JP3175173B2 - 3-Hydroxyferrandral and pest repellent containing it as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 3-hydroxyferrandal and a pest repellent containing the same as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, repellents have been used to protect humans and animals from blood-sucking pests such as mosquitoes such as house mosquitoes, falcons and anopheles, and flies such as blackflies and flies. For example, N, N-diethyl-3-toluamide (hereinafter referred to as Deet) has been used in the form of sprays, lotions, creams and the like.

Eucalyptus plants native to Australia are rich in volatile terpenoids. The essential oils of various eucalyptus leaves were examined for their insect-repelling activity. As a result, lemon eucalyptus ( Eucalyptus citriodora ) and its near-green species were identified. It has been reported that an essential oil of a certain Eucalyptus cama-lduleusis has a strong repellent activity against mosquitoes (edited by Hiroyuki Nishimura, "Future Biological Resources Eucalyptus", p. 122, Uchida Ritsuruhosha).

[0004]

Deet used as a repellent for blood-sucking pests has the drawbacks that the target pest species are limited, the efficacy of malaria vector mosquitoes against Anopheles is poor, and the residual efficacy is lacking. .

[0005]

Means for Solving the Problems The present inventors have proposed Eucalypt
As a result of intensive studies on the insect repellent active components of the essential oil of the leaves of us camalduleusis , the structural formula was

[0006]

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[0007] The novel compound 3-hydroxyferrandalal (hereinafter referred to as the compound of the present invention) has a strong repellent activity, and has completed the present invention.

The compound of the present invention is Eucalyptus camaldule
It can be obtained from the leaves of usis by ordinary natural product extraction techniques and isolation and purification operations. Specifically, it can be obtained as in the following Reference Examples.

Pests which are effective against the pest repellent containing the compound of the present invention as an active ingredient include Aedes such as Anopheles, Aedes aegypti, Aedes albopictus, Aedes albopictus,
Household mosses such as Culex pipiens and blood sucking insects such as blackflies, sand flies, sand flies and brassicae can be mentioned.

[0010] Further, since the compound of the present invention is a natural product, its residual toxicity is low.

When the compound of the present invention is used as a pest repellent, the drug substance itself can be applied to the skin or used as a composition (hereinafter, referred to as the composition of the present invention) mixed with an appropriate carrier. For example, it is prepared and used in the form of a liquid such as a lotion or an aerosol, or a cream.

Carriers used for preparing liquids include, for example, water, alcohols such as methanol, ethanol, glycerin and polyethylene glycol; ethers such as tetrahydrofuran and dioxane; hexane;
Examples thereof include aliphatic hydrocarbons such as kerosene, paraffin and petroleum benzine, and esters such as ethyl acetate.

[0013] The liquid preparations may further contain conventional emulsifiers or dispersants, spreading / wetting agents, suspending agents, preservatives, propellants and other auxiliary substances for preparation, and the like. A film forming agent may be blended.

Specifically, for example, soaps, polyoxyethylene fatty acid alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene fatty acid esters, fatty acid glycerides, Emulsifiers such as sorbitan fatty acid esters, higher alcohol sulfates, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate,

Spreading / wetting agents such as glycerin and polyethylene glycol; suspending agents such as casein, gelatin, alginic acid, carboxymethylcellulose, gum arabic, hydroxypropylcellulose, bentonite; methyl parahydroxybenzoate; ethyl paraoxybenzoate; Preservatives such as propyl benzoate, butyl paraoxybenzoate,

Propellants such as dimethyl ether, chlorofluorocarbon and carbon dioxide; cellulose derivatives such as nitrocellulose, acetylcellulose, acetylbutyrylcellulose and methylcellulose; vinyl resins such as vinyl acetate resin; Can be given.

[0017] Carriers used in preparing a cream include, for example, liquid paraffin, vaseline,
Hydrocarbons such as paraffin, dimethylsiloxane, colloidal silica, silicons such as bentonite, ethanol, stearyl alcohol, alcohols such as lauryl alcohol, polyethylene glycol, ethylene glycol, polyhydric alcohols such as glycerin, lauric acid,
Examples thereof include carboxylic acids such as stearic acid and esters such as beeswax and lanolin. Furthermore, the same formulation auxiliaries as the liquid preparations can be added and blended.

Furthermore, the composition can be prepared in a microencapsulated form and formulated into a lotion, aerosol or the like and used.

The composition of the present invention may contain other pest repellents, synergists, antioxidants, other additives, and the like.

[0020] Other pest repellent which can be blended, for example Curran-1,2-diol, D-eet, p-menthane-3,8-diol, 2,3,4,5-bis (△ ² - (Butylene) tetrahydrofurfural, di-n-propyl isosine comelonate, di-n-butyl succinate,
2-hydroxyethyloctyl sulfide and empentrin {1-ethynyl-2-methyl-2-pentenyl d-cis, trans-chrysanthemate (cis: trans ratio = 2: 8)} and the like,

Examples of the antioxidant include butylhydroxyanisole, dibutylhydroxytoluene, tocopherol, and γ-oryzanol.

The composition of the present invention prepared as described above can be directly applied to the skin or the like, and can be applied and impregnated on a suitable substrate such as a sheet, film, mesh, or band in advance. , Kneading, dropping, etc., and then using the base material to cover the exposed portion of the skin or clothing.

Examples of the material of the substrate include synthetic fibers and resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester, vinylon and nylon; animal and plant fibers such as silk, cotton and wool; and inorganic materials such as aluminum. Fibers or mixtures thereof.

When a mesh-like substrate is used, the finer the mesh, the better. However, generally, a mesh of 16 mesh or less is sufficiently effective.

The amount of the compound of the present invention, which is an active ingredient, in the composition of the present invention varies depending on the dosage form and application method. For example, when used in a liquid such as lotion or aerosol, a cream or the like, or contained in a base. If used,
The amount of the active ingredient is 0.5 to 70% by weight, preferably 3 to 40%.
% By weight.

The treatment amount of the composition of the present invention is usually 0.01 to 5 mg of the compound of the present invention per 1 cm ^{2 of} skin area.
The amount is preferably from 0.1 to 1 mg, and these amounts are also used when the compound of the present invention is treated alone.

The above-mentioned treatment amount varies depending on the type of the preparation, the species of the target pest, its density, the time of use, the weather conditions, the age of the user, etc., and can be increased or decreased regardless of the above range. Or you can.

[0028]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Preparation Examples and Test Examples, but the present invention is not limited to these.

Reference Example 5 kg of fresh Eucalyptus camalduleusis leaves collected in Matsudo city was steam distilled to obtain 1.6 g of an essential oil. This was subjected to silica gel thin layer chromatography (hexane: ethyl acetate = 4: 1 V
/ V) to give 0.25 g of the compound of the present invention. The physicochemical properties of the compound of the present invention are shown below.

Properties Oil Molecular weight 168 Molecular formula C ₁₀ H ₁₆ O ₂ Optical rotation [α] _D + 13.5 ° (C = 0.80 methanol) IR 3400 cm ⁻¹ (hydroxyl group) 2980 cm ⁻¹ (CH ₂ group) 1885 cm ^{− 1} (α, β-unsaturated aldehyde group)

[0031]

Based on the above properties, the structure of the compound of the present invention was determined to be 3-hydroxyphenlandral (3-hydroxy-4-isopropyl-1-cyclohexenyl aldehyde).

Formulation Example 1 10 parts of the compound of the present invention are dissolved in ethanol to give a total of 35 parts.
And filled into an aerosol container. Then, after attaching a valve, Freon 11 and 1 are passed through the valve portion.
An aerosol is obtained by filling 65 parts of a 1: 1 mixture (propellant) of 2 with pressure.

Formulation Example 2 To 10 parts of the compound of the present invention, 10 parts of stearic acid, 2 parts of cetyl alcohol, 1 part of lanoli, 2 parts of liquid paraffin and 62 parts of water are added, and the mixture is heated and dissolved and mixed. Inject 13 parts of heated glycerin and mix well to obtain a cream.

Formulation Example 3 6 parts of stearic acid, 0.5 part of lanolin and Tween 60
(Trade name: polyoxyethylene sorbitan monostearate) A mixture consisting of 6 parts was heated to 80 ° C.
A lotion is obtained by placing in a mixture (60 ° C.) of 75 parts of water and 2.5 parts of salicylic acid and, with rapid stirring, 10 parts of the compound of the invention.

Test Example 1 200 to 400 Aedes aegypti adults (sex ratio: about 1: 1)
(22 x 22 x 30 cm) was prepared. A circulation thermostat and two brown bottles (bottom diameter 6cm, height 10cm) are connected in series with a silicon tube as an attraction source,
A device in which warm water (38 ° C.) circulated was used.

On the surface of the semipermeable membrane cut into 6 × 6 cm, 90 μl of a acetone solution of the compound of the present invention at a predetermined concentration and Deet as a control were applied. The treatment amount was 56 mg / m ² .
After air-drying, the back surface of the semipermeable membrane was moistened with water, attached to the bottom of a brown bottle, and then adhered to one side of the cage. A brown bottle having an untreated semipermeable membrane adhered to the other surface. The total number of female mosquitoes attracted to each bottle three times, 2, 4 and 6 minutes after adhesion, was observed. Table 1 shows the results.

The repellent rate was determined by the following equation. Number of attracted insects in treated area Repellent rate (%) = (1-─────────) x 100 Number of attracted insects in untreated area

Table 1

[0040]

Industrial Applicability The compound of the present invention has an excellent repellent effect against blood-sucking pests such as mosquitoes, blackflies, sand flies, sand flies, and brassicae, and has low residual toxicity because it is a natural product.

Continuation of the front page (72) Inventor Noriotada Matsuo 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (56) References JP-A-53-103408 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A01N 35/02 C07C 47/46 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) Structural formula (1) A pest repellent comprising 3-hydroxyferrandalal as an active ingredient.