CN101891685A - Alkyl imidazole-L-proline salt chiral ionic liquid and preparation method thereof - Google Patents
Alkyl imidazole-L-proline salt chiral ionic liquid and preparation method thereof Download PDFInfo
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- CN101891685A CN101891685A CN 201010228469 CN201010228469A CN101891685A CN 101891685 A CN101891685 A CN 101891685A CN 201010228469 CN201010228469 CN 201010228469 CN 201010228469 A CN201010228469 A CN 201010228469A CN 101891685 A CN101891685 A CN 101891685A
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Abstract
The invention relates to an alkyl imidazole-L-proline salt chiral ionic liquid and a preparation method thereof. The structural formula of the alkyl imidazole-L-proline salt chiral ionic liquid is shown in formula (I), and the preparation method thereof comprises the following steps: enabling alkyl imnidazole bromide and potassium hydroxide to react in ethanol solution for 4h; removing generated salt; stirring with L- L-proline at the temperature of 0 DEG C and reacting for 12h; and carrying out vacuum drying on products for 24h. The optical rotation and optical purity OP%ee of the alkyl imidazole-L-proline salt chiral ionic liquid prepared by the invention are measured at the temperature of 25 DEG C; according to the method provided by the invention, the preparation process is green and environmental friendly, and no secondary pollution is generated; and the alkyl imidazole-L-proline salt chiral ionic liquid synthesized in the invention has favorable optical activity. The formula (I) is shown in the specification, wherein R1 is CH3 or (CH2)n-CH3, and n is from 1 to 5; R2 is H, CH3 or (CH2)n-CH3, and n is from 1 to 5; and R3 is (CH2)n-CH3, and n is from 1 to 5.
Description
Technical field
The present invention relates to a kind of ionic liquid and preparation method, design alkyl imidazole-L-proline salt ionic liquid of a kind of chirality and preparation method thereof especially.
Technical background
Ionic liquid is made up of the yin, yang ion fully, have that solvability is good, chemical stability is good, Heat stability is good, temperature range is wide, steam forces down, good conductivity, ion migration and velocity of diffusion soon, do not burn, the character of many uniquenesses such as tasteless.Ionic liquid has caused people's attention as the green replace solvents technology of electrochemistry, organic synthesis, catalysis, biological chemistry, physical chemistry, material and separation etc. in a lot of fields.Relevant both at home and abroad ion liquid research report is a lot, but fewer for the research of chiral ionic liquid (chiral ionic iquid, C IL).Contain the segmental ionic liquid of chirality and have ion liquid characteristic and chirality feature simultaneously, can be used as chiral solvent or chiral induction agent, aspects such as, chiral separation synthetic in chirality and chiral catalysis have very big application potential.1977, Howarth has reported that the first routine chirality is from synthesizing of liquid, this chiral ionic liquid is used for the asymmetric D-A reaction of (different) crotonaldehyde and cyclopentadiene, experimental result show these chiral ionic liquids in reaction as Lewis acid, can access good interior exo isomer selectivity.Jonathan utilizes N-Methylimidazole and S-Solactol ester to synthesize another kind of imidazole salt chiral ionic liquid, and has produced a series of chiral ionic liquid by ion-exchange.Amino acid is the natural chiral source of a class, utilizations such as Guillen (S)-Histidine be initiator to have prepared a series of imidazole amino acids be cationic chiral ionic liquid, reaction is from Histidine methyl esters and carbonyl dimidazoles, but its reactions steps is many; It is positively charged ion with amino acid that patent document 200410009958.3 has been described a series of, and various strong acid are anionic chiral ionic liquid, but a lot of strong acid has severe corrosive.The present invention is that the alkyl imidazole chiral ionic liquid that negatively charged ion prepares does not still have report with the L-proline(Pro).Synthesizing and being applied as the synthetic of chipal compounds of chiral ionic liquid provides new thinking and means, although obtained some significative results, also has a lot of work to do in this respect.
Summary of the invention
The object of the present invention is to provide a kind of new, nontoxic, environmental protection more, do not produce the alkyl imidazole-L-proline salt chiral ionic liquid of secondary pollution.
The contriver provides the method for a kind of synthesis of alkyl imidazoles-L-proline salt chiral ionic liquid, is negatively charged ion, is positively charged ion with the alkyl imidazole with the L-proline(Pro), has synthesized the product alkyl imidazole-L-proline salt chiral ionic liquid.The structural formula of alkyl imidazole-L-proline salt chiral ionic liquid of the present invention is represented with following formula:
R
1Be CH
3, or (CH
2)
n-CH
3, wherein n is 1～5; R
2Be H, CH
3, or
(CH
2)
n-CH
3, wherein n is 1～5; R
3Be (CH
2)
n-CH
3, wherein n is 1～5.
The synthesis step of alkyl imidazole-L-proline salt chiral ionic liquid is as follows:
(1) the N-alkyl imidazole is synthetic
Get imidazoles and potassium hydroxide, stir 5h among the DMSO, ice bath drips bromoalkane, stopped reaction behind the stirring at room 11h down.Reaction solution utilizes distilled water and chloroform to carry out separatory and handles, and uses the distilled water wash chloroform layer, anhydrous MgSO
4Drying is filtered, and rotary evaporation obtains colourless transparent liquid N-alkyl imidazole.
(2) the bromination alkyl imidazole is synthetic
Add bromoalkane in above-mentioned N-alkyl imidazole, under the argon shield, 60 ℃ are refluxed down, obtain product bromination alkyl imidazole again after the ethyl acetate washing.
(3) alkyl imidazole-L-proline salt chiral ionic liquid is synthetic
In the ethanol solution of potassium hydroxide, slowly drip the ethanolic soln of bromination alkyl imidazole under the room temperature, stirring at room 4h leaves standstill and the elimination white solid; Stir the ethanolic soln that in filtrate, adds the L-proline(Pro) down, 0 ℃ of following stirring reaction 12h.
(4) purifying of alkyl imidazole-L-proline salt chiral ionic liquid
Reaction solution steams and desolventizes, and adds anhydrous methanol-acetonitrile mixed solvent vigorous stirring, and unreacted L-proline(Pro) is separated out, and filters, and filtrate removing desolvated, vacuum-drying, and product is a light yellow viscous liquid.
The alkyl imidazole-L-proline salt chiral ionic liquid that the present invention is prepared in having measured its specific rotation in acetonitrile/methanol=9: 1 solution under 25 ℃, calculates its optical purity according to the actual measurement specific rotatory power.
According to method provided by the invention, the preparation process environmental protection does not produce secondary pollution.The invention has the beneficial effects as follows the ionic liquid alkyl imidazole-L-proline salt that has synthesized chirality, and have good optical activity.Chirality is one of natural base attribute, because special property and potential function that optically pure compound had make it all to be paid close attention to widely at numerous areas such as molectronics, molecular optics, life science, agrochemistry, foodstuff additive, spices, pharmaceutical chemistry, functional materials and catalyzer.Its research has become the focus of scientific research and a lot of high-tech new product developments.The result that huge scale market promotes is not only in the chirality revolution that rise in a plurality of fields, and also is necessary to environment protection.Chirality is synthetic can be avoided producing a large amount of, invalid even to environment and human body harmful's enantiomorph, have very important meaning for environment protection and human health.
Embodiment
Embodiment 1:1,3-dibutyl imidazoles-L-proline salt chiral ionic liquid
Raw material: imidazoles analytical reagent
The bromination of n-butane analytical reagent
L-proline(Pro) analytical reagent
The potassium hydroxide analytical reagent.
The DMSO analytical reagent
The dehydrated alcohol analytical reagent
1, the N-butyl imidazole is synthetic
In the 100mL there-necked flask, add imidazoles 4.136g (61mmol), drop into potassium hydroxide 4.099g (73mmol), add DMSO 30mL, stirring and dissolving, measure bromoalkane 73mmol behind the 5h, drip with dropping funnel under the ice bath, occur a large amount of white solids, stopped reaction behind the stirring at room 11h in the reaction.Reaction solution utilizes distilled water and chloroform to carry out separatory and handles, with (4 * 20mL) distilled water wash chloroform layers, anhydrous MgSO
4Dried overnight is filtered, and rotary evaporation obtains product N-butyl imidazole, colourless transparent liquid.
Imidazoles bromination of n-butane N-butyl imidazole
2, bromination 1,2-dibutyl imidazoles synthetic
Add the N-butyl imidazole 45mmol of step 1 preparation in the 100mL there-necked flask, bromination of n-butane 50mmol is under the argon shield; 60 ℃ are refluxed down, and stopped reaction behind the 16h is after aftertreatment; products therefrom bromination 1,3-dibutyl imidazoles ([bbim] Br) is a light yellow viscous liquid.
N-butyl imidazole bromo normal butane bromination 1,3-dibutyl imidazoles ([bbim] Br)
3,1,3-dibutyl imidazoles proline salt chiral ionic liquid synthetic
In the 100mL three-necked flask, 50mmol potassium hydroxide is dissolved in the 25mL dehydrated alcohol under 50 ℃ of agitation conditions, is cooled to room temperature, more slowly step 2 product [bbim] Br of Dropwise 5 0mmol and 10mL alcoholic acid mixing solutions in this system, stirring at room 4h leaves standstill and the elimination white solid; Filtrate is placed 50mL single port bottle, stir down the slowly ethanolic soln of the L-proline(Pro) of Dropwise 5 5mmol, TLC follows the tracks of, 0 ℃ of following stirring reaction 12h.
[bbim] Br L-proline(Pro) 1,3-dibutyl imidazoles-L-
Proline salt
4,1, the purifying of 3-dibutyl imidazoles-L-proline salt chiral ionic liquid
Reaction solution steams and to desolventize, and adds anhydrous methanol: (3 * 20ml), vigorous stirring goes out the unreacted amino acid out to the mixed solvent of acetonitrile=9: 1.Filter, the filtrate Rotary Evaporators removes and desolvates, 50 ℃ of vacuum-drying 24h, and obtaining product is light yellow viscous liquid.
The product warp
1HNMR (CDCl
3, 400MHz, δ/ppm relative to TMS) checking as follows: 0.978 (m, 6H, 2CH
3), 1.423 (m, 4H, 2CH
2-CH
3), 1.881 (m, 4H, 2CH2-CH
2CH
3), 1.924 (m, 2H, Pro-CH
2), 2.013～2.182 (m., 2H, Pro-CH
2), 3.036～3.186 (m, 2H, ProN-CH
2), 3.712 (m, 1H, Pro-CH), 4.343 (m, 4H, 2NCH
2-CH
2CH
2CH
3), 7.221 (d, 2H, imidazole rings), 10,842 (s, 1H, imidazole rings).
The product optical property is passed through the automatic polarimeter of WWW-2B type, acetonitrile/methanol=9: 1 solution, 25 ℃, sodium light light source (λ=589.44nm) measure.Measurement result shows that its specific rotation is-32.34 °, and calculating its optical purity OP%ee according to the actual measurement specific rotatory power is 96.97%.
Embodiment 2:1,2-dimethyl-3-butyl imidazole-L-proline salt chiral ionic liquid
Raw material: 1,2 dimethylimidazole analytical reagent
The bromination of n-butane analytical reagent
L-proline(Pro) analytical reagent
The potassium hydroxide analytical reagent.
The DMSO analytical reagent
The dehydrated alcohol analytical reagent
1, bromination 1,2-dimethyl-3-butyl imidazole synthetic
1,2 dimethylimidazole bromination of n-butane bromination 1,2-dimethyl-3-butyl imidazole
In the 100mL there-necked flask, add 1,2 dimethylimidazole 45mmol, bromination of n-butane 50mmol, the bromination 1 in preparation method and the example 1,2-dibutyl imidazoles synthetic identical.
2,1,2-dimethyl-3-butyl imidazole proline salt chiral ionic liquid synthetic
Bromination 1,2-dimethyl L-proline(Pro) 1,2-dimethyl-3-butyl
-3-butyl imidazole imidazoles-L-proline salt
In the 100mL three-necked flask, 50mmol potassium hydroxide is dissolved in the 25mL dehydrated alcohol under 50 ℃ of agitation conditions, be cooled to room temperature, the bromination 1 of Dropwise 5 0mmol slowly in this system again, 2-dimethyl-3-butyl imidazole and 10mL alcoholic acid mixing solutions, stirring at room 4h leaves standstill and the elimination white solid; Filtrate is placed 50mL single port bottle, stir down the slowly ethanolic soln of the L-proline(Pro) of Dropwise 5 5mmol, TLC follows the tracks of, 0 ℃ of following stirring reaction 12h.
The product warp
1H NMR (CDCl
3, 400MHz, δ/ppm relative to TMS) checking as follows: 0.976 (t, 3H, CH
3), 1.399 (m, 2H, CH
2-CH
3), 1.742 (m, 2H, CH
2-CH
2CH
3), 1.792 (m, 2H, Pro-CH
2), 1.948～2.131 (m., 2H, Pro-CH
2), 2.734 (s, 3H, imidazole ring-CH
3), 2.956～, 3.148 (m, 2H, Pro N-CH
2), 3.671 (m, 1H, Pro-CH), 3.966 (s, 3H, N-CH
3), 4.167 (t, 2H, NCH
2-CH
2CH
2CH
3), 7.403 (s, 1H, imidazole rings), 7.637 (s, 1H, imidazole rings).
Claims (2)
1. alkyl imidazole-L-proline salt chiral ionic liquid is characterized in that its structure is as follows:
It is characterized in that, in the described structural formula (I), R
1Be CH
3, or (CH
2)
n-CH
3, wherein n is 1～5, R
2Be H, CH
3, or (CH
2)
n-CH
3, wherein n is 1～5, R
3Be (CH
2)
n-CH
3, wherein n is 1～5.
2. the synthetic method of right 1 described alkyl imidazole-L-proline salt chiral ionic liquid is, in the ethanol solution of potassium hydroxide, adds the ethanolic soln of bromination alkyl imidazole, and stirring at room leaves standstill and the elimination white solid; The ethanolic soln that adds the L-proline(Pro) in the filtrate, 0 ℃ of following stirring reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951665A (en) * | 2014-04-16 | 2014-07-30 | 四川大学 | Method for preparing novel tropenol amino acid anionic chiral ionic liquid, immobilization method thereof and method for resolving DL-phenylalanine and DL-tryptophan by using same |
| CN107652380A (en) * | 2017-09-03 | 2018-02-02 | 河南师范大学 | Heterogeneous chiral catalyst based on poly ion liquid and its preparation method and application |
| CN110132672A (en) * | 2019-05-16 | 2019-08-16 | 王樱达 | A kind of histocyte fixating reagent and histocyte fixing means |
| CN115611811A (en) * | 2022-10-13 | 2023-01-17 | 上海工程技术大学 | Chiral ionic liquid and application thereof |
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| CN1749249A (en) * | 2005-09-09 | 2006-03-22 | 浙江大学 | Chiral ionic liquid and its preparing method |
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2010
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| CN1583726A (en) * | 2003-08-18 | 2005-02-23 | 浙江工业大学 | Chiral ion liquid of alkylimidazole tetrafluoroborate and its preparation |
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| CN101182308A (en) * | 2006-11-13 | 2008-05-21 | 浙江工业大学 | Imidazole chiral ionic liquids containing double function groups as well as preparation method and uses thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951665A (en) * | 2014-04-16 | 2014-07-30 | 四川大学 | Method for preparing novel tropenol amino acid anionic chiral ionic liquid, immobilization method thereof and method for resolving DL-phenylalanine and DL-tryptophan by using same |
| CN103951665B (en) * | 2014-04-16 | 2016-04-13 | 四川大学 | The method of the preparation of novel tropine alcohols amino acid anionic chiral ionic liquid, immobilization and fractionation DL-phenylalanine and DL-Trp |
| CN107652380A (en) * | 2017-09-03 | 2018-02-02 | 河南师范大学 | Heterogeneous chiral catalyst based on poly ion liquid and its preparation method and application |
| CN107652380B (en) * | 2017-09-03 | 2019-12-06 | 河南师范大学 | Heterogeneous chiral catalyst based on polyionic liquid and preparation method and application thereof |
| CN110132672A (en) * | 2019-05-16 | 2019-08-16 | 王樱达 | A kind of histocyte fixating reagent and histocyte fixing means |
| CN110132672B (en) * | 2019-05-16 | 2021-12-03 | 王樱达 | Tissue cell fixing method |
| CN115611811A (en) * | 2022-10-13 | 2023-01-17 | 上海工程技术大学 | Chiral ionic liquid and application thereof |
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Open date: 20101124 |