JP2000344687A - Production of molecule compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially obtain a molecular compound by a solid-solid reaction by mixing and/or kneading a solid host compound with a solid guest compound by using a kneader. SOLUTION: (A) A solid host compound [preferably 1,2,3,3-tetrakis(4- hydroxyphenyl)ethane] is mixed and/or kneaded with (B) a solid guest compound or (C) a liquid guest compound (e.g. 2-ethyl-4-methylimidazole, etc.), by using a kneader apparatus (preferably a multishaft type kneader). Before the component A is mixed and/or kneaded with the component B or the component C by using the kneader apparatus, preferably the component A is uniformly mixed with the component B or the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for industrially producing a large amount of a molecular compound, and more particularly, to an industrial method for producing a molecular compound using a solid-solid reaction or a solid-liquid reaction.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a molecular compound represented by an inclusion compound, a method in which a host compound and a guest compound are dissolved in a solvent and reacted in a solution is generally performed. However, in the conventional method using a solvent, a molecular compound may not be generated depending on the type of the solvent, and a compound that includes only the solvent without including the guest molecule or a part of the compound that includes the guest molecule may be used. It has been pointed out that a compound containing a solvent may be obtained, and selection of conditions is sometimes difficult.

[0003] On the other hand, there have been proposed several methods for producing a compound by directly mixing a host compound and a guest compound without using a solvent. For example, JP-A-63-35533
The publication discloses a powdered host compound having a phenyl group and a hydroxyl group in one molecule and having more than 12 carbon atoms, and a powdered guest compound having a phenyl group and a carbonyl group in one molecule, respectively. After crushing into powder,
A method of mixing and reacting, after mixing the host compound and the guest compound, a method of pulverizing and reacting, a method of mixing and reacting the host compound and the guest compound while pulverizing, and the like, are disclosed. As a specific mixing method, a method of crushing and mixing in a mortar and a method of shaking and mixing with a shaker are described.

Japanese Patent Application Laid-Open No. Hei 1-213236 discloses a clathrate in which a solid guest compound is heated and melted at room temperature, and then a powdered host compound which reacts with the guest compound to form an inclusion compound is added. Methods for making the compounds are described.

[0005] On the other hand, kneaders and granulators have hitherto been generally used for mixing foods, tableting agricultural chemicals or pharmaceuticals, or modifying and strengthening resins.

[0006]

The conventional methods for producing molecular compounds by the solid-solid reaction are all related to small-scale production, and the production of molecular compounds by the solid-solid reaction is industrially large. Implementing on a scale was never conceived. In addition, there is no known example in which a kneader or a granulator is applied to a solid-solid reaction. An object of the present invention is to provide an industrial method for producing a molecular compound by a solid-solid reaction.

[0007]

Means for Solving the Problems The present inventors have been required to carry out the industrial production of molecular compounds by a solid-solid reaction, and have found the above-mentioned problems. By mixing and / or kneading using an apparatus or a granulator, or further granulating, it was confirmed that a large amount of a molecular compound could be produced industrially, and the present invention was completed.

That is, the present invention provides a method for producing a molecular compound, comprising mixing and / or kneading a solid host compound and a solid guest compound or a solid host compound and a liquid guest compound using a kneader. Regarding 1).

Further, the present invention provides a method wherein the solid host compound comprises
2. The method for producing a molecular compound according to claim 1, wherein the compound is 1,2,2-tetrakis (4-hydroxyphenyl) ethane (claim 2), and the kneader is a multi-axis kneader. The method for producing a molecular compound according to claim 1 or 2, wherein the solid host compound and the solid guest compound, or the solid host compound and the liquid guest compound are mixed and / or kneaded using a kneader. Before the solid host compound and the solid guest compound,
4. A method for producing a molecular compound according to claim 1, wherein the solid host compound and the liquid guest compound are uniformly mixed. The method according to any one of claims 1 to 4, wherein the guest compound and the resulting molecular compound are mixed and / or kneaded in a stable temperature range.

Further, the present invention is characterized in that the solid host compound and the solid guest compound or the solid host compound and the liquid guest compound are mixed and / or kneaded using a kneader, and are further extruded and granulated. A method for producing the molecular compound according to any one of claims 1 to 5 (claim 6).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The solid host compound used in the present invention is obtained by incorporating another atom or molecule with a constant composition into a vacancy inside a three-dimensional structure formed by bonding atoms or molecules. The compound is not particularly limited as long as it can construct a specific structure. Specifically, 1,1,6,6-tetra (substituted or unsubstituted) phenyl-2,4-hexadiyne-1,6- Diol, 1,1-di (2,4-dimethylphenyl) -2-propyn-1-ol, 9,10-diphenyl-9,10-dihydroanthracene, 1,1,
2,2-theolaphenylethane-1,2-diol, 1,
1-bis (4-hydroxyphenyl) cyclohexane,
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1′-bis-2-naphthol, 3,
Examples include 3'-bis (phenylsulfonyl) -4,4'-dihydroxyphenylsulfone, 2,4-bis (phenylsulfonyl) phenol, 2,4,6-tris (phenylsulfonyl) phenol, cyclodextrins and the like. But 1,1,2,2-tetrakis (4
-Hydroxyphenyl) ethane is particularly preferred for practical use.

The solid or liquid guest compound used in the present invention can be incorporated into a vacancy inside a three-dimensional structure formed by bonding atoms or molecules with a certain composition to form a specific structure. The compound is not particularly limited as long as it is a compound, and specific examples include the following compounds.

Water, methanol, ethanol, isopropanol, n-butanol, n-octanol, 2-ethylhexanol, allyl alcohol, propargyl alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol Alcohols such as cyclohexanediol, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 4-chlorophenyl-3-iodopropargyl formal, formaldehyde, acetaldehyde,
aldehydes such as n-butyraldehyde, propionaldehyde, benzaldehyde, phthalaldehyde, α-bromocinnamaldehyde, phenylacetaldehyde, acetone, methyl ethyl ketone, diethyl ketone,
Ketones such as dibutyl ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone, 2-bromo-4'-hydroxyacetophenone, acetonitrile, acrylonitrile, n-butyronitrile, malononitrile, phenylacetonitrile, benzonitrile, cyanopyridine, 2,2-dibromomethyl Glutarnitrile,
2,3,5,6-tetrachloroisophthalonitrile, 5
Nitriles such as -chloro-2,4,6-trifluoroisophthalonitrile, 1,2-dibromo-2,4-dicyanobutane, diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, tetrahydropyran, dioxolan, trioxane and the like; Ethers, methyl acetate, ethyl acetate, butyl acetate, n-heptyl acetate, esters such as bis-1,4-bromoacetoxy-2-butene, sulfonamides such as benzenesulfonamide, N-methylformamide, N, Amides such as N-dimethylformamide, dicyandiamide, dibromonitrilepropionamide, 2,2-dibromo-3-nitrilopropionamide, N, N-diethyl-m-toluamide, dichloromethane, chloroform, dichloroethylene, tetrachloroethyl Halogenated hydrocarbons emissions such, epsilon
-Lactams such as caprolactam, lactones such as ε-caprolactone, oxiranes such as arylglycidyl ether, morpholines, phenols such as phenol, cresol, resorcinol, p-chloro-m-cresol, formic acid, acetic acid and propionic acid Carboxylic acids such as oxalic acid, citric acid, adipic acid, tartaric acid, benzoic acid, phthalic acid, salicylic acid and thiocarboxylic acids, sulfamic acids, thiocarbamic acids, thiosemicarbazides, urea, phenylurea, diphenylurea, thiourea,
Urea such as phenylthiourea, diphenylthiourea, N, N-dimethyldichlorophenylurea and thioureas, isothioureas, sulfonylureas, thiophenols, thiols such as allylmercaptan, n-butylmercaptan, benzylmercaptan, and benzylsulfide , Sulfides such as butylmethyl sulfide, disulfides such as dibutyl disulfide, dibenzyl disulfide, tetramethylthiuram disulfide, sulfoxides such as dimethyl sulfoxide, dibutyl sulfoxide, dibenzyl sulfoxide, dimethyl sulfone, phenyl sulfone, phenyl- (2- Cyano-2-chlorovinyl)
Sulfones such as sulfone, hexabromodimethyl sulfone and diiodomethyl paratolylsulfone; amino acids such as thiocyanic acid and isothiocyanic acid such as methyl thiocyanate and methyl isothiocyanate; glycine, alanine, leucine, lysine, methionine and glutamine. , Amide and urethane compounds, acid anhydrides, aromatic hydrocarbons such as benzene, toluene, xylene, alkanes, alkenes, alkynes, isocyanates such as butyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, and methylene bisthiocyanate , Thiocyanates and isothiocyanates such as methylenebisisothiocyanate, nitro compounds such as tris (hydroxymethyl) nitromethane, ammonia, methyl Min, ethylamine, propylamine, butylamine, pentylamine, hexylamine,
Allylamine, hydroxylamine, ethanolamine, benzylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, dipropylenediamine, N, N-dimethylethylenediamine, N,
N'-dimethylethylenediamine, N, N-dimethyl-
Non-functional compounds such as 1,3-propanediamine, N-ethyl-1,3-propanediamine, trimethylhexamethylenediamine, alkyl-t-monoamine, menthanediamine, isophoronediamine, guanidine, and N- (2-hydroxypropyl) aminomethanol Cycloaliphatic amines, cyclohexylamine, cyclohexanediamine, bis (4
-Aminocyclohexyl) methane, pyrrolidines, azetidines, piperidines, piperazine, N-aminoethylpiperazine, piperazines such as N, N'-dimethylpiperazine, cycloaliphatic amines such as pyrrolines, 1,8
-Diazabicyclo [5,4,0] undecene-7,1,
Crosslinked amines such as 5-diazabicyclo [4,3,0] non-5-ene, aniline, N-methylaniline, N,
N-dimethylaniline, o-phenylenediamine, m-
Phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m
-Modified polyamines such as aromatic amines such as killed diamines, polyamines added with epoxy compounds, polyamines added with Michael, polyamines added with Mannich, polyamines added with thiourea, polyamines blocked with ketones, imidazole, 2-
Methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-undecyl-1H-
Imidazole, 2-heptadecyl-1H-imidazole, 2-phenyl-1H-imidazole, 4-methyl-
2-phenyl-1H-imidazole, 1-benzyl-2
-Imidazoles such as methylimidazole, pyrrole,
Pyridine, picoline, pyrazine, pyridazine, pyrimidine, pyrazole, triazole, benzotriazole,
Triazine, tetrazole, purine, indole, quinoline, isoquinoline, carbazole, imidazoline, pyrroline, oxazole, piperine, pyrimidine, pyridazine, benzimidazole, indazole, quinazoline, quinoxaline, phthalimide, adenine, cytosine, guanine, uracil, 2-methoxycarbonylbenz Imidazole, 2,3,5,6-tetrachloro-4-
Methanesulfonylpyridine, 2,2-dithio-bis-
(Pyridine-1-oxide), N-methylpyrrolidone, methyl 2-benzimidazolecarbamate, 2-
Sodium pyridinethiol-1-oxide, hexahydro-1,3,5-tris (2-hydroxyethyl)-
s-triazine, hexahydro-1,3,5-triethyl-s-triazine, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,
N- (fluorodichloromethylthio) phthalimide, 1
-Bromo-3-chloro-5,5-dimethylhydantoin, 2-methoxycarbonylbenzimidazole, 2,
Nitrogen-containing heterocyclic compounds such as 4,6-trichlorophenylmaleimide, furan, furfuryl alcohol, tetrahydrofurfuryl alcohol, furfurylamine, pyran,
Oxygen-containing heterocyclic compounds such as coumarin, benzofuran, xanthene and benzodioxane, oxazole, isoxazole, benzoxazole, benzisoxazole,
5-methyloxazolidine, 4- (2-nitrobutyl)
Nitrogen- and oxygen-containing heterocyclic compounds such as morpholine and 4,4 ′-(2-ethyl-2-nitrotrimethylene) dimorpholine, thiophene, 3,3,4,4-tetrahydrothiophene-1,1-dioxide, , 5-dichloro-1,
Sulfur-containing heterocycles such as 2-dithiolan-3-one, 5-chloro-4-phenyl-1,2-dithiolan-3-one, 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide Compound, thiazole, benzothiazole, 5-chloro-2-methyl-4-isothiazoline-
3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-3-n-octylisothiazolin-3-one, 2-octyl-4-isothiazoline-3
-One, 1,2-benzisothiazolin-3-one, 2
Nitrogen-containing and sulfur-heterocyclic compounds such as thiocyanomethylbenzothiazole, 2- (4-thiazolyl) benzimidazole and 2-thiocyanomethylbenzothiazole; steroids such as cholesterol; alkaloids such as brucine, quinine and theophylline; Natural essential oils such as cineole, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, menthone, eugenol, linalool, dimethyloctanol, synthetic flavors such as quince, jasmine and lemon, ascorbic acid, nicotinic acid And related compounds such as vitamins and nicotinamide.

The kneader used in the present invention includes:
Any device that can sufficiently mix and / or knead the host compound and the guest compound on a large scale may be used, and a kneading machine generally used in a food field, a plastic field, or the like may be used. Any kneading machine can be used.

The kneading machine is preferably a single-shaft or two-shaft type, which is capable of mixing and / or kneading substances by rotating a paddle mounted on a shaft, and further having a small clearance between the paddle and the body. For example, JP-A-3-8
It is more preferable to use a device equipped with a jacket capable of cooling or heating the apparatus body, as described in JP-A-6223 and JP-A-9-173825.

The kneader is preferably composed mainly of a barrel called a barrel and a screw on which various screw elements are mounted, and usually has a structure in which the screw passes through a plurality of barrels. The screw elements include trapezoidal screw elements, trapezoidal cut screw elements, trapezoidal reverse cuts, ball screw elements, kneading paddles, and the like, and any combination thereof can be performed. The substance sent into the barrel is moved in the barrel by a screw, and is subjected to processing such as shearing and mixing in the barrel by a screw element such as a kneading paddle.

Further, any kneading machine having basic characteristics such as a conveying function, a mixing function, a shearing function, a compressing function, a crushing function, and a heating function which are generally used in the food and plastic fields, etc. Can be used. In particular, a twin-screw kneader such as a non-meshing type different direction or co-rotating kneader or a complete or partially intermeshing type different direction or co-rotating kneader is preferable.

Mixing the host compound and the guest compound and / or
Or, as a method of kneading, a method in which a host compound or a guest compound is charged into a kneader device, and then a guest compound or a host compound as a partner thereof is charged sequentially and at a time and mixed and / or kneaded, A method in which a guest compound is simultaneously charged and mixed and / or kneaded, a method in which a host compound and a guest compound are previously mixed and / or kneaded so as to be uniform, and then charged into a kneader, and mixed and / or kneaded. Can be adopted.

In particular, when the solid host compound or the solid guest compound has a melting point of 100 ° C. or less, heat and dissolve it in a water bath or the like, stir and mix them both uniformly, and then put them into a kneader to mix and / or mix. Alternatively, kneading is preferred. As for the degree of uniformity, it is sufficient that the two are uniformly mixed visually.

The reaction proceeds rapidly, and the reaction is completed in about 10 to 20 minutes after the starting materials are charged into the apparatus and mixing and / or kneading is started. The reaction proceeds even at room temperature. However, when the molecular compound to be produced has particularly good crystallinity, a large amount of addition is required to the reaction apparatus and mixing or kneading may be hindered. In a temperature range in which the molecular compound is stable,
The reaction is preferably performed in a temperature range of 120 ° C. In addition, when the reaction is very fast and the generated molecular compound has a high melting point, the host compound and the guest compound solidify immediately from the contact, so that even if the whole is not uniformly mixed even by stirring using a kneader device. There is. In such a case, the molecular compound can be efficiently produced by once taking out the reaction mixture, pulverizing it finely, and then mixing or kneading it again using a kneader.

When the molecular compound finally obtained has a high melting point and good crystallinity, it is pulverized at the stage of mixing and / or kneading, and can be taken out from the kneader after the reaction and used as it is. If necessary, it can be ground. Further, regardless of the melting point and the crystallinity, after mixing and / or kneading, it is also possible to granulate into a specific shape using an extrusion granulator according to the application. Further, the obtained molecular compound can be used after it is aged while keeping it at a temperature not higher than the decomposition point of the molecular compound to prepare a crystal system and the like.

As the extrusion granulator used in the present invention, any general equipment widely used in the fields of pharmaceuticals, agricultural chemicals, foods, plastic molding and the like can be used. Any type such as a roll type, a blade type, a self-molding type, and a ram type can be used.

In particular, when a multi-screw extruder is used, mixing, kneading, and granulation operations can be performed collectively, which is preferable from the viewpoint of industrial production. The main part of the extruder is mainly composed of a cylinder called a barrel, a die corresponding to an outlet, and a screw equipped with various screw elements, and is preferably one having a structure in which a screw usually passes through a plurality of barrels. . The screw elements include trapezoidal screw elements, trapezoidal cut screw elements, trapezoidal reverse cuts, ball screw elements, kneading paddles, and the like, and any combination thereof can be performed.
Then, the substance sent into the barrel moves in the barrel by a screw, and is subjected to processing such as shearing and mixing in the barrel by a screw element such as a kneading paddle, and is extruded from the pores of the die. Normally, each barrel and die can be independently temperature-controlled.

The number of rotations of the screw can be appropriately set according to the type and type of the extruder, the raw material, the shape of the screw, and the like. In addition, the discharge die can be appropriately replaced according to the purpose, and specifically, a circular discharge die having various diameters for obtaining a columnar processed product, a flat die for obtaining a plate-shaped processed product. A discharge die or the like can be used. As a specific model of a multi-axis extruder,
Examples include Labo Luder Mark II (manufactured by Japan Steel Works, Ltd.) and PCM series twin screw extruder (manufactured by Ikegai Co., Ltd.).

In the present invention, a molecular compound is a compound that can be stably present alone and has a relatively weak interaction other than a covalent bond represented by a hydrogen bond, van der Waals force, or the like with two or more kinds of component compounds. And hydrates, solvates, adducts, clathrates and the like. Here, an clathrate is a compound in which a three-dimensional structure formed by bonding atoms or molecules has pores of an appropriate size, in which other atoms or molecules have non-covalent interactions. Indicates a substance that has entered at a constant composition ratio.

Such a molecular compound is obtained by mixing a host compound and a guest compound, and has a function of enabling selective separation of a guest compound as a useful substance, chemical stabilization of the guest compound, non-volatilization and powderization. It is a useful substance in that it has. Further, by reacting two or more kinds of guest compounds, a molecular compound comprising three or more components can be obtained.

The crystallinity of a molecular compound can be confirmed mainly by examining an X-ray diffraction pattern. The presence of a polymorph in a molecular compound having the same composition can be confirmed by a thermal analysis, an X-ray diffraction pattern, and a solid-state NMR. And so on.

The use form of the molecular compound of the present invention is not particularly limited. For example, two or more kinds of molecular compounds composed of different component compounds can be used in combination. The molecular compound of the present invention can be used in combination with other substances as long as the intended function is not impaired.
An excipient or the like may be added to the molecular compound of the present invention to form granules or tablets for use. Further, they can be used by adding them to resins, paints, and their raw materials and raw material compositions. In addition, the molecular compound of the present invention can be used as it is as a raw material for organic synthesis or as a specific reaction field.

For example, using 3,3'-bis (phenylsulfonyl) -4,4'-dihydroxyphenylsulfone as a host compound, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4 -Isothiazolone bactericides such as isothiazolin-3-one, antibacterial and insecticide / insect repellents such as hinokitiol and 1,8-cineole, fragrances such as rosemary, antifoulants such as isothiazolone compounds, phthalic anhydride, tetrahydroanhydride Curing agents for resins such as phthalic acid and 1,8-diazabicyclo [5,4,0] undecene-7,1,5-diazabicyclo [4,3,0]
A catalyst such as a curing accelerator for epoxy resin such as non-5-ene or 2-ethyl-4-methylimidazole or an inclusion compound using an organic solvent such as toluene, xylene or pyridine as a guest has an action inherent to the guest compound. Besides, functions such as sustained release, reduction of skin irritation, chemical stabilization, non-volatility, powderization, selective separation of useful substances, etc. are newly added,
It is extremely useful as a catalyst and organic solvent for fungicides, antibacterial agents, insecticides / insect repellents, fragrances, antifouling agents, resin curing agents, etc. having new properties.

[0030]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

EXAMPLE 1 33.3 g (75 mmol, purity 90%) of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane
To the mixture, 17.0 g (150 mmol, purity 97%) of 2-ethyl-4-methylimidazole dissolved by heating was added with good stirring, and stirring was further continued for 5 minutes. The mixture thus obtained was gradually added to the mixer section while rotating the rotor of a kneader (Brabender Plasticorder PLV151 type, manufactured by Brabender) set at 25 ° C., and after the addition was completed, the mixture was further added for 10 minutes. Continue stirring for minutes,
The reaction product was taken out.

The reaction product was subjected to ¹ H-NMR and powder X-ray diffraction measurements, and it was confirmed that a host compound: guest compound = 1: 2 molecular compound was formed.
When the thermal behavior of the reaction product was observed by TG-DTA measurement, a weight loss was observed at 180 ° C.
It was confirmed that a molecular compound was formed. ¹ H-N
FIG. 1 shows an MR spectrum, and FIG. 2 shows a powder X-ray diffraction pattern.
FIG. 3 shows a thermal analysis (TG-DTA) chart.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the kneading temperature was changed to 70 ° C., 100 ° C., and 120 ° C., and the same TG-DTA and powder X-ray diffraction as in Example 1 were used. And a molecular compound showing infrared absorption spectrum measurement results. Thus, in the reaction between 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-methylimidazole, no difference in reactivity depending on the reaction temperature was observed.

Example 3 8.5 g of 2-ethyl-4-methylimidazole
(75 mmol, 97% purity) except that the molecular compound was a mixture of host compound: guest compound = 1: 2. From this, it was found that the molecular compound obtained even when the mixing ratio between the guest compound and the host compound was changed was always a molecular compound having a constant composition ratio. Also, 2-melted in a mixture of the above host compound: guest compound = 1: 2
8.5 g of ethyl-4-methylimidazole (75 mmol
l, purity 97%) and mixed, and then subjected to various instrumental analysis in the same manner as in Example 1.
Host compound: guest compound = 1: 2.

EXAMPLE 4 1,2,2,2-Tetrakis (4-hydroxyphenyl) ethane 222.0 g (510 mmol, purity 91.9 g).
5%) using a kneader, a bench kneader (Iriesyo)
2 manufactured by Ukai Co., Ltd.)
-Ethyl-4-methylimidazole 114.6 g (1.
(0.2 mol, purity 98.05%), and the mixture was further stirred for 20 minutes, and sampled arbitrarily from three places. Thereafter, the mixture was heated to 90 ° C. and stirred for 20 minutes to complete the reaction. After cooling, various instrumental analyzes were performed as in Example 1.

From the measurement of the sample before heating, no formation of molecular compounds was observed. After ¹ H-NMR and powder X-ray diffraction measurements were performed on the product after the reaction, a molecular compound of host compound: guest compound = 1: 2 was obtained.

Example 5 33.3 g (75 mmol, purity 90%) of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane
22.9 g (150 mmol, purity 99) of 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU)
%) Was added with good stirring, and stirring was continued for another 5 minutes. The mixture thus obtained was mixed with a kneader (Bradbender Plasticorder PLV1) set at 100 ° C.
While rotating the rotor of Model 51 (manufactured by Brabender), the mixture was gradually added to the mixer, and after the addition was completed, stirring was continued for another 10 minutes to take out the reaction product.

The reaction product was subjected to ¹ H-NMR and powder X-ray diffraction measurements, and it was confirmed that a host compound: guest compound = 1: 2 molecular compound was formed.
Further, when the thermal behavior of the reaction product was observed by TG-DTA measurement, weight loss was observed at 169 ° C. and 316 ° C., and it was confirmed that a molecular compound was generated. FIG. 4 shows the ¹ H-NMR spectrum, FIG. 5 shows a powder X-ray diffraction pattern, and FIG. 6 shows a thermal analysis (TG-DTA) chart. In addition, when the thermal behavior of the mixture before kneading by the kneader was observed by TG-DTA measurement, weight loss was observed in three stages from 124 ° C., indicating that some molecular compounds were formed. Was suggested.

[0039]

As described above, by using the method of the present invention, a large amount of molecular compounds can be industrially produced without using a solvent. The obtained molecular compound is
Unlike the case of using the solvent method, it has become possible to produce a uniform product in a short time.

[Brief description of the drawings]

FIG. 1 shows 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-ethylamine of Example 1 of the present invention.
¹ H-NMR spectrum (DMSO-d) of a molecular compound having a composition ratio of 1: 2 (molar ratio) with methyl imidazole
It is a diagram showing a ₆ solvent).

FIG. 2 shows 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-l of Example 1 of the present invention.
FIG. 3 is a view showing a powder X-ray diffraction pattern of a molecular compound having a composition ratio of 1: 2 (molar ratio) with methylimidazole.

FIG. 3 shows 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-method of Example 1 of the present invention.
FIG. 3 is a diagram showing a thermal analysis (TG-DTA) chart of a molecular compound having a composition ratio of 1: 2 (molar ratio) with methylimidazole.

FIG. 4 shows the results of Example 1, 5,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-methylbenzene.
¹ H-NMR spectrum (DMSO-d) of a molecular compound having a composition ratio of 1: 2 (molar ratio) with methyl imidazole
It is a diagram showing a ₆ solvent).

FIG. 5: Composition ratio of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU) of Example 5 of the present invention It is a figure which shows the powder X-ray diffraction pattern of the molecular compound which consists of 1: 2 (molar ratio).

FIG. 6 is a composition ratio of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU) of Example 5 of the present invention. It is a figure which shows the thermal-analysis (TA / DTA) chart of the molecular compound which consists of 1: 2 (molar ratio).

Claims (6)

[Claims] 1. A solid host compound and a solid guest compound,
Alternatively, a method for producing a molecular compound, comprising mixing and / or kneading a solid host compound and a liquid guest compound using a kneader. 2. The method according to claim 1, wherein the solid host compound is 1,1,2,2-
The method for producing a molecular compound according to claim 1, wherein the method is tetrakis (4-hydroxyphenyl) ethane. 3. The method for producing a molecular compound according to claim 1, wherein the kneader is a multi-screw kneader. 4. A solid host compound and a solid guest compound,
Alternatively, before mixing and / or kneading the solid host compound and the liquid guest compound using a kneader, the solid host compound and the solid guest compound or the solid host compound and the liquid guest compound are uniformly mixed in advance. The method for producing a molecular compound according to any one of claims 1 to 3. 5. The molecule according to claim 1, wherein the solid host compound, the guest compound and the generated molecular compound are mixed and / or kneaded in a stable temperature range using a kneader. A method for producing a compound. 6. A solid host compound and a solid guest compound,
The method for producing a molecular compound according to any one of claims 1 to 5, wherein the solid host compound and the liquid guest compound are mixed and / or kneaded using a kneader, and further extruded and granulated.