JPH06166646A - New clathrate compound and its production - Google Patents

Abstract

PURPOSE:To obtain a clathrate compound capable of including a wide variety of organic compounds and useful in the technological fields of selective separation, chemical stabilization, involatilization, pulverization, etc., by using a tetrakisphenol compound as a host compound. CONSTITUTION:The objective clathrate compound is produced by using a compound of formula [X is (CH2)n (n is 0-3); R<1> and R<2> are H, lower alkyl, (substituted)phenyl, halogen or lower alkyl excluding the case that (n) is O and both R<1> and R<2> are H], e.g. 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane as a host compound. The objective new clathrate compound can be produced in extremely high efficiency by directly adding the compound of formula to an organic compound to be used as a guest and reacting with each other when the guest compound is liquid or by directly reacting the compound of formula with a guest compound in solid phase when the guest compound is solid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel clathrate compound, and more particularly to a clathrate compound using tetrakisphenol as a host compound and a method for producing the same.

[0002]

2. Description of the Related Art An inclusion compound is a compound having a structure in which a guest molecule enters a cavity formed by a host molecule,
In recent years, application in the technical fields of selective separation, chemical stabilization, nonvolatization, powderization, etc. is expected. As a conventional clathrate compound, for example, in JP-A-61-53201, 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol or 1,1-di ( 2,4
-Dimethylphenyl) -2-propyn-1-ol,
Japanese Patent Application Laid-Open No. 62-22701 discloses 1,1'-bis-
Using 2-naphthol as a host, 5-chloro-
2-Methyl-4-isothiazolin-3-one (CMI)
It is known that guests and the like are guests. In addition, inclusion compounds having tetrakisphenols as hosts have not yet been known except those having tetrakis (4-hydroxyphenyl) ethane as a host (Tetrahedron Lett.
ers., 33 (42), 6319 (1992).).

[0003]

DISCLOSURE OF THE INVENTION The present invention provides selective separation,
It is an object of the present invention to provide a novel clathrate compound using tetrakisphenol as a host, which is useful in the technical fields of chemical stabilization, nonvolatization, pulverization and the like. At the same time, the following problems in production in the conventional method for producing an inclusion compound, 1) depending on the kind of the solvent, the inclusion compound is not formed or the solvent is included without including the guest molecule. A compound in which the solvent is included is obtained. 2) Even with a solvent that forms an inclusion compound, the conditions such as temperature, host / guest charging ratio and concentration, and stirring are limited in order to precipitate the inclusion compound of the guest molecule. Is difficult to synthesize and set isolation conditions. 3) The recovery rate based on the host compound does not reach 100%. It is an object of the present invention to provide a simple and efficient method for producing an inclusion compound.

[0004]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above-mentioned object, the present inventors have found that when a guest compound is a liquid, a host compound of a particular tetrakisphenol is used as a guest. In the case where the guest compound is a solid, by directly adding it into the reaction solution and then by putting it in the liquid containing the guest compound and reacting it, or by directly performing a solid phase reaction with the guest compound which is a solid, a novel compound The present invention has been completed by finding that the clathrate compound is produced very efficiently.

The present invention will be described in detail below. (Host compound) The host compound of tetrakisphenol used in the present invention is a compound represented by the general formula [I].

[0006]

[Chemical 2] (In the formula, X represents (CH ₂ ) n, n is 0, 1, 2 or 3, and R ¹ and R ² are each a hydrogen atom, a lower alkyl group or an optionally substituted phenyl. Group, a halogen atom or a lower alkoxy group, provided that n is 0,
Except when both R ¹ and R ² are hydrogen atoms. )

R ¹ and R ² in the general formula [I] may be the same or different from each other, for example, hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group. Group, t-butyl group, n-hexyl group, lower alkyl group such as cyclohexyl group, phenyl group optionally substituted with halogen atom or lower alkyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Examples thereof include a halogen atom, a lower alkoxy group such as a methoxy group, an ethoxy group, and a t-butoxy group.

The tetrakisphenol used in the present invention is not particularly limited as long as it is a compound represented by the general formula [I], but specific examples include 1,1,2,2-
Tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2- (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-tbutyl-) 4-hydroxyphenyl) ethane,
1,1,2,2-tetrakis (3,5-di-t-butyl-
4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane , 1,1,2,2
-Tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1, 2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane,
1,1,2,2-tetrakis (3-t-butyl-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,
2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis [(4-hydroxy-3-phenyl) phenyl] ethane, 1,1,
3,3-tetrakis (4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-) 4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4)
-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-
Dichloro-4-hydroxyphenyl) propane, 1,
1,3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1,3,3- Tetrakis (3-phenyl-4-
Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1 , 1,
3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,4,4- Tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) butane, 1,1,5,5
-Tetrakis (4-hydroxyphenyl) pentane,
1,1,5,5-tetrakis (3-methyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-dimethyl-4-hydroxyphenyl) pentane, 1,1,5, 5-tetrakis (3-chloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-dichloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3- Bromo-4
-Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-dibromo-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methoxy-4-hydroxyphenyl) pentane, 1, 1,
5,5-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-t-butyl-4-hydroxyphenyl) pentane, 1,1,5,5- Tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) pentane, 1,1,
5,5-tetrakis (3-methyl-5-t-butyl-4-
Hydroxypheni) pentane, 1,1,5,5-tetrakis (3-phenyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-diphenyl-4-hydroxyphenyl) pentane, 1 , 1, 5, 5
-Tetrakis (3,5-dicyclohexyl-4-hydroxyphenyl) pentane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-
Tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-Tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4-
Tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,4-
Tetrakis (3-methoxy-4-hydroxyphenyl)
Butane, 1,1,4,4-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) butane, 1,1,4
4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dibromo-4-hydroxyphenyl) butane and the like can be mentioned.

(Guest Compound) The guest organic compound used in the present invention is not particularly limited as long as it can form an inclusion compound containing the tetrakisphenol as a host compound. Specific examples include alcohols such as methanol, ethanol, i-propanol, n-butanol and 2-ethylhexanol, aldehydes such as formaldehyde, acetaldehyde and benzaldehyde, ketones such as acetone and methyl ethyl ketone, and nitriles such as acetonitrile. Ethers such as tetrahydrofuran, diethyl ether, methyl acetate,
Esters such as ethyl acetate and butyl acetate, cineol,
Natural essential oils such as hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, linalool, dimethyloctanol, quince, jasmine,
Synthetic perfumes such as lemon, pyridine, pyrrole, imidazole, pyrazine, pyrazole, 1,2,4-triazole, thiazole, pyrrolidine, imidazoline, pyrroline, oxazole, piperine, pyrimidine, pyridazine, triazine, 5-chloro-2-methyl-4-isothiazoline Examples thereof include monocyclic nitrogen-containing heterocyclic compounds such as 3-one.

The compound of the present invention is prepared by reacting the guest organic compound or a solution containing the guest organic compound with a host compound, tetrakisphenol, at room temperature to 100 ° C. for several minutes to several hours with stirring to react. The organic compound can be easily included in the host compound to obtain a new inclusion compound.

The inclusion compound easily releases the guest compound when heated under reduced pressure, and since the host compound does not include water, the property is utilized to remove the guest compound from the mixture of water and these guest compounds. It can be used for separation and recovery.

[0012]

According to the present invention, when the guest organic compound is a liquid, the inclusion compound having the organic compound as the guest molecule is produced with high selectivity and high yield by directly reacting the guest compound with the powder host compound. To be done.

When the guest organic compound is a solid, a solution of the guest compound or the solid is reacted with the powder host compound, whereby the inclusion compound having the organic compound as the guest molecule has high selectivity and high yield. Is generated by.

The clathrate compound of the present invention is produced by allowing a guest molecule to enter the cavity formed by the host compound.
Therefore, which compound is easily incorporated as a guest is governed by the size, stericity, polarity, solubility, etc. of the guest molecule.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. (Synthesis example-1) Synthesis of host compound (1-1) Synthesis of 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane A 40% aqueous solution of glyoxal in a 300 ml flask.
5 g and 2,4.9-xylol (54.9 g) were charged, and 100 ml of concentrated sulfuric acid / phosphoric acid (3/1, v / v) was added dropwise with stirring at a dropping temperature of 0-2 ° C over 2 hours. Then, the reaction was completed by stirring at a liquid temperature of 0 ° C. for 4 hours. After completion of the reaction, the reaction solution was poured into 600 ml of ice water, heated to 70 ° C., and the precipitated solid was collected by filtration. This solid was recrystallized from dioxane and dried in vacuum at 100 ° C. to obtain 15.0 g (yield 29.4%) of white powder. It was confirmed by IR and NMR spectra that this powder was 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane. The respective measurement charts are shown in FIGS. 1 and 2.

(1-2) Synthesis of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane A 40% aqueous solution of glyoxal in a 300 ml flask.
5 g and 51.8 g of o-cresol were charged, and 100 ml of concentrated sulfuric acid / phosphoric acid (3/1, v / v) was added dropwise at a dropping temperature of 0-2 ° C over 2 hours while stirring. Then, the liquid temperature 0 ℃
After stirring for 2 hours, the reaction was completed. After completion of the reaction, the reaction solution was poured into 600 ml of ice water, heated to 70 ° C., and the precipitated solid was collected by filtration. The solid was recrystallized from dioxane to give 1
After vacuum drying at 00 ° C., 17.0 g of white powder (yield 37.
4%). It was confirmed by IR and NMR spectra that this powder was 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane. The respective measurement charts are shown in FIGS. 3 and 4.

(1-3) Synthesis of 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane A 40% aqueous solution of 40% glyoxal in a 300 ml flask.
5 g of 2-chlorophenol and 56.6 g of 2-chlorophenol were charged, and 100 ml of concentrated sulfuric acid / phosphoric acid (3/1, v / v) was added while stirring.
The dropping was performed at a dropping temperature of 0-2 ° C for 2 hours. Then, the reaction was completed by stirring at a liquid temperature of 0 ° C. for 4 hours. After the reaction was completed, the reaction solution was poured into 600 ml of ice water, and then 100 g of salt was added.
Was added, and the reaction product was extracted with ether (100 ml × 3 times). After anhydrous sodium sulfate was added to the ether layer for dehydration, ether and unreacted 2-chlorophenol were distilled off under reduced pressure, and the residue was recrystallized with dioxane to give 100
After vacuum drying at ℃, 7.5g of white powder (yield 14.0
%) Was obtained. It was confirmed by IR and NMR spectra that this powder was 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane. The respective measurement charts are shown in FIGS. 5 and 6.

(1-4) Synthesis of 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane Glyoxal 40% aqueous solution was added to a 300 ml flask.
9 g and 27.1 g of 2-bromophenol were charged, and 70 ml of concentrated sulfuric acid / phosphoric acid (3/1, v / v) was added dropwise at a dropping temperature of 0-2 ° C over 1.5 hours while stirring. Then
The reaction was completed by stirring at a liquid temperature of 0 ° C. for 5 hours. After the reaction,
The reaction solution was poured into 500 ml of ice water, and then 80 g of salt.
Was added, and the reaction product was extracted with ether (100 ml × 3 times). After anhydrous sodium sulfate was added to the ether layer for dehydration, ether and unreacted 2-bromophenol were distilled off under reduced pressure, and the residue was recrystallized with dioxane to give 10
Vacuum dried at 0 ° C., 3.1 g of white powder (yield 5.8%)
Got This powder is 1,1,2,2-tetrakis (3
It was confirmed to be -bromo-4-hydroxyphenyl) ethane by IR and NMR spectra. Each measurement chart is shown in FIG. 7 and FIG.

(1-5) Synthesis of 1,1,4,4-tetrakis (4-hydroxyphenyl) butane A glutaraldehyde 50% aqueous solution 2 was added to a 300 ml flask.
0.0 g and 45.1 g of phenol were charged, and 200 ml of concentrated sulfuric acid / phosphoric acid (3/1, v / v) was added dropwise at a dropping temperature of 0-2 ° C. over 2 hours while stirring. Then, the liquid temperature 0 ℃
After stirring for 1.5 hours, the reaction was completed. After completion of the reaction, the reaction solution was poured into 600 ml of ice water, heated to 70 ° C., and the precipitated solid was collected by filtration. The solid was recrystallized from dioxane and dried in vacuum at 100 ° C. to obtain 11.9 g (yield 27.9%) of white powder. This powder is 1,1,4,4-
It was confirmed to be tetrakis (4-hydroxyphenyl) butane by IR and NMR spectra. The respective measurement charts are shown in FIGS. 9 and 10.

(1-6) Synthesis of 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane In a 300 ml flask, 25.0 g of succinaldehyde sodium bisulfite, 38.3 g of phenol and 5 parts of acetic acid were added.
Charge 0 ml and stir with concentrated sulfuric acid / phosphoric acid (3/1, v
/ V) 100 ml was added dropwise at a dropping temperature of 0-2 ° C over 2 hours. Then, the reaction was completed by stirring at a liquid temperature of 0 ° C. for 4 hours. After completion of the reaction, pour the reaction solution into 600 ml of ice water,
The mixture was heated to 70 ° C and the precipitated solid was collected by filtration. The solid was recrystallized from dioxane and dried at 100 ° C. under vacuum to obtain 7.0 g of white powder (yield 18.1%). This powder
It was confirmed by IR and NMR spectra that it was 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane. Each measurement chart is shown in FIG. 11 and FIG.
Shown in.

Example 1 Production of Inclusion Compound (1) Using the tetrakisphenol obtained in Synthesis Examples 1-1 to 1-6 as a host compound, the guest compound was methanol, ethanol, 2-propanol, Acetonitrile,
Acetone, THF, 1,4-dioxane, benzaldehyde, diethylamine, triethylamine, pyridine,
An inclusion compound of benzene was prepared. The production of the inclusion compound was carried out by using 2.5 mmol of the host compound and 10 of the guest compound.
It was added to the mixture in ml and stirred at 25 to 100 ° C. for 1 to 300 minutes, then immediately filtered, and the filtrate was left at room temperature for 1 to 48 hours to precipitate crystals. After this precipitate was filtered off, it was vacuum dried at room temperature to obtain the clathrate compound of the present invention. The inclusion compound was confirmed by TG-DTA measurement and IR spectrum. Guest / host m determined by the inclusion compound production conditions and TG-DTA measurement of the inclusion compound in this Example
The ol ratio and the re-release temperature of the guest compound are summarized in Table 1. In addition, IR spectra are shown in FIGS.

(Example-2) Production of clathrate compound (2) 1,1,1 obtained in Synthesis Example 1-2 as a host compound
An inclusion compound in which the guest compound was cineol was prepared using 2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane. The production of inclusion compounds is 80
1 mmol of host compound in 5 ml of methanol heated to ℃
And stir until completely dissolved, then cineole 4m
Mol was added, and the mixture was stirred at 80 ° C. for 5 minutes, immediately filtered, and the filtrate was left at room temperature for 24 hours to precipitate crystals.
After this precipitate was filtered off, it was vacuum dried at room temperature to obtain the clathrate compound of the present invention. The inclusion compound can be confirmed by TG-
It was performed by DTA measurement. Table 2 shows the guest / host molar ratio and the re-release temperature of the guest compound, which were determined by the TG-DTA measurement of the clathrate compound in the present Example for producing the clathrate compound.
The IR spectrum is shown in FIG.

(Example-3) Production of clathrate compound (3) 1,2,1 obtained in Synthesis Example 1-2 as a host compound
Using 2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, the guest compound is hinokitiol,
Inclusion compounds of thymol, menthol, citral, eugenol, carvone, geraniol, cineol, menthone and borneol were prepared. The production of inclusion compounds is
1 mm of host compound in 5 ml of methanol heated to 60 ° C
After adding ol and stirring until completely dissolved, 4 mmol of the guest compound was added, and the mixture was stirred at 60 ° C. for 5 minutes and immediately filtered, and the filtrate was left at room temperature for 24 hours to precipitate crystals. After this precipitate was filtered off, it was vacuum dried at room temperature to obtain the clathrate compound of the present invention. The inclusion compound can be confirmed by
It was performed by TG-DTA measurement. Table 3 shows the conditions for producing the clathrate compound, the guest / host mol ratio determined by the TG-DTA measurement of the clathrate compound, and the re-release temperature of the guest compound in this example. The IR spectrum is shown in FIG.

[0024]

[Table 101]

[0025]

[Table 102]

[0026]

[Table 2]

[0027]

[Table 3]

Each sample obtained by the above method was TG
-From the behavior of DTA measurement, it was confirmed to be an inclusion body.

[0029]

The novel inclusion compound having tetrakisphenol as a host compound of the present invention has the following features. 1) Various organic compounds are included as guest compounds very easily. In particular, the previously known 1,1,2,2
-Aromatic hydrocarbons that could not be included when tetrakis (4-hydroxyphenyl) ethane was the host, such as benzene, can also be included. 2) Inclusion of a compound having a boiling point near room temperature makes it possible to control volatilization. 3) It becomes possible to selectively collect an organic compound mixed in water as an inclusion body. 4) A target compound can be selectively separated and recovered as a clathrate from a mixed liquid of organic compounds having the same boiling point, which cannot be separated by distillation or the like. 5) The compound incorporated as a guest molecule can be easily separated and recovered by heating. 6) Since the clathrate is solid at room temperature, it can be tablet-molded and is extremely easy to handle. Accordingly, the present invention relates to a clathrate compound in which a wide range of organic compounds are clathrated, and provides a novel clathrate compound which is easy to handle and a method for producing the same, and its industrial significance is extremely large.

[Brief description of drawings]

FIG. 1 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) obtained in Synthesis Example 1-1.
It is an IR spectrum (KBr) figure of ethane.

FIG. 2 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) obtained in Synthesis Example 1-1
FIG. ^{1 is} a ¹ H-NMR spectrum diagram of ethane (d ⁶ -Aceton
e, TMS).

FIG. 3 is an IR spectrum diagram (KBr) of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-2.

FIG. 4 is a ¹ H-NMR spectrum diagram of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-2 (d-MeOH, TMS).

FIG. 5 is an IR spectrum diagram (KBr) of 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-3.

FIG. 6 is a ¹ H-NMR spectrum diagram of 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-3 (d-MeOH, TMS).

FIG. 7 is an IR spectrum diagram (KBr) of 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-4.

FIG. 8 is a ¹ H-NMR spectrum diagram of 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane obtained in Synthesis Example 1-4 (d-MeOH, TMS).

FIG. 9 is an IR spectrum diagram (KBr) of 1,1,4,4-tetrakis (4-hydroxyphenyl) butane obtained in Synthesis Example 1-5.

FIG. 10 ¹ H—N of 1,1,4,4-tetrakis (4-hydroxyphenyl) butane obtained in Synthesis Example 1-5
It is a MR spectrum figure (d-MeOH, TMS).

FIG. 11 is an IR spectrum diagram (KBr) of 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane obtained in Synthesis Example 1-6.

FIG. 12 ¹ H- of 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane obtained in Synthesis Example 1-6.
It is a NMR spectrum figure (d-MeOH, TMS).

FIG. 13: No. 1 in Table 1 obtained in Example 1 Inclusion compound of 7 [using 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane obtained in Example 1-2 as a host compound and acetone as a guest compound]
2 is an IR spectrum diagram (KBr) of

14 is a table showing No. 1 in Table 1 obtained in Example 1. FIG. IR spectrum of clathrate compound 13 (using 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane obtained in Example 1-3 as a host compound and acetonitrile as a guest compound) It is a figure (KBr).

15 is a table showing No. 1 in Table 1 obtained in Example 1. FIG. No. 21 inclusion compound [using 1,1,4,4-tetrakis (4-hydroxyphenyl) butane obtained in Example 1-5 as a host compound and 1,4-dioxane as a guest compound]
2 is an IR spectrum diagram (KBr) of

16 is a table showing No. 1 in Table 1 obtained in Example 1. FIG. IR spectrum of the clathrate compound of Example 23 [using 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane obtained in Example 1-6 as a host compound and 1,4-dioxane as a guest compound] It is a figure (KBr).

17 is a table showing No. 2 in Table 2 obtained in Example 2. FIG. IR spectrum of 24 clathrate compound [using 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane obtained in Example 1-1 as a host compound and cineol as a guest compound] It is a figure (KBr).

18 is a No. 3 table in Table 3 obtained in Example 3. IR spectrum of clathrate compound No. 26 [using 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane obtained in Example 1-2 as a host compound and thymol as a guest compound] It is a figure (KBr).

Claims (2)

[Claims] 1. A clathrate compound comprising tetrakisphenol represented by the general formula [I] as a host compound. [Chemical 1] (In the formula, X represents (CH ₂ ) n, n is 0, 1, 2 or 3, and R ¹ and R ² are each a hydrogen atom, a lower alkyl group or an optionally substituted phenyl. Group, a halogen atom or a lower alkoxy group, provided that n is 0,
Except when both R ¹ and R ² are hydrogen atoms. ) 2. The method for producing an inclusion compound according to claim 1, wherein the host compound of tetrakisphenol is reacted with a guest organic compound.