CN1631539A - Amino acid salt ionic liquid and preparation method thereof - Google Patents

Abstract

The invention offers a new kind of amino acids sald ion liquid and its producing way. The amino acids sald ion molecular formula is [A]n plus Xn minus, [A]n+ is amino acids positive ion, Xn is one yuan strong acid, chosen from nitric acid, 4F-B acid, 6-F-P acid, 3-F yi acid, HBr acid, HI acid, one sulphur acid, Cl sulphur acid, benzene sulphur acid, n is 1--4. The producing way is: 1. Mix the amino acids and one of nitric acid, 4F-B acid, 6-F-P acid, 3-F yi acid, HBr acid, HI acid, one sulphur acid, Cl sulphur acid, benzene sulphur acid: 2. Vaporize the liquid to dissolve the water, and we get the amino acids salt ion liquid. The amino acids salt ion liquid has the feature of ion liquid, at the same time, it has the feature of hand material and B acid, and it costs little, produce easily: no pollution and other things in the producing: the pure degree of the product is high, so it is proper to industrial production and application.

Description

Amino acid salt ionic liquid and preparation method thereof

technical field

The invention relates to an ionic liquid and a preparation method thereof, in particular to a novel amino acid salt ionic liquid and a preparation method thereof, belonging to the technical field of new chemical materials and their preparation.

Background technique

Ionic liquid is a kind of low-temperature molten salt. At close to room temperature (<150°C), it is a low-viscosity liquid composed entirely of ions. Ionic liquids are generally composed of organic cations and inorganic or organic anions. The research on ionic liquids can be traced back to 1914, when the first research object was ethylamine nitrate. As an excellent electrolyte, ionic liquids have been studied in the field of electrochemistry in the early stage. By the mid-1980s, it was discovered that ionic liquids are good solvents and brand-new catalytic materials, which have properties unmatched by organic solvents and traditional catalysts. In the field of catalytic research, ionic liquids replace traditional catalysts and organic solvents, and improve many well-known chemical reaction processes, such as Diels-Alder reaction, Friedel-Crafts reaction, Heck reaction, hydrogenation reaction and olefin hydroformylation reaction, etc. . Studies have shown that ionic liquids can greatly improve the reactivity by replacing traditional catalysts and organic solvents. They have the advantages of non-volatility, adjustable polarity, high thermal stability, etc., can provide a non-aqueous environment, are easy to recycle, and have unique properties incomparable to many molecular solvents. They are considered to be green alternatives to commonly used volatile organic solvents. solvent. Since the 1980s, research institutions such as British BP and French IFP began to systematically explore the possibility of ionic liquids as solvents and catalysts. In the 1990s, the successful synthesis of a series of stable ionic liquids made the application research in the field of catalysis and organic synthesis gradually active. The cations of existing ionic liquids are composed of alkyl quaternary ammonium cations or alkyl quaternary phosphonium cations, the most common of which are N, N-dialkylimidazolium cations and N-alkylpyridinium cations, and the anions are often Cl ^- , Br ^- , AlCl ₄ ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ COO ^- and other monovalent anions. The physical and chemical properties of ionic liquids obtained by combining different anions and cations are different. It is an important content of the application research of ionic liquids to explore the relationship between the property changes of combined ionic liquids and their structural changes. In recent years, the types of ionic liquids have increased rapidly, such as the patent document CN1383920 describing the L-amino acid sulfate type chiral ionic liquid and its preparation method, and CN1383921 describing the L-amino acid bisulfate type chiral ionic liquid and its preparation method . However, the monobasic strong acid amino acid salt ionic liquid involved in the present invention has not been disclosed so far, and its preparation method is also mentioned for the first time in the present invention.

Contents of the invention

The purpose of the present invention is to provide a new type of amino acid salt ionic liquid and a preparation method of this type of ionic liquid.

According to one aspect of the present invention, the general molecular formula of the amino acid salt ionic liquid provided by the present invention is as follows:

[A] ⁿ⁺ X _n ^-

Where [A] ⁿ⁺ is an amino acid cation selected from glycine, D-alanine, L-alanine, DL-alanine, D-valine, L-valine, DL-valine, D -Leucine, L-Leucine, DL-Leucine, D-Isoleucine, L-Isoleucine, DL-Isoleucine, D-Phenylalanine, L-Phenylalanine acid, DL-phenylalanine, D-cysteine, L-cysteine, DL-cysteine, D-cystine, L-cystine, DL-cystine, D- Threonine, L-threonine, DL-threonine, D-glutamic acid, L-glutamic acid, DL-glutamic acid, D-glutamine, L-glutamine, DL-glutamine, D -Aspartic acid, L-aspartic acid, DL-aspartic acid, D-asparagine, L-asparagine, DL-asparagine, D-methionine, L-methionine, DL-methionine, D-serine, L-serine, DL-serine, D-proline, L-proline, DL-proline, D-tyrosine, L-tyrosine, DL-tyrosine, D- Tryptophan, L-Tryptophan, DL-Tryptophan, D-Lysine, L-Lysine, DL-Lysine, D-Arginine, L-Arginine, DL-Arginine acid, D-histidine, L-histidine, DL-histidine, D-ornithine, L-ornithine, DL-ornithine, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 2-aminocaproic acid, 6-aminocaproic acid, o-aminophenylpropionic acid , p-aminophenylpropionic acid, m-aminophenylpropionic acid.

Further, the anion X _n ^- in the general formula is a monobasic strong acid, which can be nitrate, tetrafluoroborate, hexafluorophosphate, trifluoroacetate, hydrobromide, hydroiodide, methanesulfonate , any one of chlorosulfonate, benzenesulfonate, p-toluenesulfonate.

Further, the value range of n in the general formula is 1 to 4 according to the difference of amino acid cations.

According to another aspect of the present invention, the present invention also provides a method for preparing an amino acid salt ionic liquid, which includes the following steps:

(1) Carry out direct addition of amino acid and monobasic strong acid in a molar ratio of 1:1 to 1:4;

(2) Volatilize and remove water from the liquid obtained in step (1) to obtain the amino acid salt ionic liquid.

It is characterized in that the monobasic strong acid is nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid, trifluoroacetic acid, hydrobromic acid, hydroiodic acid, methanesulfonic acid, chlorosulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid of any kind. The amino acid cation is selected from: glycine, D-alanine, L-alanine, DL-alanine, D-valine, L-valine, DL-valine, D-leucine , L-leucine, DL-leucine, D-isoleucine, L-isoleucine, DL-isoleucine, D-phenylalanine, L-phenylalanine, DL- Phenylalanine, D-cysteine, L-cysteine, DL-cysteine, D-cystine, L-cystine, DL-cystine, D-threonine, L-threonine, DL-threonine, D-glutamic acid, L-glutamic acid, DL-glutamic acid, D-glutamine, L-glutamine, DL-glutamine, D-aspartic acid acid, L-aspartic acid, DL-aspartic acid, D-asparagine, L-asparagine, DL-asparagine, D-methionine, L-methionine, DL-methionine, D-serine, L-serine, DL-serine, D-proline, L-proline, DL-proline, D-tyrosine, L-tyrosine, DL-tyrosine, D-tryptophan, L-tryptophan, DL-tryptophan, D-lysine, L-lysine, DL-lysine, D-arginine, L-arginine, DL-arginine, D- Histidine, L-histidine, DL-histidine, D-ornithine, L-ornithine, DL-ornithine, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid Acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 2-aminocaproic acid, 6-aminocaproic acid, o-aminophenylpropionic acid, p-amino Phenylpropionic acid, m-aminophenylpropionic acid.

The amino acid salt ionic liquid provided by the present invention mainly includes: glycine nitrate ionic liquid, glycine tetrafluoroborate ionic liquid, glycine hexafluorophosphate ionic liquid, D-alanine nitrate ionic liquid, L-alanine Trifluoroacetate ionic liquid, L-alanine mesylate ionic liquid, L-alanine chlorosulfonate ionic liquid, L-alanine besylate ionic liquid, L-alanine pair Tosylate ionic liquid, L-leucine hydrobromide ionic liquid, DL-valine hydroiodide ionic liquid, L-histidine nitrate ionic liquid, L-arginine nitrate ionic liquid , 6-aminocaproic acid nitrate ionic liquid.

Compared with the prior art, the amino acid salt ionic liquid provided by the invention and its preparation have the following remarkable effects:

1. What the present invention provides is a new type of ionic liquid, and a new type of ionic liquid has been developed;

2. The preparation raw materials of the product provided by the present invention are easier to obtain, and the price is also relatively cheap, so the preparation cost is low;

3. The method provided by the present invention utilizes direct addition reaction, is easy to operate, requires simple equipment, can obtain very pure products, and is suitable for large-scale production and application;

4. The amino acid salt ion provided by the present invention has the characteristics of ionic liquid and the characteristics of chiral substances: such as the characteristics of chiral separation, chiral catalysis and chiral solvent, etc.;

5. The amino acid salt ion provided by the present invention has the characteristics of ionic liquid and Bronsted acidity, which can replace solid acid as an acidic material;

6. According to the method provided by the present invention, the preparation process is an atom-economic reaction that does not discharge pollutants, and belongs to an environmentally friendly green preparation process.

Detailed ways

The present invention is further illustrated below through preferred embodiments.

Embodiment 1: Glycine nitrate ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 3.75g (0.05mol) of glycine and 4.85g (0.05mol) of 65% nitric acid were dissolved in 20mL of water, and the solution was evaporated in an oil bath at 60°C to remove moisture, and dried in vacuum for 24 hours to obtain a colorless Transparent liquid, cooling to white solid, which is glycine nitrate ionic liquid. The reaction formula is:

                      

Embodiment 2: glycine tetrafluoroborate ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 3.75g (0.05mol) of glycine and 10.98g (0.05mol) of 40% tetrafluoroboric acid were dissolved in 20mL of water, and the solution was volatilized in an oil bath at 60°C to remove moisture, and dried in vacuum for 24 hours to obtain Colorless transparent liquid, namely glycine tetrafluoroborate ionic liquid. The reaction formula is:

                      

Embodiment 3: Glycine hexafluorophosphate ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 3.75g (0.05mol) of glycine and 12.16g (0.05mol) of 60% hexafluorophosphoric acid were dissolved in 20mL of water, and the solution was volatilized in an oil bath at 60°C to remove moisture, and dried in vacuum for 24 hours to obtain Colorless transparent liquid, cooling to white solid, which is glycine hexafluorophosphate ionic liquid. The reaction formula is:

                     

Embodiment 4: D-alanine nitrate ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 4.46g (0.05mol) D-alanine and 4.85g (0.05mol) 65% nitric acid were dissolved in 20mL water, and the solution was evaporated to remove moisture in an oil bath at 60°C, and dried in vacuum for 24 hours , a colorless transparent liquid is obtained, and a white solid is obtained after cooling, which is D-alanine nitrate ionic liquid. The reaction formula is:

                     

Embodiment 5: L-alanine trifluoroacetate ionic liquid and preparation method thereof

Dissolve 4.46g (0.05mol) of L-alanine and 5.75g (0.05mol) of trifluoroacetic acid in 10mL of water at a molar ratio of 1:1, evaporate the solution in an oil bath at 60°C to remove moisture, and dry in vacuum for 24 hours , a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was L-alanine trifluoroacetate ionic liquid. The reaction formula is:

                

Embodiment 6: L-alanine mesylate ionic liquid and preparation method thereof

Dissolve 4.46g (0.05mol) of L-alanine and 4.81g (0.05mol) of methanesulfonic acid in 20mL of water at a molar ratio of 1:1, evaporate the solution in an oil bath at 60°C to remove moisture, and dry in vacuum for 24 hours , a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was L-alanine mesylate ionic liquid. The reaction formula is:

                    

Embodiment 7: L-alanine chlorosulfonate ionic liquid and preparation method thereof

Dissolve 4.46g (0.05mol) of L-alanine and 5.83g (0.05mol) of chlorosulfonic acid in 20mL of water at a molar ratio of 1:1, evaporate the solution in an oil bath at 60°C to remove moisture, and dry in vacuum for 24 hours , a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was L-alanine chlorosulfonate ionic liquid. The reaction formula is:

                    

Embodiment 8: L-alanine besylate ionic liquid and preparation method thereof

Dissolve 4.46g (0.05mol) of L-alanine and 7.91g (0.05mol) of benzenesulfonic acid in 20mL of water at a molar ratio of 1:1, evaporate the solution in an oil bath at 60°C to remove moisture, and dry in vacuum for 24 hours , to obtain a colorless transparent liquid and a white solid, which is the L-alanine besylate ionic liquid. The reaction formula is:

                   

Embodiment 9: L-alanine p-toluenesulfonate ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 4.46g (0.05mol) of L-alanine and 9.51g (0.05mol) of p-toluenesulfonic acid were dissolved in 20mL of water. Hours, a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was the ionic liquid of L-alanine p-toluenesulfonate. The reaction formula is:

                

Embodiment 10: L-leucine hydrobromide ionic liquid and preparation method thereof

According to the molar ratio of 1:1, 6.56g (0.05mol) L-leucine and 4.85g (0.05mol) 65% nitric acid were dissolved in 20mL water, and the solution was evaporated to remove moisture in an oil bath at 60°C, and dried in vacuum for 24 hours , a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was L-leucine hydrobromide ionic liquid. The reaction formula is:

                        

Example 11: DL-valine hydroiodide ionic liquid and its preparation method

According to the molar ratio of 1:1, 5.86g (0.05mol) DL-valine and 4.85g (0.05mol) 65% nitric acid were dissolved in 30mL water, and the solution was evaporated in an oil bath at 60°C to remove moisture, and dried in vacuum for 24 hours , a colorless transparent liquid is obtained, and a white solid is obtained after cooling, which is DL-valine hydroiodide ionic liquid. The reaction formula is:

                        

Example 12: Preparation method of L-histidine nitrate ionic liquid

According to the molar ratio of 1:2, 3.88g (0.025mol) L-histidine 4.85g (0.05mol) 65% nitric acid was dissolved in 20mL water, the solution was volatilized in an oil bath at 60°C to remove moisture, and dried in vacuum for 24 hours. A colorless transparent liquid is obtained, and a white solid is obtained after cooling, which is L-histidine nitrate ionic liquid. The reaction formula is:

                      

Embodiment 13: L-arginine nitrate ionic liquid and preparation method thereof

According to the molar ratio of 1:4, 2.61g (0.015mol) L-arginine and 5.82g (0.06mol) 65% nitric acid were dissolved in 30mL water, and the solution was evaporated to remove moisture in an oil bath at 60°C, and dried in vacuum for 24 hours , a colorless transparent liquid is obtained, and a white solid is obtained after cooling, which is L-arginine nitrate ionic liquid. The reaction formula is:

                      

Example 14: 6-aminocaproic acid nitrate ionic liquid

Dissolve 6.56g (0.05mol) of 6-aminocaproic acid and 4.85g (0.05mol) of 65% nitric acid in 20mL of water at a molar ratio of 1:1, evaporate the solution in an oil bath at 60°C to remove moisture, and dry it in vacuum for 24 hours , a colorless transparent liquid was obtained, and a white solid was obtained after cooling, which was 6-aminocaproic acid nitrate ionic liquid. The reaction formula is:

        

Claims (6)

1. An amino acid salt ionic liquid, the molecular formula of which is: [A] ⁿ⁺ X _n ^- It is characterized in that, in the general molecular formula, [A] ⁿ⁺ is an amino acid cation, the anion X _n ^- is a monobasic strong acid radical, and the value of n ranges from 1 to 4. 2. The amino acid salt ionic liquid according to claim 1, wherein the monobasic strong acid radical is selected from the group consisting of nitrate, tetrafluoroborate, hexafluorophosphate, trifluoroacetate, hydrobromide, hydrogen iodide Acid, methanesulfonate, chlorosulfonate, benzenesulfonate, p-toluenesulfonate. 3. The amino acid salt ionic liquid according to claim 1 or 2, wherein the amino acid is selected from: glycine, D-alanine, L-alanine, DL-alanine, D-valine Acid, L-Valine, DL-Valine, D-Leucine, L-Leucine, DL-Leucine, D-Isoleucine, L-Isoleucine, DL-Isoleucine amino acid, D-phenylalanine, L-phenylalanine, DL-phenylalanine, D-cysteine, L-cysteine, DL-cysteine, D-cystine , L-cystine, DL-cystine, D-threonine, L-threonine, DL-threonine, D-glutamic acid, L-glutamic acid, DL-glutamic acid, D -Glutamine, L-Glutamine, DL-Glutamine, D-Aspartic Acid, L-Aspartic Acid, DL-Aspartic Acid, D-Asparagine, L-Asparagine, DL-Day Paragine, D-methionine, L-methionine, DL-methionine, D-serine, L-serine, DL-serine, D-proline, L-proline, DL-proline, D-tyrosine , L-tyrosine, DL-tyrosine, D-tryptophan, L-tryptophan, DL-tryptophan, D-lysine, L-lysine, DL-lysine, D -Arginine, L-arginine, DL-arginine, D-histidine, L-histidine, DL-histidine, D-ornithine, L-ornithine, DL-ornithine amino acid, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 2-aminobutyric acid Caproic acid, 6-aminocaproic acid, o-aminophenylpropionic acid, p-aminophenylpropionic acid, m-aminophenylpropionic acid. 4. A method for preparing an amino acid salt ionic liquid, comprising the steps of: (1) Carry out direct addition of amino acid and monobasic strong acid in a molar ratio of 1:1 to 1:4; (2) Volatilize and remove water from the liquid obtained in step (1) to obtain the amino acid salt ionic liquid. 5. The preparation method of amino acid salt ionic liquid according to claim 4, characterized in that the monobasic strong acid is selected from the group consisting of: nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid, trifluoroacetic acid, hydrobromic acid, hydroiodic acid, Methanesulfonic acid, chlorosulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid. 6. The preparation method of amino acid salt ionic liquid according to claim 4 or 5, characterized in that the amino acid is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, D -Valine, L-Valine, DL-Valine, D-Leucine, L-Leucine, DL-Leucine, D-Isoleucine, L-Isoleucine, DL -Isoleucine, D-phenylalanine, L-phenylalanine, DL-phenylalanine, D-cysteine, L-cysteine, DL-cysteine, D- Cystine, L-cystine, DL-cystine, D-threonine, L-threonine, DL-threonine, D-glutamic acid, L-glutamic acid, DL-glutamine Acid, D-Glutamine, L-Glutamine, DL-Glutamine, D-Aspartic Acid, L-Aspartic Acid, DL-Aspartic Acid, D-Asparagine, L-Asparagine, DL-asparagine, D-methionine, L-methionine, DL-methionine, D-serine, L-serine, DL-serine, D-proline, L-proline, DL-proline, D- Tyrosine, L-Tyrosine, DL-Tyrosine, D-Tryptophan, L-Tryptophan, DL-Tryptophan, D-Lysine, L-Lysine, DL-Lysine acid, D-arginine, L-arginine, DL-arginine, D-histidine, L-histidine, DL-histidine, D-ornithine, L-ornithine, DL-ornithine, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 2-aminocaproic acid, 6-aminocaproic acid, o-aminophenylpropionic acid, p-aminophenylpropionic acid, m-aminophenylpropionic acid.