JP2961921B2 - Host compounds and clathrates - Google Patents

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 clathrate compound, and more particularly to an organic bactericide such as 5-chloro-2-methyl-4-isothiazolin-3-one and a natural compound such as cineol as a fragrance component. The present invention relates to a host compound capable of stably releasing an essential oil or an organic solvent such as ethanol having a bactericidal action and gradually releasing the same, and an inclusion 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 the 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.

In order to solve the above-mentioned conventional problems, the present invention provides a host compound for producing an inclusion compound, which can provide excellent sustained-release antibacterial agents, sustained-release insecticides, and sustained-release fragrances. An object of the present invention is to provide an inclusion compound using the host compound.

[0011]

The host compound for producing an inclusion compound according to claim 1 is a compound having a triphenylcarbinol group represented by the following formula (hereinafter referred to as "triphenylcarbinol compound"). In some cases).

[0012]

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[0013] The clathrate compound of claim 2 comprises the host compound of claim 1 and a guest compound, wherein the guest compound is an organic fungicide, a natural essential oil or an organic solvent.

That is, the present inventors have previously proposed, as a host compound for achieving the above object, a 2,2 ′ compound represented by the following chemical formula (3).
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-based compound as the host compound of the present invention is not particularly limited, and examples thereof include compounds represented by the following chemical formulas (4) and (5). The compound,
Is a trans, cis optical isomer.

[0018]

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[0019]

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Such a triphenylcarbinol-based compound is easily produced, for example, according to the reaction formula shown in the following chemical formula 6.

[0021]

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The host compound of the present invention comprises various organic solvents,
It is useful as a host compound capable of forming a stable inclusion compound using a bactericide or a fragrance as a guest compound, and is intended to maintain its effect for a long time, such as a perfume, a pesticide, or an industrial bactericide. Field, or pH, heat,
As a stabilizing agent for stabilizing compounds that are unstable to ultraviolet light, etc. by encapsulating them, and further utilizing their selective inclusion ability, for a wide range of applications such as separation and purification of various compounds Extremely useful.

The clathrate compound of the present invention comprises the above 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 later, 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.

[0027]

The host compound of the present invention can selectively, efficiently and stably include an organic solvent, a natural essential oil, an organic germicide and 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 clathrate 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 of 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.

In addition, the inclusion of the scent component or the insecticidal component causes the scent component or the like to gradually evaporate from the clathrate compound, thereby reducing the rate of volatilization. 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.

Further, the host compound of the present invention is useful for pulverizing, stabilizing, concentrating, etc. the guest compound, and utilizing the selective inclusion of the guest compound as the host compound to form the guest compound. It is also useful for separation and purification.

[0033]

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 shown in Table 1 (compounds represented by Chemical Formulas 4 and 5) 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, a stable inclusion compound having the inclusion ratio (guest compound / host compound (molar ratio)) shown in Table 1 was obtained.

[0035]

[Table 1]

Example 2 and Comparative Examples 1 and 2 The clathrate compound of the host compound and ethanol shown in Chemical formula 4 (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. 0.2 g of ethanol alone for comparison
What was collected (Comparative Example 1),
An inclusion compound of 2'-bis (α-hydroxydiphenylmethyl) biphenyl and ethanol (molar ratio 1: 1)
With respect to a sample collected so that the ethanol content was 0.2 g (Comparative Example 2), the ethanol reduction rate was similarly 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 sustained release of ethanol.

[0037]

[Table 2]

Example 3, Comparative Examples 3 to 6 An inclusion compound (see No. 13 in Table 1) of the host compound (Example 3) and cineol shown in Chemical Formula 4 (see No. 13 in Table 1) has a cineol content of 0.2 g. In a petri dish, the reduction rate was examined in the same manner as in Example 2. Further, 0.2 g of cineol alone was collected (Comparative Example 3).
An inclusion compound (molar ratio 1: 2) of 2,2'-bis (α-hydroxydiphenylmethyl) biphenyl and cineol represented by the following formula:
In the same manner, the inclusion compound of cineol and the inclusion compound of cineol were sampled so that the cineol content was 0.2 g (Comparative Examples 4, 5, and 6), and the cineol reduction rate was similarly examined. The results are shown in Table 3. From Table 3, it is clear that the clathrate compound of the present invention is excellent in the sustained release of cineol.

[0039]

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[0040]

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[0041]

[Table 3]

[0042]

As described in detail above, the host compound of 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 clathrate compound of the present invention obtained using the host compound of the present invention can be used for pulverization, stabilization, concentration, separation, purification, etc. of water-soluble bactericides, natural essential oils and the like. In particular, as a sustained-release antibacterial agent containing the included water-soluble bactericide as an active ingredient, the active ingredient can be gradually eluted into water, so that the antibacterial activity can be maintained for a long time. Molding such as tableting is possible, and handling is easy.Since toxicity of the germicide, skin irritation, etc. are reduced, the working environment is improved and safety is improved.
It has excellent effects such as preventing the active ingredient from reacting with other substances to reduce the antibacterial activity.

Further, as a sustained-release fragrance containing natural essential oil as a fragrance component, the fragrance component gradually evaporates into the atmosphere so that 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 also useful as a sustained-release insecticide containing an organic solvent or natural essential oil as an insecticidal component.

Continuation of front page (56) References JP-A-4-283528 (JP, A) JP-A-61-233653 (JP, A) JP-A-61-93165 (JP, A) (58) Fields investigated (Int .Cl. ⁶ , DB name) C07C 33/28 C07C 63/02 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A host compound for producing an inclusion compound having a triphenylcarbinol group represented by the following formula: Embedded image 2. An inclusion compound comprising the host compound of claim 1 and a guest compound, wherein the guest compound is an organic fungicide, a natural essential oil or an organic solvent.