JPH0710820B2 - 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 (III) Wherein n is, for example, an integer of 4 to 8 and represents the number of aromatic rings forming calixarene. The name of such Karitsukusu Allen is
Aromatic ring (aren) similar to the Greek word “cup”
It is a name that is conventionally given due to having a three-dimensional structure consisting of e). The history of research, synthesis, three-dimensional structure and applications of such Calix [n] arene have been reported in detail by Gutsche et al. (J. Am.
Chem.Soc., 130, 3782 (1981); Acc.Chem.Res., 16 , 161 (1
983)). The p-alkyl-substituted calix [n] arene of the above general formula (III) is obtained by reacting the corresponding p-alkylphenol with formaldehyde in the presence of a base such as potassium hydroxide or rubidium hydroxide. be able to. The calix [n] arene represented by the general formula (III) is typically obtained by reacting pt-butylphenol with formaldehyde in the same manner as described above to obtain pt-butylcalix. It can be obtained by obtaining allene and dealkylating it.

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 generally has a higher melting point than an acyclic analog compound and is poorly water-soluble or water-insoluble. The calixcus allen that forms is unknown. However, water-soluble calixarene is required for enzymatic reaction or catalytic reaction, or for practical use as a metal transporter, and such water-soluble calixarene is a theoretical catalyst for enzymatic reaction or catalytic reaction. It will also be essential for scientific research.

Then, as a result of intensive studies to obtain a water-soluble calixarene-p-sulfone, as described in Japanese Patent Application No. 59-205990. Acid and O-n-alkylcalixarene-p-sulfonic acid were successfully obtained, and further, a novel O-ω-sulfoalkyl-p-alkylcalixarene was successfully obtained as described below. Then, the present invention was achieved. The above O-ω-sulfoalkyl-p
-Alkylcalixarene has a unique property as a host molecule or an acid catalyst because it has a hydrophilic alkylsulfonic acid group and a lipophilic alkyl group at both axial ends of the tubular structure of the molecule. Is also expected, and the use as a surfactant is also expected.

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 represents hydrogen or an alkyl group, an alkenyl group, or an aryl group having 1 to 18 carbon atoms, M represents an alkali metal, m represents an integer of 2 or more, and n represents an integer of 4 to 8. .) Is represented.

In addition, such a Calix allene has the general formula (II) according to the present invention. (Wherein R represents hydrogen or an alkyl group, an alkenyl group or an aryl group having 1 to 18 carbon atoms, and n represents an integer of 4 to 8) in a solvent in the presence of a base. Is an alkanesaltone having 2 or more carbon atoms or a general formula X (CH ₂ ) mSO ₃ M (wherein X is a halogen atom, M is an alkali metal, and m is 2).
Indicates the above integer. ) Can be obtained by reacting a metal salt of ω-halogenoalkylsulfonic acid represented by

The calixarene according to the present invention can be obtained by reacting the calixarene represented by the general formula (II) with an alkanesultone in a solvent in the presence of a base. In the calixarene represented by the general formula (II), R is hydrogen, methyl group, ethyl group, t
An alkyl group such as -butyl group, n-hexyl group, n-octyl group, and n-dodecyl group, and an aryl group such as phenyl group are preferably used.

As the solvent, those capable of dissolving the alkanesaltone used are preferable, for example, dioxane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide,
Examples thereof include sulfolane, acetonitrile, a mixed solvent of two or more kinds of these, and a mixed solvent of these and water.

As the alkane sultone, that is, the intramolecular oxysulfonic acid ester, those having 2 or more carbon atoms are not particularly limited, and arbitrary ones can be used, but those having 2 to 8 carbon atoms are usually used. Appropriate. Examples of particularly suitable alkane sultone include 1,3-propane sultone and 1,4-butane sultone.

Instead of the alkanesaltone, in the general formula X (CH ₂ ) mSO ₃ M, X is a halogen atom, M is an alkali metal such as sodium or potassium, and m is an integer of 2 or more. ) An alkali metal salt of ω-halogenoalkyl sulfonic acid represented by m is preferably 2-8
Is an integer. Specific examples include sodium 3-chloropropyl sulfonate and potassium 4-bromobutyl sulfonate.

The method for producing calixarenes according to the present invention comprises suspending the calixarenes in a solvent and reacting the alkanesaltone or ω-halogenoalkylsulfonate as described above in the presence of a base to give the calixarenes. It can be obtained by sulfoalkylating the hydroxyl group of. As the base, an inorganic base, particularly an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is preferably used. However, if necessary, a carbonate such as sodium carbonate or potassium carbonate, or an organic base containing an amine such as triethylamine or tributylamine is also used.

The reaction is usually carried out at room temperature to about 80 ° C. for several hours, but the reaction conditions are not limited thereto.
After the completion of the reaction, for example, ethanol is added to the reaction mixture and the mixture is stirred, so that the target calyx arene derivative is broken out, and this is separated by an appropriate means such as filtration.

EFFECT OF THE INVENTION As described above, the present invention provides a novel water-soluble calixarene derivative. As described above, such a compound is expected to be used as an enzyme 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, but the present invention is not limited to these examples.

Example 1 Production of O-γ-sulfopropyl-pn-hexylcalix [6] arene sodium pn-hexylcalix [6] arene 0.57 g (0.5 mm)
ol) was suspended in a mixed solvent of 10 ml of dioxane and 1.8 ml of water and stirred for 1 hour, 1.4 ml of 10N aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 2 hours. After this, 40 ℃
The temperature was raised to 1, and a solution prepared by dissolving 1.46 g of propane sultone in 3 ml of dioxane was added dropwise, and after completion of the addition, the mixture was stirred for 8 hours.

After completion of the reaction, 20 ml of ethanol was added to the reaction mixture and stirred to precipitate light yellow crystals. The crystals were separated by filtration, washed with ethanol and dried to give O-γ-sulfopropyl-pn-hexylcalix [6] arene sodium.
0.86 g (yield 85.7%) was obtained.

Elemental analysis value (C ₁₆ H ₂₃ SO ₄ Na) ₆ CH Calculated value 58.82 7.38 Experimental value 58.85 7.15 However, the calculated value is the value calculated assuming that 4.6% by weight of water is included. Nuclear magnetic resonance spectrum (D ₂ O, Reference TMS) δ (ppm) Attribution 0.70-1.20 (m, 78H) 1.80-2.20 (m, 12H) 2.80-3.25 (m, 12H) 4.12 (s, 12H) 3.82-4.45 (m, 12H) 6.75 (Br .S, 12H) However, attribution is as follows.

Example 2 0.49 g (0.5 mmol) of O-γ-sulfopropyl-pt-butyl calix [6] arene was added to 10 ml of dioxane and water.
The mixture was made turbid with a mixed solvent of 1.8 ml and stirred for 1 hour, 1.2 ml of 10N sodium hydroxide aqueous solution was added thereto, and the mixture was stirred for 2 hours. Thereafter, the temperature was raised to 40 ° C., a solution prepared by dissolving 1.48 g of propanesarton in 3 ml of dioxane was added dropwise, and after completion of the addition, the mixture was stirred for 6 hours.

After completion of the reaction, 20 ml of ethanol was added to the reaction mixture and stirred to precipitate light yellow crystals. The crystals were separated by filtration, washed with ethanol and dried to give O-γ-sulfopropyl-pt-butylcalix [6] arene sodium.
64 g (yield 69.6%) was obtained.

Elemental analysis value (C ₁₄ H ₁₉ SO ₄ Na) ₆ CH Calculated value 50.49 6.66 Experimental value 50.39 6.54 However, the calculated value is a value calculated assuming that water of 8.2% by weight is included.

Nuclear magnetic resonance spectrum (D ₂ O, reference TMS) δ (ppm) Attribution 1.10 (s, 54H) 1.80-2.20 (m, 12H) 2.80-3.20 (m, 12H) 4.16 (s, 12H) 3.80-4.40 ( m, 12H) 6.48 (Br.S, 12H) However, attribution is as follows.

Claims (8)

[Claims] 1. A general formula (I) (In the formula, R represents hydrogen or an alkyl group, an alkenyl group, or an aryl group having 1 to 18 carbon atoms, M represents an alkali metal, m represents an integer of 2 or more, and n represents an integer of 4 to 8. A calixus arene derivative characterized by being represented. 2. General formula (I) The Calixarene derivative according to claim 1, which is represented by: 3. General formula The Calixarene derivative according to claim 1, which is represented by: 4. The Calixarene derivative according to claim 3, wherein R is an n-hexyl group. 5. The Calixarene derivative according to claim 3, wherein R is a t-butyl group. 6. General formula (II) (Wherein R represents hydrogen or an alkyl group, an alkenyl group or an aryl group having 1 to 18 carbon atoms, and n represents an integer of 4 to 8) in a solvent in the presence of a base. Is an alkanesaltone having 2 or more carbon atoms or a general formula X (CH ₂ ) mSO ₃ M (wherein X is a halogen atom, M is an alkali metal, and m is 2).
Indicates the above integer. ) A general formula (I) characterized by reacting a ω-halogenoalkyl sulfonic acid metal salt represented by (In the formula, R and n are the same as above, and m represents an integer of 2 or more.) 7. General formula (II) (Wherein R represents hydrogen or an alkyl group, an alkenyl group or an aryl group having 1 to 18 carbon atoms, and n represents an integer of 4 to 8), and propane sultone is reacted with calixarene represented by the formula: General formula (I) (In the formula, R and n are the same as the above.) The method for producing a calix arene derivative according to claim 6, wherein a calix allene derivative represented by the following formula is obtained. 8. The method for producing a calyx arene derivative according to claim 6, wherein the base is an alkali metal hydroxide.