JP3052364B2 - Host compounds and clathrates - Google Patents

Description

The present invention relates to a host compound, a sustained-release substance, and a method for detecting a compound, and in particular, a novel compound that can include a fragrance, an antibacterial agent, an insect repellent, an organic solvent, and the like. An imidazole host compound, and
The present invention relates to a sustained-release substance in which a perfume, an antibacterial agent or an insect repellent is included as a guest compound with such a host compound, and a method for detecting a compound using such an imidazole-based host compound.

[Prior Art] Air fresheners used in living rooms at home, in hotel rooms and lobbies, in cars, in toilets, etc. are solid,
It is classified into three types: liquid and aerosol types.

Examples of the solid fragrance include those obtained by blending a fragrance with a plasticizer, a stabilizer, and the like and processing the plastic, and the product is considered to be used for interior decoration products.

The liquid type fragrance absorbs liquid into a volatile material such as felt or filter paper inserted into the mouth of the container, and regulates the vaporization speed by the volatile material and the container opening to maintain the fragrance.

In addition, the aerosol type fragrance is a space spray method, which has the characteristic of instantaneously, effectively and constantly giving a constant scent. The base is Freon (chlorofluorocarbon) and alcohol, LPG and water. (Using a surfactant).

Of the various fragrances, natural essential oils have many antibacterial and insect repellent effects, and thus may be used as antibacterial agents and insect repellents in addition to their use as fragrances.

On the other hand, diethyltoluamide is a colorless or faint yellow liquid insect repellent and repellent, and it has been widely used in the past to prevent biting of blood-sucking insects such as mosquitoes and gnats or to prevent the approach of flies and cockroaches. .

In addition to using it as a liquid itself, it can be used in sprays, creams, etc., or impregnated in paper, plastic, plywood, etc., or in paints or adhesives, and then applied. There is a wide variety of applications.

[Problems to be Solved by the Invention] Among the various types of conventional fragrances, solid fragrances have a drawback that it is difficult to process a low-boiling fragrance because heat is applied in the molding process. Liquid fragrances have the disadvantage that the liquid will spill if the container falls over. It is important to note that aerosol-type air fresheners should be used with fragrance components that cause chemical changes and corrosion of cans. Therefore, there was a problem that the fragrance was limited.

Similarly, diethyltoluamide is extremely effective as an insect repellent and repellent, but has a drawback of poor handling properties and moldability because it is liquid itself. Further, since it is a substance that is relatively easily volatilized, there is a disadvantage that the effect is inferior due to loss due to volatilization, and improvement thereof is desired.

On the other hand, recently, with respect to household fragrances, antibacterial agents, insect repellents, etc., the end of the effective period, that is, a visual end point such that the end point of the effective period due to volatilization of the active ingredient can be visually determined. Cognitive function is required.

The present invention has been made in view of the above conventional circumstances, and includes a novel imidazole-based host compound that can include a fragrance, an antibacterial agent, an insect repellent, an organic solvent, and the like, and a fragrance and an antibacterial agent for such a host compound. Another object is to provide a sustained-release substance in which an insect repellent is included as a guest compound, and a method for detecting a compound using such an imidazole host compound.

[Means for Solving the Problems] The host compound of the present invention is an inclusion compound-forming host compound comprising an imidazole derivative represented by the following general formula (III).

The sustained-release fragrance of the present invention comprises an imidazole derivative represented by the following general formula (I) as a host compound and a fragrance as a guest compound.

The sustained-release antibacterial agent of the present invention is obtained by using an imidazole derivative represented by the following general formula (I) as a host compound and including the antibacterial agent as a guest compound.

The sustained-release insect repellent of the present invention is obtained by using an imidazole derivative represented by the following general formula (I) as a host compound and including the insect repellent as a guest compound.

In the method for detecting a compound of the present invention, a compound selected from the following compound group (IV) is brought into contact with a host compound comprising an imidazole derivative represented by the above general formula (I), and a difference in color tone before and after the contact is obtained. By detecting the compound.

Compound group (IV): primrose, jasmine, lemon,
2-phenylethanol, benzyl alcohol, cineol, hinoki oil, cinnamon leaf, cassia oil,
Menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, mentha avensis, cis-jasmine, diethyltoluamide, eugenol, 1-α-terpineol, 1-carvone, 1-
Menthone, d-pulegone, citronellal, linalool oxide, d, 1-citronellol, cinamic aldehyde, 3,3,5-trimethylcyclohexanol, 1-
BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to natural and synthetic essential oils such as perilla aldehyde, 1-carbeol, miltenal, peppermint oil, and eucalyptus oil, DMSO (dimethyl sulfoxide), pyridine, acetonitrile, and trichloroacetic acid.

The clathrate-forming host compound of claim 1 is 2- (4-substituted phenyl) phenanthro [9,10-d] imidazole represented by the general formula (III). The clathrate-forming host compound has a fragrance as a guest compound,
An antimicrobial, insect repellent or organic solvent may be included.

Examples of the fragrance, antibacterial agent, insect repellent, and organic solvent that can be included by the clathrate-forming host compound of claim 1 include the following.

The fragrance is not particularly limited as long as it has fragrance, and examples thereof include, but are not limited to, quince, jasmine,
Lemon, 2-phenylethanol and the like. Natural essential oils such as cineole, hinoki oil, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, menthaavensis, and cis-jasmine are also used as flavors.

Examples of antibacterial agents (including fungicides and fungicides) and insect repellants include ethanol, diethyltriamide, 1-α-terpineol, 1-carbone, 1-menthone, d-pulegone, citronellal, linalool oxide, d, l−
Citronellol, cinnamic aldehyde, 3,3,5-trimethylcyclohexanol, 1-perilla aldehyde, 1-carveol, miltenal, peppermint oil, natural essential oils such as eucalyptus oil, and synthetic essential oils, but are not limited thereto. is not.

As the organic solvent, DMSO (dimethyl sulfoxide),
Examples include, but are not limited to, DMF (dimethylformamide), pyridine, dioxane, ethanol, acetonitrile, acetone, trichloroacetic acid, t-butanol, and the like.

In the sustained-release fragrance, the sustained-release antibacterial agent and the sustained-release insect repellent of the present invention, the imidazole derivative represented by the general formula (I) as a host compound is specifically represented by the following general formula: 2,4,5-trisubstituted phenylimidazole represented by (II) and 2-
(4-substituted phenyl) phenanthro [9,10-d] imidazole, but is not limited thereto.

The fragrance serving as a guest compound in the sustained release fragrance of the present invention is not particularly limited as long as it has fragrance, and examples thereof include, but are not limited to, quince, jasmine, lemon,
-Phenylethanol and the like. Natural essential oils such as cineole, hinoki oil, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, menthaavensis, and cis-jasmine are also used as flavors.

In addition, the antibacterial agents (including antibacterial agents and fungicides) which become guest compounds in the sustained-release antibacterial agent and the sustained-release insecticide of the present invention, and insecticides include, in addition to diethyltoluamide, 1-α- Terpineol, 1-carvone, 1-mentone, D-pulegone, citronellal, linalool oxide, d, 1-citronellol, cinamic aldehyde, 3,3,5-trimethylcyclohexanol, 1-perilla aldehyde,
Examples include natural essential oils such as 1-carveol, miltenal, peppermint oil, and eucalyptus oil and synthetic essential oils.

In the method for detecting a compound of the present invention, a clathrate compound is formed by contacting a compound selected from the group of compounds of the above (IV) with a host compound comprising an imidazole derivative represented by the above general formula (I). Thus, the presence of the compound is detected based on the difference in color tone before and after the contact.

Such a fragrance, an antibacterial agent, an insecticide or an organic solvent and a clathrate compound comprising the imidazole-based host compound of the present invention, a recrystallization reaction in the guest compound of both compounds, a reaction in a solvent or It can be easily produced by a solventless reaction. Of these, in the case of reaction in a solvent,
For example, a solution in which a host compound is dissolved and a guest compound are mixed and reacted with a commonly used solvent such as methanol and chloroform. As a result, the clathrate compound precipitates as a solid, and is separated by filtration by a conventional method to obtain a target clathrate compound.

The inclusion compound can be easily obtained by such a reaction in a solvent, but in the present invention, there is no need to select a solvent.

 Condition setting is relatively easy.

 There is no need for solid-liquid separation.

For such reasons, it is advantageous to carry out the reaction without solvent.

When the clathrate compound according to the present invention is produced by a solventless reaction, the guest compound and the imidazole-based host compound may be directly mixed at an appropriate ratio. Reaction temperature is 0-10
It is optional in the range of 0 ° C, but usually 10 to 50 ° C
Degree. A reaction time of about 0.1 to 24 hours is sufficient.

The clathrate compound thus obtained is usually a powdery solid and is easy to mold. Further, by changing the particle size of the powder, the shape of the molded body, and the like, the contact area with the atmosphere can be adjusted, and the degree of sustained release of the active ingredient can be easily adjusted.

The method for using the sustained-release fragrance, the sustained-release antibacterial agent, and the sustained-release insect repellent of the present invention includes the following methods.

The powdered medicinal agent is used in a container having an opening.

 This product is used after being formed into an appropriate form.

 It is mixed with paint, other resin, etc., and applied to members.

 It is attached to the surface of the object by an appropriate method.

[Action] The imidazole host compound of the present invention is a good host compound having an excellent inclusion function for selectively and efficiently including a guest compound such as a fragrance, an antibacterial agent, an insect repellent, or an organic solvent.

In such an imidazole host compound of the present invention,
An inclusion compound formed by including a fragrance, an antibacterial agent, an insect repellent, or an organic solvent as a guest compound is in a solid state. For this reason, for example, the liquid fragrance has a drawback that the liquid is spilled when the container falls down, but in the sustained-release fragrance, the sustained-release antibacterial agent, and the sustained-release insect repellent of the present invention, such concerns are raised. It is easier to handle.

In addition, inclusion of a fragrance, an antibacterial agent, or an insect repellent causes the active ingredient to volatilize gradually from the clathrate, thereby reducing the rate of volatilization, thereby increasing the sustainability of the action. This clathrate compound can adjust the surface area in contact with the atmosphere and change the volatilization rate of the active ingredient, for example, by changing its particle size. (If the particle size of the clathrate compound is increased, the sustained release of the active ingredient becomes more remarkable.) Moreover, since the clathrate compound can be formed into various shapes, it can be applied to various uses.

In addition, the host compound according to the present invention discolors upon inclusion of a fragrance, an antibacterial agent, an insect repellent or an organic solvent. Conversely, the inclusion compound of the present invention changes color to the original host compound by releasing fragrances, antibacterial agents, insect repellents or organic solvents. For this reason, the clathrate compound according to the present invention also has a function of visually notifying the end of the release of the active ingredient, that is, the end of the effect.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

Examples 1 to 13 In the general formula (II), R ₁ , R ₂ , and R ₃ are the imidazole host compounds having the substituents shown in Table 1 (the colors of the host compounds are as shown in Table 1) ) Was used in the amounts shown in Table 1, and this host compound and the amount of the guest compounds shown in Table 1 were mixed at room temperature. As a result, the reaction proceeded rapidly, and the inclusion compound formed by including the guest compound in the host compound was precipitated as a solid having the color shown in Table 1.

Each of the clathrates was exposed to hot air from a dryer to perform a guest compound release test. As a result, each clathrate changed color and returned to the original color of the host compound.

From this result, the host compound of the present invention and the clathrate compound of the present invention in which the host compound includes a guest compound such as a fragrance have different colors, and it is possible to know whether or not the guest compound is included by discoloration. It's clear what you can do.

Examples 14 and 15 The same host compound as used in Example 1 and 2-phenylethanol (Example 14) or cineol (Example 1)
5) Take 1.0 g of clathrate compound with each in a Petri dish,
The weight loss was measured over time in an open system, and the sustained release of each guest compound was examined. For comparison, the amount of reduction was also measured for unencapsulated 2-phenylethanol or cineol, 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 the active ingredient.

Examples 16 to 26 In the above general formula (III), 0.7 g of an imidazole host compound in which R ₁ and R ₂ are hydrogen atoms and R ₃ is a nitro group (the color of the host compound is black-brown). 0.3 g of the guest compound shown in Table 3 was mixed at room temperature. As a result, the reaction proceeded rapidly, and the inclusion compound formed by including the guest compound in the host compound was precipitated as a solid having the color shown in Table 3.

Each of the clathrates was exposed to hot air from a dryer to perform a guest compound release test. As a result, each clathrate changed color and returned to the original color of the host compound.

From the results, it is clear that the host compound of the present invention and the clathrate compound of the present invention in which the guest compound is included in the host compound have different colors, and the presence or absence of the inclusion of the guest compound can be known by discoloration. It is.

Examples 27 and 28The inclusion compound obtained in Example 20 in which diethyltoluamide is included as a guest compound, and the inclusion compound obtained in Example 21 in which cinamic aldehyde is included as a guest compound, Take each in a 0.5g petri dish, 25 ℃,
The weight loss was measured over time in an open system, and the sustained release of each guest compound was examined. For comparison, the amount of reduction was similarly examined for each guest compound that was not included, and the results are shown in Table 4.

From Table 4, it is clear that the clathrate compound of the present invention is excellent in sustained release of the active ingredient.

[Effects of the Invention] As described in detail above, according to the host compound of the present invention, the liquid or the guest compound having a low melting point is made into a solid state, so that the handling property is improved.

Stability is imparted by keeping various guest compounds stably and protecting them.

The sustained release of the guest compound gradually imparts a sustained effect.

And a novel host compound having excellent effects such as According to the sustained-release fragrance, sustained-release antibacterial agent and sustained-release insect repellent of the present invention in which a fragrance, an antibacterial agent or an insect repellent is included as a guest compound in such a host compound, the active ingredient Excellent long-term stability and long-lasting effect.

Since it is provided as a powdery solid, it is excellent in handleability, moldability, etc., and can be applied to a wide variety of uses.

In addition to the effects described above, the discoloration is caused by the release of the active ingredient, so that the end of the effective period can be easily visually recognized.

High-performance fragrance, antibacterial,
An insect repellent is provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 31/06 A01N 31/06 35/02 35/02 35/06 35/06 37/18 37/18 Z (56) References Mol. Cryst, Liq. Cry st. , 161 (Pt. B), 255-81 (1988) Acta Cryst. , C41 (7), 1106-8 (1985). Chem. Soc. Perkin Trans, 2, 1986 (10), 1623-9 (1986). Org. Chem. , 36 (16), 2267-72 (1971). Org. Chem. , 36 (16), 2280-4 (1971) Khim. Getrotsikl. Soedin, 1973 (3), 387-90 (1973) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 233/64 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] An inclusion compound-forming host compound comprising an imidazole derivative represented by the following general formula (III): 2. A sustained release fragrance comprising an imidazole derivative represented by the following general formula (I) as a host compound and a fragrance as a guest compound. 3. A sustained-release antibacterial agent comprising an imidazole derivative represented by the following general formula (I) as a host compound and an antibacterial agent as a guest compound. 4. A sustained-release insect repellent comprising an imidazole derivative represented by the following general formula (I) as a host compound and an insect repellent as a guest compound. 5. A compound selected from the group consisting of the following compounds (IV) is brought into contact with a host compound comprising an imidazole derivative represented by the following general formula (I), and the difference in color tone between before and after the contact is determined. A method for detecting a compound, comprising: detecting a compound. Compound group (IV): primrose, jasmine, lemon,
2-phenylethanol, benzyl alcohol, cineol, hinoki oil, cinnamon leaf, cassia oil,
Menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, mentha avensis, cis-jasmine, diethyltoluamide, eugenol, 1-α-terpineol, 1-carvone, 1-
Menthone, d-pulegone, citronellal, linalool oxide, d, 1-citronellol, cinamic aldehyde, 3,3,5-trimethylcyclohexanol, 1-
Natural and synthetic essential oils such as perilla aldehyde, 1-carbeol, miltenal, peppermint oil, eucalyptus oil, DMSO (dimethyl sulfoxide), pyridine, acetonitrile, trichloroacetic acid