JPH0114897B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, n is 2 or 3, and R ¹ and R ² are a hydrogen atom or an alkyl group.) The present invention relates to a cation transport method using a polyether derivative represented by the following formula as a transport carrier. The polyether derivatives of the present invention are useful as cation carriers, and in particular, when n=2, they act selectively on barium ions, and when n=3, depending on the transport conditions, they act selectively on calcium ions. It has the characteristics of selectively acting on magnesium ions and selectively acting on magnesium ions. Although several substances have been reported that exhibit the property of transporting alkaline earth metal ions, there are few that exhibit high selectivity toward alkaline earth metal ions, and in particular, there is a high selectivity between alkaline earth metal ions. There are very few that have this difference. The present inventors have previously conducted various studies on the development of compounds useful as ionophores, and this time, we have discovered that the polyether derivative represented by the above compound () has excellent performance as an ionophore, and that its chain structure The selective transport ability for alkaline earth ions changes depending on the type of alkylene chain, and the transport ability for alkali metal ions is low.
It was discovered that the concentration gradient can be generated by a concentration difference, and the present invention was completed. The polyether derivative () in the present invention is synthesized by the following reaction using catechol or its alkyl substituted product as a raw material. The reaction of catechol or its alkyl substituted product with twice the molar amount of the compound () is carried out in an alkaline medium from 60 to
After carrying out at a reaction temperature of 120 °C, in the presence of pyridine,
Compound () can be obtained by treatment with thionyl chloride. The reaction between compound () and compound () is carried out in an alkaline medium at a temperature of 30-150°C, preferably 60-150°C.
It can be carried out at 120°C. Further, hydrolysis of the compound () can be carried out by a conventional method,
For example, it is carried out at a temperature of 60 to 80°C in a solvent such as water in which an alkali such as sodium hydroxide or potassium hydroxide is dissolved, or an alcohol such as methanol or ethanol. By neutralizing the hydrolysis product with an organic or inorganic acid, the desired product () can be obtained.
get. In addition, as the alkaline medium shown above,
An alkaline substance dissolved in an inert solvent is used. In this case, examples of the inert solvent include dimethylformamide, hexamethylphosphoramide, dimethyl sulfoxide, dioxane, etc. Examples include potassium t-butoxy, sodium hydride, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and the like. In addition, in the above general formula, when R ¹ or R ² represents an alkyl group, this alkyl group has 1 carbon number.
-4, any one of methyl, ethyl, and propylbutyl groups can be used. This alkyl group increases the oil solubility of the polyether compound () and reduces its elution from an organic solvent into an acidic or alkaline aqueous solution. R ³ serves as a reactive protecting group for a carboxyl group, and any hydrocarbon group can be used, but it is usually an alkyl group having 1 to 4 carbon atoms, an aryl group such as phenyl, benzyl, tolyl, xylyl, Aralkyl groups are applicable. The polyether derivatives () of the present invention act as cation transport agents, ie ionophores, and are applied to transport cations dissolved in one solution to another. In this case, the cation is
Various ions include alkaline earth metal ions such as magnesium, calcium, barium, etc. The polyether derivatives () of the present invention have high selectivity for different types of alkaline earth metal ions depending on their structures and transport conditions. In order to transfer cations using the polyether derivative () of the present invention as an ionophore, two solutions A and B may be brought into contact indirectly through the polyether derivative () of the present invention. good. For example, polyether derivative () is added to solution A
is dissolved in an organic solvent that is substantially immiscible with solution B, and the solution A and solution B are brought into indirect contact using the solution of this polyether derivative () as an intermediate solution layer. A method of indirect contact between polyether derivative solutions housed in compartments partitioned by a diaphragm, and a polyether derivative () in which solutions A and B are supported on a support such as a polymer membrane or paper. There are methods such as indirect contact via . Next, with reference to the drawings, a specific example will be shown in which cations are transferred by bringing solution A and solution B into contact via solution M of polyether derivative (). 1 indicates a U-shaped container, cylindrical containers 2 and 3,
It is composed of a connecting pipe 4 that connects their lower parts. 5 and 6 are stirrers. First, a solution M containing a polyether derivative () is poured into the container 1 as an intermediate solution layer, and then a solution A is poured into one cylindrical container 2 and a solution B is poured 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 an alkaline solution with a pH of 8 to 12. Solution B is for receiving the transferred cations, and is an acidic solution, generally 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. An aqueous solution containing PH 1 to 6 is 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, the polyether derivative () can transport cations against the ion concentration gradient, so that the concentration of cations contained in solution B is lower than the concentration of cations contained in solution A. can also be in high concentrations. The solvent used to form solution M is
Substantially immiscible with solutions A and B, e.g.
When 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 used. When the solutions A and B are brought into indirect contact as described above, the cations in the neutral or alkaline solution A are captured by the polyether derivative (), and the polyether derivative () that captures the cations
contacts solution B and releases its trapped cations into acidic solution B. In this way, solution A
The cations therein are transferred into solution B. When using the polyether derivative () of the present invention as an ionophore, as described above, the solution A
In this case, even if the concentration of cations in solution B is higher than that in solution A, the cations contained in the solution can be transferred against the concentration gradient. Cations can be transferred from solution A to solution B. According to the invention, therefore, in addition to the transfer of cations from solution A to solution B, it is also possible to concentrate the cations in solution A into solution B. The polyether derivative () of the present invention exhibits high selectivity for barium ions when n=2, and when n=3,
Since it shows high selectivity for calcium or magnesium ions, by applying the polyether derivative of the present invention to solution A containing these ions and other cations, from that solution,
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. Production method of ionophore (1) Production of 1,2-bis{3'-(o-carboxylphenyloxy)propyloxy}-4-t-butylbenzene t-Butylcatechol and potassium carbonate in DMF under nitrogen stream While stirring, add 2 times the mole of 3-chloropropanol and stir at 70°C for 1 day.
After treatment and vacuum distillation, 1,2-bis(3'-
Hydroxypropyloxy)-4-t-butylbenzene was obtained with a yield of 76%. This was refluxed in benzene with pyridine and thionyl chloride, and 86
% of 1,2-bis(3'-chloropropyleneoxy)-4-t-butylbenzene was obtained. 5g ethyl salicylate in 20ml DMF and 0.55
After stirring 1 g of NaH to make a homogeneous solution, 3.2 g
1,2-bis(3'-chloropropyloxy)
-Add 4-t-butylbenzene and 70℃ for 2 days
Stir with After benzene extraction and drying, the obtained solid was recrystallized (n-hexane) to give 2.8g.
1,2-bis{3'-(o-ethoxycarbonylphenyloxy)propyloxy}-4-t
-Butylbenzene was obtained. This in ethanol
The mixture was heated and stirred with KOH, and 1,2-bis{3'-(o-carboxylphenyloxy)propyloxy}-4-t-butylbenzene was obtained by column chromatography. The product was a transparent glassy solid, and the structure of the compound was confirmed by elemental analysis, NMR, and IR spectroscopy. Next, the NMR spectrum of this compound is shown.
(Using CDCl ₃ as a solvent and TMS as an internal standard) δ (ppm): 1.29 [singlet, 9H, C(CH ₃ ) ₃ ] 2.1
~2.7 [multiplet, 4H, OCH ₂ , CH ₂ CH ₂ O] 4.1 ~ 4.6 [multiplet, 8H, OC H ₂ CH ₂ C H
₂ O] 6.9-7.8 [multiplet, 9H, aromatic proton] 8.20 [quadruplet, 2H, aromatic proton] 9-10 [broad, 2H, COOH] (2) 1,2-bis{2'-(o- Production of carboxylphenyloxy)ethyloxy}-4-t-butylbenzene The desired product (transparent glassy solid) can be obtained in a good yield in the same manner as in (1). NMR _spectrum δ (ppm): 1.32 [singlet, 9H, C( _CH3 ) ₃ ] 4.2-4.8 [multiplet, 8H, OC H2C H2O ] 6.8-7.8 [multipelt, _9H , aromatic proton] 7.98 [ quadruplet, 2H, aromatic proton] 9-10 [broad, 2H, COOH] Cation transport test (1) A cation transport test was conducted using the apparatus shown in the drawing. As the ionophore, the above compound () (n=3 in the formula) was used. Solutions A, B and M
The component composition of is as follows. Solution A: 0.1M MgCl ₂ adjusted with Tris buffer,
Mixed aqueous solution containing 0.1M CaCl ₂ and 0.1M BaCl ₂
15ml (PH8.28 or 9.10) Solution B: 15ml aqueous solution containing 0.1MH3PO4 (PH8.28 _{or 9.10} )
1.30) Solution M: A solution formed by dissolving 1.5 × 10 ^-4 mol of the above compound ( show.

[Table] From the results shown in Table 1, when it comes to cation transfer from solutions containing Mg, Ca, and Ba, while Mg and Ba are only slightly transferred, Ca is transferred with good selectivity. I understand that. Furthermore, of solution A
The higher the pH, the greater the amount of transport. Test (2) Test (1) was conducted under exactly the same conditions except that Compound ( ) (n=2 in the formula) was used as the ionophore in solution M. The results are shown in Table 2.

[Table] The results show that ionophore () has a high selectivity for barium ions, and that the smaller the ion diameter compared to calcium and magnesium, the more difficult it is to be transported. Test (3) The test was conducted in the same manner as in Test (1) except that solution A having the following composition was used. Solution A: 0.1M _MgCl2 , 0.1M _CaCl2 , 0.1M
15 ml of a mixed aqueous solution containing BaCl ₂ and 0.1M LiOH (or 0.2M LiOH) This aqueous solution A immediately produces a white precipitate due to the addition of LiOH, but it was confirmed that the white precipitate did not migrate into solution M. 100% Mg(OH) ₂ (50 for 0.1M LiOH addition)
% Mg ²⁺ remaining in solution, with 0.2M LiOH added
The test was conducted to confirm that no Mg ²⁺ was present in the solution. The results are shown in Table 3.

[Table] The results show that, contrary to the results in test (1), there is greater selectivity for magnesium ions than for calcium ions, and that the amount of transport is also significantly increased. Also, almost no lithium ion transfer is observed. Until now, no natural ionophore has been found to have high selectivity for magnesium ions. It has been confirmed that no transport occurs under these conditions or without ionophore. The test was conducted in the same manner as in Test (1) except that solution B having the following composition was used. Solution B: 0.1M MgCl ₂ , 0.1M CaCl ₂ , 0.1M
Mixed solution containing BaCl ₂ and 0.2M HCl The results are shown in Table 4.

[Table] Even when solutions A and B contain the same concentration of cations as initial conditions for transport, calcium ions are selectively transported into solution B against the concentration gradient. Test (5) The test was conducted in the same manner as in Test (1) except that solutions A and B having the following compositions were used. Solution A: 0.1M LiOH, 0.1M NaOH, 0.1M
15ml mixed aqueous solution containing KOH and 0.1MH ₂ SO ₄
(PH12.4) Solution B: 0.1M LiOH, 0.1M NaOH, 0.1M
15ml mixed aqueous solution containing KOH and 0.2MH ₂ SO ₄
(PH2.0) The results are shown in Table 5.

[Table] The results show that the transport of alkali metal ions by the ionophore () is small and the selectivity is also low. As seen in test (3), in the coexistence with alkaline earth metal ions, lithium ions, which migrate in the largest amount in this test, hardly migrate, indicating that this ionophore is excellent for alkaline earth metal ions. It is clear that it has transportability.

[Brief explanation of drawings]

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 (1)

[Claims] 1. General formula (In the formula, n is 2 or 3, and R ¹ and R ² are a hydrogen atom or an alkyl group.) A polyether derivative represented by the following. 2 General formula (where n, R ¹ and R ² are the same as above) is used as an ionophore, and the cations contained in solution A are transferred to solution B.
A cation transport method characterized by transporting cations to.