CN105152949A - Amino-acid ester derivative cation type chiral ionic liquid and preparation method thereof - Google Patents
Amino-acid ester derivative cation type chiral ionic liquid and preparation method thereof Download PDFInfo
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Abstract
The invention provides an amino-acid ester derivative cation type chiral ionic liquid and a preparation method thereof. A general formula of the amino-acid ester derivative cation type chiral ionic liquid is A<+>X<->, wherein A<+> represents an amino-acid ester cation derivative, and X<-> represents one of BF4<->, PF6<-> and HSO4<->. The preparation method comprises steps as follows: amino acid, methyl alcohol and thionyl chloride react at the low temperature, and amino acid ester hydrochloride is obtained; amino acid ester hydrochloride has a Mannich reaction with paraformaldehyde and acetone, and amino acid ester derivative Mannich base is obtained; amino acid ester derivative Mannich base reacts with bromo-hydrocarbon, and a bromate type chiral ionic liquid of the amino-acid ester derivative is obtained; bromide ions of the bromate type chiral ionic liquid of the amino-acid ester derivative are exchanged, and the amino-acid ester derivative cation type chiral ionic liquid is obtained. The amino-acid ester derivative cation type chiral ionic liquid has the multiple advantages of high selectivity of a chiral substance as well as non-volatility, non-toxicity and pollution prevention of an ionic liquid, and is suitable for large-scale production of the fine chemical industry.
Description
Technical field
The present invention relates to a kind of amino acid derivative cationic ion liquid and preparation method thereof, especially relate to cationic chiral ionic liquid of a kind of amino acid ester derivative and preparation method thereof, belong to chemical material and preparing technical field thereof.
Background technology
Ionic liquid is made up of organic cation and organic or inorganic negatively charged ion, room temperature or close near room temperature temperature under in the salt of liquid state.Ionic liquid has that excellent physicochemical property are forced down as having steam, good conductivity, strong polarity, wider electrochemical window, thermostability is high and have the characteristics such as good solvability and catalytic performance to Cucumber, and/zwitterion the structure of modulation can be modified, and can recycle, be considered to the novel green solvent substituting conventional volatile organic solvent, be widely applied at chemical field.
Along with the development of ionic liquid design and synthesis technology, chiral centre is introduced in some scholars design that to begin one's study in ionic liquid in recent years, expands research field and the range of application of ionic liquid.Chiral ionic liquid combines advantage and the characteristic of ionic liquid and chiral material, can be applicable to the fields such as chiral recognition, asymmetric synthesis, Chiral Separation, stereoselective polymerization, gas-chromatography, NMR shift reagent and liquid crystal.
Therefore, development chiral ionic liquid, introduces green medium and has important practical significance in chiral synthesize field.At present, existing many reports in the synthesis and applied research thereof of chiral ionic liquid, as synthesized a series of chiral ionic liquid using α-pinene, menthol, ephedrine etc. as chiral source.
Amino acid is the natural chiral source of a class, is that chiral source synthesis of chiral ionic liquid starting material is easy to get, greatly reduces the cost of synthesis of chiral ionic liquid by natural amino acid.In recent years, the report synthesizing ionic liquid using amino acid as chiral source increases gradually, as Chinese patent CN1383920A, CN104693056A and CN1383921A respectively describes the technical scheme of a kind of L-sulforamidate type chiral ionic liquid and preparation method thereof and L-sulforamidate type chiral ionic liquid and preparation method thereof, CN1621152A describes amino acid ester cationic ion liquid and preparation method, technical scheme disclosed in these has enriched the kind of amino acid ion liquid, application for ionic liquid provides benefits our pursuits, but the amino acid ion liquid preparation method that above-mentioned patent application describes is coarse, amino acid acid cationic structural simple (not being there is carboxyl to there is amino exactly), which has limited its use range.Therefore, the cationic chiral ionic liquid of amino acid of necessary exploration invention complex construction, expands its Application Areas.
Summary of the invention
Goal of the invention of the present invention is for prior art Problems existing, one is to provide a kind of amino acid ester bromination salt form chiral ionic liquid simultaneously with the chirality of Chiral properties and ionic liquid feature, the chirality position of this ionic liquid on amino acid positively charged ion, two preparation methods being to provide the cationic chiral ionic liquid of a kind of amino acid ester derivative.
Realize foregoing invention object by the following technical solutions:
The cationic chiral ionic liquid of a kind of amino acid ester derivative, its structural formula is as follows:
, described amino acid is D-, ALANINE.
As preferably, in described amino acid positively charged ion, R
'for CH
3or CH
3cH
2; Described X
-for BF
4 -, PF
6 -, HSO
4 -in any one.
As preferably, the general formula of the cationic chiral ionic liquid of described amino acid ester derivative is A
+x
-, wherein A
+for amino acid ester cationic derivative, X
-for BF
4 -, PF
6 -, HSO
4 -.
A preparation method for the cationic chiral ionic liquid of amino acid ester derivative, the reactive material used in preparation process comprises: a-amino acid, sulfur oxychloride, paraformaldehyde, monobromethane, NaBF
4, KPF
6, NaHSO
4, and alcoholic solvent; Preparation process is as follows:
(1) under-14 DEG C ~-10 DEG C low temperature environments, sulfur oxychloride is slowly added drop-wise in methyl alcohol, drips off rear continuation reaction 1 hour, be warming up to room temperature, add amino acid in batches, 50 DEG C of insulated and stirred are revolved after 4 hours and are steamed except desolventizing, and obtain the hydrochloride of amino acid ester, this material is viscous liquid;
(2) Mannich reaction: paraformaldehyde is joined in methyl alcohol, adjust pH to 5 with dilute hydrochloric acid, heating is until paraformaldehyde dissolves, then product amino acid ester hydrochloride and acetone that room temperature adds step (1) is down to, reflux 48 hours, revolve and steam except desolventizing, crude product adopts column chromatography purification, obtains amino acid ester derivative Mannich base;
(3) quaterisation: the product amino acid ester derivative Mannich base alcoholic solvent of step (2) is dissolved, then monobromethane is added, pH to 8 ~ 9 are adjusted by NaOH solution, reflux 2 ~ 3 hours, slough partial solvent, removed by filtration NaBr, then desolvation, obtain the chiral ionic liquid of amino acid ester derivative Bromide;
(4) negatively charged ion is exchanged: the amino acid ester derivative Bromide ionic liquid obtain step (3) and NaBF
4, KPF
6, NaHSO
4in any one be proportionally mixed in round-bottomed flask, add solvent reaction, reaction terminate after obtain the cationic chiral ionic liquid product of amino acid ester derivative.
As preferably, the amount of substance of described amino acid, sulfur oxychloride, methyl alcohol is than being 1:1:20 ~ 30.
As preferably, the amount of substance ratio of described paraformaldehyde, acetone, alanine ester derivant hydrochloric acid salt is 2 ~ 3:2 ~ 3:1;
As preferably, described monobromethane is 1 ~ 2:1 with the ratio of the amount of substance of amino acid ester derivative Mannich base;
As preferably, described amino acid ester derivative Bromide ionic liquid and NaBF
4, KPF
6, NaHSO
4in any one the amount of substance of add-on than for 1:1 ~ 1.5.
As preferably, in Mannich reaction, the eluent of crude product column chromatography purification adopts methyl alcohol and methylene chloride volume than the mixed solution for 1:20.
As preferably, the solvent exchanging negatively charged ion step is water or acetone, and when using water as solvent, after reaction terminates, layering, discards liquid last time, with vacuum-drying after lower floor's liquid washed with diethylether, obtains product; When using acetone as solvent, after reaction terminates, suction filtration removing solid NaBr and the complete raw material of unreacted, then underpressure distillation removing acetone solvent obtains product.
Adopt technique scheme, compared with prior art, the general formula of amino acid ester derivative chiral ionic liquid of the present invention is A
+x
-, wherein A
+for amino acid ester derivative positively charged ion, X
-for BF
4 -, PF
6 -, HSO
4 -in any one; By amino acid and methyl alcohol, sulfur oxychloride are obtained by reacting amino acid ester derivative hydrochloride at low temperatures; Amino acid ester derivative hydrochloride and paraformaldehyde, acetone are obtained tertiary amine (amino acid ester derivative Mannich base) through Mannich reaction; The tertiary amine of amino acid ester and hydrobromic ether are obtained by reacting the chiral ionic liquid of amino acid ester derivative Bromide; Desired amino acid ester derivant cationic ion liquid is obtained by exchanging negatively charged ion.Abundant raw material source, cheap, simple to operate.The chiral amino acid ester derivant cationic ion liquid chirality position obtained by above-mentioned steps is on the positively charged ion of L-Ala, and amino is connected with bulky group, and stereoselectivity is stronger; Negatively charged ion has the degree of freedom of larger structure design, has structure diversity and designability.Chiral amino acid ester derivant ionic liquid provided by the invention not only has the characteristic of ionic liquid but also has the characteristic of chiral material simultaneously, as: liquid range is wide, steam forces down, good conductivity, polarity strong, can be used for chiral catalysis and chiral separation.There is the highly selective of chiral material, non-volatile, nontoxic, pollution-free plurality of advantages that chiral induction effect also has ionic liquid, be applicable to Fine Chemical scale production, expanded the new variety of ionic liquid.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
The cationic chiral ionic liquid of amino acid ester derivative, its structural formula is as follows:
, described amino acid is D-, ALANINE
In described amino acid derivative positively charged ion, R
'for CH
3or CH
3cH
2.Described X
-for BF
4 -, PF
6 -, HSO
4 -in any one.
The general formula of the cationic chiral ionic liquid of described amino acid ester derivative is A
+x
-, wherein A
+for amino acid ester cationic derivative, X
-for BF
4 -, PF
6 -, HSO
4 -.
Embodiment 2
The preparation method of the cationic chiral ionic liquid of amino acid ester derivative
(1) under-14 DEG C ~-10 DEG C low temperature environments, sulfur oxychloride is slowly added drop-wise in methyl alcohol, drips off rear continuation reaction 1 hour, be warming up to room temperature, add amino acid in batches, 50 DEG C of insulated and stirred are revolved after 4 hours and are steamed except desolventizing, and obtain the hydrochloride of amino acid ester, this material is viscous liquid;
(2) Mannich reaction: paraformaldehyde is joined in methyl alcohol, adjust pH to 5 with dilute hydrochloric acid, heating is until paraformaldehyde dissolves, then product amino acid ester hydrochloride and acetone that room temperature adds step (1) is down to, reflux 48 hours, revolve and steam except desolventizing, crude product adopts column chromatography purification (eluent methyl alcohol and methylene chloride volume are than the mixed solution being 1:20), obtains amino acid ester derivative Mannich base;
(3) quaterisation: the product amino acid ester derivative Mannich base alcoholic solvent of step (2) is dissolved, then monobromethane is added, pH to 8 ~ 9 are adjusted by NaOH solution, reflux 2 ~ 3 hours, slough partial solvent, removed by filtration NaBr, then desolvation, obtain the chiral ionic liquid of amino acid ester derivative Bromide.
(4) negatively charged ion is exchanged: the amino acid ester derivative Bromide ionic liquid obtain step (3) and NaBF
4, KPF
6, NaHSO
4in any one be mixed in by a certain percentage in round-bottomed flask, add deionized water or acetone as solvent, stirring at normal temperature 3 ~ 24h, when using water as solvent, after reaction terminates, layering, discard liquid last time, with vacuum-drying after lower floor's liquid washed with diethylether, obtain product; When using acetone as solvent, after reaction terminates, suction filtration removing solid NaBr and the complete raw material of unreacted, then underpressure distillation removing acetone solvent obtains product.
The amount of substance of described amino acid, sulfur oxychloride, methyl alcohol is than being 1:1:20 ~ 30.
The amount of substance ratio of described paraformaldehyde, acetone, alanine ester derivant hydrochloric acid salt is 2 ~ 3:2 ~ 3:1;
Described monobromethane is 1 ~ 2:1 with the ratio of the amount of substance of amino acid ester derivative Mannich base;
Described amino acid ester derivative Bromide ionic liquid and NaBF
4, KPF
6, NaHSO
4in any one the amount of substance of add-on than for 1:1 ~ 1.5.
In Mannich reaction, the eluent of crude product column chromatography purification adopts methyl alcohol and methylene chloride volume than the mixed solution for 1:20.
The solvent exchanging negatively charged ion step selects deionized water or acetone, and when making solvent with deionized water, after reaction terminates, layering, discards liquid last time, with vacuum-drying after lower floor's liquid washed with diethylether, obtains product; When using acetone as solvent, after reaction terminates, suction filtration removing solid NaBr and the complete raw material of unreacted, then underpressure distillation removing acetone solvent obtains product.
concrete preparation method's embodiment
Embodiment 3
The preparation of the cationic chiral ionic liquid of alanine methyl ester derivative
(1) synthesis of alanine methyl ester
Get 125mL methyl alcohol, be added to 250mL three-necked flask and (should guarantee during reaction that environment is anhydrous, band drying installation; Reaction can generate HCl and SO
2gas, uses alkali liquor absorption device) in, in cryogenic thermostat reactive bath technique, cool it to-14 DEG C, under magnetic agitation, slowly drip 10mL (0.138mol) SOCl
2, control temperature of reaction during dropping below-10 DEG C, after dropwising, continue reaction 1h.Reaction solution is gone to 250mL round-bottomed flask, temperature rises to room temperature naturally, adds 12.21g (0.137mol) L-Ala, under magnetic stirring heating reflux reaction stopped reaction after 4 hours.Product being revolved steaming, after steaming solvent, obtains alanine methyl ester hydrochloride, is yellow, viscous liquid, productive rate 98%, need not purify and can be directly used in next step synthesis.
(2) synthesis of alanine methyl ester derivative Mannich base
Get alanine methyl ester hydrochloride 10.43g(0.0747mol) in 250mL three-necked flask; be dissolved in 80mL methyl alcohol; add 12.21g(0.21mol) acetone, then add 6.25g(0.21mol) paraformaldehyde, drip dilute hydrochloric acid to pH=5; protection gas reflux 48h is under magnetic stirring made with nitrogen; react complete, suction filtration removes insolubles, and filtrate is revolved steaming; steam solvent, obtain dark brown liquid.
Crude product adopts column chromatography purification, and eluent methyl alcohol and methylene chloride volume are than the mixed solution of 1:20, and productive rate is 86%.
(3) synthesis of alanine methyl ester derivative positively charged ion Bromide
Get previous step product alanine methyl ester derivation Mannich base 4.0g (0.0143mol) in 100mL round-bottomed flask, add 40mL methyl alcohol, adjust pH=9, add 1.66g (0.0152mol) monobromethane again, reflux 2h, after completion of the reaction, crosses and filters insolubles, filtrate revolves steaming, obtains yellow liquid crude product.
Product column chromatography purification, the mixed solution of eluent methyl alcohol and methylene dichloride 1:20, productive rate is 92%.
(4) get alanine methyl ester derivative positively charged ion Bromide ionic liquid 4.5g (0.0116mol) that step (3) obtains and put into 100mL there-necked flask, add 2.15g (0.0117mol) KPF
6, add 30mL deionized water, stirring at normal temperature 10 hours, stopped reaction, stratification, discards liquid last time, and lower floor's liquid is with after 20mL washed with diethylether twice, and vacuum-drying, obtains product, productive rate 80%.
Embodiment 4
(1) synthesis of alanine methyl ester
Get 120mL methyl alcohol, be added to 250mL three-necked flask and (should guarantee during reaction that environment is anhydrous, band drying installation; Reaction can generate HCl and SO
2gas, uses alkali liquor absorption device) in, in cryogenic thermostat reactive bath technique, cool it to-13 DEG C, under magnetic agitation, slowly drip 9mL (0.124mol) SOCl
2, control temperature of reaction during dropping below-10 DEG C, after dropwising, continue reaction 1h.Reaction solution is gone to 250mL round-bottomed flask, temperature rises to room temperature naturally, adds 11.14g (0.125mol) L-Ala, under magnetic stirring heating reflux reaction stopped reaction after 4 hours.Product being revolved steaming, after steaming solvent, obtains alanine methyl ester hydrochloride, is yellow, viscous liquid, productive rate 97%, need not purify and can be directly used in next step synthesis.
(2) synthesis of alanine methyl ester derivative Mannich base
Get alanine methyl ester hydrochloride 9.85g(0.0705mol) in 250mL three-necked flask; be dissolved in 80mL methyl alcohol; add 12.05g(0.207mol) acetone, then add 6.04g(0.203mol) paraformaldehyde, drip dilute hydrochloric acid to pH=5; protection gas reflux 48h is under magnetic stirring made with nitrogen; react complete, suction filtration removes insolubles, and filtrate is revolved steaming; steam solvent, obtain dark brown liquid.
Crude product adopts column chromatography purification, and eluent methyl alcohol and methylene chloride volume are than the mixed solution of 1:20, and productive rate is 85%.
(3) synthesis of alanine methyl ester derivative positively charged ion Bromide
Get previous step product alanine methyl ester derivation Mannich base 4.08g (0.0146mol) in 100mL round-bottomed flask, add 40mL methyl alcohol, adjust pH=9, add 1.85g (0.0169mol) monobromethane again, reflux 2h, after completion of the reaction, crosses and filters insolubles, filtrate revolves steaming, obtains yellow liquid crude product.
Product column chromatography purification, the mixed solution of eluent methyl alcohol and methylene dichloride 1:20, productive rate is 94%.
(4) get alanine methyl ester derivative positively charged ion Bromide ionic liquid 4.30g (0.0111mol) that step (3) obtains and put into 100mL there-necked flask, add 1.50g (0.0125mol) NaHSO
4, add 30mL acetone, stirring at normal temperature 24 hours, stopped reaction, suction filtration removing solid NaBr and excessive hydrosulfate, then underpressure distillation removing acetone solvent obtains target product, productive rate 95%.
Embodiment 5
(1) synthesis of alanine methyl ester
Get 120mL methyl alcohol, be added to 250mL three-necked flask and (should guarantee during reaction that environment is anhydrous, band drying installation; Reaction can generate HCl and SO
2gas, uses alkali liquor absorption device) in, in cryogenic thermostat reactive bath technique, cool it to-12 DEG C, under magnetic agitation, slowly drip 9.5mL (0.131mol) SOCl
2, control temperature of reaction during dropping below-10 DEG C, after dropwising, continue reaction 1h.Reaction solution is gone to 250mL round-bottomed flask, temperature rises to room temperature naturally, adds 11.59g (0.130mol) L-Ala, under magnetic stirring heating reflux reaction stopped reaction after 4 hours.Product being revolved steaming, after steaming solvent, obtains alanine methyl ester hydrochloride, is yellow, viscous liquid, productive rate 98%, need not purify and can be directly used in next step synthesis.
(2) synthesis of alanine methyl ester derivative Mannich base
Get alanine methyl ester hydrochloride 10.22g(0.0730mol) in 250mL three-necked flask; be dissolved in 82mL methyl alcohol; add 12.01g(0.206mol) acetone, then add 6.01g(0.202mol) paraformaldehyde, drip dilute hydrochloric acid to pH=5; protection gas reflux 48h is under magnetic stirring made with nitrogen; react complete, suction filtration removes insolubles, and filtrate is revolved steaming; steam solvent, obtain dark brown liquid.
Crude product adopts column chromatography purification, and eluent methyl alcohol and methylene chloride volume are than the mixed solution of 1:20, and productive rate is 85%.
(3) synthesis of alanine methyl ester derivative positively charged ion Bromide
Get previous step product alanine methyl ester derivation Mannich base 3.98g (0.0142mol) in 100mL round-bottomed flask, add 41mL methyl alcohol, adjust pH=9, add 1.73g (0.0158mol) monobromethane again, reflux 2h, after completion of the reaction, crosses and filters insolubles, filtrate revolves steaming, obtains yellow liquid crude product.
Product column chromatography purification, the mixed solution of eluent methyl alcohol and methylene dichloride 1:20, productive rate is 95%.
(4) get alanine methyl ester derivative positively charged ion Bromide ionic liquid 4.25g (0.0111mol) that step (3) obtains and put into 100mL there-necked flask, add 1.37g (0.0125mol) NaBF
4, add 30mL acetone, stirring at normal temperature 5 hours, stopped reaction, suction filtration removing solid NaBr and excessive Sodium tetrafluoroborate, then underpressure distillation removing acetone solvent obtains target product, productive rate 96%.
Claims (10)
1. the cationic chiral ionic liquid of amino acid ester derivative, is characterized in that, its structural formula is as follows:
, described amino acid is D-, ALANINE.
The cationic chiral ionic liquid of 2.=amino acid ester derivative according to claim 1, is characterized in that, in described amino acid positively charged ion, and R
'for CH
3or CH
3cH
2; Described X
-for BF
4 -, PF
6 -, HSO
4 -in any one.
3. the cationic chiral ionic liquid of amino acid ester derivative according to claim 1, is characterized in that, the general formula of the cationic chiral ionic liquid of described amino acid ester derivative is A
+x
-, wherein A
+for amino acid ester cationic derivative, X
-for BF
4 -, PF
6 -, HSO
4 -.
4. a preparation method for the cationic chiral ionic liquid of amino acid ester derivative, is characterized in that, the reactive material used in preparation process comprises: a-amino acid, sulfur oxychloride, paraformaldehyde, monobromethane, NaBF
4, KPF
6, NaHSO
4, and alcoholic solvent; Preparation process is as follows:
(1) under-14 DEG C ~-10 DEG C low temperature environments, sulfur oxychloride is slowly added drop-wise in methyl alcohol, drips off rear continuation reaction 1 hour, be warming up to room temperature, add amino acid in batches, 50 DEG C of insulated and stirred are revolved after 4 hours and are steamed except desolventizing, and obtain the hydrochloride of amino acid ester, this material is viscous liquid;
(2) Mannich reaction: paraformaldehyde is joined in methyl alcohol, adjust pH to 5 with dilute hydrochloric acid, heating is until paraformaldehyde dissolves, then product amino acid ester hydrochloride and acetone that room temperature adds step (1) is down to, reflux 48 hours, revolve and steam except desolventizing, crude product adopts methyl alcohol and methylene chloride volume to carry out column chromatography purification than the mixed solution for 1:20 and obtains amino acid ester derivative Mannich base;
(3) quaterisation: the product amino acid ester derivative Mannich base alcoholic solvent of step (2) is dissolved, then monobromethane is added, pH to 8 ~ 9 are adjusted by NaOH solution, reflux 2 ~ 3 hours, slough partial solvent, removed by filtration NaBr, then desolvation, obtain the chiral ionic liquid of amino acid ester derivative Bromide;
(4) negatively charged ion is exchanged: the amino acid ester derivative Bromide ionic liquid obtain step (3) and NaBF
4, KPF
6, NaHSO
4in any one be mixed in by a certain percentage in round-bottomed flask, add solvent reaction, reaction terminate after obtain the cationic chiral ionic liquid product of amino acid ester derivative.
5. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, is characterized in that, the amount of substance of described amino acid, sulfur oxychloride, methyl alcohol is than being 1:1:20 ~ 30.
6. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, it is characterized in that, the amount of substance ratio of described paraformaldehyde, acetone, alanine ester derivant hydrochloric acid salt is 2 ~ 3:2 ~ 3:1.
7. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, it is characterized in that, described monobromethane is 1 ~ 2:1 with the ratio of the amount of substance of amino acid ester derivative Mannich base.
8. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, is characterized in that, described amino acid ester derivative Bromide ionic liquid and NaBF
4, KPF
6, NaHSO
4in any one the amount of substance of add-on than for 1:1 ~ 1.5.
9. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, is characterized in that, in Mannich reaction, the eluent of crude product column chromatography purification adopts methyl alcohol and methylene chloride volume than the mixed solution for 1:20.
10. the preparation method of the cationic chiral ionic liquid of amino acid ester derivative according to claim 4, it is characterized in that, the solvent exchanging negatively charged ion step is water or acetone, when using water as solvent, after reaction terminates, layering, discards liquid last time, with vacuum-drying after lower floor's liquid washed with diethylether, obtain product; When using acetone as solvent, after reaction terminates, suction filtration removing solid NaBr and the complete raw material of unreacted, then underpressure distillation removing acetone solvent obtains product.
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| CN106397239A (en) * | 2016-08-29 | 2017-02-15 | 唐山师范学院 | Amino acid ester cationic chiral ionic liquid and preparation method thereof |
| CN107021886A (en) * | 2017-05-10 | 2017-08-08 | 中国科学院过程工程研究所 | One class quaternary amines chiral ionic liquid and preparation method thereof |
| CN111004138A (en) * | 2019-12-12 | 2020-04-14 | 南京恒道医药科技有限公司 | Green production method and device of levetiracetam key intermediate S-2-methyl aminobutyric acid |
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| CN105152949B (en) | 2017-03-29 |
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