JPH0710791A - New inclusion compound and its productions - Google Patents

Abstract

PURPOSE:To simply and efficiently obtain the subject compound having heat stability, capable of being heat-treated, by reacting a heat compound of a specific tetrakisphenol with an industrial germicide as a guest compound. CONSTITUTION:(A) A tetrakisphenol of the formula as a host compound [X is (CH2)n ((n) is 0, 1, 2 or 3); R<1> to R<8> are H, lower alkyl, halogen, lower alkoxy or (substituted)phenyl] is reacted with (B) an industrial germicide (preferably alpha-bromocinnamic aldehyde or n-octanol) as a guest compound at normal temperature to 100 deg.C for several minutes to several hours under stirring to give the objective compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel clathrate compound, and more particularly to a novel clathrate compound having an industrial fungicide as a guest compound and tetrakisphenols 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 the cavity of a host molecule, and is expected to be used in the technical fields of selective separation, chemical stabilization, nonvolatization, powderization and the like. ing.

As a conventional clathrate compound, for example, in JP-A-61-53201, 1,1,6,6-tetraphenyl-2,4-hexadione-1,6-diol, or 1 , 1-di (2,4-dimethylphenyl)-
2-Propin-1-ol is disclosed in JP-A-62-22701.
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that 1,1'-bis-2-naphthol is used as a host and 5-chloro-2-methyl-4-isothiazolin-3-one is used as a guest.

[0004] Further, no inclusion compound containing tetrakisphenol as a host has been known, except that containing tetrakis (4-hydroxyphenyl) ethane as a host and an organic solvent as a guest (Tetrahedro).
n Letters. , 33 (42), 6319, (1
992))).

On the other hand, industrial fungicides represented by 5-chloro-2-methyl-4-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol and the like are used in the water treatment field and the like. It is used in a wide range of fields, and its significance is great. However, many of these industrial bactericides have a great influence on the human body during use due to problems such as skin irritation and irritating odor, which has been a problem in handling.

[0006]

The present invention has been made to solve the above problems, and is useful in the technical fields of selective separation, chemical stability, nonvolatization, pulverization and the like. It is an object of the present invention to provide a novel clathrate compound in which an industrial fungicide is used as a guest compound, using a class of compounds as a host.

At the same time, the following problems in production in the conventional method for producing an inclusion compound are as follows: 1) The inclusion compound is not formed depending on the type of the solvent. 2) The solvent is included without including the guest molecule. Inclusion to obtain a solvent inclusion compound 3) In order to precipitate an inclusion compound of a guest molecule even with a solvent that forms an inclusion compound, temperature, host / guest charging ratio and concentration, stirring, etc. Since conditions are limited, it is difficult to set conditions. 4) 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.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have extremely efficiently included various industrial fungicides in which a specific tetrakisphenol host compound is a guest compound. The inventors have found that they contact each other and completed the present invention.

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 2.

[0010]

[Chemical 2]

(In the formula, X represents (CH ₂ ) n, n represents 0, ¹ , 2 or 3, and R ^{1 to} R ⁸ are each a hydrogen atom, a lower alkyl group, a halogen atom or a lower alkoxy group. Or any of the optionally substituted phenyl groups.)

Specific examples of the tetrakisphenol host compound used in the present invention include 1,1,2,2
-Tetrakis (4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,3
5-dimethyl-4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,3
5-dichloro-4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,3
5-dibromo-4-hydroxyphenyl) ethane, 1,
1,2,2-Tetrakis (3-t-butyl-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-di-fluoro-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-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-bis (4-hydroxyphenyl) -2,2-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -2,2 -Bis (3-chloro-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -2,2-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) 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
-Di-methyl-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 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-di-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-methoxy-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-di-chloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-bromo-4-hydroxyphenyl) pentane,
1,1,5,5-tetrakis (3,5-di-bromo-4
-Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methoxy-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-di-methoxy-4-hydroxyphenyl) Pentane, 1, 1,
5,5-tetrakis (3-t-butyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3
-Methyl-5-tbutyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-di-t
Butyl-4-hydroxyphenyl) pentane, 1,1,
5,5-tetrakis (3-phenyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,3
5-diphenyl-4-hydroxyphenyl) pentane,
1,1,5,5-tetrakis (3,5-di-cyclohexyl-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 (3,5dimethyl-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 etc. are mentioned.

(Guest Compound) As the guest industrial germicide used in the present invention, α-bromocinnamaldehyde, n-octanol, n-heptyl acetate, phenylacetaldehyde, N, N-diethyl-m.
-Toluamide, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-
3-one, 1,2-benzisothiazolin-3-one,
2-methoxycarbonylbenzimidazole, 2,3
5,6-Tetochloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4
-Methanesulfonylpyridine, 2-thiocyanomethylbenzothiazole, 2,2-dithio-bis (pyridine-1
-Oxide), 3,3,4,4-tetrahydrothiophene-1,1-dioxide, 4,5-dichloro-1,
2-dithiolan-3-one, 5-chloro-4-phenyl-1,2-dithiolan-3-one, N-methylpyrrolidone, phenyl- (2-cyano-2-chloro-vinyl) sulfone, methylenebisthiocyanate, 2- Bromo-2
-Nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 2-bromo-4'-hydroxyacetophenone, dibromonitrile propionamide, 2-bromo-2-bromomethylglutaronitrile , Diiodomethyl paratolyl sulfone, tetramethyl thiuram disulfide, N- (fluorodichloromethylthio) phthalimide, 2- (4-thiazolyl) benzimidazole, 2-methylthio-4-t-butylamino-6-cyclopropylamino- Examples thereof include s-triazine.

The compound of the present invention comprises a sterilizer for guest industry or a solution containing the sterilizer for guest industry and tetrakisphenol as a host compound at room temperature to 100.
The guest industrial fungicide is easily included in the host compound by stirring at a temperature of several minutes to several hours for reaction to obtain a novel inclusion compound.

Specific examples of the clathrate compound of the present invention include those shown in Table 1 below.

[Table 101]

[0016]

[Table 102]

[0017]

According to the present invention, when the guest industrial bactericide is a liquid, the inclusion compound having the industrial bactericide as the guest molecule has a high selectivity by directly reacting the industrial bactericide with the powder host compound. And produced in high yield. Therefore,
According to the method of the present invention, since there is no need for an organic solvent or the like for dissolving the host compound, various manufacturing problems caused by the use of the solvent are solved.

When the guest industrial bactericide is a powder, the inclusion compound containing the industrial bactericide as a guest molecule is increased by reacting the solution of the guest compound or its solid with the powder host compound. It is produced with high selectivity and high yield.

[0019]

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.

Example 1 1.0 g of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was added to 10 ml of methanol,
Stir while warming until 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane is completely dissolved. 2,3,5,6-tetrachloro-4- (methanesulfonyl) pyridine (manufactured by ICI, trade name De
0.8 g of nsil S100) was added and reacted at 60 ° C. for 2 minutes while stirring. The reaction solution was allowed to stand at room temperature for 30 minutes, then the precipitate was suction filtered, and the residue was vacuum dried at room temperature to give 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane: 2,3,5. , 6-Tetrachloro-4- (methanesulfonyl) pyridine = 1: 4 mol of a white powder inclusion compound was obtained. The inclusion compound was confirmed by TG-DTA analysis and IR analysis. The obtained clathrate compound, the guest compound 2,3,5,6-tetrachloro-4- (methanesulfonyl) pyridine, and the host compound 1,
An IR spectrum of 1,2,2-tetrakis (4-hydroxyphenyl) ethane (KBr method, the same applies hereinafter) is shown in FIG.
2 and 3 respectively.

Example 2 1.0 g of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was added to 30 ml of ethanol,
Stir with warming until 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane is completely dissolved. To this, 2.1 g of α-bromocinnamaldehyde was added and reacted at 70 ° C. for 30 minutes while stirring. The reaction solution was allowed to stand at room temperature for a whole day and night, the precipitate was suction-filtered, the filter cake was vacuum dried at room temperature, and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane: α-bromocinnamaldehyde = 1: 0.3 mol of a pale brown white powder inclusion compound was obtained. The inclusion compound was confirmed by TG-DTA analysis and IR analysis. The IR spectra of the obtained clathrate compound and guest compound α-bromocinnamaldehyde are shown in FIGS. 4 and 5, respectively.

Example 3 1,1,2,2-tetrakis (3
0.5 g of -methyl-4-hydroxyphenyl) ethane was added, and 1,1,2,2-tetrakis (3-methyl-4-) was added.
Stir while warming until the hydroxyphenyl) ethane is completely dissolved. To this, 1.1 g of α-bromocinnamaldehyde was added and reacted at 60 ° C. for 30 minutes while stirring. The reaction solution was allowed to stand overnight at room temperature, the precipitate was suction filtered, and the residue was vacuum dried at room temperature to give 1,1,2,2.
-Tetrakis (3-methyl-4-hydroxyphenyl)
An inclusion compound of a pale brown-white powder with ethane: α-bromocinnamaldehyde = 1: 3 mol was obtained. To check inclusion compounds,
It was performed by TG-DTA analysis and IR analysis. The resulting clathrate compound and host compound 1,1,2,2-
The IR spectra of tetrakis (3-methyl-4-hydroxyphenyl) ethane are shown in FIGS. 6 and 7, respectively.

Example 4 0.5 g of 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane was added to 7 ml of ethanol to prepare 1,1,2,2-tetrakis (3). , 5
-Stir with warming until the dimethyl-4-hydroxyphenyl) ethane is completely dissolved. 1.1 g of α-bromocinnamaldehyde was added thereto and reacted at 70 ° C. for 30 minutes while stirring. The reaction solution was allowed to stand at room temperature for 30 minutes, then the precipitate was suction filtered, and the residue was vacuum dried at room temperature to give 1,1,2,2-tetrakis (3,5-dimethyl-4).
-Hydroxyphenyl) ethane: α-bromocinnamaldehyde = 1: 3 mol of a pale brown white powder inclusion compound was obtained. The inclusion compound was confirmed by TG-DTA analysis and IR.
It was done by analysis. The IR spectra of the clathrate compound and the host compound 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane obtained are shown in FIGS. 8 and 9, respectively.

Example 5 1.0 g of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was added to 30 ml of 2-propanol to prepare 1,1,2,2-tetrakis (4-hydroxyphenyl). Stir with warming until the ethane is completely dissolved. 1.9 g of N, N-diethyl-m-toluamide
Was added and reacted at 80 ° C. for 30 minutes while stirring. After allowing the reaction solution to stand at room temperature for a whole day and night, the precipitate was suction-filtered,
The residue was vacuum dried at room temperature to obtain 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane: N, N-diethyl-m-toluamide = 1: 2 mol of a pale brown white powder inclusion compound. It was The inclusion compound was confirmed by TG-DTA analysis and IR analysis. I of the obtained inclusion compound and guest compound N, N-diethyl-m-toluamide
The R spectrum is shown in FIGS. 10 and 11, respectively.

The production conditions of the clathrates described in Examples 1 to 5, the guest / host molar ratio of the clathrates, and the re-release temperature of the guest molecules are summarized in Table 2 below.

[0026]

[Table 2]

[0027]

INDUSTRIAL APPLICABILITY The novel inclusion compound having tetrakisphenol as a host compound and an industrial fungicide as a guest compound has the following various characteristics. 1) Various industrial germicides are included as guest compounds very easily. 2) Inclusion of an industrial bactericide having a boiling point near room temperature makes it thermally stable and enables heat treatment (such as injection molding). 3) It is possible to solidify and stabilize an industrial germicide that is a liquid. 4) Inclusion of an industrial bactericidal agent, which has a large effect on the human body such as skin irritation, reduces the effect on the human body and facilitates handling. Therefore, the clathrate compound of the present invention can be applied in a wide range of applications such as slime control agents, antifungal paints, cutting agent additives, resin kneading agents and ship bottom paints, and its industrial significance is extremely large.

[Brief description of drawings]

FIG. 1 is an IR spectrum diagram of the clathrate compound obtained in Example-1.

FIG. 2 is an IR spectrum diagram of guest compound 2,3,5,6-tetrachloro-4- (methanesulfonyl) pyridine.

FIG. 3 is an IR spectrum of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host compound.

FIG. 4 is an IR spectrum diagram of the clathrate compound obtained in Example-2.

FIG. 5 is an IR spectrum diagram of a guest compound α-bromocinnamaldehyde.

FIG. 6 is an IR spectrum diagram of the clathrate compound obtained in Example-3.

FIG. 7: I of host compound 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane
It is an R spectrum figure.

FIG. 8 is an IR spectrum diagram of the clathrate compound obtained in Example-4.

FIG. 9 is an IR spectrum diagram of 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane as a host compound.

FIG. 10 is an IR spectrum diagram of the clathrate compound obtained in Example-5.

FIG. 11 is a guest compound N, N-diethyl-m-
It is an IR spectrum figure of toluamide.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 35/04 9155-4H 37/02 9155-4H 37/18 Z 9155-4H 37/32 101 9155 -4H 37/34 101 9155-4H 104 9155-4H 37/44 9155-4H 41/10 A 9155-4H 43/10 G 9155-4H H 9155-4H 43/36 C 9155-4H 43/40 101 E 9155 -4H L 9155-4H 43/52 9155-4H 43/68 9155-4H 43/80 102 9155-4H 47/04 101 9155-4H 47/26 9155-4H 47/30 B 9155-4H 47/48 9155- 4H C07C 37/86 39/367 9159-4H 43/23 D 7419-4H C07D 339/04 // A01N 25/22 9155-4H 25/32 9155-4H C07D 213/71 275/03

Claims (3)

[Claims] 1. An inclusion compound comprising a host compound of tetrakisphenol represented by the general formula 1 and an industrial fungicide which is a guest compound. [Chemical 1] (In the formula, X represents (CH ₂ ) n, n represents 0, ¹ , 2 or 3, and R ^{1 to} R ⁸ are each a hydrogen atom, a lower alkyl group, a halogen atom, a lower alkoxy group or a substituted one). Or any of the phenyl groups which may be present.) 2. An industrial germicide which is a guest compound is α-
Bromcinnamaldehyde, n-octanol, n-heptyl acetate, phenylacetaldehyde, N, N
-Diethyl-m-toluamide, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-methoxycarbonyl Benzimidazole, 2,3,5,6-tetochloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2,4
6-trichlorophenylmaleimide, 2,3,5,6-
Tetrachloro-4-methanesulfonylpyridine, 2-thiocyanomethylbenzothiazole, 2,2-dithio-bis (pyridine-1-oxide), 3,3,4,4-tetrahydrothiophene-1,1-dioxide, 4,5
-Dichloro-1,2-dithiolan-3-one, 5-chloro-4-phenyl-1,2-dithiolan-3-one, N
-Methylpyrrolidone, phenyl- (2-cyano-2-chlorovinyl) sulfone, methylenebisthiocyanate,
2-bromo-2-nitropropane-1,3-diol,
2,2-dibromo-2-nitroethanol, 2-bromo-4'-hydroxyacetophenone, dibromonitrilepropionamide, 2-bromo-2-bromomethylglutaronitrile, diiodomethylparatolylsulfone, tetramethylthiuramdi Sulfide, N- (fluorodichloromethylthio) phthalimide, 2- (4-thiazolyl) benzimidazole and 2-methylthio-4-t-
The inclusion compound according to claim 1, which is at least one selected from the group consisting of butylamino-6-cyclopropylamino-s-triazine. 3. The method for producing an inclusion compound according to claim 1, wherein the host compound of tetrakisphenol represented by the general formula 1 is reacted with an industrial germicide which is a guest compound.