WO2007023814A1

WO2007023814A1 - Phosphonium-type ionic compounds containing amino acids as constituent ion

Info

Publication number: WO2007023814A1
Application number: PCT/JP2006/316418
Authority: WO
Inventors: Hiroyuki Ono; Kenta Fukumoto; Junko Kagimoto; Takashi Inagaki
Original assignee: Katayama Seiyakusyo Co., Ltd.; National University Corporation Tokyo University Of Agriculture And Technology
Priority date: 2005-08-23
Filing date: 2006-08-22
Publication date: 2007-03-01
Also published as: JP2008285414A

Abstract

Quaternary phosphorus compounds represented by the general formula (I): [wherein Ph+ as the cation moiety is (R1R2R3R4)P+ (wherein R1, R2, R3 and R4 are each independently substituted or unsubstituted lower alkyl) or a cation derived from a substituted or unsubstituted heterocycle containing one or more phosphorus atoms as ring constituent(s) by bonding one proton or one alkyl group to the phosphorus atom; and the anion moiety is an amino- carboxylate anion (wherein R is hydrogen or forms a four- to seven-membered ring together with NH-Y; and Y is a residue derived from an aminocarboxylic acid by removing the amino and carboxyl groups)]. The invention provides low environment load type chiral derivatives which can be easily prepared at low cost and low-viscosity ionic liquids useful as novel solvents.

Description

Phosphonium-type ionic compounds containing amino acids as constituent ions

Technical field

The present invention relates to an organic ionic liquid that is a quaternary phosphorus compound represented by general formula I.

Background art

[0002] An ionic liquid is a generic term for salts having a melting point of about 100 ° C or less, which is also called an ionic liquid, and is attracting attention as a third solvent after water and organic solvents (for example, Non-Patent Document 1). . An ionic liquid is synthesized by combining a cation and a key which are advantageous for forming an ionic liquid. The cations that have been used so far include imidazolium cations, pyridinium cations, and anorequinoleum ammonium cations. Examples of cation are BF ^_ , PF ^_ , CF

4 6 3

SO _, imido-one ((CF SO) N_), CH COO ", CF COO", NO-, (CN)

3 3 3 2 3 3 3 2

N—etc.

[0003] The characteristics of these ionic liquids include a very wide temperature range for maintaining a liquid state! In addition, since they are liquids, there is almost no vapor pressure, so they are non-volatile and non-flammable, and liquids that only have ions. Therefore, it has high ionic conductivity, has high solubility in various organic compounds, and can provide a liquid phase that depends on the combination of ions but is not miscible with water or general-purpose organic solvents. . Based on these characteristics, ionic liquids can be used not only as synthetic solvents, separation / extraction solvents, and enzyme reaction solvents, but also as energetic materials for electrolyte materials such as knotteries and fuel cells (for example, Patent Document 1). Has been studied.

[0004] Among these applications, reports as various synthetic solvents are outstanding. The characteristics of ionic liquids are useful for minimizing diffusion into the living environment and are excellent for repeated use. Therefore, they are considered to be suitable as environmentally friendly solvents and substitutes for conventional solvents. It has been. So far, there have been reports on Friedel-Crafts reaction, Diels-Alder reaction, Heck reaction, Suzuki coupling reaction, Beckmann transfer reaction, etc. (For example, Patent Document 2). These are just a few examples, and a very large number of reactions are under consideration. In both cases, it has been clarified that ionic liquid can be repeatedly used as a reaction solvent, and that yields and reaction selectivity superior to conventional solvents can be obtained depending on the reaction.

[0005] One of the most important reactions among these organic syntheses is an asymmetric synthesis reaction. Asymmetric synthesis occupies an extremely important position not only in the field of organic chemistry but also in the fields of biochemistry and pharmacology. So far, as chiral derivatives, chiral ionic liquids that have chirality in the chiral cation or the cation, in which chiral catalysts have been used as optically active reagents, have already been studied. When a chiral ionic liquid is used in the Diels-Alder reaction, the reaction time is shortened, the yield is improved, and the selectivity of the reaction position is improved, even though an asymmetric derivative is not added. The result is obtained. However, there are many points that have been reported to date, and there are many points that should be improved for chiral ionic liquids.

[0006] The disadvantages of conventional chiral ionic liquids are as follows: (1) A system having a chiral moiety in a cation structure such as an imidazolium cation or an ammonium cation has a complicated synthesis procedure and yields a highly pure product. (2) The synthesis of ionic liquids using chiral salts is expensive, since it is synthesized by a key-on exchange reaction as in the conventional system; (3) Optical purity is 100% (5) Many systems have a melting point higher than room temperature; (6) High viscosity (there is a problem such as heat denaturation if racemicization occurs because heat treatment is required).

[0007] There have been reports of attempts to synthesize chiral ionic liquids starting from natural amino acids (for example, Non-Patent Document 2), but the synthesis of the target substance requires a multi-step operation, When the precursor is synthesized, the functional group is substituted with a carboxyl group alcohol, and a bulky amino acid derivative is introduced into the side chain of the imidazolium cation, so that the melting point of the resulting salt becomes relatively high, and the ionic liquid I couldn't say anything. In addition, an ionic liquid synthesized by combining a natural amino acid with an organic cation (Patent Document 3) may have a very high viscosity depending on the side chain structure of the amino acid.

Patent Document 1: Japanese Patent Laid-Open No. 2000-3620

Patent Document 2: Japanese Patent Laid-Open No. 2002-275118

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-269414

Non-patent document 1: Hiroyuki Ohno, “Organic ionic liquid, polar liquid that does not evaporate, future materials 2002, No. 2 No. 9, 6-: L 1 page Non-Patent Document 2: Weiliang Bao, Zhimiang Wang and Yuxia Li, Journal of Organic Chemi stry, 2003, 68 (2), 591-593.

Disclosure of the invention

Problems to be solved by the invention

[0008] It is an object of the present invention to provide a new ionic liquid.

Means for solving the problem

[0009] The present invention provides compounds of the general formula I:

[Chemical 1]

0

Ph ⁺ RNH Y GO— (I)

[Wherein the cation moiety Ph + is (Κ ⁴ ) Ρ ⁺ (where

R ² , R ³ , and R ⁴ are each independently a non-substituted or substituted lower alkyl group) or a ring member containing one or more phosphorus atoms as ring members. A cation in which a proton or an alkyl group is bonded to a substituted or substituted hetero ring phosphorus atom, and the cation is an amino carboxylate cation (where R represents a hydrogen atom, Or NH—Y together with a 4-membered to 7-membered ring, where Y represents a component other than the amino and carboxyl groups of an aminocarboxylic acid.]

An organic ionic liquid which is a quaternary phosphorus compound represented by the formula:

Here, the lower alkyl group refers to a saturated linear or branched hydrocarbon residue having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. This refers to a hydrogen residue. For example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, hexyl and the like can be mentioned, preferably ethyl, propyl, isopropyl, butyl, pentyl, hexyl, More preferred are propyl and butyl.

[0011] Examples of the substituent of the lower alkyl group include hydroxy, lower alkoxy having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms substituted by the alkoxy group, an amino group, and the like. As the substituent of the heterocyclic ring of formula I, a lower alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, hydroxy, 1 carbon atom is preferable. The lower alkyl group having 4 to 4 carbon atoms, the lower alkyl group having 1 to 4 carbon atoms substituted by the same alkoxy group, and the amino group are applicable. Of the lower alkyl groups, propyl and butyl are particularly preferred.

The 4-membered to 7-membered ring that R may constitute with NH—Y is a nitrogen-containing heterocyclo ring, and as such aminocarboxylic acid, proline, particularly L-proline is preferred. The aminocarboxylic acid of the cation moiety is not limited to hyaminic acid, but is not particularly limited as long as it is an optically active aminocarboxylic acid, but natural α-amino acids are preferred, with a-amino acids being preferred.

The invention's effect

[0012] The present invention provides an organic ionic liquid that is a quaternary phosphorus compound having an amino acid, particularly a natural amino acid that is inexpensive and easily available, as a constituent ion. According to the present invention, a low-viscosity and optically active environment that has been difficult to synthesize in the past can be easily obtained at low cost. In other words, according to the present invention, a salt is formed together with an appropriate phosphonium cation using a natural amino acid or the like, so that the optical purity is 100% and the liquid is obtained in a wide temperature range from below freezing to 300 ° C. The present invention provides a chiral ionic liquid that maintains the state and has a low viscosity. This ionic liquid can be used in all application fields of ordinary ionic liquids, and also has the potential to be used for the creation of various functional molecules as reaction precursors of amino acids.

Brief Description of Drawings

FIG. 1 is a ¹ H-NMR chart of n-tetrabutylphospho-mualanine salt (Example 1). BEST MODE FOR CARRYING OUT THE INVENTION

[0014] Examples of lower alkyl group cations ⁴ ) P + include lower alkyl phosphorous, and examples of heterocyclic cations include phosphorium, phospholium, dibenzophospholium, and phosphine dream. , Phosphorinium, Dibenzophosphoninium, Phosphorinoindolium, Phosphoniabicyclooctane, Phospholinophosphinoridinum, Phosphorinopyrimidium, Phosphorinium, Phosphinolymeum, Phosphinodridium Among them, preferred are phospholium and phosphorinalium. [0015] The cation is preferably a natural oc-amino acid, more preferably a cation of D- or L-amino acid, and more preferably L-asparagine, L-aspartic acid, L-alanine, L Arginine, L—Isoleucine, Glycine, L Glutamine, L Glutamic acid, L Cystein, L Serine, L Tyrosine, L Tryptophan, L Threonine, L Norrin, L Histidine, L Phenylalanin, L Proline, L—Methionine, L Lysine or L-leucine is also a key amino acid chosen.

[0016] General method for producing quaternary phosphorus compound of the present invention

About 1 to 1.4 parts by weight, preferably about 1.0 part by weight of an amino acid to form a cation RNH—Y—C (═O) —0_ in an aqueous solvent of a Ph + hydroxy compound in the cation part. The resulting mixed solution is stirred under ice-cooling, the solvent is distilled off under reduced pressure, and unreacted amino acids are removed from the residue by an appropriate method to obtain a quaternary phosphorus compound as a desired ionic liquid. .

The hydroxy compound of Ph + can be easily prepared by using a commercially available product or by ion-exchange of the halogen ion of the corresponding phosphor halide. Example

[0017] One application of ionic liquids is the use of poorly soluble polysaccharides such as cellulose as solvents. Thus, the cellulose solubility of the ionic liquid of the present invention was tested.

Test example

Tetrabutylphospho-mulanine salt (see Example 1 below) 5g heated at 80 ° C for 24 hours, vacuum dried, mixed with 50mg cellulose (filter paper) under nitrogen atmosphere, sealed, and heated while dissolving cellulose Was recorded. As a result, the temperature at which 50 mg of cellulose was completely dissolved was 100 ° C.

As shown in this test result, tetrabutylphospho-mulanine salt can dissolve 1 to 2% by weight of cellulose at 100 ° C. Solubility varies depending on the type of amino acid.

Hereinafter, the present invention will be described specifically by way of examples. In any of the Examples, the target product was obtained as a liquid substance at room temperature, but the present invention is not limited to these. In these examples, the progress of neutralization reaction between tetraalkylphosphoric acid hydroxide and amino acid is! Confirmed by NMR measurement! [0018] Example 1

41. 5 g of L-alanine was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. After that, the crystals precipitated by filtration (unreacted unreacted alanine) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mualanin l lg (yield 80%) was obtained. Obtained. The results of ¹ H-NMR measurement of this product are as shown in Fig. 1. The progress of the reaction was confirmed from the chemical shift of proton and the integrated intensity.

— NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 0.982 (t, 3H, J = 7 Hz), 1. 369— 1. 503 (m, 16H), 2.214 (m, 8H, J = 30Hz), 2.769 (q, 1H, J = 20Hz)

[0019] Example 2

41. 4 g of L-glycine was added to 26.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, and the excess water was removed by drying under reduced pressure while stirring. Acetonitrile 6 Oml and methanol 40ml were added thereto and stirred. Thereafter, the crystals precipitated by filtration (unreacted unreacted glycine) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol to obtain tetrabutylphospho-umglycine l lg (yield 83%). It was. As a result of 1H-N MR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.

— NMR (DMSO, δ / ppm TMS standard): 0.918 (t, 12H, J = 14 Hz), 1. 3 68-1. 500 (m, 16H), 2. 200 (m, 8H, J = 30 Hz), 2.630 (q, 1H, J = 6.5 Hz)

[0020] Example 3

41. 7 g of L-aspartic acid was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted aspartic acid added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 10 g of tetrabutylphospho-muaspartic acid (yield 65%). Got. As a result of ¹ H-NMR measurement of this product, the progress of the reaction was confirmed from the chemical shift of proton and the integrated intensity.

— NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.369-1.502 (m, 16H), 2.191 (m, 8H, J = 29.5 Hz), 2.188 (m , 2H, J = 139 Hz), 3.170 (t, 1H, J = 14 Hz)

[0021] Example 4

7.6 g of L-glutamic acid was added to 26.6 g of 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted glutamic acid added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol. Tetrabutylphospho-umglutamic acid 10 g (yield 65%) Got. As a result of ¹ H-NMR measurement of this product, the progress of the reaction was confirmed in terms of the chemical shift of the proton and the integrated intensity force.

— NMR (DMSO, δ / ppm TMS standard): 0.918 (t, 12H, J = 14 Hz), 1.3 68-1.498 (m, 16H), 2.179 (m, 8H, J = 30 Hz), 1.620— 2.131 ( m, 4H

)

[0022] Example 5

To 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, 5 g of L-lysine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted unreacted lysine) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain 13 g of tetrabutylphospho-umricin (yield 78%). . As a result of ¹ H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.

— NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.245-1.878 (m, 22H), 2.216 (m, 8H, J = 30 Hz), 2.679 (q , 1H, J = 12

Hz)

[0023] Example 6

Add 41.6wt% tetrabutylphosphonium hydroxide aqueous solution to 26.6g 7.6 g of gin was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted asparagine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain 10 g of tetrabutylphospho-muasparagine (yield 70%). It was. As a result of ¹ H-NMR measurement of this product, the progress of the reaction was confirmed in terms of the chemical shift of the proton and the integrated intensity force.

— NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.369- 1. 501 (m, 16H), 2. 198 (m, 8H, J = 23 Hz), 1. 910— 2. 389 (m, 2H), 3. 037 (s, 1H), 6. 557 (s, 1H), 8. 213 (s, 1H)

[0024] Example 7

41. 7.5 g of L-glutamin was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted glutamine added excessively) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mummglutamine l lg (yield 72%) is obtained. Obtained. As a result of ¹ H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.

— NMR (DMSO, δ / ppm TMS standard): 0.915 (t, 12H, J = 20 Hz), 1. 3 69-1. 685 (m, 18H), 2.042 (m, 2H, J = 80 Hz), 2.236 (m, 8H, J = 30 Hz), 2.764 (q, 1H, J = 12.5 Hz)

[0025] Example 8

41. To 66.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, 7 g of L-histidine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted histidine added in excess) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol to obtain 13 g of tetrabutylphospho-humhistidine (yield 80%). It was. As a result of ^ -NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed f * i. H—NMR (CDC13, δ / ppm TMS standard): 0.968 (t, 12H, J = 14 Hz), 1.5 00 (m, 16H, J = 15 Hz), 2.331 (m, 8H, J = 29.5 Hz), 2.958 (m, 2H, J = 335 Hz), 3.417 (q, 1H, J = 17 Hz), 6.754 (s, 1H), 7.430 (s, 1H)

[0026] Example 9

8 g of L-isoleucine was added to 26.6 g of a 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted isoleucine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 13 g of tetrabutylphospho-isoleucine (yield 83%) Got. As a result of ¹ H-NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed.

— NMR (DMSO, δ / ppm TMS standard): 0.750— 0.783 (m, 6H), 0.917 (t, 12H, J = 14 Hz), 0.9845 (m, 1H, J = 30.5 Hz), 1.309— 1.585 (m , 18H), 2.228 (m, 8H, J = 30 Hz), 2.612 (d, 1H, J = 4.5 Hz)

[0027] Example 10

To 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, 6.8 g of L-necked isine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted alanine added in excess) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-muleucine llg (70% yield) was obtained. Obtained. As a result of ¹ H-NMR measurement of this product, it was confirmed that the chemical shift of protons and the progress of the integrated strength force reaction proceeded.

— NMR (DMSO, δ / ppm TMS standard): 0.819 (q, 6H, J = 25 Hz), 0.91 8 (t, 12H, J = 14.5 Hz), 1.006 (m, 1H, J = 42.5 Hz), 1.359 — 1.500 (m, 16H), 1.680 (m, 1H, J = 33.5 Hz), 2.205 (m, 8H, J = 29.5 Hz), 2. 699 (s, 1H)

[0028] Example 11

41.6% Tetrabutyl Phosphorum Hydroxide Aqueous Solution 26.6g Alanine (8.5 g) was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted ferrolanine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 13 g of tetrabutyl phosphomuferallanine (yield). 75%) was obtained. As a result of ¹ H-NMR measurement of this product, the progress of the reaction was confirmed from the chemical shift and integrated intensity of proton.

— NMR (DMSO, δ / ppm TMS standard): 0.916 (t, 12H, J = 14.5 Hz), 1.367—1. 487 (m, 16H), 2. 208 (m, 8H, J = 29.5 Hz), 2. 365 (q, 1H, J = 25.5 Hz), 2. 983 (m, 2H, J = 45.5 Hz), 7. 107— 7. 236 (m, 5H )

[0029] Example 12

41. 5.5 g of L-serine was added to 26.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, and the excess water was removed by drying under reduced pressure while stirring. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted serine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain tetrabutylphospho-muselin l lg (yield 73%). It was. As a result of ¹ H— NM R measurement of this product, it was confirmed that the chemical shift of proton and the progress of the integrated intensity force reaction — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14 Hz), 1. 3 69— 1. 500 (m, 16H), 2. 191 (m, 8H, J = 29.5 Hz), 2. 775 (q, 1H, J = l 5.5 Hz ), 3. 133 (q, 1H J = 30.5 Hz), 3. 255 (q, 1H, J = 15.5 Hz) [0030] Example 13

41. 6.2 g of L-threon was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted threonine added excessively) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mu-threonine l lg (yield 70%) is obtained. Obtained. As a result of ¹ H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed. H—NMR (DMSO, δ / ppm TMS standard): 0.880 (d, 3H, J = 6 Hz), 0.918 (t, 12H, J = 14 Hz), 1.383-1.488 (m, 16H), 2.193 (m, 8H, J = 30.5 Hz), 2.842 (d, 1H, J = 4 Hz), 3.443 (m, 1H, J = ll Hz)

[0031] Example 14

7.7 g of L-methione was added to 26.6 g of 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted methionine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 12.2 g of tetrabutylphospho-ummethionine (75% yield) was obtained. Obtained. As a result of ¹ H-NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed.

'H-NMRCCDCl, δ / ppm TMS standard): 0.918 (t, 12H, J = 14.5 Hz), 1.

Three

511-1.549 (m, 16H), 1.721— 2.148 (m, 5H), 2.413 (m, 8H, J = 29.5 Hz), 2.666 (m, 8H, J = 29.5 Hz), 3.218 (q, 1H, J = 12.5 Hz) [0032] Example 15

4.6 g of L-proline was added to 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted proline added in excess) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphosphomproline llg (yield 77%) is obtained. Obtained. As a result of ¹ H-NMR measurement of this product, it was confirmed that the chemical shift of protons and the progress of the integrated strength force reaction proceeded.

— NMR (CDC1, δ / ppm TMS standard): 0.976 (t, 12H, J = 14 Hz), 1.52

Three

7 (m, 16H, J = 19 Hz), 1.657 (m, 2H, J = 51 Hz), 1.870 (m, 1H, J = 32.5 Hz), 2.082 (m, 1H, J = 36 Hz), 2.395 (m, 8H, J = 29 Hz), 2.784 (m, 1H, J = 17.5 Hz), 3.097 (m, 1H, J = 23 Hz), 3.511 (m, 1H, J = 14.5 Hz)

Industrial applicability The ionic liquid provided by the present invention can be used not only as a solvent for various synthetic reactions, as a separation / extraction solvent, and as an enzyme reaction solvent, but also as an electrolyte material for knotters and fuel cells. .

Claims

Claim [1] General Formula I:

[Chemical 1]

0

D + DMU V A "/ End,

ΓΠ 1 Π ^— 1 ^— UU ([)

[Wherein the cation moiety Ph + is (Κ ⁴ ) Ρ ⁺ (where

R ² , R ³ and R ⁴ are each independently an unsubstituted or substituted lower alkyl group), or an unsubstituted or substituted group containing one or more phosphorus atoms as ring members A cation in which a proton or an alkyl group is bonded to the phosphorus atom of the heterocyclic ring, and the cation is an aminocarboxylic acid cation (where R represents a hydrogen atom or NH—Y And a 4- to 7-membered ring, and Y represents a component other than the amino group and carboxyl group of the aminocarboxylic acid.)].

[2] Ph + force (R ¹ ) P + (where R ¹ is an unsubstituted or substituted lower alkyl group)

Four

The quaternary phosphorus compound according to claim 1.

[3] R ¹ is a butyl group, a quaternary phosphorous compound according to claim 2.

[4] The quaternary phosphorus compound according to any one of claims 1 to 3, wherein the amino acid ion is an α amino acid ion.

[5] The quaternary phosphorus compound according to any one of [1] to [4], wherein the amino acid ion is a natural α-amino acid ion.

[6] The above amino acid cation is L-sip Ishin, L-Fe-alanine, L-isoleucine, glycine, L-glutamic acid, L-parin, L-aspartic acid, L-tryptophan, L-alanine, L-arginine, L The amino acid--one selected from the group consisting of asparagine, L-cysteine, L-glutamine, L-histidine, L-lysine, L-methionine, L-serine, L-threonine, L-proline and L-orchicin. The quaternary phosphorus compound according to any one of 5 above.