JPH08208549A - New clathrate compound and its production - Google Patents

Abstract

PURPOSE: To obtain a new host compound including a guest organic compound and useful in engineering fields of selective separation, chemical stabilization, nonvolatilization, powdering, etc. CONSTITUTION: This compound is expressed by the formula (R<1> to R<4> are each H, an alkyl, an alkenyl, an aralkyl, an acyl or cinnamyl, with the proviso that R<1> to R<4> are not simultaneously H), e.g. 1,2,2-tris(4-hydroxyphenyl)-1-(4- methoxyphenyl)ethane. The compound of the formula is obtained by reacting, e.g. a tetrakisphenol such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane with a dialkyl sulfate, an alkyl halide, an alkenyl halide, an aralkyl halide or an acid halide in the presence of an alkali.

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 a tetraphenylethane derivative 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.

Examples of conventional clathrate compounds include 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol or 1,1 in JP-A-61-53201. -Di (2,4-dimethylphenyl) -2-propyn-1-ol, and JP-A-62-22701, using 1,1'-bis-2-naphthol as a host, 5-chloro- It is known to use 2-methyl-4-isothiazolin-3-one (CMI) as a guest.

Further, as an inclusion compound having a tetrakisphenol as a host, a compound having 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host is known (Tetrahedron Letters., 33 (42), 6319 (1992).).

[0005]

The methodologies that occupy the mainstream of the above-mentioned solid phase clathrate compounds are intermolecular (host-guest) interactions due to hydrogen bonds and the like. In the case of the formation of a compound, the properties of the guest compound, such as a proton donor or an acceptor, whether acidic or basic, having a polar group in the molecule or not, or sterically unreasonable at the time of forming a hydrogen bond between the host and the guest. The inclusion ability is significantly affected by whether it occurs or not.

The present invention has been made in view of the above circumstances, and includes a wide range of guest organic compounds, regardless of whether or not hydrogen bonds between molecules (host-guest) are present, and selectively separates and chemists It is an object of the present invention to provide a novel clathrate compound having a tetraphenylethane derivative as a host, which is useful in the technical fields of static stabilization, nonvolatization, powderization and the like.

At the same time, the following problems in production in the conventional method for producing an inclusion compound are as follows: 1) Depending on the type of solvent, the inclusion compound is not formed or the target molecule is not included. A compound in which a solvent is clathrated in is obtained. 2) Even with a solvent that forms an inclusion compound, conditions such as temperature, charging ratio and concentration of host / guest, stirring, etc. are limited in order to precipitate the inclusion compound of guest molecules. It is difficult to synthesize compounds and set isolation conditions. 3) Low recovery rate based on host and guest compounds. It is an object of the present invention to provide a simple and effective method for producing an inclusion compound.

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present invention has revealed that a host compound of a specific tetraphenylethane derivative is affected by the hydrogen bond between the host and the guest. By forming a stable inclusion compound easily with a wide range of organic compounds without adding it, and by reacting this host compound directly in the liquid containing the organic compound as a guest, the novel inclusion compound can be made extremely efficient. The present invention was completed by finding out that it is produced.

The present invention will be described in detail below. (Host Compound) The present invention is an inclusion compound having a tetraphenylethane derivative represented by the general formula [I] as a host compound.

[0010]

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In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an acyl group or a cinnamyl group. Is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples thereof include isobutyl group, t-butyl group, n-pentyl group, neopentyl group and the like.

The alkenyl group is preferably a linear or branched alkenyl group having 3 to 5 carbon atoms, and examples thereof include a propenyl group, a 2-butenyl group, a 3-butenyl group, a 2-pentenyl group and a 3-pentenyl group. Can be mentioned.

The aralkyl group has an alkylene chain having 1 to 5 carbon atoms, and the phenyl group has an alkyl group,
Optionally substituted with a halogen atom or the like,
For example, 4-position methyl group, 3-position methyl group, 2-position methyl group,
Examples thereof include a benzyl group, a phenethyl group, and an α-methylbenzyl group, which may have a substituent such as a 4-position chloro group, a 3-position chloro group and a 2-position chloro group.

As the acyl group, an alkyl group, a benzoyl group which may be substituted with a halogen atom or the like, for example,
Examples thereof include benzoyl group, 4-methylbenzoyl group, 4-chlorobenzoyl group, 2-fluorobenzoyl group, 3-methylbenzoyl group, acetyl group, propionyl group, butyryl group, cinnamoyl group, phenacyl group and pyridylcarbonyl group. it can.

The following can be exemplified as the tetraphenylethane derivative which is the host compound of the clathrate compound of the present invention. (1) 1,2,2-Tris (4-hydroxyphenyl) -1- (4-methoxyphenyl) ethane Melting point (° C) 223-229 (2) 1,2,2-Tris (4-hydroxyphenyl)- 1- (4-isopropoxyphenyl) ethane melting point (° C) 108-116 (3) 1- (4-ethoxyphenyl) -1,2,2-
Tris (4-hydroxyphenyl) ethane Melting point (° C) 188-193 (4) 1,2-bis (4-hydroxyphenyl)-
1,2-bis (4-methoxyphenyl) ethane Melting point (° C) 224-227 (5) 1- (4-benzyloxyphenyl) -1,
2,2-Tris (4-hydroxyphenyl) ethane Melting point (° C) 207-210 (6) 1- (4-hydroxyphenyl) -1,2,2
-Tris (4-methoxyphenyl) ethane Melting point (° C) 132-137 (7) 1,2,2-Tris (4-benzyloxyphenyl) -1- (4-hydroxyphenyl) ethane Melting point (° C) 183-186 (8) 1- (4-allyloxyphenyl) -1,2,
2-Tris (4-hydroxyphenyl) ethane Melting point (° C) 195-198 (9) 1- (4-benzoyloxyphenyl) -1,
2,2-Tris (4-hydroxyphenyl) ethane Melting point (° C) 139-141 (10) 1,1,2,2-Tetrakis (4-methoxyphenyl) ethane Melting point (° C) 187-189 (11) 1, 1,2,2-Tetrakis (4-acetyloxyphenyl) ethane Melting point (° C) 280-284 (12) 1,1,2,2-Tetrakis [4- (4-methylbenzoyloxy) phenyl] ethane Melting point (° C ) 287-288 (13) 1,1,2,2-tetrakis [4- (4-pyridylcarbonyloxy) phenyl] ethane Melting point (° C) 302-304 (14) 1,1,2,2-Tetrakis [4 -(3-Pyridylcarbonyloxy) phenyl] ethane Melting point (° C) 311-316 (15) 1,2,2-tris (4-hydroxyphenyl) -1- (4-propoxy Phenyl) ethane (16) 1- (4-oxyphenyl) -1,2,
2-Tris (4-hydroxyphenyl) ethane (17) 1,2,2-Tris (4-hydroxyphenyl) -1- (4-pentyloxyphenyl) ethane (18) 1,1-bis (4-hydroxyphenyl) ) −
2,2-bis (4-methoxyphenyl) ethane (19) 1,1-bis (4-ethoxyphenyl) -2,
2-bis (4-hydroxyphenyl) ethane (20) 1,2-bis (4-ethoxyphenyl) -1,
2-bis (4-hydroxyphenyl) ethane (21) 1,2,2-tris (4-hydroxyphenyl) -1- (4-isopentyloxyphenyl) ethane (22) 1,2,2-tris (4 -Hydroxyphenyl) -1- (4-phenethyloxyphenyl) ethane (23) 1- (4-butyryloxyphenyl) -1,
2,2-tris (4-hydroxyphenyl) ethane (24) 1,2,2-tris (4-hydroxyphenyl) -1- (4-propionyloxyphenyl) ethane (25) 1- (4-acetyloxyphenyl) ) -1,
2,2-Tris (4-hydroxyphenyl) ethane (26) 1- [4- (4-methylbenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (27) 1- [ 4- (2-Methylbenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (28) 1- [4- (3-Methylbenzyloxy) phenyl] -1,2,2- Tris (4-hydroxyphenyl) ethane (29) 1- [4- (4-chlorobenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (30) 1- [4- (2 -Chlorobenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (31) 1- [4- (3-chlorobenzyloxy) phenyl] -1,2,2-tris 4-hydroxyphenyl) ethane (32) 1- [4- (2-butenyloxy) phenyl]
-1,2,2-Tris (4-hydroxyphenyl) ethane (33) 1- [4- (3-butenyloxy) phenyl]
-1,2,2-Tris (4-hydroxyphenyl) ethane (34) 1- [4- (2-pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (35) 1- [4- (3-Pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (36) 1- [4- (4-pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (37) 1- (4-methallyloxyphenyl) -1,
2,2-tris (4-hydroxyphenyl) ethane (38) 1- (4-cinnamyloxyphenyl) -1,
2,2-Tris (4-hydroxyphenyl) ethane (39) 1- (4-cinnamoyloxyphenyl)-
1,2,2-tris (4-hydroxyphenyl) ethane

The compound represented by the above-mentioned general formula [I] is, for example, dialkyl sulfates, alkyl halides and alkenyl halides with respect to tetrakisphenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. , Aralkyl halides or acid halides are reacted in the presence of alkalis.

Examples of the alkali used include hydroxides of alkali metals such as caustic soda, caustic potash and lithium hydroxide, carbonates of alkali metals such as sodium carbonate, potassium carbonate and lithium carbonate, amines such as pyridine and triethylamine. Is mentioned.

Examples of the solvent used include water or ether solvents such as tetrahydrofuran and dioxane, aromatic solvents such as benzene, toluene, xylene and chlorobenzene, ketones such as methyl isobutyl ketone, diethyl ketone, ethyl methyl ketone and cyclohexanone. A system solvent, an ester solvent such as ethyl acetate, butyl acetate, and amyl acetate can be used alone or in combination.

The reaction temperature is generally -20 ° C to 140 ° C.
C. is preferable, and more preferably 10 to 70.degree.

(Guest Compound) The guest organic compound used in the present invention is not particularly limited as long as it can form an inclusion compound using the tetraphenylethane derivative as a host compound. Specific examples include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol and 2-ethylhexanol, aldehydes such as formaldehyde, acetaldehyde and benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones, nitriles such as acetonitrile, tetrahydrofuran, diethyl ether, ethers such as 1,4-dioxane and esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, cineol, hinokitiol, menthol, terpineol, borneol , Nopol, citral, citronellol, citronellal, geraniol, linalool, dimethyloctanol and other natural or synthetic essential oils, quince, jasmine, les Blended fragrance such as down, pyridine, pyrrole, imidazole, pyrazine, pyrazole, 1,2,4-triazole, thiazole, pyrrolidine, imidazoline, pyrroline, oxazole, piperine, pyrimidine, pyridazine, triazine,
2-Methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,
Nitrogen-containing heterocyclic compounds such as 2-benzisothiazolin-3-one, organic acids such as acetic acid, propionic acid, citric acid, sulfamic acid, benzene, toluene, o-xylene, m
Examples thereof include aromatic compounds such as -xylene and p-xylene.

The clathrate compound of the present invention comprises the guest organic compound or a solution containing the guest organic compound and a tetraphenylethane derivative as a host compound at room temperature to room temperature.
The guest organic compound can be easily clathrated by the host compound by stirring at 100 ° C. for several minutes to several hours to cause a reaction, whereby a new clathrate compound can be obtained.

The inclusion compound easily releases the guest compound when heated under normal pressure or reduced pressure, and the host compound selectively encapsulates the guest compound in accordance with the cavity type created by itself. The property can be utilized for selective separation and recovery of a specific guest compound from a mixture containing several components.

[0023]

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

When the guest organic compound is 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.

Which compound is more likely to be incorporated as a guest in the host compound of the clathrate compound of the present invention is governed by the size, stericity, polarity and solubility of the guest molecule.

[0026]

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. A. Synthesis of tetraphenylethane derivative (Reference Examples 1 to 1)
8) A tetraphenylethane derivative was synthesized as follows. The compound was identified by IR and NMR spectra.

Reference Example 1 Synthesis of 1,2,2-tris (4-hydroxyphenyl) -1- (4-methoxyphenyl) ethane (Compound (1)) 200 ml of water was placed in a 500 ml four-necked flask, To this, 2 g of caustic soda is added and dissolved. Into this 1,
20 g of 1,2,2-tetrakis (4-hydroxyphenyl) ethane (hereinafter referred to as “TEP”), 200 ml of methyl isobutyl ketone and 6.4 g of dimethylsulfate were added, and the mixture was heated under reflux for 2 hours. After the reaction was completed, the aqueous layer was separated, the organic layer was washed with 100 ml of water twice, and the solvent was distilled off under reduced pressure to obtain a brown oily substance. This was purified by column chromatography to obtain 14 g of compound (1). mp: 223
-229 ° C yield 68%

Reference Example 2 Synthesis of 1- (4-benzyloxyphenyl) -1,2,2-tris- (4-hydroxyphenyl) ethane (Compound (5)) 200 ml of water was put into a 500 ml four-necked flask. Then, 2 g of caustic soda was added thereto and dissolved. Into this TEP
20 g and 200 ml of methyl isobutyl ketone were added, and 6.4 g of benzyl chloride was added to this while stirring.
The mixture was added dropwise over a period of time, and after the addition was completed, the mixture was heated under reflux for 3 hours. After the reaction was completed, the aqueous layer was separated, the organic layer was washed twice with 100 ml of water, and the solvent was distilled off under reduced pressure to obtain a brown oily substance. Purification by column chromatography gave 13.5 g of compound (5). mp: 207-210 ° C Yield 57%

Reference Example 3 Synthesis of 1- (4-benzoyloxyphenyl) -1,2,2-tris- (4-hydroxyphenyl) ethane (Compound (9)) 200 ml of water was put into a 500 ml four-necked flask. Then, 2 g of caustic soda was added thereto and dissolved. Into this TEP
20 g and 200 ml of methyl isobutyl ketone were added, and further, 7.1 g of benzoyl chloride was added to this while stirring.
It was added dropwise over 0 minutes. After the reaction, the aqueous layer was separated, the organic layer was washed twice with 100 ml of water, and the solvent was distilled off under reduced pressure to obtain an off-white solid. This was purified by column chromatography to obtain 18 g of compound (9). mp: 1
39-141 ° C Yield 72%

Reference Example 4 Synthesis of 1- (4-hydroxyphenyl) -1,2,2-tris (4-methoxyphenyl) ethane (Compound (6)) 200 ml of water was placed in a 500 ml four-necked flask, To this, 2 g of caustic soda is added and dissolved. Into this TEP
20 g, 200 ml of methyl isobutyl ketone and 19.2 g of dimethylsulfate were added, and the mixture was heated under reflux for 2 hours. After the reaction was completed, the aqueous layer was separated, the organic layer was washed with 100 ml of water twice, and the solvent was distilled off under reduced pressure to obtain a brown oily substance. This was purified by column chromatography to give compound (6) 2
2 g was obtained. mp: 132-137 ° C Yield 60%

Reference Example 5 Synthesis of 1,1,2,2-tetrakis (4-methoxyphenyl) ethane (Compound (10)) 21.2 g of potassium carbonate and 500 g of a four-necked flask were obtained in Reference Example 4. 22 g of compound (6), 200 ml of methyl isobutyl ketone, and 21.3 g of methyl iodide were added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the mixture was cooled, the organic layer was washed twice with 100 ml of water, and the solvent was distilled off under reduced pressure to obtain an off-white solid. This was purified by column chromatography to obtain 11.5 g of compound (10). m
p: 187-189 ° C. Yield 50%

Reference Example 6 1,1,2,2-tetrakis (4-acetyloxyphenyl) ethane (Compound (1
1)) Synthesis 6 g of TEP and 3 g of acetic anhydride were placed in a 100 ml four-necked flask.
0.1 g was added and reacted at 80 ° C. for 7 hours. After the reaction was completed, the reaction solution was cooled to room temperature, poured into 50 ml of ice water, and the precipitated solid was collected by filtration. The obtained solid was washed twice with 5 ml of methanol and dried under reduced pressure to obtain 6.3 g of compound (11). mp: 280-
284 ° C, yield 74%

Reference Example 7 Synthesis of 1,1,2,2-tetrakis [4- (4-methylbenzoyloxy) phenyl] ethane (Compound (12)) 140 ml of water was placed in a 300 ml four-necked flask. 14.1 g of caustic soda and 5 g of TEP were added to and dissolved. While stirring, 35.0 g of p-methylbenzoyl chloride was added dropwise thereto at 25 ° C. over 25 minutes, and after completion of dropping, the mixture was stirred at 15 ° C. for 2 hours. The precipitated solid is collected by filtration,
The solid obtained was washed several times with water. This was dried under reduced pressure to obtain 7.6 g of compound (12). m
p: 287-288 ° C Yield 69%

Reference Example 8 Synthesis of 1,1,2,2-tetrakis [4- (4-pyridylcarbonyloxy) phenyl] ethane (Compound (13)) Tetrahydrofuran 70 m in a 200 ml four-necked flask.
1 was added, and 50 g of pyridine and 4 g of TEP were added and dissolved therein. 8.5 g of isonicotinic acid chloride hydrochloride was added dropwise thereto with stirring at 25 ° C. over 30 minutes, and after the completion of dropping, the mixture was stirred at 65 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into 200 ml of ice water, and the precipitated solid was collected by filtration. The obtained solid was washed 3 times with 5 ml of a 3% aqueous solution of sodium hydrogen carbonate 5 times and 10 ml of water.
This was washed once, and further, washed with 5 ml of methanol three times, and dried under reduced pressure to obtain 4.4 g of the compound (13). mp: 3
02-304 54% yield

B. Production of Inclusion Compound (Examples 1 to 11) An inclusion compound having a tetraphenylethane derivative as a host was produced as follows. Check the inclusion compound by T
It was performed by G-DTA measurement and IR, NMR spectrum.

Example 1 Reference Example 1 as host compound
Using the compound (1) synthesized in 1., an inclusion compound in which an organic compound as a guest compound is ethanol, 1-propanol, 2-propanol, acetonitrile, acetone, tetrahydrofuran, 1,4-dioxane, ethyl acetate, pyridine is produced. did. For the production of the inclusion compound, 0.5 mmol of the host compound is used as the guest and 2 m of the organic compound is desired.
The resulting mixture was added to 1 L, stirred at 40 to 80 ° C. for 2 to 10 minutes, immediately filtered, and the filtrate was allowed to stand at room temperature for 24 to 336 hours to precipitate crystals. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the inclusion compound of this example are shown in Table 1, and the NMR and TG- of the inclusion compound are shown.
Table 2 shows the guest / host mol ratio and the re-emission temperature of the guest compound, which are obtained from the DTA measurement.

Example 2 Reference Example 1 as host compound
Was synthesized in. Using compound (1), an inclusion compound of benzene, toluene, m-xylene and p-xylene was produced as a guest. The production of the inclusion compound is carried out using the host compound 0.
5 mmol was added to 2 ml of an organic compound to be used as a guest, and the reaction solution was heated to room temperature until the reaction solution boiled, or when a guest compound having a boiling point of 100 ° C. or higher was used, the reaction solution was stirred at room temperature for 1 to 5 minutes. It was left for 24 hours to precipitate crystals. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the clathrate compound in this Example are shown in Table 1, and the NMR and TG-DT of the clathrate compound are shown.
The guest / host mol ratio and the re-emission temperature of the guest compound obtained from the A measurement are summarized in Table 2.

Example 3 Reference Example 4 as host compound
Acetone, 1,4-dioxane, benzene, m-xylene, p as a guest using the compound (6) synthesized in
An inclusion compound of xylene was prepared. For the production of the inclusion compound, 0.5 mmol of the host compound was added to 2 ml of the organic compound to be used as a guest, the mixture was stirred at 40 to 80 ° C. for 2 to 10 minutes, immediately filtered, and the filtrate was left at room temperature for 24 to 336 hours. Then, crystals were precipitated. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the clathrate compound of this example are shown in Table 1, and the N of the clathrate compound is
Guest / host m determined from MR and TG-DTA measurements
Table 2 shows the ol ratio and the re-release temperature of the guest compound.

Example 4 Reference Example 5 as host compound
Acetone, 1,4-dioxane, benzene, toluene, m- as a guest using the compound (10) synthesized in 1.
An inclusion compound of xylene and p-xylene was produced. For the production of the inclusion compound, 0.5 mmol of the host compound was added to 2 ml of the organic compound to be used as a guest, the mixture was stirred at 60 to 80 ° C. for 5 to 10 minutes, immediately filtered, and the filtrate was stirred at room temperature for 2 minutes.
It was left standing for 4 hours to precipitate crystals. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the inclusion compound of the present invention. The conditions for producing the clathrate compound of this example are shown in Table 1, and the N of the clathrate compound is
Guest / host m determined from MR and TG-DTA measurements
Table 2 shows the ol ratio and the re-release temperature of the guest compound.

(Example 5) Reference example 7 as a host compound
Using the compound (12) synthesized in 1.
An inclusion compound of 4-dioxane was prepared. For the production of the inclusion compound, 0.5 mmol of the host compound was added to 2 ml of the organic compound to be used as a guest, the mixture was stirred at 80 ° C. for 10 minutes, immediately filtered, and the filtrate was left at room temperature for 24 hours to precipitate crystals. It was The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the clathrate compound in this example are shown in Table 1, and the NMR and TG-D of the clathrate compound are shown.
Table 2 shows the guest / host mol ratio and the re-emission temperature of the guest compound obtained from the TA measurement.

Example 6 Reference Example 8 as host compound
An inclusion compound of acetonitrile, 1,4-dioxane, pyridine, and acetic acid as a guest was produced using the compound (13) synthesized in (3). For the production of the inclusion compound, 0.5 mmol of the host compound is used as the guest and 2 ml of the organic compound is desired.
The mixture was added to the mixture, stirred at 60 to 80 ° C. for 5 to 10 minutes, immediately filtered, and the filtrate was left at room temperature for 24 to 48 hours to precipitate crystals. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the clathrate compound in this Example are shown in Table 1, and the NMR and TG-DT of the clathrate compound are shown.
The guest / host mol ratio and the re-emission temperature of the guest compound obtained from the A measurement are summarized in Table 2.

Example 7 Compound (14) 1,1,2,2-tetrakis [4- (3-pyridylcarbonyloxy) phenyl] ethane was used as a host compound, and 1,4-dioxane and pyridine were used as guests. , An inclusion compound of acetic acid was produced. For the production of the inclusion compound, 0.5 mmol of the host compound was added to 2 ml of the organic compound to be used as a guest, the mixture was stirred at 80 ° C. for 10 minutes, immediately filtered, and the filtrate was left at room temperature for 24 to 48 hours to form crystals. It was deposited.
The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain the clathrate compound of the present invention. The conditions for producing the clathrate compound in this example are shown in Table 1, and the guest / host mol ratio and the re-emission temperature of the guest compound, which are obtained by NMR and TG-DTA measurements of the clathrate compound, are shown in Table 2.

Example 8 Reference Example 1 as host compound
0.5 mmol of the compound (1) synthesized in 1. was added to 2 ml of a mixed solvent of 2-propanol: acetone = 1: 1 mol, stirred at 40 ° C. for 5 minutes, immediately filtered, and the filtrate was left at room temperature for 72 hours. To precipitate crystals. The precipitate was collected by filtration and dried under reduced pressure at room temperature to give a colorless transparent crystal. From the NMR spectrum of this crystal, it was found that this crystal was an inclusion compound of compound (1): 2-propanol = 1: 1.5 mol.

Example 9 Reference Example 1 as host compound
0.5 mmol of the compound (1) synthesized in 1. was added to 2 ml of a mixed solvent of tetrahydrofuran: 1,4-dioxane = 1: 1 mol, stirred at 40 ° C. for 5 minutes and immediately filtered, and the filtrate was allowed to stand at room temperature for 72 hours. It was left to stand to precipitate crystals. The precipitate was collected by filtration and dried under reduced pressure at room temperature to give a colorless transparent crystal. From the NMR spectrum of this crystal, this crystal shows that the compound (1): 1,4-dioxane = 1:
It was found to be an inclusion compound of 1.5 mol.

Example 10 0.5 mmol of the compound (1) synthesized in Reference Example 1 as a host compound was added to 2 ml of a mixed solvent of m-xylene: p-xylene = 1: 1 mol, and the mixture was heated at 90 ° C. for 10 minutes. After heating and stirring, the reaction solution was left at room temperature for 24 hours to precipitate crystals. The precipitate was collected by filtration and then dried under reduced pressure at room temperature to obtain a white crystalline substance. From the NMR spectrum of this crystal, it was found that this crystal was an inclusion compound of compound (1): p-xylene = 1: 1 mol.

Example 11 0.5 mmol of the compound (1) synthesized in Reference Example 1 as a host compound was added to 2 ml of a mixed solvent of chloroform: ethanol = 20: 1 mol, and the mixture was stirred at 25 ° C. for 1 hour. The reaction suspension was left at room temperature for 24 hours to grow crystals. The crystals thus grown were collected by filtration and then dried under reduced pressure at room temperature to obtain white crystals. From the NMR spectrum of this crystal, it was found that this crystal was an inclusion compound of compound (1): ethanol = 2: 3 mol.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

The novel clathrate compound using the tetraphenylethane derivative of the present invention as a host compound has the following characteristics. 1) Various organic compounds are included as guest compounds very easily. In particular, the previously known 1,1,2,2
-Tetrakis (4-hydroxyphenyl) ethane (Tetr
ahedron Letters., 33 (42), 6319 (1992).), it is possible to include aromatic hydrocarbons such as benzene, toluene, xylene, and organic acids such as acetic acid, which cannot 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 water and organic compounds mixed in various organic solvents as inclusion bodies. 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 formulated into powder, suspension, granules, tablets and the like, and is extremely easy to handle. Therefore, 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.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C07C 69/78 C07D 213/79

Claims (2)

[Claims] 1. An inclusion compound having a tetraphenylethane derivative represented by the general formula [I] as a host compound. Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an acyl group or a cinnamyl group, provided that R ¹ , R ² , R ³
And R ⁴ are not hydrogen atoms at the same time. ) 2. The method for producing an inclusion compound according to claim 1, wherein the host compound of the tetraphenylethane derivative represented by the general formula [I] is reacted with a guest organic compound.