JPH0312060B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula This relates to a diamide derivative having two quinolyl groups represented by: The compound () according to the present invention is a new compound, and due to the heteroatoms (nitrogen and oxygen atoms) it contains, divalent copper ions can selectively transfer divalent copper ions dissolved in water into organic solvents. As a selective extractant and as a divalent copper ion solubilizer capable of solubilizing solid copper ions into an organic solvent, in a liquid film system consisting of solution A-solution M-solution B, copper in one solution A It is useful as a divalent copper ion transport agent that selectively transports ions to solution B. The compound () according to the invention is produced by reacting dibutylmalonic acid dichloride, obtained by the reaction of dibutylmalonic acid with thionyl chloride, and twice the molar amount of 8-aminoquinoline. When carrying out this reaction, the reaction temperature is 20 to 120°C, preferably 40 to 80°C, and the above malonic acid diclide and 8-aminoquinoline are dissolved as a reaction medium, and an inert aprotic solvent is used as the reaction medium. Any solvent can be used, and examples of such solvents include benzene, cyclohexane, chloroform, dioxane, and tetrahydrofuran, with benzene and chloroform being particularly preferred. The compound () of the present invention is a colorless crystal, purified from cyclohexane by a recrystallization method, and exhibits excellent performance in extracting, solubilizing, and transporting divalent copper ions. That is, in order to extract divalent copper ions present in an aqueous solution using the compound () according to the present invention, a solution dissolving the compound () according to the present invention is added to and mixed with the metal-containing aqueous solution, and the aqueous phase is What is necessary is to phase-separate the oil phase and the oil phase. By this operation, divalent copper ions dissolved in water are efficiently extracted and transferred to the oil phase. In this case, even in the coexistence of the extracted divalent copper ion and other ions, only the divalent copper ion is extracted, and alkali, alkaline earth ions, and the same transition metal ions such as divalent nickel, zinc, cobalt, and mercury are extracted. , not interfered with by lead, divalent and trivalent iron, monovalent copper ions, etc. Alternatively, by stirring a solution dissolving the compound () of the present invention with a solid powder of divalent copper compound,
It becomes possible to solubilize copper ions in the oil phase.
Similarly, only divalent copper ions are solubilized in the coexistence of the other metal ions mentioned above. To transport cations using the compound () of the present invention as an ionophore, two solutions A
and B may be contacted indirectly via the compound () of the present invention. For example, a method in which the compound () is dissolved in an organic solvent that is substantially immiscible with the solutions A and B, and the solution A and the solution B are brought into indirect contact with each other using the solution of the compound () as an intermediate solution layer; A method in which A and B are brought into indirect contact with each other through a solution of the compound () contained in a compartment partitioned by a diaphragm, and solutions A and B are supported on a support such as a polymer membrane or paper. There is a method of making indirect contact via a compound () that has been prepared. Next, a specific example in which cations are transferred by bringing solution A and solution B into contact with each other via solution M of compound () will be shown with reference to the drawings. 1 indicates a U-shaped container, and cylindrical containers 2 and 3
and a connecting pipe 4 that connects their lower parts. 5 and 6 are stirrers. First, a solution M containing the compound () is put into the container 1 as an intermediate solution layer, and then a solution A is put into one cylindrical container and a solution B is put into the other cylindrical container 3. Note that solution M is substantially immiscible with solutions A and B. Solution A contains cations to be transferred, and is usually an aqueous solution, but is not necessarily limited to an aqueous solution, and may also be a mixed solution of an organic solvent and water, or a solution of an organic solvent such as alcohol. Applicable. Moreover, this solution A is normally used as a neutral or weakly acidic solution with a pH of 3 to 7. Solution B
is for receiving the transferred cations, and an acidic solution is used, typically a PH3 solution containing inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as formic acid, acetic acid, and organic sulfonic acids. The following aqueous solutions are used. Solution B can contain various cations, and can contain the same type of cations as the cations to be transferred, which are contained in solution A.
Moreover, in the case of the present invention, compound ( ) is capable of transporting cations against the ion concentration gradient, so that the cation concentration contained in solution B is higher than that contained in solution A. concentration. The solvent used to form solution M is one that is substantially immiscible with solutions A and B, for example, when solutions A and B are aqueous solutions, an organic halide such as chloroform, tetrachlormethane, dichloroethane, etc. , hydrocarbons such as benzene and toluene, and poorly water-soluble alcohols such as hexanol and octanol. When the solutions A and B are brought into indirect contact as described above, the cations in the neutral or weakly acidic solution A are captured by the compound (), and the compound () that has captured the cations is brought into contact with the solution B. and releases the trapped cations into acidic solution B. In this way, cations in solution A are transferred into solution B. When the compound () of the present invention is used as an ionophore, the cations contained in solution A can be transferred to solution B as described above,
Moreover, in this case, even if the cation concentration in solution B is higher than the cation concentration in solution A, the cations can be transferred from solution A to solution B against the concentration gradient. According to the invention, therefore, in addition to the transfer of cations from solution A to solution B, it is possible to concentrate the cations in solution A in solution B. Since the compound () of the present invention exhibits high selectivity toward divalent copper ions, by applying the polyether derivative of the present invention to solution A containing these ions and other cations, the solution From inside, only these ions can be selectively separated and concentrated into another solution B. Next, the present invention will be explained in more detail with reference to Examples. Example A Preparation of diamide derivative () 2.2 g (10 mmol) of dibutylmalonic acid and 3 g (13 mmol) of thionyl chloride were added to anhydrous benzene.
After refluxing in 20 ml for 2 hours, the solvent and excess thionyl chloride are distilled off under reduced pressure. The resulting residue, dibutylmalonic acid dichloride, was mixed with 3.0 g (21 mmol) of 8-aminoquinoline and 2.0 g of tosoethylamine.
g (10 mmol) is added to the benzene solution and refluxed for 4 hours. After cooling, the benzene solution is washed with water and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the product was separated by column chromatography and recrystallized from cyclohexane to obtain 3.8 g (yield: 81%) of the desired product. This product was confirmed to be a diamide derivative having the structure shown by the formula () by NMR, IR, and elemental analysis.

[Table] B Metal ion extraction test (1) Test 1 The diamide derivative obtained above was dissolved in chloroform to prepare a solution with a concentration of 1.0 x 10 ^-3 mol/. On the other hand, separately, cupric acetate was dissolved in water to 1.0×10 ^-2 mol/, 1.0× ^{10 -3} mol/, respectively.
0.5×10 ⁻³ / and 0.2×10 ⁻³ mol/ were prepared without buffer. After putting 5 ml of each of these solutions into one vial and stirring at 25°C for 2 hours, the concentration of copper ions remaining in the water was determined by atomic absorption spectrometry, and the extracted amount was determined. Copper ions are 0.9×10 ^-3 mol/, 0.20× ^{10 -3} mol/, 0.22 ^{×10 -3} mol/, and 0.17×10 ^{-3 ,} respectively.
mol/, extracted into chloroform. (2) Test 2 Cupric acetate, nickel acetate, cobalt acetate,
and zinc acetate at 1.0×10 ^-2 each.
An aqueous solution containing mol/each was prepared. Separately, the diamide derivative prepared in Test 1 was added at 1.0×10 ^-3
After putting 5 ml of the chloroform solution containing mol/mol/ml and 5 ml of the above aqueous solution into one vial and stirring at 25°C for 2 hours, the concentration of various metal ions remaining in the water was determined by atomic absorption spectrometry, and the extracted amount was found to be 0.4 Only ×10 ^-3 mol/copper ions were extracted into chloroform. (3) Test 3 Same as Test 1 above, 1.0×10 ^-3 mol/
An aqueous solution containing each of nickel acetate, cobalt acetate, zinc acetate, mercury acetate, lead acetate, ferrous ammonium sulfate, and ferric ammonium sulfate was prepared and an extraction test was conducted.
Compound () did not cause any extraction, indicating that compound () exhibits selectivity for divalent copper ions. (4) Test 4 An aqueous solution containing 1.0×10 ^-3 mol/each of copper acetate, nickel acetate, cobalt acetate, and zinc acetate was prepared using a buffer solution at pH 1.14, 2.97, 3.30,
3.76, 4.23, 5.11, 5.95, and 6.19.
The compound () was prepared in the same manner as in Test 1 above.
5ml of chloroform solution containing 1.0×10 ^-3 mol/
An extraction test was conducted using 5 ml of the various PH solutions mentioned above, and as shown in the table below, it was found that the extraction ability was dependent on the PH and that only copper ions were extracted.

[Table] C Solubilization test Powdered divalent ^copper acetate,
Nickel acetate, cobalt acetate, zinc acetate, and monovalent cuprous iodide were each added and stirred at room temperature for 2 hours. As a result, only copper acetate was quantitatively solubilized in the solution and formed a copper ion complex with compound (). D. Transport test A cation transport test was conducted using the apparatus shown in the drawing. The above compound () was used as the ionophore, and the component compositions of solutions A, B, and M were as follows. Solution A: with 0.2N acetic acid and 0.2M sodium acetate
10mM Cn(OAc) ₂ adjusted to PH=6.20,
Mixed aqueous solution _containing 10mM Ni(OAc) ₂ , 10mM Co(OAc) ₂ and 10mM Zn(OAc)215
ml. Solution B: 15 ml of an aqueous solution containing IN sulfuric acid. Solution M: 3.0 × 10 ^-4 mol of the above compound (),
A solution formed by dissolving in 30 ml of chloroform. When the amount of each cation was measured by atomic absorption spectrometry two days after it was transported from solution A to solution B, it was found that copper ions were 15μmol (1mM) and zinc ions were 15μmol (1mM).
Although 0.37 μmol was transported, Ni and Co were almost 0.

[Brief explanation of the drawing]

The drawing is an explanatory diagram of an apparatus for transporting cations using the polyether derivative of the present invention as an ionophore. 1... U-shaped container, 2, 3... Cylindrical container, 4...
... Connecting pipe, 5, 6... Stirrer.

[Claims]

1st order general formula [] [In the formula, R ₁ represents hydrogen or lower alkyl. _R2
represents hydrogen or methoxy-substituted benzyl. R ₃ represents hydrogen. R ₄ represents hydrogen or halogen. _R5
represents hydrogen or halogen, R ₆ represents halogen, or R ₅ and R ₆ combine with each other to form methylenedioxy. R ₇ represents hydrogen. ] or a pharmacologically acceptable salt thereof.

Claims (1)

A method for producing a diamide derivative represented by 3 formulas A divalent copper ion selective extractant consisting of a diamide derivative represented by 4 formula A divalent copper ion selective solubilizer consisting of a diamide derivative represented by: 5 formula A divalent copper ion selective transport agent consisting of a diamide derivative represented by