CN1150994C - L-sulforamidate type chiral ionic liquid and its prepn - Google Patents
L-sulforamidate type chiral ionic liquid and its prepn Download PDFInfo
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- CN1150994C CN1150994C CNB021116873A CN02111687A CN1150994C CN 1150994 C CN1150994 C CN 1150994C CN B021116873 A CNB021116873 A CN B021116873A CN 02111687 A CN02111687 A CN 02111687A CN 1150994 C CN1150994 C CN 1150994C
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Abstract
The present invention relates to a novel L-sulforamidate type chiral ionic liquid and a preparation method thereof, which belongs to the technical field of a novel chemical material and preparation thereof. L-amino acid is prepared into a water solution and sufficiently reacts with sulfuric acid having the concentration of 98% to acquire sulforamidate type chiral ionic liquid. The prepared sulforamidate type chiral ionic liquid has the characteristics of ionic liquid, and simultaneously, has the characteristics of chiral matter. The chiral ionic liquid has the advantages of no pollutant discharge in reaction, no by-product, high product purity and low cost, is suitable for application to large-scale industrial production and possibly becomes an important novel material on the aspect of green chemical industry in future.
Description
(I) technical field
The invention relates to an ionic liquid and a preparation method thereof, in particular to a novel L-amino acid sulfate 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 liquid attracts wide attention as a green solvent or a catalyst, is commonly used in some chemical reaction processes such as organic synthesis, chemical separation, electrochemistry and the like, and has the bifunctional 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. By different combinations of the cations and the anions, ionic liquids with various characteristics are prepared, but the L-amino acid sulfate type ionic liquid related to the invention has 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 are 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 wide liquid range, low vapor pressure, good conductivity, wide electrochemical window, strong polarity, and dissolution of some substancesSelectivity of catalysis. At present, no report is found about L-amino acid sulfate 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 in combination with aluminium trichlorideThe application is easy to cause pollution, and the application of the fertilizer in green chemical industry is influenced.
Disclosure of the invention
The invention aims to provide an L-amino acid sulfate type chiral ionic liquid which has the excellent characteristics of chiral substances and good characteristics of ionic liquid, and a preparation method of the ionic liquid.
The L-amino acid sulfate type chiral ionic liquid provided by the invention has the following structural formula:
[amino acid]m[SO4]n
depending on the valency of the different L-amino acid cations, m is in the range from 1 to 2 and n is in the range from 1 to 3, i.e. m is 2 and n is 1 when the valency of the L-amino acid cation is 1, m is 1 and n is 1 when the valency of the L-amino acid cation is 2, m is 2 and n is 3 when the valency of the L-amino acid cation is 3, and m is 1 and n is 2 when the valency of the L-amino acid cation is 4.
The preparation method of the L-amino acid 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 2: 1, when the valence of the L-amino acid cation is 2, the molar ratio is 1: 1, when the valence of the L-amino acid cation is 3, the molar ratio is 2: 3, when the valence of the L-amino acid cation is 4, the molar ratio is 1: 2, after full reaction, water is evaporated to obtain the final product L-amino acid sulfate type chiral ionic liquid. The reaction formula is shown as:
m[amino acid]+nH2SO4→[amino acid]m[SO4]n
the invention relates to L-amino acid sulfate 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 sulfate type chiral ionic liquid related to the present invention is preferably: alanine sulfate chiral ionic liquid [ Ala]]2SO4Valine sulfate chiral ionic liquid [ Val]2SO4Chiral ionic liquid of leucine sulfate[Leu]2SO4Glycine sulfate chiral ionic liquid [ Gly]2SO4Tyrosine sulfate chiral ionic liquid [ Tyr]2SO4Glutamic acid sulfate chiral ionic liquid [ Glu]2SO4Proline sulfate chiral ionic liquid [ Pro]2SO4Lysine sulfate chiral ionic liquid [ Lys]SO4Histidine sulfate chiral ionic liquid [ His]]2[SO4]3And arginine sulfate chiral ionic liquid [ Arg]][SO4]2One of them.
The L-amino acid sulfate type chiral ionic liquid [ aminoacid]provided by the invention]m[SO4]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 sulfate type chiral ionic liquid to be prepared.
In addition to the above-mentioned sulfates and their preparation, other amino acid sulfates 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. By using RVT-TB, RVT-TE, RVT2#Type viscometer, the result of which is 10 at normal temperature2-103The viscosity size difference is large between cP (except solid state).
The L-amino acid sulfate 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 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 descriptionof the preferred embodiments
Example 1: alanine sulfate 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 dosage is 2.81g (0.028mol), namely the mol ratio of the reaction raw materials is 2: 1, the transparent mixed solution is continuously 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 sulfate chiral ionic liquid is obtained. The reaction formula is as follows:
example 2: valine sulfate chiral ionic liquid
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 2.1g (0.021mol), i.e.the molar ratio of the starting materials was 2: 1. The transparent mixed solution is stirred for 1 hour at room temperature and then transferred to a rotary evaporator at 40 ℃ -Evaporating to remove water at 50 ℃, then heating to 80-85 ℃ for evaporating for 2 hours, and finally obtaining the colorless transparent valine sulfate chiral ionic liquid. The reaction formula is as follows:
example 3: leucine sulfate chiral ionic liquid
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), H2SO4Dosage ofIt was 1.9g (0.019mol), i.e., the molar ratio of the reaction raw materials was 2: 1. And continuously stirring the transparent mixed solution at room temperature for 1 hour, transferring the transparent 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 tryptophan sulfate chiral ionic liquid without tryptophan. The reaction formula is as follows:
example 4: glycine sulfate 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 3.3g (0.033mol), i.e. the molar ratio of the starting materials for the reaction was 2: 1. The clear mixture was stirred for an additional 1 hour at room temperature. Transferring the solution to a rotary evaporator, evaporating at 40-50 ℃ to remove water, heating to 80-85 ℃ to evaporate for 3 hours, and finally obtaining colorless transparent liquid glycine sulfate chiral ionic liquid. The reaction formula is as follows:
example 5: chiral ionic liquid of tyrosine sulfate
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 1.4g (0.014mol), i.e., the molar ratio of the starting materials was 2: 1. And continuously stirring the transparent mixed solution at room temperature for 1 hour, transferring the transparent mixed solution into a rotary evaporator, evaporating at 40-50 ℃ to remove water, heating to 80-85 ℃ to evaporate for 2 hours, and finally cooling and crystallizing the product to obtain the chiral ionic liquid of tyrosine sulfate. The reaction formula is as follows:
example 6: glutamic acid sulfate chiral ionic liquid
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 1.7g (0.017mol), i.e.the molar ratio of the starting materials for the reaction was 2: 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 glutamic acid sulfate chiral ionic liquid. The reaction formula is as follows:
example 7: proline sulfate 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 2.1g (0.021mol), i.e.the molar ratio of the starting materials was 2: 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 3 hours, and finally obtaining the colorless transparent proline sulfate chiral ionic liquid. The reaction formula is as follows:
example 8: lysine sulfate chiral ionic liquid
5.00g of lysine (0.034mol, purity over 99%, available from Shanghai Gill Biochemical Co., Ltd.) was weighed into a beaker containing 50ml of distilled H2O, and 98% H was added dropwise while stirring2SO4(analytically pure), H2SO4The amount used was 3.4g (0.034mol), i.e.the molar ratio of the starting materials was 1: 1. Stirring the transparent mixed solution at room temperature for 1 hour, transferring into a rotary evaporator, evaporating at 40-50 deg.C to remove water, heating to 80-85 deg.C, evaporating for 2 hours to obtain colorless solutionMinlysine sulfate chiral ionic liquid. The reaction formula is as follows:
example 9: chiral ionic liquid of histidine sulfate
5.00g of arginine (0.032mol, purity over 99%, available from Shanghai Jier Biochemical Co.) was weighed into 50ml of distilled H2In a beaker of O, 98% H was added dropwise with stirring2SO4(analytically pure), H2SO4The amount used was 4.81g (0.048mol), i.e.the molar ratio of the starting materials was 2: 3. 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 histidine sulfate chiral ionic liquid. The reaction formula is as follows:
example 10: arginine sulfate chiral ionic liquid
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 5.6g (0.056mol), i.e.the molar ratio of the starting materials was 1: 2. 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 arginine sulfate chiral ionic liquid. The reaction formula is as follows:
the preparation process of the chiral ionic liquid of the L-amino acid sulfate is simple acid-base neutralization reaction, no pollutant is discharged, no by-product is generated, a very pure product can be obtained without excessive operation, the cost is low, the chiral ionic liquid of the L-amino acid sulfate is suitable for large-scale industrial production and application, and the chiral ionic liquid of the L-amino acid sulfate is likely to become an important novel material in the aspects of green chemical industry in future.
Claims (4)
1. An L-amino acid sulfate type chiral ionic liquid is characterized by having a structural formula as follows:
[amino acid]m[SO4]n
depending on the valency of the different L-amino acid cations, m is in the range from 1 to 2 and n is in the range from 1 to 3, i.e. m is 2 and n is 1 when the valency of the L-amino acid cation is 1, m is 1 and n is 1 when the valency of the L-amino acid cation is 2, m is 2 and n is 3 when the valency of the L-amino acid cation is 3, and m is 1 and n is 2 when the valency of the L-amino acid cation is 4.
2. The L-amino acid sulfate type chiral ionic liquid of claim 1, wherein the L-amino acid ions are: one of alanine ion, valine ion, leucine ion, glycine ion, tyrosine ion, glutamic acid ion, proline ion, lysine ion, histidine ion, and arginine ion.
3. A preparation method of L-amino acid sulfate type chiral ionic liquid is characterized by comprising the following preparation processes:
preparing amino acid into an aqueous solution, and dropwise adding sulfuric acid with the concentration of 98% while stirring, wherein the molar ratio of the L-amino acid to the concentrated sulfuric acid is as follows: when the valence of the L-amino acid cation is 1, the molar ratio is 2: 1, when the valence of the L-amino acid cation is 2, the molar ratio is 1: 1, when the valence of the L-amino acid cation is 3, the molar ratio is 2: 3, when the valence of the L-amino acid cation is 4, the molar ratio is 1: 2, after full reaction, water is evaporated to obtain the final product L-amino acid sulfate type chiral ionic liquid.
4. The method for preparing L-amino acid sulfate type chiral ionic liquid as claimed in claim 3, 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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| US20060014955A1 (en) | 2004-07-09 | 2006-01-19 | Advanced Separation Technologies Inc. | Optically enhanced chiral ionic liquids |
| US8168830B2 (en) | 2004-07-23 | 2012-05-01 | Sigma-Aldrich Co. Llc | High stability diionic liquid salts |
| CA2574460A1 (en) | 2004-07-23 | 2006-02-02 | 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 |
| CN101195096B (en) * | 2006-12-04 | 2011-03-23 | 中国科学院大连化学物理研究所 | Chiral latex catalyst, production method and application thereof |
| EP3124490A1 (en) | 2007-01-31 | 2017-02-01 | Sigma-Aldrich Co. LLC | High stability polyionic liquid salts |
| CN101624183B (en) * | 2009-07-21 | 2011-02-02 | 华东师范大学 | Method for synthesizing nano-porous zirconium phosphate by using hybridization of ionic liquid |
| CN102190589A (en) * | 2010-03-04 | 2011-09-21 | 中国科学院过程工程研究所 | Amino acid ionic liquid for foodstuffs and medical treatments |
| CN102442919B (en) * | 2010-10-13 | 2013-09-04 | 中粮生物化学（安徽）股份有限公司 | Method for producing lysine product |
| CN102274754B (en) * | 2011-06-16 | 2013-04-10 | 北京化工大学 | Method for raising multiphase asymmetric catalytic activity and asymmetric selectivity |
| CN110078615B (en) * | 2019-04-26 | 2021-11-09 | 浙江永太科技股份有限公司 | Chiral resolution method of naproxen |
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