JPH0753427A - Host compound and clathrate compound - Google Patents

Abstract

PURPOSE:To obtain a new host compound, composed of specific tetrakis(hydroxyphenyl)xylenes and capable of changing its own color following the capturing and releasing of an organic compound to be a guest such as an industrial germicide, various perfumes or an essential oil. CONSTITUTION:This host compound is composed of a tetrakis(hydroxyphenyl) xylene expressed by the formula (R1 to R16 are each H, halogen, an alkyl, an alkoxy), e.g. alpha,alpha,alpha',alpha'-tetrakis(4-hydroxyphenyl)-p-xylene. Furthermore, this new clathrate compound is composed of the tetrakis(hydroxyphenyl)xylene expressed by the formula and a guest organic compound, e.g. a clathrate compound in which the host compound is the alpha,alpha,alpha',alpha'-tetrakis(hydroxyphenyl)-p- xylene and the guest compound is acetonitrile. The exemplified host compound is obtained by reacting terephthaladehyde with phenol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a host compound and an inclusion compound, and more specifically to tetrakis (hydroxyphenyl) xylene as a host compound so that trapping and release of a guest organic compound can be visually recognized. Clathrate compound.

[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,
JP-A-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, an inclusion compound having tetrakisphenol as a host is known to have tetrakis (4-hydroxyphenyl) ethane as a host (Tetrahedron Letters., 33 (42), 6319).
(1992).).

Further, as an inclusion compound whose color is changed by inclusion of an organic compound, JP-A-3-232 is known.
The one described in Japanese Patent No. 861 is known.

[0004]

The bonding methodology which occupies the mainstream of the above-mentioned solid phase clathrate compounds is intermolecular (host-guest) interaction due to hydrogen bonding, etc., but this effect is confirmed. Infrared spectroscopy is the only method available as a means, and has been a cause of putting a framework within its application range (for example, a sensor).

The present invention has been made in view of such circumstances, and comprises a host compound of tetrakis (hydroxyphenyl) xylene capable of including a guest organic compound, and a guest organic compound included in the host compound. It is an object of the present invention to provide a clathrate compound which improves the stability, handleability, processability, etc. of an active ingredient and is capable of visually recognizing trapping and release of a guest organic compound.

[0006]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present invention revealed that a specific tetrakis (hydroxyphenyl) xylene host compound was
The present invention has been completed by discovering that the color of the organic compound used as a guest is changed, that is, the inclusion compound is generated, and the guest is released. The present invention will be described in detail below.

The present invention is a host compound composed of tetrakis (hydroxyphenyl) xylene represented by the general formula 2, and an inclusion compound using the compound as a host compound.

[0008]

[Chemical 2]

In the above general formula 2, R _{1 to} R ₁₆ are
Hydrogen atom, halogen atom such as F, Cl, Br, I, etc., alkyl group such as methyl group, ethyl group, isopropyl group, propyl group, butyl group, t-butyl group, sec-butyl group, methoxy group, ethoxy group, etc. , Any one selected from the group consisting of alkoxy groups such as isopropoxy group, butoxy group and t-butoxy group.

In addition to the compound represented by the above general formula 2,
In the present invention, tetrakis (hydroxyphenyl) xylene having a hydroxyl group substituted at the 2- or 3-position of the benzene ring can also be used as a host compound as long as it has an inclusion ability.

The tetrakis (hydroxyphenyl) xylenes of the present invention include, for example, α, α, α ', α'.
-Tetrakis (4-hydroxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxyphenyl) -m-xylene, α, α, α', α'-tetrakis (4-hydroxy) Phenyl) -o-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methylphenyl) -p-xylene, α, α, α ′,
α'-tetrakis (4-hydroxy-3-chlorophenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3-fluorophenyl) -p-xylene, α, α, α' , Α′-Tetrakis (4-hydroxy-3-ethylphenyl) -p-xylene, α, α,
α ', α'-tetrakis (4-hydroxy-3-isopropylphenyl) -p-xylene, α, α, α', α '
-Tetrakis (4-hydroxy-3-chlorophenyl)
-M-xylene, α, α, α ', α'-tetrakis (4
-Hydroxy-3-fluorophenyl) -m-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methylphenyl) -m-xylene, α, α, α ′,
α′-tetrakis (4-hydroxy-3-ethylphenyl) -m-xylene, α, α, α ′, α′-tetrakis (4-hydroxy-3-isopropylphenyl) -m-
Xylene, α, α, α ′, α′-tetrakis (4-hydroxy-3-methylphenyl) -o-xylene, α,
α, α ', α'-tetrakis (4-hydroxy-3-chlorophenyl) -o-xylene, α, α, α', α'-
Tetrakis (4-hydroxy-3-fluorophenyl)-
o-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-ethylphenyl) -o-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Isopropylphenyl) -o-xylene, α, α,
α ', α'-tetrakis (4-hydroxy-3-t-butylphenyl) -p-xylene, α, α, α', α'-
Tetrakis (4-hydroxy-3-bromophenyl)-
p-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-iodophenyl) -p-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methoxyphenyl) -p-xylene, α, α, α ′,
α'-Tetrakis (4-hydroxy-3-ethoxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3-isopropoxyphenyl)-
p-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-t-butoxyphenyl) -p-xylene, α, α, α ′, α′-tetrakis (3-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetrakis (3- Hydroxy-4-chlorophenyl) -p-
Xylene, α, α, α ′, α′-tetrakis (3-hydroxy-4-bromophenyl) -p-xylene, α,
α, α ', α'-tetrakis (3-hydroxy-4-iodophenyl) -p-xylene, α, α, α', α'-
Tetrakis (3-hydroxy-4-methoxyphenyl)
-P-xylene, α, α, α ', α'-tetrakis (3
-Hydroxy-4-ethoxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (2-hydroxyphenyl) -p-xylene, α, α, α', α'-tetrakis (2-hydroxy) -4-chlorophenyl) -p-
Xylene, α, α, α ′, α′-tetrakis (2-hydroxy-4-methylphenyl) -p-xylene, α,
α, α ′, α′-tetrakis (2-hydroxy-4-methoxyphenyl) -p-xylene, α, α, α ′,
α'-tetrakis (4-hydroxy-3,5-dichlorophenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3,5-dimethylphenyl)
-P-xylene, α, α, α ', α'-tetrakis (4
-Hydroxy-3-chloro-5-methylphenyl) -p
-Xylene, α, α, α ', α'-tetrakis (4-hydroxyphenyl) -3-chloro-p-xylene, α,
α, α ′, α′-tetrakis (4-hydroxyphenyl) -3-fluoro-p-xylene, α, α, α ′, α ′
-Tetrakis (4-hydroxyphenyl) -3-methyl-p-xylene, α, α, α ', α'-tetrakis (4
-Hydroxyphenyl) -3-methoxy-p-xylene, α, α-bis (4-hydroxyphenyl) -α ′,
α'-bis (3-chloro-4-hydroxyphenyl)-
p-xylene, α, α-bis (4-hydroxyphenyl) -α ′, α′-bis (3-fluoro-4-hydroxyphenyl) -p-xylene, α, α-bis (4-hydroxyphenyl)- α ', α'-bis (3-methyl-4-
Hydroxyphenyl) -p-xylene, α, α-bis (4-hydroxyphenyl) -α ′, α′-bis (3-
Methoxy-4-hydroxyphenyl) -p-xylene,
α, α-bis (4-hydroxyphenyl) -α ', α'
-Bis (3-fluoro-4-hydroxyphenyl) -p-
Xylene, α, α, α′-tris (4-hydroxyphenyl) -α′-3-chlorophenyl-p-xylene,
α, α, α'-tris (4-hydroxyphenyl)-
α′-3-methylphenyl-p-xylene, α, α,
α'-tris (4-hydroxyphenyl) -α'-3-
Examples thereof include methoxyphenyl-p-xylene, α, α, α′-tris (4-hydroxyphenyl) -α′-3-fluorophenyl-p-xylene.

The guest organic compound included in the tetrakis (hydroxyphenyl) xylene of the present invention includes:
Water, methanol, ethanol, isopropanol, 2-
Alcohols such as propanol, ketones such as acetonitrile, acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane and ethyl ether, acetic acid esters such as methyl acetate, ethyl acetate and isopropyl acetate, even if substituted Good pyridine, optionally substituted pyrrole, optionally substituted pyrimidine, optionally substituted pyridazine, optionally substituted imidazole, optionally substituted nitrogen-containing heterocyclic compound such as pyrazole, Organic acids such as acetic acid, propionic acid, citric acid, sulfamic acid, 5-chloro-2-methyl-4-isothiazolin-3-one (CM
I), hinokitiol, cineole, thymol, menthol, terpineol, borneol, nopol, citral, citroneol, citraneol, linalool, dimethyloctanol, quince wax, jasmine, essential oils such as lemon, fragrances and the like.

The clathrate compound of the present invention usually comprises an organic compound as a guest and a tetrakis (hydroxyphenyl) xylene of the present invention as a host at room temperature to 100 ° C. in the presence of an inert solvent. It can be obtained by stirring for 1 minute to several hours to react.

The present invention will be described in more detail below with reference to examples. Example 1 (Host Compound) Synthesis of TXP (α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene) In a 500 ml-3 neck flask equipped with a stir bar and thermometer,
Terephthalaldehyde 10.0g (0.071mo
1) and 70.0 g (0.74 mol) of phenol were charged, and 5 ml of 35% hydrochloric acid was added dropwise while stirring at 50 ° C. Then, the reaction was terminated by stirring at 50 ° C. for 3 hours as it was. After the reaction was completed, unreacted phenol was removed under reduced pressure at 100 ° C. to obtain an orange solidified product. The solidified product was washed with chloroform and vacuum dried at 100 ° C. to obtain 32.0 g (yield 91.2%) of pale orange powder. It was confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum that this powder was α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene. H ^{1 of} TXP
NMR spectrum (solvent: d ⁴ -MeOH, internal standard: T
MS) is shown in FIG. 1, and IR spectrum (KBr method, the same applies hereinafter) is shown in FIG.

(Example 2) Preparation of samples: 1 to 5 TXP [α, α, α ', α'-tetrakis (4-hydroxyphenyl) -p-xylene] as a host compound
2.11 mmol (1.0 g) was added to 10 ml of an organic compound to be used as a guest, and TXP was completely dissolved and then reacted for a predetermined time, and the reaction solution was allowed to stand at room temperature to precipitate crystals. After this precipitate was separated by filtration, it was vacuum dried at room temperature to obtain Samples 1 to 5 as the inclusion compound of the present invention. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E. (Commission
International d'Eclariag
e) Color measurement values based on the display method are summarized in Table 1.

The IR spectrum of the obtained inclusion compound of the present invention in which the guest compound is acetonitrile (Sample 2) is shown in FIG. 3, which is 1,4-dioxane (Sample 3).
The IR spectrum of benzaldehyde (Sample 4) is shown in FIG. 5, and the IR spectrum of pyridine (Sample 5) is shown in FIG.

(Example 3) Preparation of sample: 6 2.11 mmol (1.0) of TXP as a host compound
g) was added to 10 ml of benzene as a guest compound, and the mixture was heated and stirred until benzene boiled, and then the reaction solution was allowed to stand at room temperature to precipitate crystals. After the crystals were separated by filtration, vacuum drying was carried out at room temperature to obtain a clathrate compound sample 6 of the present invention. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E. (Commission
International d'Eclariag
e) Table 1 shows color measurement values based on the display method.

(Example 4) Preparation of sample: 7 TXP 2.11 mmol (1.0
g) was added and stirred with warming until the TXP was completely dissolved. 5 ml of the guest compound, cineole, was gradually added dropwise to this, and the mixture was reacted at 50 ° C. for 5 minutes with stirring.
The reaction solution was left at room temperature to precipitate crystals. After this precipitate was separated by filtration, it was vacuum dried at room temperature to obtain Sample 7, which was the inclusion compound of the present invention. The inclusion compound can be confirmed by TG
-DTA measurement and IR measurement were performed. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E.
(Commission International
Table 1 shows the color measurement values based on the d'Eclarage) notation. The IR spectrum of Sample 7 is shown in FIG.

(Example 5) Preparation of sample: 8 2.11 mmol (1.0 g) of TXP was added to 10 ml of water, and the mixture was stirred at 50 ° C for 20 minutes. Here caisson WT
(Rohm & Haas) 20g (11.4 as CMI
(mmol) was gradually added dropwise, and the mixture was reacted at 25 ° C. for 24 hours while stirring. Then, this liquid was allowed to stand at room temperature for a while, the precipitate was suction-filtered, and the filtered product was vacuum dried at room temperature to obtain a red-orange powder sample 8. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Also,
The color tone of the clathrate compound was measured using a colorimeter. C.
I. E. (Commission Internet
Table 2 shows the color measurement values based on the nal d'Eclairage) display method. The analytical values of the water-soluble bactericide (Caisson WT) used in Example 5 are as follows. CMI (5-chloro-2-methyl-4-isothiazolin-3-one): 10.1 wt% MI (2-methyl-4-isothiazolin-3-one): 3.8 wt% Remainder: magnesium chloride + magnesium nitrate + water The IR spectrum of Sample 8 is shown in FIG.

(Example 6) Sample: Change in color tone due to re-release of guest compounds 1 to 5 The inclusion compounds obtained in Example 1 were each exposed to the hot air of a dryer to perform a guest compound release test. The color of each clathrate compound changed to the original color of the host compound.

From these results, the host compound of the present invention,
It is clear that the host compound has a different color from the clathrate compound of the present invention in which the guest compound is clathrated, and the presence or absence of the guest compound can be known by the color change.

(Example 7) Sample: Sustained release of guest compound of 7 Sample 7 obtained in Example 3 and comparative sample 1,8-cineole alone were adjusted to 0.6 g in terms of guest compound. Then, it was collected in a petri dish and set in a desiccator kept at 25 ° C. Dry air was introduced into this at a rate of 250 ml / min, and the weight loss was measured over time. The results are shown in Table 3. From Table 3, it is clear that the clathrate compound of the present invention is excellent in sustained release of the active ingredient.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

INDUSTRIAL APPLICABILITY The present invention is an inclusion compound in which the color tone of a host compound is changed by including an organic compound as a guest. Conventionally, it was not possible to determine whether or not the guest molecule was clathrated only by the visual sense, but according to the clathrate compound of the present invention, industrial fungicides, various flavors, trapping and release of guest organic compounds such as essential oils can be performed. A visually recognizable inclusion compound is provided.

Furthermore, the host compound of the present invention, tetrakis (hydroxyphenyl) xylene, can include a wide range of organic compounds, and the stability, handleability, processability and the like of the host compound are improved.

[Brief description of drawings]

FIG. 1 H ¹ —N of TXP, a guest compound of the present invention
MR spectrum

FIG. 2 is an IR spectrum of TXP which is a guest compound of the present invention.

FIG. 3 is an IR spectrum of Sample 2 which is an inclusion compound of the present invention.

FIG. 4 is an IR spectrum of Sample 3, which is an inclusion compound of the present invention.

FIG. 5: IR spectrum of sample 4 which is an inclusion compound of the present invention

FIG. 6 is an IR spectrum of Sample 5, which is an inclusion compound of the present invention.

FIG. 7: IR spectrum of sample 7, which is an inclusion compound of the present invention

FIG. 8 is an IR spectrum of Sample 8 which is an inclusion compound of the present invention.

Claims (2)

[Claims] 1. A host compound comprising tetrakis (hydroxyphenyl) xylene represented by the general formula 1. [Chemical 1] (In the formula, each of R _{1 to} R ₁₆ represents one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group.) 2. An inclusion compound comprising the tetrakis (hydroxyphenyl) xylene according to claim 1 and a guest organic compound.