CN1383921A - L-hydrosulformidate type chiral ionic liquid and its prepn - Google Patents
L-hydrosulformidate type chiral ionic liquid and its prepn Download PDFInfo
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- CN1383921A CN1383921A CN 02111688 CN02111688A CN1383921A CN 1383921 A CN1383921 A CN 1383921A CN 02111688 CN02111688 CN 02111688 CN 02111688 A CN02111688 A CN 02111688A CN 1383921 A CN1383921 A CN 1383921A
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Abstract
The present invention relates to a new type chemical material and its preparation. L-hydrosulforamidate-type chiral ionic liquid is prepared through the full reaction of aqueous L-amino acid solution with 98% sulfuric acid. The produced L-hydrosulforamidate-type chiral ionic liquid has the features of both ionic liquid and chiral matter. The reaction has high product purity, low cost, no exhausted pollutant and no side product, and is suitable for application in large scale industrial production. The new material is capable of becoming environmentally friendly important chemical material.
Description
(I) technical field
The invention relates to an ionic liquid and a preparation method thereof, in particular to a novel L-amino acid bisulfate type chiral ionic liquid and a preparation method thereof, belonging to the technical field of novel chemical materials and preparation thereof.
(II) background of the invention
In recent years, ionic liquids have attracted wide attention as green solvents or catalysts, and are commonly used in organic synthesis, chemical separation, and electrochemical processesIn chemical reaction processes, the catalyst has the dual-function characteristic of a solvent catalyst. In "chemical reagents", 2001, 23(4), pages 211-215, "synthesis and application of ionic liquids" by ruxiong et al, it is mentioned that there are 4 types of cations in ionic liquids: alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, alkyl imidazolium ions, and alkyl pyridinium ions; the anion being predominantly Cl-、Br-、BF4 -、PF6 -、(CF3SO3)2N-、CF3COO-And the like. Through different combinations of the cations and the anions, ionic liquids with various characteristics are prepared, but the L-amino acid hydrogen sulfate type ionic liquids related to the invention have not been reported so far. Moreover, these ionic liquids have in common that none of the previously reported ionic liquids have the characteristics of chiral substances, i.e., chiral catalytic characteristics, chiral separation characteristics and chiral solvent characteristics, and thus they are not chiral ionic liquids. Chiral substances refer to a class of objects that cannot be subjected to mirror image coincidence, and the stereoselectivity of chiral substances based on intramolecular asymmetric induction plays an important role in organic synthetic chemistry, but the chiral substances generally do not have the wide liquid range, low vapor pressure, good conductivity, wide electrochemical window, strong polarity, and selectivity for dissolution and catalysis of some substances of ionic liquids. At present, no report is found about L-amino acid bisulfate type chiral ionic liquid, and a preparation method thereof is also the first mentioned in the invention. The prior ionic liquid preparation also has a plurality of defects: the raw materials are short, the cost is high, and the cost is generally more than 2 times of that of a common organic solvent; the preparation is difficult, the product is difficult to purify, and the method is not suitable for large-scale industrial production and application; usually with trichlorinationThe aluminum is combined, so that pollution is easily caused, and the application of the aluminum in the green chemical industry is influenced.
Disclosure of the invention
The invention aims to provide a novel L-amino acid bisulfate type chiral ionic liquid which not only has the excellent characteristics of chiral substances, but also has the good characteristics of ionic liquid, and provides a preparation method of the ionic liquid.
The L-amino acid bisulfate type chiral ionic liquid provided by the invention has the following structural formula:
[amino acid][HSO4]n
wherein n is in the range of 1-4 for different L-amino acid cations, i.e. n is 1 when the valency of the L-amino acid cation is 1, n is 2 when the valency of the L-amino acid cation is 2, n is 3 when the valency of the L-amino acid cation is 3, and n is 4 when the valency of the L-amino acid cation is 4.
The preparation method of the L-amino acid hydrogen sulfate type chiral ionic liquid provided by the invention comprises the following steps: preparing an aqueous solution of L-amino acid, and dropwise adding sulfuric acid with the concentration of 98% while stirring, wherein the molar ratio of the L-amino acid to concentrated sulfuric acid is as follows: when the valence of the L-amino acid cation is 1, the molar ratio is 1: 1, when the valence of the L-amino acid cation is 2, the molar ratio is 1: 2, when the valence of the L-amino acid cation is 3, the molar ratio is 1: 3, when the valence of the L-amino acid cation is 4, the molar ratio is 1: 4, after full reaction, water is evaporated to obtain the final product L-amino acid hydrogen sulfate type chiral ionic liquid. The reaction formula is shown as:
the invention relates to L-amino acid bisulfate type chiral ionic liquid, wherein L-amino acid [ amino acid]]Preferably: alanine [ Ala]]Valine [ Val]]Leucine [ Leu]]Glycine [ Gly]]Tyrosine [ Tyr]Glutamic acid [ Glu]Proline [ Pro]]Lysine [ Lys]]Histidine [ His]]And arginine [ Arg]]One of them. That is to say, the L-amino acid bisulfate type chiral ionic liquid related to the invention is preferably: alanine bisulfate chiral ionic liquid [ Ala]]HSO4Valine hydrosulfate chiral ionic liquid [ Val]HSO4Leucine hydrogen sulfateSalt chiral ionic liquid [ Leu]HSO4Glycine bisulfate chiral ionic liquid [ Gly]HSO4Tyrosine bisulfate chiral ionic liquid [ Tyr]HSO4Glutamic acid bisulfate chiral ionic liquid [ Glu]HSO4Proline bisulfate chiral ionic liquid [ Pro]HSO4Lysine bisulfate chiral ionic liquid [ Lys][HSO4]2Histidine bisulfate chiral ionic liquid [ His]][HSO4]3And arginine bisulfate chiral ionic liquid [ Arg]][HSO4]4One of them.
The L-amino acid hydrogen sulfate type chiral ionic liquid [ aminoacid]provided by the invention][HSO4]nThe preferable scheme of the preparation method is as follows: the L-amino acids in the preparation method are respectively treated with alanine [ Ala]Valine [ Val]]Leucine [ Leu]]Glycine [ Gly]]Tyrosine [ Tyr]Glutamic acid [ Glu]Proline [ Pro]]Lysine [ Lys]]Histidine [ His]]And arginine [ Arg]]One of the two is substituted to obtain the L-amino acid hydrogen sulfate type chiral ionic liquid
In addition to the acid hydrogensulfates described above and their preparation, other amino acid hydrogensulfates consisting of L-amino acids such as tryptophan were also tested. Most of the new compounds have low melting points, generally about-20 ℃, and some of them are below-80 ℃. Their electrical conductivity was found to be 10 at 60 ℃3-104The general rule is also followed between (the unit is mu S/cm), and the conductivity tends to increase along with the temperature increase, and the increase range is different. And the ionic liquid has a refractive index of between 1.4 and 1.5 measured at that temperature. The thermal stability data of a series of new compounds were obtained from a TG/SDTA851e differential thermal analyzer from Mettler corporation, and it was found that most of them exhibited better thermal stability and started to decompose at temperatures above 200 ℃ depending on the properties of each amino acid. The results of the measurements were 10 at room temperature using model RVT-TB, model RVT-TE, model RVT22-103The viscosity size difference is large between cP (except solid state).
The L-amino acid bisulfate chiral ionic liquid provided by the invention has the following beneficial effects:
(1) the ionic liquid has the characteristics of an ionic liquid and chiral substances, such as: chiral separation, chiral catalysis, and chiral solvent properties that are not normally available with ionic liquids.
(2) The chiral compound has the characteristics of an ionic liquid, such as: wide liquid range, low vapor pressure, good conductivity, wide electrochemical window, strong polarity, and selectivity for dissolution and catalysis of certain substances, which are not available in common chiral substances.
The preparation method of the L-amino acid hydrogen sulfate type chiral ionic liquid provided by the invention has the following remarkable effects:
(1) the raw materials are easy to obtain and the price is low, so the preparation cost is low;
(2) the neutralization reaction has simple preparation, needs less equipment, can obtain a very pure product without excessive operation, and is suitable for large-scale industrial production and application;
(3) the preparation process does not discharge pollutants and byproducts, and belongs to an atom-economic green preparation process;
(4) the melting point and the acid-base strength of the designed product can be adjusted in the preparation process, which is only performed by the ionic liquid containing aluminum trichloride.
(IV) detailed description of the preferred embodiments
Example 1: alanine bisulfate chiral ionic liquid
5.00g alanine (0.056mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) was weighed into 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The using amount is 5.62g (0.056mol), namely the mol ratio of the reaction raw materials is 1: 1, the transparent mixed solution is stirred for 1 hour at room temperature, transferred to a rotary evaporator, evaporated at 40-50 ℃ for dehydration, and then heated to 80-85 ℃ for evaporation for 2 hours, and finally the colorless transparent alanine bisulfate chiralionic liquid is obtained. The reaction formula is as follows:
example 2: chiral ionic liquid of valine hydrogen sulfate
5.00g of valine (0.043mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) was weighed into a 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 4.2g (0.043mol), i.e.the molar ratio of the starting materials was 1: 1.And continuously stirring the transparent mixed solution at room temperature for 1 hour, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, then heating to 80-85 ℃ to evaporate for 2 hours, and finally obtaining the colorless transparent valine hydrosulfate chiral ionic liquid. The reaction formula is as follows:
example 3: chiral ionic liquid of leucine hydrogen sulfate
5.00g leucine (0.038mol, purity over 99%, available from Shanghai Gill Biochemical Co., Ltd.) was weighed into 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 3.8g (0.038mol), i.e.the molar ratio of the starting materials was 1: 1. Stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, heating to 80-85 ℃ to evaporate for 2 hours, and finally obtaining colorless transparent bright amino acid bisulfate chiral ionic liquid. The reaction formula is as follows:
example 4: glycine bisulfate chiral ionic liquid
5.00g of glycine (0.067mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) was weighed into 50ml of distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 6.6g (0.067mol), i.e.the molar ratio of the starting materials was 1: 1. The clear mixture was stirred for an additional 1 hour at room temperature. Turning to rotary evaporationEvaporating water at 40-50 ℃, then heating to 80-85 ℃ for evaporating for 3 hours to finally obtain a colorless transparent liquid glycine bisulfate chiral ionic liquid. The reaction formula is as follows:
example 5: chiral ionic liquid of tyrosine bisulfate
Weighing 5.00g tyrosine (0.028mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) in 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 2.8g (0.028mol), i.e. the molar ratio of the starting materials was 1: 1. Stirring the transparent mixed solution at room temperature for 1 hr, transferring into rotary evaporator, evaporating at 40-50 deg.C to remove water, heating to 80-85 deg.C, evaporating for 2 hr, and cooling to crystallizeObtaining the chiral ionic liquid of tyrosine bisulfate. The reaction formula is as follows:
example 6: chiral ionic liquid of glutamic acid bisulfate
5.00g glutamic acid (0.034mol, purity over 99%, available from Shanghai Gill Biochemical Co., Ltd.) was weighed into 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 3.4g (0.034mol), i.e.the molar ratio of the starting materials was 1: 1. And continuously stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, then heating to 80-85 ℃ to evaporate for 2 hours, and finally obtaining colorless transparent glutamic acid bisulfate chiral ionic liquid. The reaction formula is as follows:
example 7: proline bisulfate chiral ionic liquid
5.00g proline (0.043mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) was weighed into 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 4.2g (0.043mol), i.e.the molar ratio of the starting materials was 1: 1. And continuously stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating water at 40-50 ℃, heating to 80-85 ℃ for evaporating for 3 hours, and finally obtaining colorless transparent proline bisulfate chiral ionic liquid. The reaction formula is as follows:
example 8: lysine bisulfate chiral ionic liquid
5.00g of lysine (0.034mol, purity over 99%, available from Shanghai Gill Biochemical Co., Ltd.) was weighed into 50ml of distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 6.8g (0.068mol), i.e.the molar ratio of the starting materials was 1: 2. And continuously stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, then heating to 80-85 ℃ to evaporate for 3 hours, and finally obtaining the colorless transparent lysine bisulfate chiral ionic liquid. The reaction formula is as follows:
example 9: histidine bisulfate chiral ionic liquid
5.00g of histidine (0.032mol, purity over 99%, available from Shanghai Jier Biochemical Co.) were weighed into a 50ml distillation H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 9.62g (0.096mol), i.e. the molar ratio of the starting materials was 1: 3. And continuously stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, then heating to 80-85 ℃ to evaporate for 3 hours, and finally obtaining colorless transparent histidine bisulfate chiral ionic liquid. The reaction formula is as follows:
example 10: chiral ionic liquid of arginine bisulfate
Weighing 5.00g arginine (0.029mol, purity over 99%, available from Shanghai Jier Biochemical Co., Ltd.) in 50ml distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 11.2g (0.116mol), i.e.the molar ratio of the starting materials was 1: 4. And continuously stirring the transparent mixed solution for 1 hour at room temperature, transferring the mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, then heating to 80-85 ℃ to evaporate for 2 hours, and finally obtaining colorless transparent arginine bisulfate chiral ionic liquid. The reaction formula is as follows:
the L-amino acid bisulfate chiral ionic liquid provided by the invention belongs to simple acid-base neutralization reaction in the preparation process, does not discharge pollutants or by-products, can obtain a very pure product without excessive operation, has low cost, is suitable for large-scale industrial production and application, and is likely to become an important novel material in the aspect of green chemical industry in the future.
Claims (4)
1. The invention relates to L-amino acid bisulfate type chiral ionic liquid which is characterized by having the following structural formula:
[amino acid][HSO4]n
wherein n ranges from 1 to 4 according to different L-amino acid cations.
2. The invention relates to a preparation method of L-amino acid hydrogen sulfate type chiral ionic liquid, which is characterized by comprising the following preparation processes: preparing an aqueous solution of L-amino acid, and dropwise adding sulfuric acid with the concentration of 98% while stirring, wherein the molar ratio of the L-amino acid to concentrated sulfuric acid is as follows: when the valence of the L-amino acid cation is 1, the molar ratio is 1: 1, when the valence of the L-amino acid cation is 2, the molar ratio is 1: 2, when the valence of the L-amino acid cation is 3, the molar ratio is 1: 3, when the valence of the L-amino acid cation is 4, the molar ratio is 1: 4, after full reaction, water is evaporated to obtain the final product L-amino acid hydrogen sulfate type chiral ionic liquid.
3. The chiral ionic liquid of claim 1, wherein the L-amino acid bisulfate ion is selected from the group consisting of alanine ion, valine ion, leucine ion, glycine ion, tyrosine ion, glutamic acid ion, proline ion, lysine ion, histidine ion, and arginine ion.
4. The method for preparing L-amino acid bisulfate type chiral ionic liquid as claimed in claim 2, wherein the L-amino acid is selected from one of alanine, valine, leucine, glycine, tyrosine, glutamic acid, proline, lysine, histidine and arginine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465155C (en) * | 2004-10-11 | 2009-03-04 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| US7776582B2 (en) | 2004-07-09 | 2010-08-17 | Sigma-Aldrich Co. | Optically enhanced chiral ionic liquids |
| CN101948434A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Chiral tyrosine radical ionic liquid |
| US8168830B2 (en) | 2004-07-23 | 2012-05-01 | Sigma-Aldrich Co. Llc | High stability diionic liquid salts |
| US8182581B2 (en) | 2004-07-23 | 2012-05-22 | Sigma-Aldrich Co. Llc | High stability diionic liquid salts |
| US8481722B2 (en) | 2007-01-31 | 2013-07-09 | Sigma-Aldrich Co. Llc | High stability polyionic liquid salts |
-
2002
- 2002-05-16 CN CNB021116881A patent/CN1151887C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776582B2 (en) | 2004-07-09 | 2010-08-17 | Sigma-Aldrich Co. | Optically enhanced chiral ionic liquids |
| US8168830B2 (en) | 2004-07-23 | 2012-05-01 | Sigma-Aldrich Co. Llc | High stability diionic liquid salts |
| US8182581B2 (en) | 2004-07-23 | 2012-05-22 | Sigma-Aldrich Co. Llc | High stability diionic liquid salts |
| US8956445B2 (en) | 2004-07-23 | 2015-02-17 | Sigma-Aldrich Co. | High stability diionic liquid salts |
| CN100465155C (en) * | 2004-10-11 | 2009-03-04 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| US8481722B2 (en) | 2007-01-31 | 2013-07-09 | Sigma-Aldrich Co. Llc | High stability polyionic liquid salts |
| CN101948434A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Chiral tyrosine radical ionic liquid |
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| CN1151887C (en) | 2004-06-02 |
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