CN101948434A - Chiral tyrosine radical ionic liquid - Google Patents
Chiral tyrosine radical ionic liquid Download PDFInfo
- Publication number
- CN101948434A CN101948434A CN2010102973040A CN201010297304A CN101948434A CN 101948434 A CN101948434 A CN 101948434A CN 2010102973040 A CN2010102973040 A CN 2010102973040A CN 201010297304 A CN201010297304 A CN 201010297304A CN 101948434 A CN101948434 A CN 101948434A
- Authority
- CN
- China
- Prior art keywords
- chiral
- tyrosine
- ionic liquid
- chirality
- ion
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses chiral tyrosine radical ionic liquid, which consists of positive ions [C]<+> and chiral tyrosine radical ions [A]<-> and has a structural general formula: [C]<+> [A]<->. The [A]<-> represents chiral L-tyrosine radical ions or chiral D-tyrosine radical ions; and the positive ions [C]<+> may be imidazole positive ions, N-alkyl pyridine positive ions, quaternary ammonium salt positive ions, quaternary phosphonium salt positive ions or N,N-dialkyl pyridine positive ions. The invention provides the ionic liquid in which the chiral positions are on the positive ions. As the positive ions have greater structural and performance design freedom degree, the ionic liquid has structural diversity and designability. The chiral tyrosine radical ionic liquid prepared in the invention has the advantages of almost no volatilization, no toxicity, wide liquid temperature range and the like of ionic liquid and has the characteristics of high selectivity, chiral inductive effect and the like of chiral materials.
Description
Technical field
The invention belongs to the chemical material technical field, relate to chiral ionic liquid, particularly a kind of chirality tyrosine radical ion liquid.
Background technology
Environmental pollution is one of significant problem of facing of the mankind, and chemical materials is the main source that produces environmental pollution, and wherein volatile organic solvent (VOC) commonly used is the important source that chemical industry pollutes in the chemical engineering industry.Along with the aggravation of environmental problem and the raising of people's environmental consciousness, scientists is striving to find the substitute to environmentally hazardous substance always.At present, the ionic liquid that is used for substituting volatile organic solvent becomes one of research focus of Green Chemistry chemical industry.
Ionic liquid is constituted, is the salt of liquid state under near temperature room temperature or the room temperature by organic cation and inorganic anion.In recent years, become the focus of domestic and international research owing to the performance of ionic liquid excellence.Domestic and international many patent documentation US 6797853, US 6623659, US6395948, US6288281, US 6139723, CN 1123031A, CN 1140422A, CN 1225617A, CN1247856N, CN 1292372A disclose preparation method of ionic liquid and in the application in a plurality of fields.
Although non-volatile, not flammable, plurality of advantages such as thermal capacity big, Heat stability is good, ionic conductivity height, decomposition voltage height that above-mentioned ionic liquid has, but owing to do not have the chirality feature, promptly do not have chiral catalysis characteristic, chiral separation feature and chiral solvent feature, can't in chirality is synthetic, be used widely, so some investigators have prepared novel chiral ionic liquid again.
Chiral ionic liquid also has the advantageous feature that general fluent material does not have except that the functional character with general chiral object.As: 1. lower volatility and the vapour pressure that does not almost observe at normal temperatures; 2. non-flammable; 3. many organic and inorganicss there is good solubility; 4. be a class polar, non-coordinate solvent; The liquid scope that 5. non-constant width is arranged; 6. can regulate and control by selecting its physico-chemical property of yin, yang ion pair.
Chiral ionic liquid has the dual-use function of chiral material and fluent material, can replace traditional organic solvent in many aspects, has avoided shortcomings such as poisonous, corrodibility, is green, environment amenable material.Equally, because different thermodynamics and kinetics behaviors is arranged with traditional organic solvent, organic and enzyme catalysis also shows better properties aspect synthetic at chiral metal for they, has strengthened the stability of organometallic reagent and enzyme catalyst, improves selectivity and transformation efficiency.In addition, also have that product is easy to separate, fluent material can the catalysis use etc. characteristics.Their application simultaneously also expands to analytical chemistry, electrochemistry, isolation technique and materialogy field.
Publication number is that the Chinese patent of CN 1583726A discloses a class chirality alkyl tetrafluoroborate ionic liquid and a preparation method.At first, adopting chirality α-Ben Yian, ammoniacal liquor, oxalic dialdehyde and formaldehyde is starting raw material synthesis of chiral N-(α-Jia Jibianji) imidazoles; Then, the reaction of chirality N-(α-Jia Jibianji) imidazoles and halon generates chirality alkyl imidazoles spare quaternary ammonium salt; At last, chirality alkyl imidazoles spare quaternary ammonium salt and Tetrafluoroboric acid reactant salt obtain chirality alkyl tetrafluoroborate ionic liquid.This ionic liquid had both had ion liquid general characteristic, had the chirality feature again.
At present, the kind of chiral ionic liquid is also considerably less, and its applied research still is in the starting stage.Because ion liquid cationic kind is limited, the fine setting of ion liquid physical properties and chemical property simultaneously also mainly is to rely on the multifarious substituting group of regulating on the positively charged ion, and the chirality position of above-mentioned chiral ionic liquid is all on positively charged ion, make that the kind of present chiral ionic liquid is limited, and be difficult to ion liquid physical properties and chemical property are regulated as required.
Summary of the invention
The problem of solution of the present invention is to provide a kind of chirality tyrosine radical ion liquid that has chirality feature and ionic liquid feature simultaneously, this ion liquid chirality position is on negatively charged ion, positively charged ion has the bigger structure and the degree of freedom of functional design, thereby has structure diversity and designability.
The present invention is achieved through the following technical solutions:
A kind of chirality tyrosine radical ion liquid is by positively charged ion [C]
+With chirality tyrosine radical ion [A]
-Constitute, its general structure is:
[C]
+[A]
-。
Described chirality tyrosine radical ion [A]
-Be chirality L-tyrosine root or D-tyrosine root negatively charged ion, its structural formula is as follows:
Described positively charged ion [C]
+Be selected from following cationic a kind of:
Imidazoles N-alkyl pyridine class quaternary ammonium salt quaternary phosphine salt N, N-dialkyl group pyridines
Positively charged ion positively charged ion positively charged ion positively charged ion positively charged ion
Wherein, R
1, R
2, R
3, R
4Be selected from C
1～C
12Alkyl, C
3～C
12Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
2～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
5Be selected from H atom, methyl, the ethyl any one.
Compared with prior art, the present invention has following beneficial technical effects:
With respect to the chiral ionic liquid of chirality position on positively charged ion, the invention provides the ionic liquid of chirality position on negatively charged ion, negatively charged ion is the L-tyrosine radical ion of chirality or the D-tyrosine radical ion of chirality, the chirality position is on negatively charged ion, positively charged ion has the bigger structure and the degree of freedom of functional design, thereby have structure diversity and designability, will be more widely used at the Green Chemistry chemical field as chiral material and ionic liquid simultaneously.
The method for preparing chiral ionic liquid provided by the invention, technology is simple, reaction conditions is gentle, the reaction times is short, cost is low, is easy to realize, helps large-scale industrial production.
The chirality tyrosine radical ion liquid that the present invention makes not only has plurality of advantages such as ionic liquid volatilizees hardly, nontoxic, liquid temperature wide ranges, and have the chirality feature such as selectivity height, chiral induction effect of chiral material, be expected to be used widely aspect the Green Chemistry chemical industry such as chiral catalyst, chiral solvent.
Embodiment
Below the present invention is done detailed description, the explanation of the invention is not limited.
Chiral glutamate ionic liquid provided by the invention, negatively charged ion are the L-tyrosine radical ion of chirality or the D-junket ammonia propylhomoserin radical ion of chirality; Positively charged ion has structure diversity, can be imidazoles positively charged ion, N-alkyl pyridine cationoid, quaternaries cation or quaternary alkylphosphonium salt cationoid; Chirality negatively charged ion and positively charged ion keep ionization equilibrium.
Embodiment 1:L-tyrosine-1-methyl-3-butyl imidazole is ion liquid synthetic
Chloro-1-methyl-3-the butyl imidazole that takes by weighing 50g is put in the there-necked flask, the L-Sodium L-tyrosinate that adds 150ml acetone soln, 58.15g successively, and add rotor, nitrogen feeds from an inlet, the good drying tube of another spout plug, the flow velocity of control nitrogen is bubble in 1 second; There-necked flask is placed on the magnetic stirring apparatus stirs, stirred 3 days;
After reaction is finished, adopt whizzer, remove insoluble NaCl, obtain buttery liquid 160ml.Add then after the 1.5g activation Al
2O
3, and add rotor, after stirring 30min on the magnetic stirring apparatus, filter and remove Al
2O
3
Remove Al
2O
3Afterwards, remove acetone with rotary evaporation rapidly, being controlled at temperature is 48-52 ℃, obtain oily liquids, put it in the vacuum drying oven, controlled temperature is removed residual acetone at 120 ℃, obtains the 81.68g oily liquids at last, be L-tyrosine-1-methyl-3-butyl imidazole ionic liquid, encapsulation is put in the exsiccator preserves.
Embodiment 2:L-tyrosine-1-methyl-3-butyl imidazole is ion liquid synthetic, compares with embodiment 1, and its difference is, chloro-1-methyl-3-butyl imidazole adopts following synthesizing, not only save cost, and improved final ion liquid production rate, be specially:
The N-Methylimidazole of 100ml and the chlorination normal butane of 150ml are joined in the there-necked flask of 500ml, reflux under the silicone oil bath condition: at first, the control silicone oil bath is 80 ℃, rise to 100 ℃ after stablizing 10min, the control reflux temperature is 100 ℃, rising silicone oil bath temperature behind the backflow 36h, and controlled temperature is 110 ℃, backflow 24h stops heating; It is two-layer to find that product is divided into, and the upper strata is remaining chlorination normal butane, and lower floor is target product chloro-1-methyl-3-butyl imidazole.
To remove remaining chlorination normal butane with rotary evaporation rapidly, and obtain lurid oily liquids, and put it in the vacuum drying oven, controlled temperature is removed residual acetone at 120 ℃, final chloro-1-methyl-3-butyl imidazole, and quality product is: W=210g.Encapsulation is put in the exsiccator preserves.
Subsequent preparation L-tyrosine-1-methyl-ion liquid step of 3-butyl imidazole is identical with embodiment 1.
Embodiment 3:D-tyrosine-1-methyl-3-butyl imidazole is ion liquid synthetic, compares with embodiment 1, and its difference is the negatively charged ion difference of chiral ionic liquid, is specially:
At first, ion exchange reaction: the chloro-1-methyl-3-butyl imidazole that takes by weighing 50g is put in the there-necked flask, the D-Sodium L-tyrosinate that adds 150ml anhydrous propanone, 58.15g successively, and adding rotor, nitrogen feeds from an inlet, the good drying tube of another spout plug, the flow velocity of control nitrogen is bubble in 1 second; There-necked flask is placed on the magnetic stirring apparatus stirs, stirred 3 days;
After reaction is finished, adopt whizzer, remove insoluble NaCl, obtain buttery liquid 160ml.Add then after the 1.5g activation Al
2O
3, and add rotor, after stirring 30min on the magnetic stirring apparatus, filter and remove Al
2O
3
Remove Al
2O
3Afterwards, remove acetone with rotary evaporation rapidly, being controlled at temperature is 48-52 ℃, obtain oily liquids, put it in the vacuum drying oven, controlled temperature is removed residual acetone at 120 ℃, obtains the 76.52g oily liquids at last, be D-tyrosine-1-methyl-3-butyl imidazole ionic liquid, encapsulation is put in the exsiccator preserves.
Synthesizing of embodiment 4:L-tyrosine-1-methyl-3-propyl imidazole, compare with embodiment 1, the raw material that its difference is to provide the positively charged ion of chiral ionic liquid to be is chloro-1-methyl-3-propyl imidazole, the mol ratio of itself and L-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Synthesizing of embodiment 5:D-tyrosine-1-methyl-3-propyl imidazole, compare with embodiment 3, its difference is that it is chloro-1-methyl-3-propyl imidazole that the cationic raw material of chiral ionic liquid is provided, the mol ratio of itself and D-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Embodiment 6:L-tyrosine-1, synthesizing of 2-dimethyl-3-propyl imidazole, compare with embodiment 1, its difference is that it is chloro-1 that the cationic raw material of chiral ionic liquid is provided, 2-dimethyl-3-propyl imidazole, the mol ratio of itself and L-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Embodiment 7:D-tyrosine-1, synthesizing of 2-dimethyl-3-propyl imidazole compared with embodiment 6, and its difference is that it is the D-Sodium L-tyrosinate that the anionic raw material of chiral ionic liquid is provided, and all the other synthesis steps are identical.
Synthesizing of embodiment 8:L-tyrosine-1-propyl group-pyridine, compare with embodiment 1, its difference is that it is chloro-1-propyl group-pyridine that the cationic raw material of chiral ionic liquid is provided, the mol ratio of itself and L-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Synthesizing of embodiment 9:D-tyrosine-1-propyl group-pyridine, to compare with embodiment 8, its difference is that it is the L-sodium pyroglutamate that the anionic raw material of chiral ionic liquid is provided, all the other synthesis steps are identical.
Synthesizing of embodiment 10:D-tyrosine-three hexyl Shi Si Wan Ji Phosphonium, compare with embodiment 1, the cationic raw material that chiral ionic liquid is provided is chloro-1-three hexyl Shi Si Wan Ji Phosphonium, the mol ratio of itself and D-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Synthesizing of embodiment 11:L-tyrosine-1-methyl-3-butyl quaternary ammonium salt, compare with embodiment 2, the cationic raw material that chiral ionic liquid is provided is chloro-1-methyl-3-butyl quaternary ammonium, the mol ratio of itself and L-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Embodiment 12:L-tyrosine-1, synthesizing of 2-dimethyl-pyridine, compare with embodiment 1, the cationic raw material that chiral ionic liquid is provided is a chloro-1,2-dimethyl-pyridine, the mol ratio of itself and L-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Embodiment 13:D-tyrosine-1, synthesizing of 2-dimethyl-pyridine, compare with embodiment 2, the cationic raw material that chiral ionic liquid is provided is a chloro-1,2-dimethyl-pyridine, the mol ratio of itself and D-Sodium L-tyrosinate is 1: 1, and the ion exchange reaction system, to remove NaCl identical with the step of removing acetone.
Claims (3)
1. a chirality tyrosine radical ion liquid is characterized in that, by positively charged ion [C]
+With chirality tyrosine radical ion [A]
-Constitute, its general structure is:
[C]
+[A]
-。
2. chirality tyrosine radical ion liquid as claimed in claim 1 is characterized in that described chirality Xie Ansuan radical ion [A]
-Be chirality L-tyrosine root negatively charged ion or D-tyrosine root negatively charged ion, its structural formula is as follows:
3. chirality tyrosine radical ion liquid as claimed in claim 1 is characterized in that described positively charged ion [C]
+Be selected from following cationic a kind of:
Imidazoles N-alkyl pyridine class quaternary ammonium salt quaternary phosphine salt N, N-dialkyl group pyridines
Positively charged ion positively charged ion positively charged ion positively charged ion positively charged ion
Wherein, R
1, R
2, R
3, R
4Be selected from C
1～C
12Alkyl, C
3～C
12Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
2～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
5Be selected from H atom, methyl, the ethyl any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102973040A CN101948434A (en) | 2010-09-29 | 2010-09-29 | Chiral tyrosine radical ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102973040A CN101948434A (en) | 2010-09-29 | 2010-09-29 | Chiral tyrosine radical ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101948434A true CN101948434A (en) | 2011-01-19 |
Family
ID=43452078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102973040A Pending CN101948434A (en) | 2010-09-29 | 2010-09-29 | Chiral tyrosine radical ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101948434A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230812A (en) * | 2014-05-07 | 2014-12-24 | 合肥工业大学 | Imidazole chiral ionic monomer and preparation method thereof |
| WO2017136976A1 (en) * | 2016-02-14 | 2017-08-17 | 陈铭 | Ionic liquid having methanofullerene carboxylate as anion, and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383921A (en) * | 2002-05-16 | 2002-12-11 | 华东师范大学 | L-hydrosulformidate type chiral ionic liquid and its prepn |
-
2010
- 2010-09-29 CN CN2010102973040A patent/CN101948434A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383921A (en) * | 2002-05-16 | 2002-12-11 | 华东师范大学 | L-hydrosulformidate type chiral ionic liquid and its prepn |
Non-Patent Citations (4)
| Title |
|---|
| 《J. Chromatogr. A》 20080902 Fei Tang et al. Quantification of amino acid ionic liquids using liquid chromatography-mass spectrometry 175-181 1-3 , * |
| FEI TANG ET AL.: "Quantification of amino acid ionic liquids using liquid chromatography–mass spectrometry", 《J. CHROMATOGR. A》 * |
| HIROYUKI OHNO ET AL.: "Amino Acid Ionic Liquids", 《ACC. CHEM. RES.》 * |
| JUNKO KAGIMOTO ET AL.: "Effect of tetrabutylphosphonium cation on the physico-chemical properties of amino-acid ionic liquids", 《CHEM. COMMUN.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230812A (en) * | 2014-05-07 | 2014-12-24 | 合肥工业大学 | Imidazole chiral ionic monomer and preparation method thereof |
| WO2017136976A1 (en) * | 2016-02-14 | 2017-08-17 | 陈铭 | Ionic liquid having methanofullerene carboxylate as anion, and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shamsuri et al. | Ionic liquids: Preparations and limitations | |
| Sun et al. | An engineering‐purpose preparation strategy for ammonium‐type ionic liquid with high purity | |
| CN107447228A (en) | A kind of method of electro-catalysis reduction carbon dioxide | |
| CN108727427A (en) | A kind of succinct glufosinate-ammonium synthetic method | |
| CN102605011B (en) | (S)-4-chloride-3-ethyl 3-hydroxybutyrate biological preparation method | |
| CN102816182A (en) | Phosphorus-containing dication ionic liquid as well as preparation method and application thereof | |
| CN102131730A (en) | Process for production of hydrogen | |
| CN101948434A (en) | Chiral tyrosine radical ionic liquid | |
| CN102728402B (en) | Synthetic propylene carbonate catalyst, preparation method and application thereof | |
| CN103665369B (en) | A kind of polyoxyethylene glycol functionalization polyoxometalate ionic liquid and preparation method thereof | |
| CN101967126A (en) | Chiral leucine ion liquid | |
| CN101591258A (en) | A kind of chiral glutamate ionic liquid | |
| CN102336677A (en) | Chiral valine radical ionic liquid and preparation method thereof | |
| JP4322073B2 (en) | Purification method of ionic liquid | |
| CN105797739A (en) | Preparation method and application of iron hydroxide/bismuth vanadate composite photocatalyst | |
| CN101773785B (en) | Method for concentrating ion liquid by electrodialysis | |
| Lee et al. | Three Phase Boundary Engineering Using Hydrophilic–Hydrophobic Poly (N-isopropylacrylamide) with Oxygen-Vacant TiO2 Photocatalysts for Photocatalytic N2 Reduction | |
| CN101153018A (en) | Br*nsted acidity ion liquid containing N-alkyl pyrrolidone group, producing method and use of the same | |
| CN104926869B (en) | A kind of bidentate difunctionalization imidazole type ion liquid and preparation method thereof | |
| CN101781250A (en) | Method for synthesizing low bromine content iminazole ionic liquid | |
| CN105837627B (en) | A kind of difunctionalization quaternary ammonium salt ionic liquid and preparation method thereof | |
| CN104262175A (en) | Ionic liquids capable of adjusting phase behavior by using CO2, and preparation method and application thereof | |
| CN102139893B (en) | Method for preparing potassium carbonate | |
| CN101798286A (en) | 1-(3-chlorine-2-hydroxyl-propyl)-3-alkyl imidazole ionic liquid and preparation method thereof | |
| CN103787847B (en) | A kind of take ionic liquid as the technique of solvent continuous production trimethyl orthoacetate |
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: 20110119 |