JPH0729993B2 - Novel Calix allene derivative and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel calixarene derivative and a method for producing the same.

Conventional Technology Calixarene or Calixarene [n]
Allen is the general formula (VII) In the cyclic compound represented by, n is, for example, an integer of 4 to 8 and represents the number of rings forming calixarene. Such a name of Calixcus arene is a name given conventionally because it has a three-dimensional structure composed of an aromatic ring (arene) similar to the Greek "calix". For the history of research, synthesis, three-dimensional structure and applications of such calix [n] arene, see Gu, for example.
It was reported in detail by Tsche et al. (J. Am. Chem. So
c., 103 , 3782 (1981); Acc.Chem.Res., 16 , 161 (198
3)), the calix [n] arene represented by the above formula is typically obtained by reacting pt-butylphenol with formaldehyde in the presence of a base such as potassium hydroxide or rubidium hydroxide. Thus, p-t-butylcalixarene is obtained, which can be obtained by dealkylation.

Problems to be Solved by the Invention The above-mentioned calixarene has a three-dimensional structure of a molecule having a cylindrical structure having a hole surrounded by a benzene ring in the center of the molecule, and moreover, this hole has It is closed in the direction of the p-position with respect to the hydroxyl group. Therefore, such calixarene is attracting attention as an inclusion compound for forming a stable host-guest complex in an enzymatic reaction, for example. For example, Calix allene is conventionally known to include relatively small molecules such as chloroform and toluene in the solid state. Further, it has been attracting attention as a transporter of metal ions through a hydrophobic liquid film by utilizing the function of the hydroxyl group surrounding the pores as a selective ligand for metals.

However, conventionally known Calixarene is generally poorly soluble in many organic solvents in addition to having a high melting point as compared with acyclic analogs, and is conventionally water-soluble. Karitsukusu Allen is unknown. Therefore, Calixarene which naturally forms a host-guest complex in an aqueous solution is not known. But,
Water-soluble calixarene is required for practical use as an enzyme reaction, a catalytic reaction, or as a metal transporter.
In addition, such water-soluble Calixarene will be indispensable for theoretical studies of enzymatic reactions and catalytic reactions.

Therefore, as described in Japanese Patent Application No. 59-205990, the inventors of the present invention have already disclosed water-soluble calixarene-p-sulfonic acid and On-alkylcalixarxarene-p-sulfone. Succeeded in obtaining acid,
For p-nitrocalixarene, which could not be obtained by direct nitration of calixarene,
The above-mentioned potassium allene-p-sulfonic acid has been successfully obtained by a method in which the sulfonic acid group is replaced with a nitro group by treating it with nitric acid or a nitrate.

The above calixarene-p-sulfonic acid has a peculiar property as a host molecule or an acid catalyst because it has a phenolic hydroxyl group and an anionic group at both ends in the axial direction of the axial structure of the tubular structure of the molecule. It is expected to have and is also interesting as a surfactant. On the other hand, p-nitrocalixarene is important as a raw material for synthesizing various calixarene.

As a result of further promotion of researches on calixus allene, the present inventors have been able to obtain more novel derivatives from p-nitrocalixus allene, and in particular, in contrast to the above-mentioned calixus allene-p-sulfonic acid, The present invention has been completed by finding that an ionic p-trialkylammonio-O-alkylcalixarene can be obtained.

Therefore, it is an object of the present invention to provide a novel calixarene derivative and a method for producing the same.

Means for Solving the Problems The novel potassium allen according to the present invention has the general formula (I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms, Z is a substituent selected from the group consisting of a nitro group, an amino group, and a trialkylammonium in which the alkyl group has 1 to 5 carbon atoms, and n is 4 to An integer of 8, n '= 0 when Z is a nitro group or an amino group, and xa ^- represents a counter anion when Z is a trialkylammonium, and a is the valence of this counter anion. And n '= n / a)).

That is, according to the present invention, firstly, as a novel potassium allene, the general formula (II) Secondly, a p-nitro-O-alkylcalixarene is represented by the general formula (III) And p-amino-O-alkylcalixarene represented by the following general formula (IV) (In the formula, R'represents an alkyl group having 1 to 5 carbon atoms.), P-trialkylammonio-O-alkylcalixarenes are respectively provided.

The present invention will be described in detail below.

The p-nitro-O-alkylcalixarenes represented by the general formula (II) can be obtained by alkylating the corresponding alkali metal salt of p-nitrocalixarenes with an alkylating agent. p-Nitrocalixarene can be obtained by substituting a nitro group for a sulfonic acid group of calixarene-p-sulfonic acid. This calixarene-p-sulfonic acid is described in Japanese Patent Application No. 59-205990 as described above. For example, calixarene is suspended in concentrated sulfuric acid and the temperature is 80 ° C. or higher, preferably 90 ° C. It can be obtained by heating and melting at a temperature of ℃ or more.

First, the production of p-nitrocalix arene will be described. In order to produce p-nitrocalixarene, calixarene-p-sulfonic acid may be once produced, separated and then subjected to a sulfonic acid group-nitro group substitution reaction. When it is not necessary to separate p-sulfonic acid, sulfonation of calixarene may be followed by a sulfonic acid group-nitro group substitution reaction.

That is, Kallix allene is suspended in concentrated sulfuric acid having a concentration of 90% or more, preferably 95% or more, and 80 ° C or more, preferably 90
Heating to a temperature above 0 ° C. to form calixarene-p-sulfonic acid, which is then taken out without removal.
The reaction mixture is diluted by adding water to a sulfuric acid concentration of 30 to 70%, and then nitric acid or a nitrate such as sodium nitrate or potassium nitrate is added under cooling to replace the sulfonic acid group with a nitro group. .

In this reaction, the amount of nitric acid or nitrate used is preferably 1 to 1.2 mol per phenol unit of the raw material calix arene used. The use of an excessive amount of nitric acid or nitrate is not preferable because side reactions such as oxidation reaction increase and the yield decreases. The reaction temperature is usually 10 ° C or lower, but 5 ° C or lower is particularly preferable. The reaction time is usually several hours to several tens of hours. After this nitration reaction, the reaction mixture is diluted with water, and the precipitated crystals are separated and washed with water, whereby p-nitrocalixarene can be obtained.

The alkali metal salt of p-nitrocalixarene, for example, hexasodium salt, is prepared by dissolving the above-mentioned p-nitrocalixarene in an aqueous sodium hydroxide solution, decolorizing with activated carbon, separating the activated carbon by filtration, and then adding about 5 to the filtrate. It can be obtained by salting out p-nitrocalixarene by adding sodium hydroxide in an amount of% by weight, filtering off and washing with saline.

In addition, this sodium salt of p-nitrocalixarene is dissolved in water, and this solution is acidified with hydrochloric acid or sulfuric acid,
By separating the precipitated crystals by filtration, washing with water, and drying,
Higher purity p-nitrocalixarene can be obtained.

Next, the alkali metal salt of p-nitrocalixarene thus obtained is subjected to O 2 with an alkylating agent in a solvent.
-By alkylation, the p-nitro-O-alkylcalixarenes of the present invention represented by the general formula (II) can be obtained. The alkylating agent used is appropriately selected according to the desired p-nitro-O-alkylcalixarene. For example, an alkyl halide, a dialkyl sulfuric acid, a p-toluenesulfonic acid ester or the like can be used, but an alkyl halide is particularly preferable. As such an alkyl halide, for example, chloride, bromide or iodide having an alkyl group having 1 to 18 carbon atoms is suitable, for example, methyl iodide,
Examples thereof include n-butyl chloride, n-octyl bromide and n-dodecyl bromide.

As the solvent, an aprotic polar organic solvent such as tetramethylene sulfone, dimethyl sulfoxide, dimethylformamide and the like is preferable.

By reducing the nitro group of this p-nitro-O-alkylcalixarene to an amino group with a reducing agent, the p-nitro-O-alkylcalixarene of the present invention represented by the above general formula (III) is obtained. be able to. As the reducing agent, usually, a reducing agent that reduces the nitro group of an aromatic nitro compound to an amino group can be optionally used. For example, hydrazine hydrate is used in the presence of iron chloride as a catalyst and activated carbon. Is preferred. The solvent used is preferably methyl cellosolve.

The p-amino-O-alkylcalixarene thus obtained is then subjected to quaternary salification with an alkyl under halogen according to a method known in the art to give the above-mentioned general formula P according to the present invention represented by (IV)
-Trialkylammonio-O-alkylcalixarenes can be obtained. As a typical method, for example,
If an alkyl halide is reacted with p-amino-O-alkylcalixarene in the presence of a base as an acid scavenger such as potassium carbonate in an aprotic polar solvent such as dimethylformamide. Good. As the halogen alkyl, various ones can be used in the same manner as described above, but, for example, methyl iodide, methyl bromide, methyl chloride, ethyl iodide, propyl iodide, butyl iodide, etc. are used. be able to. Usually, carbon number 1
Alkyl under halogen with an alkyl group of 5 is preferred, especially methyl iodide.

However, when methyl iodide is used as the alkyl halide, the reaction product may be colored by iodine produced as a by-product. Such coloration of the reaction product due to iodine can be removed, for example, by dissolving the reaction product in an aqueous ethanol solution and blowing sulfur dioxide gas into the solution.

Further, p-trimethylammonio-O-alkylcalixarene iodide obtained by using methyl iodide as an alkyl halide generally has a low solubility in water, but it has a low solubility in chlorides, bromides or other compounds. By exchanging anions with anions, p-trimethylammonio-O-alkylcalixarenes generally having high solubility in water can be obtained. For example, when p-trimethylammonio-O-alkylcalixarene iodide is dissolved in an aqueous ethanol solution and treated with a chloride ion-type anion exchange resin, and iodine ions are ion-exchanged with chloride ions, chloride p- Trimethylammonio-O-alkyl calixarenes can be obtained.

EFFECT OF THE INVENTION As described above, the present invention provides a novel calixarene derivative. As described above, such a compound is expected to be used as an oxygen reaction, a catalytic reaction, or a metal ion transporter, or can be used as a raw material for producing other calixarene derivatives.

Examples The present invention will be described below with reference to Examples along with Reference Examples, but the present invention is not limited to these Examples.

Reference Example 1 Production of p-nitrocalix [6] arene and its hexasodium salt Calix [6] arene (5.0 g) was added to concentrated sulfuric acid (50 ml) at 80 ° C.
After the sulfonation reaction was carried out at the temperature of 4 hours, the mixture was cooled and 90 ml of cold water was added to dilute it.

Then, 5.5 g of 61% nitric acid was added to the obtained reaction mixture, and the reaction of substituting the sulfonic acid group with a nitro group was carried out for 10 hours while maintaining the temperature at 0 to 5 ° C. After the completion of this substitution reaction,
The reaction mixture was diluted with water, the formed crystals were separated, washed with water and dried to obtain crude p-nitrocalix [6] arene. The yield is 35% based on Calix [6] arene
It was.

Next, 5.0 g of this crude p-nitrocalix [6] arene
Was heated and dissolved in 300 ml of water containing 1.5 g of sodium hydroxide, 2 g of activated carbon was added thereto, and the activated carbon was filtered off.

To the obtained filtrate, 15 g of sodium hydroxide (5% by weight of the solution amount) was added, and a hexasodium salt was salted out to deposit. This is filtered, washed with brine, dried,
A hexa sodium salt of purified p-nitrocalix [6] arene was obtained.

This hexasodium salt contained sodium chloride and water, and as a result of analysis, the purity of p-nitrocalix [6] arene as a hexasodium salt was 63%. The yield is based on the crude p-nitrocalix [6] arene.
It was 45%.

4.0 g of the hexasodium salt of purified p-nitrocalix [6] arene was dissolved in 100 ml of water by heating, 1 ml of concentrated hydrochloric acid was added to the solution with heating, and the precipitated crystals were separated by filtration, washed with water and dried. Pure p-nitrocalix [6] arene
2.1 g was obtained. The yield was 96% based on the hexasodium salt of p-nitrocalix [6] arene.

Melting point 300 ° C or higher Elemental analysis value (C ₇ H ₅ NO ₃ ) ・ 4H ₂ O C H N Calculated value 51.53 3.89 8.59 Experimental value 51.94 3.32 8.59 Infrared absorption spectrum (KBr method) Wavenumber (cm ^-1 ) Attribution 3450 νOH 1330 νNO ₂ 1480 νNO ₂ Nuclear magnetic resonance spectrum (CDCl ₃ , reference TMS) δ (ppm) Attribution integrated intensity ratio 3.96 −CH ₂ −12H 8.10 ArCH ₂ Ar 12H In addition, p-nitrocalix [n] arene having various environments. Is obtained in the same manner as in Japanese Patent Application No. 60-
132720.

Example 1 Preparation of p-nitro-O-n-octylcalix [6] arene p-nitrocalix [6] arene hexasodium salt
3.0 g (4 mmol) was dissolved by heating in 40 ml of tetramethylene sulfone, 5.0 g (30 mmol) of n-octyl bromide was added thereto, and the mixture was stirred with heating at a temperature of 100 to 120 ° C for 6 to 8 hours.
After cooling, it was diluted with water, the precipitate formed was filtered off and recrystallized from benzene. Melting point 198 ° C, yield 3.0 g (yield 48
%).

Elemental analysis value (C ₁₅ H ₂₁ NO ₃ ) ₆ C H N Calculated value 68.44 7.98 5.32 Experimental value 68.44 8.11 5.31 Infrared absorption spectrum (KBr method) Wavenumber (cm ^-1 ) Attribution 2920,2850 νCH 1610,1590 νC = C ( Aromatic) 1520 νasNO ₂ 1460 νs-CH ₂ − (sandwich) 1350 νsNO ₂ 1220 νCOC Nuclear magnetic resonance spectrum (CDCl ₃ , reference TMS) δ (ppm) Attributable integrated intensity ratio 8.50-6.40 ArH 2H 4.00 ArCH ₂ Ar 4H ArOCH ₂ −2.20−1.00 —CH ₂ −12H 0.80 —CH ₃ 3H Example 2 In Example 1, except that n-octyl bromide was replaced by methyl bromide and n-dodecyl bromide. In the same manner as in Example 1, p-nitro-O-methylcalix [6] arene and p-nitro-O-n-dodecylcalix [6] arene were obtained.

These melting points and elemental analysis values are shown.

p- nitro -O- methyl potash try [6] arene melting point 300 ° C. or higher elemental analysis _{(C 8 H 7 NO 3)} 6 C H N Calculated 58.18 4.27 8.46 Found 58.01 4.30 8.30 p- nitro -O-n- Dodecyl calix [6] arene Melting point 155 to 156 ° C Elemental analysis value (C ₁₉ H ₂₉ NO ₃ ) ₆ CH N Calculated value 71.16 9.09 4.39 Experimental value 71.47 9.21 4.34 Example 3 p-amino-O-n-octyl potassium Preparation of lux [6] arene p-nitro-O-n-octylcalix [6] arene
1.5 g (0.95 mmol) was added to 80 ml of methyl cellosolve, 0.3 g of activated carbon and 0.05 g of ferric chloride hexahydrate were added thereto,
The mixture was stirred with heating at a temperature of ° C for 30 minutes. Next, 10 ml of hydrazine monohydrate was added dropwise, and the mixture was further heated and stirred for 6 hours, and then activated carbon was filtered off by hot filtration. The filtrate was cooled, the precipitated crystals were filtered off and recrystallized from ethanol. Melting point 208-209 ° C, yield 1.2 g (yield 90%).

Elemental analysis value (C ₁₅ H ₂₃ NO) ₆・ 2.5H ₂ O CH N calculated value 74.84 9.91 5.82 experimental value 74.89 10.01 5.22 infrared absorption spectrum (KBr method) wavenumber (cm ^-1 ) attribution 3400 νNH 2900 νCH 1610 νC = _{C, δNH 1480 νs-CH 2} - 1220 νC-O-C nuclear magnetic resonance spectrum (CDCl _3, reference TMS) δ (ppm) attributable integrated intensity ratio _{6.00 ArH 2H 3.72 ArCH 2 Ar 4H} ArOCH 2 - 2.60 -NH 2 2H 1.80 —OCH ₂ CH ₂ —3H 1.20 —CH ₂ —10H 0.84 —CH ₃ 3H Example 4 In Example 3, p-nitro-O-n-octylcalix [6] arene was replaced by p-nitro-. Example 3 except that O-methylcalix [6] arene and p-nitro-On-dodecylcalix [6] arene were used.
In the same manner as in p-amino-O-methylcalix [6] arene and p-amino-O-n-dodecylcalix [6] arene, respectively.

The melting points and elemental analysis values of these compounds are shown.

p-Amino-O-methylcalix [6] arene Melting point 280 ° C or higher Elemental analysis value (C ₈ H ₉ NO ₃ ) ₆ CH N Calculated value 71.18 6.72 10.38 Experimental value 71.00 6.85 10.25 p-Amino-O-n- Dodecyl calix [6] arene Melting point 164 to 167 ° C Elemental analysis value (C ₁₉ H ₃₁ NO ₃ ) ₆ CH N Calculated value 78.89 10.73 4.84 Experimental value 78.41 10.94 4.32 Example 5 p-trimethylammonio-O-n chloride -Preparation of octylcalix [6] arene p-amino-O-n-octylcalix [6] arene
1.0 g (0.7 mmol) is dissolved in 30 ml of dimethylformamide, 1.0 g (73 mmol) of potassium carbonate is added, and further 10 ml (0.17 mol) of methyl iodide is added thereto, and the temperature is 60 to 65 ° C for 48 hours. It was stirred. After cooling, the mixture was diluted with water, and the deposited precipitate was separated by filtration and washed with water.

Thus obtained p-trimethylammonioiodide-
The On-octylcalix [6] arene was dissolved in ethanol / water (2/1), and sulfur dioxide was blown into the solution to remove the coloring by iodine, and then the chloride ion type anion exchange resin was used. Treated, evaporated to dryness, p-chloride
-Trimethylammonio-O-n-octylcalix [6] arene was obtained. Melting point 180-182 ° C, yield 1.0 g (yield
76%).

Elemental analysis value (C ₁₈ H ₃₀ NOCl) ₆・ 9.81H ₂ O C H N Cl Calculated value 63.36 9.76 4.11 10.41 Experimental value 63.47 9.90 4.20 9.62 Infrared absorption spectrum (KBr method) Wavenumber (cm ^-1 ) Attribution 2920,2840 νCH 1600 νC = C 1460 νs-CH ₂ -1370 δsN-CH ₃ 1210 νC-O-C Nuclear magnetic resonance spectrum (CD ₃ O, reference TMS) δ (ppm) Attribution integrated intensity ratio 8.00-6.50 ArH 2H 4.20-3.00 ArCH ₂ Ar 11H ArOCH ₂ −, −N ⁺ CH ₃ 1.80 −OCH ₂ CH ₂ −2H 1.32 −CH ₂ −12H 0.85 −CH ₃ 3H Example 6 Chlorinated p-trimethylammonio-O-methylcalix [6] Production of allene In Example 5, except that p-amino-O-n-octylcalix [6] arene was replaced with p-amino-O-n-methylcalix [6] arene. 5
In the same manner as in the above, chloride-p-trimethylammonio-
O-methyl calix [6] arene was obtained.

Melting point 280 ℃ or higher Elemental analysis value (C ₁₁ H ₁₆ NOCl) ₆ 3H ₂ O CHN Calculated value 59.33 7.64 6.29 Experimental value 59.21 7.71 6.32

Claims (17)

[Claims] 1. A general formula (I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms, Z is a substituent selected from the group consisting of a nitro group, an amino group, and a trialkylammonium in which the alkyl group has 1 to 5 carbon atoms, and n is 4 to An integer of 8, n '= 0 when Z is a nitro group or an amino group, Xa ^- represents a counter anion when Z is a trialkylammonium, and a is the valence of this counter anion. And n '= n / a.). 2. General formula (II) The Calixarene derivative according to claim 1, which is represented by: 3. General formula (III) The Calixarene derivative according to claim 1, which is represented by: 4. A general formula (IV) (In the formula, R'represents an alkyl group having 1 to 5 carbon atoms.) The calixarene derivative according to claim 1, wherein 5. The Calixarene derivative according to claim 4, wherein R'is a methyl group and X is a halogen atom. 6. The calixarene derivative according to claim 5, wherein the halogen atom is a chlorine atom. 7. A general formula (V) (In the formula, M is an alkali metal, and n is an integer of 4 to 8.) The general formula (II) is characterized in that p-nitrocalixarene represented by the formula (2) is alkylated with an alkylating agent in a solvent. ) (In the formula, R represents an alkyl group having 1 to 18 carbon atoms, and n is the same as the above.) A method for producing a p-nitro-O-alkylcalixarene. 8. The method for producing p-nitro-O-alkylcalixarene according to claim 7, wherein the alkylating agent is an alkyl halide. 9. General formula (II) (In the formula, R represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 4 to 8.) The p-nitro-O-alkylcalixarene represented by the formula is reduced with a reducing agent. General formula (II
I) (In formula, R and n are the same as the above.) The manufacturing method of p- amino-O- alkyl calix arene represented by these. 10. The method for producing p-amino-O-alkylcalixarenes according to claim 9, wherein the reducing agent is hydrazine. 11. The method for producing p-amino-O-alkylcalixarene according to claim 9, which comprises reducing iron chloride and activated carbon with hydrazine as a catalyst. 12. General formula (III) (In the formula, R represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 4 to 8.) The p-amino-O-alkylcalixarene represented by the formula is halogenated in a solvent in the presence of a base. General formula (VI) characterized by reacting with alkyl (Wherein X represents a halogen atom, R and n are the same as above), and a method for producing a p-trialkylammonio-O-alkylcalixarene. 13. The method for producing a p-trialkylammonio-O-alkylcarex arene according to claim 12, wherein R'is a methyl group and X is a halogen atom. 14. The p- according to claim 13, wherein the halogen atom is chlorine, bromine or iodine.
Method for producing trialkylammonio-O-alkylcalixarene. 15. The method for producing a halogenated p-trialkylammonio-O-alkylcalixus arene according to claim 12, wherein methyl iodide is used as the alkyl halide. 16. Methyl iodide is used as an alkyl halide to obtain p-trimethylammonio-O-alkylcalixarene iodide, which is anion-exchanged with chloride ion to form p-trimethylammonio-chloride chloride. -A process for producing a halogenated p-trialkylammonio-O-alkylcalixus arene according to claim 12, characterized in that -alkylcalixarene is obtained. 17. A p-trimethylammonio-O-alkylcalixarene iodide is obtained by using methyl iodide as an alkyl halide, which is anion-exchanged with a bromine ion to form p-trimethylammonio-O bromide. -A process for producing a halogenated p-trialkylammonio-O-alkylcalixus arene according to claim 12, characterized in that -alkylcalixarene is obtained.