JPS6254782B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula () (In the formula, R ¹ , R ² and R ³ are hydrogen atoms or have 1 to 1 carbon atoms.
30 alkyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a benzyl group, a 2-phenylethyl group, or a 3-(naphthyl-1-oxy)propyl group) It concerns derivatives. The polyether derivatives of the present invention are useful as cation carriers (ionophores), in particular:
It has the characteristics of acting selectively on lithium ions and being able to transport them against the concentration gradient. The present inventors have conducted various studies on the development of compounds useful as ionophores, and this time, the polyether derivative represented by the general formula () has shown excellent performance as an ionophore, and is particularly useful for lithium ions. We found that they exhibited greater selective transport ability than the previously reported polyether derivatives containing quinolyl groups, and also caused cation transport to occur against the concentration gradient. They found that the permeation rate does not change depending on the type of anion present, unlike those contained, and have completed the present invention. The polyether derivative () of the present invention is synthesized by the following reaction using catechol or its alkyl substituted product as a raw material. The reaction between compound () and equimolar amount of 2-(3-chloropropyloxy)tetrahydropyran is carried out in an alkaline medium at a reaction temperature of 60 to 120°C, and after removal of the protecting group by acid treatment, the presence of pyridine is removed. under,
Compound () can be obtained by treatment with thionyl chloride. The reaction of compound () with catechol or its alkyl substituted product can be carried out in an alkaline medium. The reaction temperature is 60-120°C. The reaction between compound () and 1,3-dichloropropane is carried out in an alkaline medium in the presence of an excess of 1,3-dichloropropane. Reaction temperature is 60-120
It is ℃. The reaction between compound () and compound () is carried out in an alkaline medium at a temperature of 30-150°C, preferably 60-120°C.
It can be carried out under conditions of ℃. Further, hydrolysis of the compound () can be carried out by a conventional method, for example, in water containing an alkali such as sodium hydroxide or potassium hydroxide, or in a solvent such as an alcohol such as methanol or ethanol, at a temperature of 60°C. Performed at ~80°C. The desired product () is obtained by neutralizing the hydrolysis product with an organic acid or an inorganic acid. 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. Furthermore, in each of the above general formulas, R ¹ , R ² , R ³ or R ⁴
When represents an alkyl group, any alkyl group can be used, regardless of lower alkyl or higher alkyl, and usually one having 1 to 30 carbon atoms is used. This alkyl group increases the water solubility of the polyether compound () and reduces its elution from an organic solvent into an acidic or alkaline aqueous solution. R ⁵ serves as a reactive protective 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, etc. 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, for example, ions of alkali metals such as sodium, potassium, and lithium. The polyether derivative () of the present invention has a particularly high selectivity to lithium ions, and a solution in which cations other than lithium ions, such as alkali metal ions such as sodium, potassium, rubidium, and cesium, coexist. From this, lithium ions can be selectively transferred. To transport cations using the polyether derivative () of the present invention as an ionophore,
Two types of solutions A and B may be brought into contact indirectly via the polyether derivative () of the present invention.
For example, a polyether derivative () is dissolved in an organic solvent that is substantially immiscible with solutions A and B, and the solution A and solution B are brought into indirect contact using the solution of the polyether derivative () as an intermediate solution layer. A method in which solutions A and B are brought into indirect contact with each other via a polyether derivative solution contained in a compartment partitioned by a diaphragm, A method in which solutions A and B are brought into contact with each other through a support such as a polymer membrane or paper There is a method of indirect contact via a polyether derivative supported on the body. 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 solvent with a pH of 8 to 12. Solution B is for receiving the cations to be transferred, and is an acidic solution, generally containing an inorganic acid such as an acid salt or sulfuric acid, or an organic acid such as formic acid, acetic acid, or an organic sulfonic acid. -6 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,
Polyether derivatives () can transport cations against the ion concentration gradient, so
The concentration of cations contained in solution B can be higher than the concentration of cations contained in solution A. 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 solutions A and B are brought into indirect contact as described above, the cations in neutral or alkaline solution A are captured by the polyether derivative (),
The polyether derivative () that has captured this cation comes into contact with solution B and releases the captured cation into acidic solution B. In this way,
Cations in solution A are transported 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. Since the polyether derivative () of the present invention exhibits high selectivity for lithium ions, by applying the polyether derivative of the present invention to solution A containing lithium ions and other cations, the solution From inside,
Only lithium 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: 1-{3'-(O-carboxylphenoxy)propyloxy}-2-{3'-O-ethoxyphenyloxy)propyloxy}-4 (or 5)-t
-Production of butylbenzene 115ml of 33g of ethyl salicylate and 5g of NaH
After stirring in DMF to make a homogeneous solution, add 40
g of 2-(3-chloropropyloxy)tetrahydropyran is added and stirred at 70°C for 24 hours. After cooling in air, the reaction solution was poured into water and extracted with benzene, and the benzene phase was thoroughly washed with water and dried with _MgSO4 .
After removing the solvent and distilling the residue (180℃/0.5
mmHg), 36 g (80%) of ethyl 2-(3-hydroxypropyloxy)benzoate were obtained. This was chlorinated in benzene using pyridine and thionyl chloride in a conventional manner to obtain ethyl 2-(3-chloropropyloxy)benzoate (2) in a yield of 83%. 50 g of 4-t-butylcatechol and 6.0 g of t
- BuOK was stirred in 150 ml of DMF under a nitrogen atmosphere to make a homogeneous solution, then 13 g of ethyl 2-(3-chloropropyloxy)benzoate was added, and the mixture was heated at 70°C for 2 hours.
Stir for days. After extraction with benzene and the same post-treatment as above, excess t-butylcatechol was removed by vacuum distillation and the residue was purified by column chromatography (alumina, CHCl ₃ ) to obtain 14.5 g (76%) of 1{3-
(O ethoxycarbonylphenyloxy)propyloxy}-2-hydroxy-4(or 5)-t-
Butylbenzene () was obtained. On the other hand, 3-
(O-ethoxyphenyloxy)propyl chloride can be obtained by reacting O-ethoxyphenol and excess 1,3-dichloropropane in dioxane, or
Alternatively, it could be obtained in good yield by reacting equimolar amounts of O-ethoxyphenol and 3-chloropropanol, followed by chlorination with SOCl ₂ and pyridine. 1.9g () and 0.6g t-BuOK in 30ml DMF
After stirring to make a homogeneous solution, 2.2 g of 3-(O
-Ethoxyphenyloxy)propyl chloride is added and stirred at 70°C for 1 day. After benzene extraction,
After post-treatment as described above and purification by column chromatography (alumina, CHCl ₃ ), 1.7 g (65%) of the ethyl ester compound ( ) was obtained. The ester () was hydrolyzed with KOH in ethanol, worked up and purified by column chromatography (silica gel, CHCl ₃ ) to give the product in 81% yield. ¹ HNMR (CDCl ₃ δ): 1.30 [singlet, 9H, C
(CH ₃ ) ₃ ], 1.40 [triplet, 3H, OCH ₂ C H ₃ ],
2.0 _~ 2.6 [multiplet, 4H, OCH2CH2CH2O _{] ,}
4.06 [quadruplet, 2H, OC H ₂ CH ₃ ], 4.1-4.7
[multiplet, SH, OC H ₂ CH ₂ CH ₂ O], 6.93
[singlet, 4H, aromatic proton], 6.8-7.8
[multiplet, 6H, aromatic proton], 8.22
[quadruplet, 1H proton], ca.9-10
[broad, 1H, COOH] 1-{3-(Ocarboxylphenyloxy)propyloxy}-2-[3-{2-(2-phenylethoxy)phenyloxy}propyloxy]
-Production of 4(or 5)-t-butylbenzene According to the above method, compound () and 3-{2
The product was obtained by reaction with -(2-phenylethoxy)phenyloxy}propyl chloride. ¹ HNMR (CDCl _3.δ ): 1.30 [singlet, 9H, C
( _CH3 ) ₃ 〕, 2.0~2.6〔multiplet, 4H, _OCH2C
H ₂ CH ₂ O], 3.10 [triplet, 2H, OCH ₂ C H ₂ −
Ph], 4.0 to 4.6 [multiplet, 10H, OC H ₂ CH ₂ C
H ₂ O and OC H ₂ CH ₂ Ph], 6.93 [singlet, 4H,
Aromatic proton], 6.8-7.8 [multiplet, 6H,
aromatic proton], ca.9-10 [broad, 1H,
COOH] 1-{3-(O-carboxylphenyloxy)propyloxy}-2-[3-[2-{3-
(1-naphthyloxy]propyloxy}phenyloxy]propyloxy]-4 (or 5)-
Production of t-butylbenzene According to the above method, compound () and 3-[2
-{3-(1-naphthyloxy)propyloxy}
phenyloxy]propyl chloride (this is 2-
The product was obtained by reaction with {obtained by reaction of 3-(1-naphthyloxy)propyloxy}phenol and 1,3-dichloropropane). ¹ HNMR (CDCl ₃ , δ): 1.27 [singlet, 18H,
C( _CH3 ) ₃ 〕2.0~2.65〔multiplet, 6H,
OCH ₂ C H ₂ CH ₂ O], 4.0 to 4.6 [multiplet,
12H , _OC H2CH2CH2O ] _{, 6.7-8.5}
[multiplet, 17H, aromatic proton], ca.9-10
[broad, 1H, COOH] 1-{3-(Ocarboxylphenyloxy)propyloxy}-2-{3-(2-sterialoxyphenyloxy)propyloxy}-4
(or 5) Production of -t-butylbenzene According to the above method, compound () and 3-(2
The product was obtained by reaction with -stearyloxyphenyloxy)propyl chloride, which is obtained by reaction of 2-stearyloxyphenol with 1.3 dichloropropane. ¹ HNMR ( _CDCl3 , δ): 0.9 [broad, 3H, O-(CH2)-17CH3 _{] , 1.28} [singlit, _32H , _COH2- ( CH2 )-
₁₆ CH ₃ ], 1.30 [singlet, 9HC(CH ₃ ) ₃ ), 2.0 to 2.6 [multiplet, 4H, OCH ₂ C H ₂ CH ₂ O], 3.8 to 4.7 [multiplet, 10 H, OC H ₂ , CH ₂ C H
₂ O and OC H2- ( _CH2 ) _{-16 CH3} ], 6.92 [singlet, 4H, aromatic proton], 6.9-7.8 _] multiplet, 6H, aromatic proton], 8.25 [quadruplet, 1 aromatic proton] , ca.9-10 [droad, 1H, COOH] 1-{3-(Ocarboxylphenyloxy)propyloxy}-2-{3-(2-hydroxyphenyloxy)propyloxy}-4 (or 5 ) - Production of t-butylbenzene 1-{3-(O-carboxylphenyloxy)propyloxy}-2-(3-
The product was obtained by reaction of (chloropropyloxy)-4(or 5)-t-butylbenzene and catechol. ¹ HNMR ( _CDCl3 , δ): 1.30 [singlet _, 9H, C( _CH3 ) ₃ ], 2.0-2.65 [multiplet, 4H, OCH2CH
₂ CH ₂ O], 4.0 to 4.7 [multiplet, 8H, OC H ₂ CH ₂ C H
₂ O], 6.7-7.8 [multiplet, 10H, aromatic proton], 8.22 [quadruplet, 1H aromatic proton], ca.9-10 [broad, 2H, COOH and OH] B: Cation transport test test ( 1) A cation transport test was conducted using the equipment shown in the drawing. As the ionophore, the compound () obtained above (in formula 1, R ¹ = t-butyl, R ² =
H, R ³ =H, R ⁴ =Et). The component compositions of solutions A, B and M are as follows. Solution A: 0.1N LiOH, 0.1N NaOH, 0.1N
Mixed aqueous solution of specified KOH and 0.2 normal H ₂ SO ₄
115ml (PH=12.4) (The solution is circulated with a pump.) Solution B: 15ml of an aqueous solution of 0.1N H ₂ SO ₄ (PH=
2.0) Solution M: A solution formed by dissolving 1.5 x 10 ^-4 moles of the above compound in 30 ml of chloroform. This test was conducted at 25°C, and the liquid was stirred using a glass stirring rod for each solution A, B, and M. was performed at 200 rpm. The following experiments were also conducted under similar conditions. Table 1 shows the transfer rate (μmole/hr) and selectivity of each cation transferred from solution A to solution B. [Table] From the results shown in Table 1, it can be seen that Li is selectively transferred relative to Na and K in the presence of three types of cations. This result shows that under the same conditions, the ionophore has superior selectivity to the ionophore having an 8-quinoline terminal group instead of an O-ethoxyphenyl terminal group (previously reported). The amount of Li transported for two days reached 0.92 mmole. Test (2) In test (1), the compound obtained above (in the formula R ¹ = t
-butyl, ^R2 = ^R3 = H, ^R4 = 2-phenylethoxy).
The results are shown in Table 2. [Table] It can be seen that this test shows even better lithium selectivity than Test (1). Test (3) In test (1), the compound obtained above (in the formula R ¹ = t-
The test was conducted in the same manner except that butyl, R ² =R ³ =H, and R ⁴ =3-(naphthyloxy)propyl) were used. The results are shown in Table 3. [Table] According to Table 3, this ionophore was tested (1) and (2).
It can be seen that the lithium selectivity is even better than that of the ionophore used in . Test (4) In test (1), the component composition of solution A is
0.1N LiOH, 0.1N NaOH, 0.1N
KOH, 0.1 normal RbOH, 0.1 normal CsOH and 0.4
Using 115 ml of the specified mixed aqueous solution of H ₂ SO ₄ and using the compound obtained above as the ionophore in solution M (in the formula, R ¹ = t-butyl, R ² = R ³ =
H, R ⁴ =3-(1-naphthyloxy)propyl)
The test was conducted in the same manner except that . The results are shown in Table 4. [Table] Table 4 shows that the selectivity to lithium ions is excellent even in the presence of five types of alkali ions. Test (5) In test (1), the compound obtained above (in the formula R ¹ = t-
The test was conducted in the same manner except that (butyl, R ² =R ³ =H, R ⁴ =stearyl) was used. The result is the fifth
Shown in the table. [Table] Test (6) In test (1), the compound obtained above (in the formula R ¹ = t-
The test was conducted in the same manner except that butyl (R ² =R ³ =R ⁴ =H) was used. The results are shown in Table 6. [Table] From Table 6, it can be seen that although this ionophore has a lower cation transfer rate than the others, it exhibits very good Li selectivity.

[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 (1)

[Claims] 1. General formula (In the formula, R ¹ , R ² and R ³ are hydrogen atoms or have 1 to 1 carbon atoms.
30 alkyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a benzyl group, a 2-phenylethyl group, or a 3-(naphthyl-1-oxy)propyl group) derivative. 2 General formula (In the formula, R ¹ , R ² and R ³ are hydrogen atoms or have 1 to 1 carbon atoms.
30 alkyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a benzyl group, a 2-phenylethyl group, or a 3-(naphthyl-1-oxy)propyl group, and R ⁵ is a reactive protecting group. General formula characterized by hydrolyzing a polyether derivative represented by ) under alkaline conditions. (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.) A method for producing a polyether derivative represented by the following. 3 General formula (In the formula, R ¹ , R ² and R ³ are hydrogen atoms or have 1 to 1 carbon atoms.
30 alkyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a benzyl group, a 2-phenylethyl group, or a 3-(naphthyl-1-oxy)propyl group) Using the derivative as an ionophore, the cations contained in solution A are transferred to solution B.
A cation transport method characterized by transporting cations to.