JP2999889B2 - 1,3-Alternate-type calixarene derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel calixarene derivative which can be used for extracting a specific metal.

[0002]

2. Description of the Related Art Calixarenes are cyclic oligomers having a structure in which a plurality of phenol units are linked by a methylene group. It is gradually attracting attention as a material from practical aspects.

In particular, a calixarene having four phenol units, that is, a derivative of calix [4] arene, has been extensively studied with respect to the affinity for a metal and the like. This calix [4] arene is formed by the inversion of the benzene ring (phenol ring).
It is known to adopt different conformations. That is, four benzene rings (phenol units) oriented in the same direction are regarded as cones (cone:
1A) a partial cone in which only one benzene ring is inverted with respect to the other three benzene rings, a partial cone in which two opposed benzene rings are inverted, and 3-Alternate (1,3-alte
rnate: B) in FIG. 1 and a compound obtained by inverting two adjacent benzene rings were converted to 1,2-alternate (1,2-al
ternate).

[0004] Despite the indication of the existence of such a conformation, conventional functional developments relating to calix [4] arenes have been mainly directed to the "corn" type. This is because the four benzene rings are oriented in the same direction and form a cylindrical shape as a whole while four hydroxyl groups (FIG. 1)
This is because the “cone” type calix [4] arene in which the “OR” part is aligned on the same side is considered to exhibit a hard ring structure having a pore diameter suitable for a metal atom. Thus, for example, it is known that calix [4] arene derivatives having a cone structure in which an acetic acid ester is introduced into a hydroxyl group of a phenol ring exhibit remarkable Na ⁺ selectivity.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present inventor has found a new calix [4] arene derivative which is different from the conventionally known calix [4] arene derivative while conducting research on calixarene. Was. That is, the present invention relates to 1,3-formula represented by the following general formula [Formula 1].
The present invention relates to an alternate calix [4] arene derivative.

[0006]

Wherein R is selected from an alkyl group having 3 or more carbon atoms or an alkoxyethyl group.

[0007] As shown in the above [Chemical formula 1], the calix [4] arene derivative of the present invention has a structure in which a 1,3-altanate is fixed via crosslinking with benzyl catechol. The calix [4] arene derivative has extremely high affinity for specific metal ions (Ag ⁺ , K ⁺ ). Thus, the present invention replaces calix [4] arene-based metal ionophores, which were hitherto mainly limited to the "cone" type, with "1,3-
Provided is a novel calix [4] arene derivative that can be a metal ionophore of the "alternate" type.

In the calix [4] arene derivative of the present invention represented by Chemical Formula 1, R can achieve a desired object if it is an alkyl group or an alkoxyethyl group having 3 or more carbon atoms. However, if R is too large, synthesis becomes difficult, and it is not actually available. Therefore,
The carbon number of R is generally 10 or less, particularly preferably 8 or less.

The calix [4] arene derivative of the present invention can be synthesized by a method as shown in FIG. The inventor has determined that the 1,3-alternate-type calix [4] arene derivative of the present invention requires 1,3-alternate.
They have found a means of synthesizing an alternate intermediate compound. That is, such intermediates are also compounds established by the present inventors.

Specifically, the calix [4] arene derivative of the present invention can be synthesized by a route from (1) to (5) as shown in FIG. First, compound (1) can be obtained by heating t-butylphenol and formaldehyde to a high temperature in an alkali according to a known method. Compound (2) is obtained by mixing this compound with aluminum chloride in toluene as is known.

The present inventors have established a means for selectively synthesizing a 1,3-alternate-type calix [4] arene derivative from the calix [4] arene shown in (2). That is, by reacting this compound (2) with an alkyl halide or an alkoxyalkyl halide in the presence of cesium carbonate, a 1,3-alternate of calixarene as shown in (3) can be obtained. At this time, if a compound other than cesium carbonate is used as an alkali, care must be taken because a conformational isomer other than the target 1,3-alternate may be obtained, or a mixture of both may be obtained. Further, the compound (3) is halogenated with a halogenated methyl ether such as chloromethyl methyl ether to give a compound (4). Finally, this compound (4)
By reacting catechol with catechol in the presence of an alkali, the calix [4] arene derivative of the present invention can be synthesized.

The calix [4] arene derivative of the present invention obtained as described above has a unique property that it has an affinity for K ⁺ ions and Ag ⁺ ions, and that these ions can be selected by an extraction operation. Demonstrate the nature. The reason for having such a property is that, in the 1,3-alternate-type calix [4] arene derivative of the present invention, two benzene rings facing in parallel (the rectangular portion in FIG. 1, B)
Are two adjacent oxygen atoms (-OR in FIG. 1, B)
And O) to interact specifically with metal ions. In this regard, the calixarene derivative of the present invention is different from the conventional cone-type calix [4] arene (see FIG. 1, A) which presents a vacancy consisting of four oxygen atoms for the metal ion to be captured. To provide a new ionophore with a completely different structure.

In particular, when an aqueous solution containing silver ions is brought into contact with an organic solvent in which the calixarene derivative of the present invention is dissolved, silver ions (Ag ⁺ ) can be extracted into the organic solvent. Heretofore, silver has been recovered from a bluing method, that is, a solution obtained by mixing a cyanide compound with mineral mud, and the low recovery rate and danger have been regarded as problems.
The calix [4] arene derivative of the present invention is a novel compound that is industrially useful in that it has extremely high selectivity for silver ions and can efficiently recover silver ions from silver-containing waste liquid.

Hereinafter, the present invention will be described with reference to Examples to further clarify the features of the present invention.

[0015]

【Example】

<< Preparation Example 1 >> A calix [4] arene derivative of the present invention represented by the following [Chemical Formula 2] was synthesized by the following method.

[0016]

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First, 1.18 mmol of calix [4] arene (compound (2) in FIG. 2) was added to 100 ml of acetone.
And 46.96 mmol of propyl iodide and 18.85 mmol of cesium carbonate were added. The mixture was stirred at a reflux temperature for 48 hours under a nitrogen stream. After cooling, the solvent was distilled off under reduced pressure. The residue was neutralized with 1N hydrochloric acid and extracted with chloroform. After washing with water three times, it was dried over anhydrous magnesium sulfate. The solvent and excess alkyl halide were removed under heating and reduced pressure, and recrystallized from chloroform-methanol to obtain white crystals of 1,3-altanate of o-propylcalix [4] arene shown in [Chemical Formula 3]. . 243-244 ° C.

[0018]

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1.00 g of 1,3-alternate of o-propylcalix [4] arene represented by the following formula:
(1.69 mmol) and p-formaldehyde 0.81
g was suspended in 75 ml of dioxane. 4.05 g of acetic acid
(67.5 mmol), 13.22 g of phosphoric acid (135 m
mol), and 11.3 ml of concentrated hydrochloric acid (12N, 135
mmol) and stirred at 80 ° C. for 36 hours. afterwards,
After cooling to room temperature, water was added on an ice bath, and the precipitated crystals were collected by filtration. The crystals were dissolved in chloroform, washed twice with water, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the residue was recrystallized from chloroform-hexane to obtain white crystals of o-propyl-p-chloromethylcalix [4] arene represented by [Chemical Formula 4]. Yield 67
%. Melting point 283-285 [deg.] C. Elemental analysis (C ₄₄ H ₅₂ O ₄
Cl ₄ ): Calculated value (H 6.66%, C 67.18)
%,), Found (H 6.59%, C 67.20%).

[0020]

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1.00 g (1.27 mmol) of 1,3-alternate of o-propyl-p-chloromethylcalix [4] arene represented by the following formula
The mixture was heated and dissolved under a stream of nitrogen. To this, 35.14 g (254 mmol) of potassium carbonate was added, and the mixture was further refluxed for 1 hour.

On the other hand, catechol 1.
A solution in which 12 g (10.2 mmol) was dissolved was put into a dropping funnel and slowly dropped into the solution. After 24 hours, the mixture was allowed to cool to room temperature. The mixture was acidified with 1N hydrochloric acid, and further extracted with chloroform. After washing three times with water, it was dried over magnesium sulfate. The solvent was distilled off by heating under reduced pressure, and the residue was recrystallized from chloroform-methanol to obtain the desired white crystal of the 1,3-altanate-type calix [4] arene derivative represented by [Chemical Formula 2]. Yield 81% (0.89 g). Melting point> 310 ° C
(Disassembly). Elemental analysis value (as C ₅₆ H ₆₀ O ₈ ): calculated value (H 7.02%, C 78.11%), measured value (H 6.7)
2%, C78.02%). The results of NMR measurement are shown in the following Table 1 while showing the assignments in the following [Chemical Formula 5].

[0023]

[Table 1]

[0024]

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<Preparation Example 2> As another example of a 1,3-alternate-type calix [4] arene derivative according to the present invention, a compound represented by the following [Chemical Formula 6] was synthesized as follows.

[0026]

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1.00 g (2.36 mmol) of calix [4] arene (compound (2) in FIG. 2) was added to acetone 7
It was dissolved in 0 ml. To this, under a nitrogen stream, 12.28 g (37.7 mmol) of cesium carbonate and 8.01 g (47.1 mmol) of 2-bromoethyl ethyl ether were added. After refluxing and stirring for 48 hours, the mixture was allowed to cool to room temperature. The solvent was distilled off under reduced pressure, 1N hydrochloric acid was added to the residue to make it neutral, and the mixture was extracted with chloroform. The chloroform phase was washed twice with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from chloroform-methanol to obtain white crystals of 1,3-alternate of o-ethoxyethyl calixarene. Melting point 1
76-177 ° C. Elemental analysis (as C ₄₄ H ₅₆ O _8):
Calculated value (H 7.92%, C 74.13%), measured value (H
7.44%, C73.67%).

1.00 g of 1,3-alternate of o-ethoxyethylcalix [4] arene, 0.67 g of p-formaldehyde, 75 m of dioxane, 3.3 acetic acid
7 g (56.1 mmol), phosphoric acid 11.00 g (11
9.35 ml of concentrated hydrochloric acid (12N, 11
2 mmol), and in the same manner as in Preparation Example 1,
A 1,3-alternate of o-ethoxyethyl-p-chloromethylcalix [4] arene represented by the following Chemical Formula 7 was synthesized. Yield 86% (yield 1.09 g). 200-201 ° C. Elemental analysis value (as C ₄₈ H ₆₀ O ₈ Cl ₄ ): calculated value (H 6.67%, C 63.51%), measured value (H 6.67%, C 63.58%).

[0029]

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0.30 g (0.33 mmol) of 1,3-alternate of o-ethoxyethyl-p-chloromethylcalix [4] arene of [Chemical Formula 7], 9.14 g (66.2 mmol) of potassium carbonate, catechol 0.29
g (2.65 mmol) was used to synthesize the target compound [Chemical Formula 6] in the same manner as in Preparation Example 1. Yield 86% (yield 0.28 g). Elemental analysis value (as C ₆₀ H ₆₈ O ₁₂ ): calculated value (H 6.99%, C 73.45%), measured value (H
6.91%, C72.98%). The NMR measurement results are shown below together with [Chemical Formula 8] indicating the assignment.

[0031]

[Table 2]

[0032]

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<< Comparative Preparation Examples >> For the purpose of comparison, a compound represented by the formula
And a cone of calix [4] arene shown in [Chemical Formula 10] was synthesized. The compound of the formula [Formula 9] is prepared in Preparation Example 1.
In synthesizing the 1,3-alternate compound of the formula [3], sodium carbonate or potassium carbonate is used instead of cesium carbonate. The corn body of calix [4] arene of Chemical Formula 10 is synthesized by using NaH instead of cesium carbonate when preparing the 1,3-alternate form of o-ethoxyethyl calixarene in Preparation Example 2. (Melting point 124.0-125.0 ° C).

[0034]

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[0035]

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<< Measurement Examples >> Metal ion extraction experiments were carried out using the calix [4] arene derivatives of the present invention represented by [Chemical Formula 2] and [Chemical Formula 6]. For comparison, the corn-type calixarene derivatives obtained in Comparative Preparation Examples (Chemical Formula 9 and Chemical Formula 10)
A similar experiment was performed for

The extraction experiment was carried out as follows: the methylene chloride solution containing the calix [4] arene derivative (2.5 × 10 ⁻³ M) was used as the organic phase, while the picric acid (2) was used as the aqueous phase. .38 × 10 ^-4 M) and an aqueous solution containing MNO ₃ (M: metal, 0.01M), 5 ml of both phases
Each into a sample bottle with screw cap,
Shake at 12 ° C. for 12 hours. After standing for 10 minutes, separate the aqueous phase and instantaneous multi-photometry system (MCPD-100)
The absorbance was measured with. Extraction rate = [(AB) / A] × 1
The extraction rate was determined as 00. Here, A is the absorbance after the extraction operation in the absence of the calixarene derivative,
B is the absorbance after the extraction operation in the presence of the calixarene derivative.

The results of the extraction experiment are shown in Table 3 below.

[Table 3]

As can be understood from the above results, the 1,3-altanate-type calix [4] arene derivative according to the present invention has an excellent affinity for silver ions, and is dissolved in an organic solvent to form silver ions. The ions can be extracted into the organic solvent by contact with the aqueous solution.

In some of the chemical structural formulas described in this specification, some of carbon atoms and hydrogen atoms are omitted according to customary conventions.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram schematically showing a cone-type and 1,3-alternate-type conformation of calix [4] arene which is an object of the present invention.

FIG. 2 is a flowchart showing a synthesis step of a calix [4] arene derivative of the present invention.

Claims (1)

(57) [Claims] 1. 1,3 represented by the following general formula [1]
-Alternate calix [4] arene derivatives. Embedded image (Wherein, R is selected from an alkyl group having 3 or more carbon atoms or an alkoxyethyl group).