JPH05163187A - New clathrate compound - Google Patents

Abstract

PURPOSE:To provide a new clathrate compound excellent in the sustained releasability of essential oils or perfumes and excellent in the durability of the effects. CONSTITUTION:The new clathrate compound contains a tetrakis(hydroxyphenyl) ethane of the formula as a host compound and an essential oil or a perfume as a guest compound. Since the clathrate compound is excellent in the re- releasing characteristics of the essential oil or perfume, in the durability of the effects and in the stability of the active ingredient, the clathrate compound is useful as a sustained release aromatic agent, an antibacterial agent, an insecticide, etc. The obtained compound has a solid state, can be molded into an arbitrary shape at the ordinary temperature, and can be processed with maintaining its stability even in the case of a low boiling point. Further, the sustained release rate can also readily be adjusted.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inclusion compound, and more particularly to a novel package useful as a slow-release aromatic agent, antibacterial agent, insecticide, insect repellent, etc., which uses tetrakis (hydroxyphenyl) ethane as a host. It is related to contact compounds.

[0002]

BACKGROUND OF THE INVENTION Fragrances are widely used in living spaces of homes, guest rooms and lobbies of hotels, in cars, toilets, etc., and are roughly classified into aerosols, liquids and solids according to their forms. Most of the aerosol fragrances are used in a spray method, and the effect is immediate, and since the fragrance composition is constant, the fragrance has little change over time. Liquid fragrance is sucked up by a porous base such as sponge or felt attached to the mouth of a container such as a glass bottle, and the strength and duration of the fragrance are controlled by the degree of opening and closing of this base and the shutter of the container. .. As the solid fragrance, there is a fragrance mixed with a plasticizer, a stabilizer, and a porous carrier, and the mixture is kneaded and molded into plastic, which is used for toys, interior products and the like. As an example of an inclusion compound having a guest compound such as an antibacterial agent, an insecticide, and an aromatic agent, the description of JP-A-2-178243 is known, but the inclusion compound containing tetrakis (hydroxyphenyl) ethane as a host compound is known. No contact compound is known.

[0003]

In the above-mentioned conventional aerosol type fragrance, the use of the fragrance component which causes the chemical change and the corrosion of the can container requires special consideration from the viewpoint of safety. If the fragrance is used, it will cause valve clogging due to change of fragrance and destabilization of emulsion. Therefore, there are great restrictions on the selection of fragrances. In addition, since the liquid type uses an open container, a liquid leakage accident due to a fall is unavoidable, and there is a problem in handleability.
Further, the solid type has a drawback that it is difficult to process a low boiling point fragrance because a heat molding step is included. The present invention is
The present invention has been made in view of such circumstances, and an object thereof is to provide a novel clathrate compound having improved effect persistence, stability, handleability, processability and the like, and further having sustained release. ..

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, use essential oils or fragrances as guest molecules and tetrakis (hydroxyphenyl) ethane as host molecules. The present invention has been completed by finding that the intended object can be achieved by providing a novel inclusion compound. The present invention comprises an essential oil or fragrance and tetrakis (hydroxyphenyl) represented by the following general formula [1].
It is an inclusion compound characterized by comprising ethane.

[0005]

[Chemical 2]

The present invention will be described in detail below. In the present invention, as the guest compound, the essential oil or fragrance may be natural or synthetic. Examples of the essential oil mainly include natural essential oils such as cineol, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, linalool and dimethyloctanol. On the other hand, examples of the fragrance include oyster wax, jasmine, lemon and the like. All of these are useful as fragrances, but in the case of essential oils, they further have bactericidal action, insecticidal action, insecticidal action and the like. These compounds may be used alone or in admixture of two or more, if necessary.

In the present invention, the host compound tetrakis (hydroxyphenyl) ethane represented by the following general formula [1] is used.

[0008]

[Chemical 3] Specific examples of the compound represented by the general formula [1] include:
1,1,2,2-tetrakis (p-hydroxyphenyl) ethane (hereinafter abbreviated as “TEP-DF”), 1,1,
2,2-tetrakis (m-hydroxyphenyl) ethane and the like can be mentioned. Among them, TEP-DF is particularly preferably used because the clathrate compound obtained is a solid at room temperature and is easy to handle.

The inclusion compound of the present invention can be easily produced with or without a solvent. When a solvent is used, the host compound is dissolved in a solvent such as methanol, ethanol, isopropanol or methyl ethyl ketone, and then liquefied essential oil or fragrance is added to this solution for reaction. After the reaction, if necessary, the solvent is evaporated off or the clathrate compound is precipitated by cooling. This precipitate is separated by filtration by a conventional method to obtain the target clathrate compound.
When a solvent is not used, tetrakis (hydroxyphenyl) ethane is directly added to the liquid of essential oil or fragrance to react. After that, the precipitated solid matter may be separated in the same manner as the above method. In the case of both, the reaction temperature is 0-100.
℃, preferably 10 to 60 ℃, the reaction time is 5 minutes ~
24 hours. The clathrate compound obtained as described above is usually in the form of powder, and the clathrate compound can be obtained according to the intended use by changing the particle size or forming a molded product having a different shape.

The inclusion compound of the present invention having tetrakis (hydroxyphenyl) ethane as a host can usually include 2 to 4 moles of guest compound with respect to the host compound.

The clathrate compound of the present invention can be used in the following modes. Use this agent in powder form by putting it in a container with open holes. Use this agent by molding it into an appropriate shape. Knead it with paint, resin, etc. and apply it to members etc. Specifically, it can be applied to the following uses. Indoor and vehicle aromatic, insecticidal, insect-proof ornaments Aromatic, insecticidal, insect-proof or mildew-proof building materials and floor materials Aroma, insecticidal, insect-proof or mildew-proof furniture Aromatic, insecticidal, Insect-proof bedding Toiletry products (cosmetics, bath agents, detergents, etc.) Aromatic toys Aromatic accessories, Aromatic accessories, Aromatic stationery Office supplies

[0012]

In the present invention, the essential oil or fragrance forms an inclusion compound with tetrakis (hydroxyphenyl) ethane, so that the essential oil or fragrance is slowly released. The volatilization rate can be easily controlled by appropriately changing the particle size or changing the shape of the molded body. The essential oil or fragrance of the guest compound used in the present invention is used as a fragrance. When the essential oil is used, it also exhibits insecticidal and bactericidal effects.

The present invention will be described below with reference to Examples and Comparative Examples.
Further details will be described. However, the scope of the present invention is not limited by these examples.

Example 1 TEP-DF (manufactured by Asahi Organic Materials Co., Ltd.) in 5 ml of methanol 1.
Add 0 g (2.51 mmol) and stir while warming until TEP-DF is completely dissolved. 1.58 g (10.04 mmol) of 1,8-cineole was gradually added dropwise thereto, and the mixture was reacted at 60 ° C. for 10 minutes while stirring, then immediately filtered, and the filtrate was left at room temperature to precipitate crystals. This precipitate was separated by filtration and then vacuum dried at room temperature to obtain a white crystalline sample A-1.

Example 2 1.0 g (2.51 mmol) of TEP-DF was added to 5 ml of methanol, and the mixture was stirred with heating until TEP-DF was completely dissolved. 1.65 g (10.04 mmol) of hinokitiol was gradually added dropwise to this, and after reacting at 60 ° C. for 10 minutes while stirring, it was immediately filtered and the filtrate was left at room temperature to precipitate crystals. This precipitate was separated by filtration and then vacuum dried at room temperature to obtain a white crystalline sample A-2.

Example 3 1.0 g (2.51 mmol) of TEP-DF was added to 5 ml of benzene and suspended and dispersed while stirring. To this, 1.57 g (10.04 mmol) of 1-menthol was added, reacted at 40 ° C. for 30 minutes with stirring, and then allowed to cool to room temperature. After the suspension was filtered off, it was vacuum dried at room temperature to obtain a white powder sample A-3.

Example 4 TEP-D was added to 1.55 g (10.04 mmol) of α-terpineol.
F 1.0 g (2.51 mmol) was added, and it was made to react at 60 degreeC, stirring, and the solid substance was obtained. After crushing this solid substance, it vacuum-dried at room temperature and obtained the white powder sample A-4.

Each sample (A-1 to A-4) obtained above
Production conditions, guest / host mol of the obtained inclusion compound
The ratios and the re-emission temperature of the guest are shown in Table 1.

[0019]

[Table 1]

The A-1 to A-4 samples obtained by the above method were confirmed to be clathrate compounds by IR spectrum, X-ray diffraction and DTA.

Example 5 Samples A-1 and A-2 obtained in Examples 1 and 2 and comparative sample 1,8-cineole (R-1), hinokitiol (R
-2) 0.6 g of each of the single compounds in terms of guest compound
It was taken in a Petri dish so that it would become, and set in a desiccator kept at 25 ° C and 40 ° C. 2 dry air to this
It was introduced at 50 ml / min, and the weight loss was measured over time. The results are shown in Table 2. The release curves are shown in FIGS. 8 and 9.

[0022]

[Table 2]

The inclusion compound sample A-2 obtained in the present invention,
A DTA chart of hinokitiol which is a guest compound is shown in FIG. The IR spectrum of Sample A-2 is shown in FIG. As is clear from FIG. 2, absorption of a hydroxyl group associated with inclusion is observed at around 3182 cm ^-1 , and further absorption of a carbonyl group is observed at 1594 cm ^-1 .
Furthermore, from the X-ray diffraction pattern of the sample A-2 shown in FIG.
It turns out that 2 is a crystalline substance. Therefore, it was confirmed that the sample A-2 obtained in the present invention was an inclusion compound.

[0024]

The inclusion compound obtained by including the essential oil or fragrance as the guest compound of the present invention in the host compound of tetrakis (hydroxyphenyl) ethane is excellent in sustained release and stability of the active ingredient, The sustained release rate can be easily adjusted, and the aroma effect, insecticidal and bactericidal effect can be maintained over a long period of time. The clathrate compound of the present invention is capable of clathrating 4 times or more moles of guest essential oil or fragrance with respect to the host compound, and has extremely high clathrate efficiency. Further, the clathrate compound of the present invention has a solid state, can be appropriately molded into an arbitrary shape at room temperature, and can be processed without modifying a low-boiling-point fragrance, and therefore is excellent in handleability and processability.

[0025]

[Brief description of drawings]

FIG. 1 shows a DTA chart of a clathrate compound sample A-2.

FIG. 2 shows an IR spectrum of inclusion compound sample A-2.

FIG. 3 shows an IR spectrum diagram of TEP-DF which is a host compound.

FIG. 4 shows an IR spectrum diagram of hinokitiol which is a guest compound.

FIG. 5 shows an X-ray diffraction pattern of clathrate compound sample A-2.

FIG. 6 shows an X-ray diffraction pattern of TEP-DF which is a host compound.

FIG. 7 shows an X-ray diffraction pattern of hinokitiol, which is a guest compound.

FIG. 8 shows a release curve obtained by performing a release test on the inclusion compound samples A-1 and 1,8-cineole alone and measuring the release amount.

FIG. 9 is a diagram showing a release curve obtained by performing a release test on the inclusion compound sample A-2 and hinokitiol alone and measuring the release amount. (Below margin)

Claims (1)

[Claims] 1. An inclusion compound comprising an essential oil or a fragrance and tetrakis (hydroxyphenyl) ethane represented by the following general formula [1]. [Chemical 1]