JPH04283528A - Method for producing clathrate compounds and clathrate compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to host compounds and clathrate compounds, and in particular organic fungicides such as 5-chloro-2-methyl-4-isothiazolin-3-one and natural compounds such as cineole, which is a fragrance component. The present invention relates to a host compound that stably clathrates an essential oil or an organic solvent such as ethanol having a bactericidal effect to achieve sustained release, and an clathrate compound using this host compound.

0002

2. Description of the Related Art In water systems such as cooling water systems of various factory facilities and pulp and paper manufacturing systems, slimes of various fungi and animals and plants adhere, causing various problems.

Conventionally, in order to prevent problems caused by slime and the like, antibacterial agents (slime control agents) have generally been used because the treatment method is relatively simple and inexpensive. Therefore, 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter referred to as "
It is abbreviated as "Cl-MIT". ) has excellent antibacterial activity, and is widely used as a slime control agent, bactericide, algaecide, and fungicide for various water systems such as cooling water systems, paper pulp, and swimming pools.

[0004] This Cl-MIT is generally
It is produced by a method in which thioketoamide is halogenated in an inert organic ester solvent such as acetic acid ester, and β-substituted thiocyanoacrylamide or thiosulfate acrylamide is treated with acid to obtain an isothiazolone, which is then further halogenated ( Special Publication No. 46-21240)
.

[0005]

[Problem to be solved by the invention] However, the above ■
In both methods of and (1), Cl-MIT
It is not possible to selectively obtain only 2-methyl-MIT, and as a by-product, 2-methyl-
Only a product containing 4-isothiazolin-3-one (hereinafter abbreviated as "MIT") can be obtained.

Moreover, with conventional techniques, it is not possible to selectively extract only Cl-MIT from the reaction product mixture;
The reality is that MIT, which has poor antibacterial activity, is unavoidably used in a mixed state.

On the other hand, although such Cl-MIT is an antibacterial agent having a certain degree of excellent antibacterial activity, it is extremely irritating to the skin and requires great care in handling. Furthermore, when used in water, it reacts with organic substances (amines, reducing substances, etc.) in the water and loses its activity, making it difficult to maintain antibacterial activity for a long period of time. Moreover, since it is easily soluble in water, when used in combination with underwater antifouling paint,
Since it quickly dissolves into water, it has the problem that its antifouling effect cannot be maintained for a long period of time.

[0008] As described above, the water-soluble antibacterial agents that have been commonly used have extremely disadvantages in terms of handling, antibacterial effects, etc. due to toxicity, decreased antibacterial activity, solubility in water, etc. Met.

The same can be said about organic solvents such as ethanol which have a bactericidal effect and natural essential oils such as cineole which is an aromatic agent. For example, natural essential oils such as 1,8-cineole (hereinafter abbreviated as "cineole") can be used as fragrances, antibacterial agents, and fungicides, but many natural essential oils are highly volatile, and their effectiveness was difficult to maintain for a long period of time. Therefore, it is desired to develop sustained-release insecticides and sustained-release fragrances that can maintain their insecticidal effects and fragrance for a long period of time and are easy to handle.

[0010] In order to solve the above-mentioned conventional problems, the present invention provides a host compound and a host compound for producing clathrate compounds that can provide excellent sustained-release antibacterial agents, sustained-release insecticides, and sustained-release fragrances. The object of the present invention is to provide an clathrate compound using this host compound.

[0011]

[Means for Solving the Problems] The host compound for producing an clathrate compound according to claim 1 is a compound containing a triphenylcarbinol group (hereinafter referred to as a "triphenylcarbinol compound") represented by the following formula. ).

0012

[Case 2]

[0013] The clathrate compound according to claim 2 is characterized in that it comprises the host compound according to claim 1 and a guest compound, and the guest compound is an organic fungicide, a natural essential oil, or an organic solvent.

That is, the present inventors first developed a 2,2' compound represented by the formula 3 as a host compound to achieve the above object.
A host compound for producing an clathrate compound consisting of -bis(α-hydroxydiphenylmethyl)biphenyl was discovered and a patent application was previously filed (Japanese Patent Laid-Open No. 2-178243).

[0015]

[Chemical formula 3]

The present invention was completed as a result of extensive research in order to obtain even more superior effects than the host compound disclosed in JP-A-2-178243.

The present invention will be explained in detail below. The triphenylcarbinol compound that is the host compound of the present invention is not particularly limited, but examples thereof include compounds (1) to (4) shown in formulas 4 to 9 below.

[0018]

[C4]

[0019]

[C5]

[0020]

[C6]

[0021]

[C7]

[0022]

[Chemical formula 8]

[0023]

[Chemical formula 9]

Such triphenyl carbinol compounds can be easily produced, for example, according to the reaction formulas shown in Formulas 10 to 12 below. In addition, in the following, Me represents a methyl group and Et represents an ethyl group. First, compounds 1 to 2 are prepared using o, m, p-brobenzoic acid as a starting material.
It can be synthesized as 0.

[0025]

[Chemical formula 10]

Compounds (1) to (2) can be synthesized as shown in Chemical Formulas 11 and 12 using the intermediate products of the above synthesis as starting materials.

[0027]

[Chemical formula 11]

[0028]

[Chemical formula 12]

Further, the host compound of the present invention can be expressed by the following formula 1.
The azobenzene compounds (1) and (2) shown in 3 may also be used. In addition, compound (1) and compound (2) are cis, tran
They are s isomers; for example, the trans form (2) takes in one molecule of acetone, and the cis form (2) takes in two molecules of acetone. However, cis that incorporated two molecules of acetone
By heating, the body (2) crystal changes into a trans body (2) crystal that incorporates one molecule of acetone. Conversely, upon irradiation with ultraviolet rays, the trans form (■) becomes the cis form (2).

[0030]

[Chemical formula 13]

The host compound of the present invention can be used in various organic solvents,
It is useful as a host compound that can form stable clathrate compounds with disinfectants, fragrances, etc. as guest compounds, and is intended to maintain its effects for a long period of time, such as perfumes, agricultural chemicals, and industrial fungicides. field, or pH, heat,
It has a wide range of uses, including as a stabilizer for stabilizing compounds that are unstable to ultraviolet light by clathrating them, and also for separating and purifying various compounds by utilizing its selective clathration ability. Extremely useful.

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

In the clathrate compound of the present invention, examples of organic solvents include DMSO (dimethyl sulfoxide) and DMF (
dimethylformamide), pyridine, dioxane, ethanol, acetonitrile, acetone, trichloroacetic acid,
Examples include t-butanol and other compounds listed in the guest compound section below, but are not limited thereto. Natural essential oils include cineole, cypress oil, osmanthus, jasmine, lemon, cassia oil,
Examples include cinnamon leaf, menthol, rosemary, palmarosa oil, lavender, spearmint oil, and mentha arvensis.

[0034] In addition, as an organic fungicide, the above-mentioned Cl-
Examples include MIT and hydrazine.

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

[0036]

[Operation] The host compound of the present invention can selectively, efficiently and stably include organic solvents, natural essential oils, organic fungicides, etc. as guest compounds.

[0037] The clathrate compound in which the organic fungicide is included in the host compound can be in a solid state. Since the bactericidal component gradually dissolves into water from the clathrate compound, its antibacterial activity can be maintained for an extremely long period of time. Furthermore, by clathrating the disinfectant, its toxicity, skin irritation, etc. are reduced. Moreover, it is also prevented from reducing antibacterial activity due to reaction with other substances during use.

Therefore, the resulting clathrate compound can be effectively used as a sustained-release antibacterial agent that can maintain antibacterial activity for an extremely long period of time.

On the other hand, organic solvents and natural essential oils also become a solid state when they are made into clathrate compounds with the host compound of the present invention. For this reason, for example, liquid fragrances have the disadvantage that the liquid spills if the container falls over, but the clathrate compound of the present invention eliminates such concerns and is easy to handle.

Furthermore, by clathrating the aroma component or insecticidal component, the aroma component etc. gradually volatilize from the clathrate compound and the volatilization rate decreases, thereby increasing the sustainability of the aroma and insecticidal effect. By changing the particle size of this clathrate compound, the contact area with the atmosphere can be adjusted, and the rate of volatilization of aroma components and insecticidal components can be adjusted. Furthermore, it is easy to mold into various shapes.

Furthermore, the host compound of the present invention is useful for pulverizing, stabilizing, concentrating, etc. the guest compound, and also utilizes selective inclusion of the guest compound as a host compound. It is also useful for separation and purification.

[0042]

[Examples] The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Example 1 The host compounds shown in Table 1 (compounds 1 to 2 shown in formulas 5 to 9 above) and guest compounds were mixed in a molar ratio of host compound:guest compound=1:1 or 1:2. were mixed at room temperature. As a result, the crystal forms shown in Table 1, m. p
．． A stable clathrate compound with an inclusion ratio g/h (guest compound/host compound (molar ratio)) was obtained. In Table 1, N indicates needle crystal, P indicates prism crystal, and nc indicates unknown.

[0044]

[Table 1]

Example 2, Comparative Examples 1 and 2 A clathrate compound (see No. 2 in Table 1) of the host compound (2) represented by Chemical Formula 5 and ethanol was prepared with an ethanol content of 0.
A total weight of 2 g was placed in a petri dish and left open at room temperature, and the ethanol reduction rate was determined from the change in weight. The results are shown in Table 2. For comparison, 0.2g of ethanol only
Collected (Comparative Example 1), 2,2 shown in above-mentioned 3
Similarly, a clathrate compound of '-bis(α-hydroxydiphenylmethyl)biphenyl and ethanol (molar ratio 1:1) was collected so that the ethanol content was 0.2 g (Comparative Example 2). Check the ethanol reduction rate,
The results are shown in Table 2. From Table 2, it is clear that the clathrate compound of the present invention has excellent sustained release properties of ethanol.

[0046]

[Table 2]

[0047] Inclusion compound of host compound (Example 3), ■ (Example 4) shown in Examples 3 and 4, Comparative Example 3, 4, 5 and 8 and cineole (No. 15 in Table 1) ) were placed in a petri dish so that the cineole content was 0.2 g, and the reduction rate was examined in the same manner as in Example 2. In addition, 0.2 g of cineole alone was collected (Comparative Example 3), and a clathrate compound of 2,2'-bis(α-hydroxydiphenylmethyl)biphenyl and cineole shown in Chemical Formula 3 (molar ratio 1:2) was used. ), the cineole content is 0.2
Regarding the sample collected so as to be g (Comparative Example 4),
Similarly, the cineole reduction rate was investigated, and the results are shown in Table 3. From Table 3, it is clear that the clathrate compound of the present invention has excellent sustained release properties of cineole.

[0048]

[Table 3]

Example 5, Comparative Examples 5 and 6 A clathrate compound (molar ratio 1:1) of the host compound (1) represented by chemical formula 5 and Cl-MIT was prepared with a Cl-MIT content of 0.2.
Pour it into 1 liter of ultrapure water so that it is 500 g.
The dissolution rate of Cl-MIT into water was investigated while stirring with a stirrer at rpm. Similarly, only Cl-MIT was added to 0.
When 2g was added (Comparative Example 5), 2 shown in the above chemical formula 3
,2'-bis(α-hydroxydiphenylmethyl)biphenyl and Cl-MIT clathrate (molar ratio 1:1)
was added so that the Cl-MIT content was 0.2 g (Comparative Example 6), the Cl-MIT elution rate was also investigated, and the results are shown in Table 4. From Table 4, it is clear that the clathrate compound of the present invention has excellent sustained release properties of Cl-MIT.

[0050]

[Table 4]

[0051]

EFFECTS OF THE INVENTION As detailed above, the host compound of the present invention is extremely useful as a host molecule that stably includes organic solvents, natural essential oils, organic fungicides, and the like. Therefore, the clathrate compound of the present invention obtained using the host compound of the present invention can be used for powdering, stabilizing, concentrating, separating, purifying, etc. water-soluble disinfectants, natural essential oils, etc. In particular, as a sustained-release antibacterial agent containing a clathrated water-soluble bactericide as an active ingredient, it is able to maintain its antibacterial activity for a long time because the active ingredient gradually dissolves into water, and is solid. Therefore, it can be molded into tablets, etc., and is easy to handle. ■ The toxicity and skin irritation of disinfectants are reduced, which improves the working environment and improves safety. It has excellent effects such as preventing the active ingredient from reacting with other substances and reducing antibacterial activity.

[0052] Furthermore, as a sustained-release aromatic agent containing natural essential oil as an aromatic component, (1) the aromatic component gradually evaporates into the atmosphere, so the aromatic property can be maintained for a long time; and (2) it is solid, so It is easy to handle and can be easily molded; ■ The volatilization of aroma components can be easily controlled by changing the particle size of the clathrate compound, and any desired sustained release properties can be obtained; Excellent effects such as these can be achieved. Furthermore, it is useful as a sustained-release insecticide containing organic solvents and natural essential oils as insecticidal ingredients.

Claims (2)

[Claims] 1. A host compound for producing an clathrate compound containing a triphenylcarbinol group, which is represented by the following formula. [Chemical formula 1] 2. A clathrate 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.