JPH0699400B2 - Triamide derivative of glutamic acid - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a triamide derivative of glutamic acid useful as an ion transfer agent (ionophore) for selectively and continuously separating divalent copper ions from an aqueous solution in the presence of various ions.

[0002]

2. Description of the Related Art The technology for separating copper ions from other heavy metal ions and the like is extremely important from the viewpoints of resource recovery / concentration, removal of specific ions, and analysis. For this reason, selective extractants and transport agents for copper ions have been created so far, but not only those that show good separation only for copper ions, or continuous extraction, that is, liquid membrane method. There are only a few that exhibit excellent performance as ion transfer agents in. Also, excellent extractants do not always show excellent performance as ionophores,
There has been a demand for the development of ionophores capable of continuously separating copper ions.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a novel compound capable of separating copper ions from a copper ion-containing aqueous solution with high efficiency selectively and continuously, a process for producing the same and a novel ionophore. The task is to do.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific triamide derivative of glutamic acid has an excellent selective transport property for divalent copper ions. This has led to the completion of the present invention. That is, according to the present invention, the general formula

[0005]

[Chemical 4]

A triamide derivative of glutamic acid having two quinolyl groups represented by the formula (wherein R represents an alkyl group, an arylalkyl group or an aryl group) is provided. Further, according to the present invention, after reacting a mixed acid anhydride of glutamic acid protected with an amino group and 2 equivalents of 8-aminoquinoline, the protecting group for the amino group is subsequently removed,
There is provided a method for producing a triamide derivative of glutamic acid represented by the above general formula, which comprises reacting 1 equivalent of an acid halide. Further, according to the present invention, there is provided a divalent copper ion selective transport agent comprising a triamide derivative of glutamic acid represented by the above general formula.

The triamide derivative (I) of the present invention is a novel compound, and because of the heteroatoms (nitrogen and oxygen atoms) contained therein, one solution A in the liquid film system consisting of solution A-solution M-solution B is used. It is useful as a divalent copper ion transfer agent that selectively transfers the copper ions in the solution B to the solution B.

The triamide derivative (I) of the present invention comprises a mixed acid anhydride of glutamic acid obtained by reacting amino group-protected glutamic acid with 2 equivalents of an acid halide such as pivalic acid chloride, and 2 equivalents of 8-amino acid. It is prepared by reacting with aminoquinoline, then removing the protecting group of amino group, and reacting with 1 equivalent of an acid halide.

Any glutamic acid may be used as long as its amino group is protected by a protecting group such as benzyloxycarbonyl group or t-butyloxycarbonyl group which can be easily removed by a method such as hydrogenation. It may be something like this.

When carrying out this reaction, the reaction temperature is 0-12.
It is preferably 0 to 30 ° C. at 0 ° C., and any solvent can be used as a reaction medium as long as it dissolves the above-mentioned glutamic acid, acid halide and 8-aminoquinoline and is an aprotic solvent inert to them. . These include, for example, benzene, cyclohexane, chloroform, dioxane, tetrahydrofuran and the like, especially benzene,
Tetrahydrofuran is preferred.

To carry out the cation transfer using the triamide derivative (I) of the present invention as an ionophore, two solutions A and B are indirectly contacted via the triamide derivative (I). Good. For example, the triamide derivative (I) is dissolved in an organic solvent which is substantially immiscible with the solution A and the solution B, and the solution of the triamide derivative (I) is used as an intermediate solution to indirectly contact the solution A and the solution B. Method, a method of indirect contact with each of the solutions A and B via a solution of the triamide derivative (I) housed in a compartment partitioned by a septum, and a method of contacting the solutions A and B with a polymer membrane or a paper There is a method of indirectly contacting via a triamide derivative (I) supported on a support.

Next, referring to the drawing, the solution A and the solution B are
A specific example of the case in which cations are transferred by bringing them into contact with each other through the solution M of the triamide derivative (I) will be shown. FIG. 1 is an explanatory diagram of an apparatus in which a cation is transferred using the triamide derivative of the present invention as an ionophore. This measure
It is composed of a container 1, cylindrical containers 2 and 3, and a connecting pipe 4 connecting their lower parts. 5 and 6 are agitators. First, the solution M containing the triamide derivative (I) was placed in the container 1 as an intermediate solution layer, and then the one cylindrical container 2
Solution A and solution B in the other cylindrical container 3. The solution M is substantially immiscible with the solutions A and B.

The solution A contains a cation to be transferred, and an aqueous solution is usually used. However, the solution A is not necessarily limited to the aqueous solution, and may be a mixed solution of an organic solvent and water, or an organic material such as alcohol. Media solutions are also applied. The solution A is usually used as a neutral or weakly acidic solution having a pH of 3 to 7. Solution B is for receiving the cations to be transferred, and an acidic solution is used, and generally,
An aqueous solution having a pH of 3 or less containing an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as formic acid, acetic acid or organic sulfonic acid is used. The solution B can contain various cations, and can contain the same kind of cation as the transfer target contained in the solution A. Moreover, in the case of the present invention,
Since the triamide derivative (I) can transfer cations against the ionic concentration gradient, the cation concentration contained in the solution B can be higher than the cation concentration contained in the solution A. . The solvent used to form the solution M is substantially immiscible with the solutions A and B, for example, when the solutions A and B are aqueous solutions, organic halides such as chloroform, methane tetrachloride and dichloroethane, Hydrocarbons such as benzene and toluene, and poorly water-soluble alcohols such as hexanol and octanol are applied.

As described above, when the solutions A and B are brought into indirect contact with each other, the cation in the neutral or weakly acidic solution A is trapped by the triamide derivative (I), and the triamide derivative (I) trapped by this cation is trapped. ) Contacts solution B and releases its trapped cations into acidic solution B.
In this way, the cations in solution A are transferred into solution B.

[0015]

When the triamide derivative (I) of the present invention is used as an ionophore, the solution A is used as described above.
The cations contained therein can be transferred into the solution B, and in this case, the cation concentration in the solution B is
Even if the cation concentration is higher than the cation concentration, the cations can be transferred from the solution A to the solution B against the concentration gradient. Thus, according to the invention, it is possible to transfer cations from solution A to solution B as well as to concentrate the cations in solution A into solution B. Since the triamide derivative (I) of the present invention has a large selective transporting ability to the divalent copper ion, the triamide derivative (I) of glutamic acid of the present invention is used as a solution A containing these ions and other cations. By applying to, it is possible to selectively separate and concentrate only these ions from the solution into another solution B.

Example (A) Preparation of Triamide Derivative (I) (1) N, N'-bis (8-quinolyl) -2-putyrylaminoglutaric acid amide (Compound 1: R = n-propyl) N- Benzoxycarbonyl glutamic acid 2.81 g (1
0 mmol) and 4.44 g (44 mm) of triethylamine
2.65 g (22 mmol) of pivalic acid chloride is added to 30 ml of anhydrous tetrahydrofuran containing ol) under ice cooling and the mixture is stirred for about 2 hours. Furthermore, 8-aminoquinoline 3.
A solution of 17 g (22 mmol) of tetrahydrofuran (1
0 ml) is added and stirred overnight. Chloroform is added to the reaction solution, washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the product was separated by column chromatography to obtain a diamide derivative (1.2 g, yield 23%). This diamide 5
Stir 00 mg (0.94 mmol) with an equal amount of palladium on carbon in formic acid (3 ml) for about 1 hour to remove the amine protecting group. The obtained product was mixed with triethylamine (0.5 ml) in anhydrous tetrahydrofuran 5 ml.
Dissolve in, and under ice cooling, 120 mg of n-butyric acid chloride
(1.13 mmol) is added and stirred overnight at room temperature.
Ethyl acetate is added to the reaction solution, washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the product was separated by column chromatography to obtain the target triamide derivative (246 m
g, 56% yield). This was confirmed to be a triamide derivative having the structure shown in Chemical formula 1 (R = n-propyl) by NMR, IR, and mass spectrometry. MS: calcd _{469.2112 (C 27 H 27 N 5} O 3) Found 469.2080

(2) N, N'-bis (8-quinolyl)-
2-Acetyl acid amide (Compound I: R = methyl) 252 mg (yield 61%) of N, in the same manner except that 57 mg (1.13 mmol) of acetyl was used instead of butyryl chloride in A- (1) above. N'-bis (8-quinolyl) -2-acetylaminoglutaric acid amide was obtained. Mass spectrometry: Calculated value 441.1799 (C ₂₅ H ₂₃ N ₅ O ₃ ) Measured value 441.1780

(3) N, N'-bis (8-quinolyl)-
2-p-toluoylaminoglutaric acid amide (Compound I: R = p-tolyl) Except that 175 mg (1.13 mmol) of p-toluic acid chloride was used instead of butyric acid chloride in the above A- (1). As a result, 242 mg (yield 50%) of N, N′-bis (8-quinolyl) -2-p-toluoylaminoglutaric acid amide was obtained. Mass spectrometry: Calculated value 517.2112 (C ₃₁ H ₂₇ N ₅ O ₃ ) Measured value 517.2146

(B) Transport Experiment Test 1 A cation transport test was conducted using the apparatus shown in FIG. As the ionophore, the above triamide derivative (I) (R = methyl) was used, and the component compositions of the solutions A, B, and M are as follows. Solution A: 10 mM Cu (OA adjusted to pH = 6.2
c) ₂ , 10 mM Ni (OAc) ₂ , 10 mM Co
15 ml of a mixed aqueous solution containing (OAc) ₂ and 10 mM Zn (OAc) ₂ . Solution B: 15 ml of an aqueous solution containing 0.1 N sulfuric acid (25
C). Solution M: A solution formed by dissolving 3.0 × 10 ⁻⁴ mol of the above triamide derivative (I) (R = methyl) in 30 ml of chloroform. When the amount of each cation 2 days after being transported from solution A to solution B was measured by atomic absorption spectrometry, only copper ions were
129 μmol was transported.

Test 2 Instead of the composition of Solution A in Test 1, p as Solution A was used.
A transport test was conducted in exactly the same manner except that 15 ml of an aqueous solution containing only 10 mM Cu (OAc) ₂ adjusted to H6.2 was used. 0,5 transported from solution A to solution B,
When the amount of copper ions after 1 or 2 days was measured by atomic absorption spectrometry, the copper ions were transported with the time course as shown in Table 1.

[0021]

[Table 1]

These results show that copper ions are transported against the concentration gradient by utilizing the pH difference between solutions A and B.

As an ionophore, for comparison, dibutylbis (8-quinolyl) malonamide (A), N,
N'-bis (8-quinolyl) succinamide (B), commercially available Kelex 100 (C) and N, N'-bis (quinolyl) glutaric acid amide (D) 3 × 10 ⁻⁴ mol each,
3 × 10 ^-4 mol, 6 × 10 ^-4 mol and 3 × 10 ^-4 m
When a transport experiment was conducted in exactly the same manner except that ol was used, the results are shown in Table 2.

[0024]

[Table 2]

From these results, it is clear that (I) according to the present invention has the highest transport rate, and that (C) having excellent extraction performance is inferior to (I) in transport.

Test 3 Instead of the composition of Solution A in Test 1, p as Solution A was used.
A transport test was conducted in exactly the same manner except that 15 ml of an aqueous solution containing only 10 mM Ni (OAc) ₂ adjusted to H6.2 was used. The transport amount from solution A to solution B after 2 days was 0.

Test 4 Instead of the composition of Solution A in Test 1, p as Solution A was used.
15 ml of an aqueous solution containing only 10 mM Cu (OAc) ₂ adjusted to H6.2 was used, and 1 × 10 ⁻⁴ m of the above triamide derivative (I) (R = n-propyl) was added to the solution M.
A transportation test was conducted in exactly the same manner except that ol was used.
The transport amount of Cu ² + after 0.5 and 1 day is 7.7 μmo each
1, 13.4 μmol.

[0028]

As described above, the triamide derivative of glutamic acid can not only selectively and efficiently transport and separate divalent copper ions among heavy metal ions, but also
It is possible to concentrate against a concentration gradient by utilizing the pH difference between both aqueous phases.

[Brief description of drawings]

FIG. 1 is an explanatory view of an apparatus when a triamide derivative of the present invention is used as an ionophore to transfer cations.

[Explanation of symbols]

 1 U-shaped container 2 Cylindrical container 3 Cylindrical container 4 Connecting pipe 5 Stirrer 6 Stirrer

Claims (3)

[Claims] 1. A general formula: (In the formula, R represents an alkyl group, an arylalkyl group or an aryl group.) A triamide derivative of glutamic acid. 2. After reacting a mixed acid anhydride of glutamic acid protected with an amino group with 2 equivalents of 8-aminoquinoline, the protecting group of the amino group is subsequently removed and 1 equivalent of an acid halide is reacted. Characteristic general formula: (In the formula, R represents an alkyl group, an arylalkyl group or an aryl group), and a method for producing a triamide derivative of glutamic acid. 3. A general formula: (In the formula, R represents an alkyl group, an arylalkyl group or an aryl group), a divalent copper ion selective transport agent comprising a triamide derivative of glutamic acid.