410045298.8A CN104803917A (en) | 2014-01-26 | 2014-01-26 | Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104803917A true CN104803917A (en) | 2015-07-29 |
Family
ID=53689156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410045298.8A Pending CN104803917A (en) | 2014-01-26 | 2014-01-26 | Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104803917A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868662A (en) * | 2017-12-05 | 2019-06-11 | 财团法人纺织产业综合研究所 | Pretreatment fluid constituent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215200A (en) * | 2008-03-10 | 2009-09-24 | Tokyo Institute Of Technology | Imidazolium derivative salt and its application |
| CN102952078A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of alkyl imidazole carboxylate ionic liquid |
| CN103012796A (en) * | 2011-09-23 | 2013-04-03 | 北京师范大学 | Method for preparing polysulfones |
| KR20130044038A (en) * | 2011-10-21 | 2013-05-02 | 부경대학교 산학협력단 | Method for preparing 5-hydroxymethylfurfural directly from cellulose |
-
2014
- 2014-01-26 CN CN201410045298.8A patent/CN104803917A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215200A (en) * | 2008-03-10 | 2009-09-24 | Tokyo Institute Of Technology | Imidazolium derivative salt and its application |
| CN102952078A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of alkyl imidazole carboxylate ionic liquid |
| CN103012796A (en) * | 2011-09-23 | 2013-04-03 | 北京师范大学 | Method for preparing polysulfones |
| KR20130044038A (en) * | 2011-10-21 | 2013-05-02 | 부경대학교 산학협력단 | Method for preparing 5-hydroxymethylfurfural directly from cellulose |
Non-Patent Citations (1)
| Title |
|---|
| YVES GÉNISSON等: "New chiral imidazolinic derivatives", 《TETRAHEDRON: ASYMMETRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868662A (en) * | 2017-12-05 | 2019-06-11 | 财团法人纺织产业综合研究所 | Pretreatment fluid constituent |
| CN109868662B (en) * | 2017-12-05 | 2022-04-29 | 财团法人纺织产业综合研究所 | Pretreatment liquid composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Covalent organic framework as an efficient, metal-free, heterogeneous photocatalyst for organic transformations under visible light | |
| Chang et al. | Synthesis and characterization of dicationic ionic liquids that contain both hydrophilic and hydrophobic anions | |
| EP1698631B1 (en) | Ionic liquid, method for producing same, double layer capacitor comprising same, and lithium battery | |
| CN101225163B (en) | Method for preparing polyether-type macroion liquid by polyepichlorohydrin | |
| Chen et al. | Dialkoxy functionalized quaternary ammonium ionic liquids as potential electrolytes and cellulose solvents | |
| WO2013029236A1 (en) | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof | |
| CN107074868A (en) | For by CO2Selective electrochemical reduction is CO Porphyrin Molecule catalyst | |
| CN101633641A (en) | Preparation method of imidazole type ionic liquid | |
| Zhou et al. | Low-viscous, low-melting, hydrophobic ionic liquids: 1-alkyl-3-methylimidazolium trifluoromethyltrifluoroborate | |
| CN101654438A (en) | Imidazole ionic liquid production technology | |
| CN101941986A (en) | Y aromatic ligand ionic liquid and preparation method thereof | |
| US11056705B2 (en) | Organic anolyte materials for flow batteries | |
| CN107417588B (en) | A kind of novel ion liquid and the method using its electrolytic preparation nano aluminum | |
| CN104803917A (en) | Preparation method of aryl-substituted imidazolium tetrafluoroborate ionic liquid | |
| WANG et al. | Synthesis and physico-chemical properties of new green electrolyte 1-butyl-3-methylimidazolium perchlorate | |
| CN105924465A (en) | POSS-base high-temperature-resisting room temperature ionic liquid and preparation method thereof | |
| CN106622364A (en) | Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst | |
| CN104262127B (en) | Brush-type two fluorine monomer and synthetic method thereof | |
| WO2014061482A1 (en) | Ionic liquid | |
| CN101781250A (en) | Method for synthesizing low bromine content iminazole ionic liquid | |
| CN101575752B (en) | Interfacial synthesis method of conductive polymer/silver chloride compound nanofiber | |
| CN104326893A (en) | Side-chain-type difluoro monomer and synthesis method thereof | |
| CN104262224A (en) | Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions | |
| US20140166921A1 (en) | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof | |
| CN105440729B (en) | A kind of organic dyestuff and preparation method thereof and the sensitization solar cell comprising the organic dyestuff |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150729 |