JP3082264B2 - Method for producing clathrate compound and clathrate compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an clathrate compound and to a clathrate compound, and more particularly to 5-chloro-2-methyl-clathrate.
An inclusion compound using a host compound that stably includes an organic germicide such as 4-isothiazolin-3-one or an organic solvent such as ethanol having a bactericidal action or a natural essential oil such as cineol as a fragrance component and gradually releases the same . And a clathrate compound using the host compound.

[0002]

2. Description of the Related Art In a water system such as a cooling water system or a paper pulp papermaking system of various factory facilities, slime of various fungi or animals and plants adheres and causes various obstacles.

[0003] Conventionally, in order to prevent obstacles due to slime and the like, antibacterial agents (slime control agents) are generally used because their treatment methods are relatively simple and inexpensive. In particular, 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as "Cl-MIT") as an antibacterial agent is excellent in antibacterial activity, and is therefore suitable for paper pulp for cooling water systems. It is widely used as a slime control agent for various water systems, such as for swimming pools, fungicides, algicides, and fungicides.

This Cl-MIT is generally obtained by halogenating β-thioketoamide in an inert organic ester solvent such as acetate, treating β-substituted thiocyanoacrylamide or thiosulfatoacrylamide with an acid to obtain isothiazolone. It is further produced by a method of halogenation (Japanese Patent Publication No. 46-21240).

[0005]

However, in any of the above and the above methods, the Cl-MIT
Cannot be selectively obtained, and as a by-product, 2-methyl-, which has an antibacterial activity 10 times lower than that of Cl-MIT,
Only those containing 4-isothiazolin-3-one (hereinafter abbreviated as "MIT") are obtained.

Moreover, according to the prior art, it is not possible to selectively remove only Cl-MIT from the reaction product mixture.
In fact, MIT, which has inevitable antibacterial activity, is used in a mixed state.

On the other hand, such Cl-MIT is an antibacterial agent having an excellent antibacterial activity to some extent, but it is extremely irritating to the skin and requires great care in handling. In addition, when it is put into water and used, it loses its activity by reacting with organic substances (amines, reducing substances, etc.) in the water, so that it has been difficult to maintain antibacterial activity for a long time. Moreover, because it is easily soluble in water, when used in underwater antifouling paints,
Since it is quickly eluted in water, it has a problem that its antifouling effect cannot be maintained for a long time.

As described above, conventionally used water-soluble antibacterial agents are extremely inconvenient in handling, antibacterial effect, etc. due to toxicity, decrease in antibacterial activity, solubility in water, and the like. Met.

The same can be said for organic solvents such as ethanol having a bactericidal action and natural essential oils such as cineol which is a fragrance. For example, natural essential oils such as 1,8-cineole (hereinafter abbreviated as "cineole") can be used as fragrances, antibacterial agents, fungicides, etc., but natural essential oils are often highly volatile, and their effects are high. Was difficult to maintain for a long time. Therefore, development of a sustained-release insecticide or a sustained-release fragrance that can maintain the insecticidal effect and fragrance for a long period of time and has excellent handleability is desired.

[0010] The present invention is to solve the above conventional problems, superior sustained release antimicrobial agent, slow-release insecticide, using sulfo strike compound can provide sustained release fragrance capsule Bonding
It is an object of the present invention to provide a method for producing a product and an inclusion compound using the host compound.

[0011]

Manufacturing <br/> method for producing clathrate compound of the present invention, in order to solve the problem] is represented by the following formula, compounds containing triphenyl carbinol group (hereinafter, "triphenyl carbinol compound it may be referred to as a ".), and inclusion compound
Characterized in that it is used as a host compound for producing
And

[0012]

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[0013] clathrate compound of the present invention, above host compound
A triphenylcarbinol compound, wherein the guest compound is an organic germicide, a natural essential oil, or an organic solvent.

That is, the present inventors have previously proposed 2,2 ′ represented by Chemical Formula 4 as a host compound to achieve the above object.
A host compound for producing an inclusion compound comprising -bis (α-hydroxydiphenylmethyl) biphenyl was found, and a patent application was previously filed (JP-A-2-178243).

[0015]

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The present invention has been completed as a result of intensive studies to obtain more excellent effects than the host compound described in JP-A-2-178243.

Hereinafter, the present invention will be described in detail.

The triphenylcarbinol compound as the host compound according to the present invention is not particularly limited.
For example, compounds represented by the following formulas 5 to 10 can be mentioned.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025] Such triphenyl carbinol compound may, for example, according to the reaction formula shown in the following chemical formula 1 1 to 1 3 are readily prepared. In the following, Me indicates a methyl group and Et indicates an ethyl group.

First, Compound ( 1 ) can be synthesized as in Chemical Formula 11 using o, m, p-bromobenzoic acid as a starting material.

[0027]

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Further, compounds ~ is an intermediate product of the synthesis as starting material, of 1 2, it may be synthesized as of 1 3.

[0029]

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[0030]

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[0031] The host compound according to the present invention may be a azobenzene compound, represented by the following formula 1 4. The compounds and compounds are cis, tr
For example, the trans form takes in one molecule of acetone, and the cis form takes up two molecules of acetone. Then, c which took in two molecules of acetone
The is-form crystal is transformed into a trans-form crystal in which one molecule of acetone is taken in by heating. Conversely, the trans-form becomes a cis-form by irradiation with ultraviolet rays.

[0032]

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The host compound according to the present invention is useful as a host compound capable of forming a stable inclusion compound by using various organic solvents, bactericides, fragrances and the like as guest compounds, and is useful as a perfume, agrochemical, industrial bactericidal agent. Agents, etc. for the purpose of maintaining its effect for a long time, or pH,
As a stabilizer for stabilizing compounds that are unstable to heat, ultraviolet light, etc. by encapsulating them, and further utilizing its selective inclusion ability, it is widely used for separation and purification of various compounds. Very useful for applications.

The clathrate compound of the present invention comprises the above-mentioned triphenylcarbinol compound as a host compound and a guest compound containing an organic solvent, a natural essential oil or an organic fungicide.

In the clathrate compound of the present invention, as an organic solvent, DMSO (dimethyl sulfoxide), DMF
(Dimethylformamide), pyridine, dioxane, ethanol, acetonitrile, acetone, trichloroacetic acid, t-butanol, and others described in the column of guest compounds described below, but are not limited thereto. Examples of natural essential oils include cineol, cypress oil, quince, jasmine, lemon, cassia oil, cinnamon leaf, menthol, rosemary, palmarosa oil, lavender, spearmint oil, and mentha avensis.

As the organic fungicide, the above-mentioned Cl-
MIT, hydrazine and the like.

The clathrate compound of the present invention can be easily synthesized, for example, by mixing a host compound and a guest compound at a predetermined ratio at room temperature.

[0038]

The host compound according to the present invention can selectively, efficiently and stably include an organic solvent, a natural essential oil, an organic germicide or the like as a guest compound.

The clathrate compound in which the host compound is clathrated with an organic fungicide can be in a solid state. Since the fungicide component gradually dissolves in water from the inclusion compound, the antibacterial activity can be maintained for an extremely long time.
The inclusion of the fungicide reduces its toxicity, skin irritation and the like. In addition, it is possible to prevent the antibacterial activity from decreasing due to reaction with other substances during use.

Therefore, the obtained inclusion compound can be effectively used as a sustained-release antibacterial agent capable of maintaining the antibacterial activity for an extremely long time.

On the other hand, the organic solvent and the natural essential oil also become a solid state by being included in the inclusion compound with the host compound according to the present invention. For this reason, for example, a liquid fragrance has a drawback that the liquid is spilled when the container falls down, but the clathrate compound of the present invention eliminates such a concern and simplifies the handling.

Further, by making the fragrance component or the insecticidal component clathrate, the fragrance component and the like gradually evaporate from the clathrate compound, and the volatilization rate is reduced, so that the fragrance and the insecticidal effect can be maintained more continuously. By changing the particle size of the clathrate, the contact area with the atmosphere can be adjusted, and the volatilization rate of the fragrance component and the insecticidal component can be adjusted. Moreover, it can be easily formed into various shapes.

[0043] Furthermore host compound according to the present invention, the powder of the guest compound, stabilization, on which also helps concentration and the like, by utilizing the fact that the contact selectively packaging a guest compound as a host compound, a guest compound It is also useful for separation and purification of.

[0044]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 A host compound (compounds 6 to 10 ) shown in Table 1 and a guest compound were used in a molar ratio of host compound: guest compound = 1: 1 or 1: 2. And mixed at room temperature.

As a result, the crystal forms, m.p. p.
A stable inclusion compound having an inclusion ratio of g / h (guest compound / host compound (molar ratio)) was obtained. In Table 1,
N indicates needle crystals, P indicates prism crystals, and nc indicates unknown.

[0047]

[Table 1]

Example 2, Comparative Examples 1 and 2 The clathrate compound of the host compound and ethanol shown in Chemical formula 6 (see No. 2 in Table 1) was prepared in such a manner that the ethanol content was 0.
It was taken in a petri dish so as to become 2 g, left at room temperature in an open state, and the ethanol reduction rate was determined from the weight change. Table 2 shows the results.

[0049] For comparison, only those 0.2g collected ethanol (Comparative Example 1), 2,2 represented by the aforementioned formula 4 '
An inclusion compound (molar ratio 1: 1) of -bis (α-hydroxydiphenylmethyl) biphenyl and ethanol was collected so that the ethanol content was 0.2 g (Comparative Example 2). The reduction rate was examined, and the results are shown in Table 2.

From Table 2, it is clear that the clathrate compound of the present invention is excellent in the sustained release of ethanol.

[0051]

[Table 2]

Examples 3 and 4 and Comparative Examples 3 and 4 The host compounds shown in Chemical formulas 6 and 9 (Example 3),
(Example 4) Inclusion Compound of Cineol (N in Table 1)
o. 14) were taken in a petri dish so that the cineol content became 0.2 g, and the reduction rate was examined in the same manner as in Example 2. Further, only cineole those 0.2g collected (Comparative Example 3), represented by Formula 4 2,2'
Similarly, the inclusion compound (comparative example 4) of the inclusion compound of bis (α-hydroxydiphenylmethyl) biphenyl and cineol (molar ratio 1: 2) having a cineol content of 0.2 g was similarly reduced in cineol. The rate was checked and 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 cineol.

[0054]

[Table 3]

Example 5, Comparative Examples 5 and 6 The clathrate compound (molar ratio 1: 1) of the host compound and Cl-MIT shown in Chemical Formula 6 was prepared by adding Cl-MIT content of 0.2.
g into 1 liter of ultrapure water and 500
The dissolution rate of Cl-MIT into water was examined while stirring with a stirrer at rpm.

[0056] Similarly, when only Cl-MIT was 0.2g introduced (Comparative Example 5), represented by Formula 4 2,2'
An inclusion compound (molar ratio 1: 1) of bis (α-hydroxydiphenylmethyl) biphenyl and Cl-MIT was converted to Cl
Also in the case where the MIT content was adjusted to be 0.2 g (Comparative Example 6), the elution rate of Cl-MIT was examined, and the results are shown in Table 4.

As shown in Table 4, the clathrate compound of the present invention was
It is clear that MIT has excellent sustained release properties.

[0058]

[Table 4]

[0059]

As described in detail above, the host compound according to the present invention is extremely useful as a host molecule that stably includes an organic solvent, a natural essential oil, an organic germicide and the like.

Thus, the method for producing the clathrate compound of the present invention
Clathrate compound of the present invention obtained by a water-soluble disinfectant,
It can be used for powdering, stabilizing, concentrating, separating, purifying natural essential oils and the like.In addition, as a sustained-release antibacterial agent containing an enclosed water-soluble bactericide as an active ingredient, Slowly elutes into water to maintain antibacterial activity for a long time. Solid form enables easy molding such as tableting, easy handling, fungicide toxicity, skin irritation, etc. Thus, the present invention has excellent effects such as improvement of the working environment and improvement of safety, and prevention of the active ingredient from reacting with other substances to reduce the antibacterial activity.

Also, as a sustained-release fragrance containing natural essential oil as a fragrance component, the fragrance component gradually evaporates into the atmosphere, so that the aromaticity can be maintained for a long time. It is easy to mold, easy to mold, and easy to control the volatilization of fragrance components by changing the particle size of the clathrate compound. The effect is achieved.

Further, it is useful as a sustained-release insecticide containing an organic solvent or natural essential oil as an insecticidal component.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09K 3/00 110 C09K 3/00 110 C11B 9/00 C11B 9/00 Z (72) Inventor Minoru Yagi Minoru Nishishinjuku, Shinjuku-ku, Tokyo 3-4-7 Kurita Water Industries Ltd. (56) Reference Chem. Ber. , 1990, Vol. 123, No. 11, p. 2207-2226 Chem. Ber. No. 103, No. 103, Vol. 4, p. 1107-1118 (58) Field surveyed (Int. Cl. ⁷ , DB name) C07B 63/02 C07C 33/28 C07C 245/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound having a triphenylcarbinol group represented by the following formula is used for producing an inclusion compound.
Clathration characterized by being used as a host compound for
Manufacturing method of compound . Embedded image 2. A host compound and a guest compound and become more clathrate compound, a host compound is represented by the following formula,
A compound containing a triphenylcarbinol group,
An inclusion compound in which the guest compound is an organic fungicide, a natural essential oil, or an organic solvent. Embedded image