JP3219471B2 - Termite control agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a termite control agent.

[0002]

2. Description of the Related Art In recent years, damage to wood pests in houses, buildings, warehouses, factories, and the like has increased with changes in living environments. In particular, the damage caused by termites is not limited to building materials, but also furniture,
It covers a wide range of leather and textiles, vinyl processed goods, electric wires and cables, etc. Conventionally, examples of chemicals that have been used as termite control agents include chlorpyrifos, phoxime and pyridafenthion of the organic phosphorus type, monochloronaphthalene of the naphthalene type, and tripropyl isocyanurate of the triazine type. However,
All of these chemicals have problems in safety and residual toxicity, and not only direct damage to sprayers, but also accumulation in the environment has become a serious social problem. for that reason,
There is an increasing need for pesticides that are safe and have low residual toxicity.

In India, neem (Azadirachtaindica A. Juss), a neem plant, has been used as an insecticide and anthelmintic for a long time in India, and its mechanism of action and insects to be anthelmintic are already known. (J. Davi
d Warthen Jr., Proc.Entomol.Soc.Wash. , 91 (3) , pp.
367-388, (1989) ・ M. Jacobson, ACS Symposium Series
No.296 pp.220~232 (1986)). Azadirachtin, which is a main active ingredient contained in neem, is known to be the strongest active ingredient among natural products in insects such as grasshoppers, moths and beetles. However, it is known that this azadirachtin itself does not show control activity against termites (Butterworth and Morgan, J. Insect).
Physiol. , 17 pp. 969-977, (1971)). Therefore, the effect of neem itself on termites was unknown.

The present inventors have conducted repeated studies to select a natural product having a high termite control effect from natural products having high safety and low residual toxicity, and as a result, the active ingredient is unknown but the neem extract has high termite control. It was found that it had an effect, and an application was filed earlier (Japanese Patent Laid-Open No. 3-41011). However, the neem extract has a peculiar unpleasant odor, has a viscous form, and is colored (brown). Nevertheless, their handling and dispensing methods are limited, and their use is currently limited to outdoors under buildings such as underfloor and soil. In addition, it has been pointed out that treatment with neem extract alone has an excellent termite control effect, but is weaker and slower than existing drugs in terms of insecticidal activity.

Accordingly, an object of the present invention is to solve the problems of such neem extract, and to easily handle and prepare the neem extract, which can be used for a wide range of applications, and at the same time, has high safety and low dosage. Another object of the present invention is to provide a termite controlling agent having an excellent controlling effect. Another object of the present invention is to provide a termite control agent which is used in combination with a conventionally used termite insecticide to reduce the amount of use of the insecticide and which is safe and has insecticidal activity. is there.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have purified each component in the neem extract and conducted intensive research on each component. As a result, they have found that compounds of the neem extract represented by the following formulas (1) to (10) are effective components for termite control. In addition, one or more of these components and a pyrethroid insecticide,
The present inventors have found that a high termite control effect and a high insecticidal effect can be exhibited at a low dose by mixing and applying one or more of an organic phosphorus insecticide or a carbamate insecticide, thereby completing the present invention. That is, the present invention provides a termite control agent, preferably an active ingredient, which comprises, as an active ingredient, one or more purified substances selected from the group consisting of triterpenes represented by the formulas (1) to (10). A termite control agent wherein all or a part of the triterpenes is selected from the group consisting of formulas (2), (5), (6) and (7), and furthermore, formulas (1) to (10) one or more fine selected from the group consisting of triterpenes represented in
The present invention relates to a termite-controlling agent comprising, as active ingredients, a substance produced and at least one member selected from the group consisting of a pyrethroid insecticide, an organophosphorus insecticide and a carbamate insecticide.

[0007]

Embedded image

The triterpenes represented by the formulas (1) to (10) used in the termite control agent of the present invention are azadiradione, 17-hydroxyazadiradione,
7-epiazaziradion, epoxy azadirazione, gejunin, deacetylgejunin, sarannin, deacetylsalanin, ninbin, deacetylninbin, and each compound is a neem, a neem, a neem, a neem or the like. It can be easily separated, extracted and purified from neem plants.

The method for extracting the above triterpenes is not particularly limited, and the triterpenes can be easily extracted by ordinary methods such as an organic solvent extraction method and a press extraction method. Examples of the organic solvent used for extraction by the organic solvent extraction method include alcohols such as methanol, ethanol, propanol, isopropanol, butanol and octanol; polyols such as propylene glycol, ethylene glycol, hexylene glycol and glycerin; methyl ether Ethers such as ethyl ether, propyl ether and isopropyl ether; ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate; halogenated hydrocarbons such as chloroform and dichloromethane; hexane, isooctane, kerosene, paraffin, benzene, Hydrocarbons such as toluene and xylene, or hydrates thereof may be used, but alcohols such as methanol and ethanol, Halogenated hydrocarbons and hydrate thereof such Rometan are preferred.

The means for purifying the triterpenes after the extraction is not particularly limited, and ordinary methods such as column chromatography, thin-layer chromatography, high-performance liquid chromatography, precipitation by recrystallization, and an appropriate combination of these methods can be used. Used. Further, the triterpenes used in the termite control agent of the present invention are not limited to the use of chemically synthesized products other than the method of obtaining from the above-mentioned plants, and are appropriately selected in consideration of economy, safety, and the like. can do.

The termite control agent of the present invention is obtained by blending, as an active ingredient, one or more substances of the triterpenes represented by the formulas (1) to (10) obtained as described above. Although these triterpenes have an excellent termite control action, they have the property of weak insecticidal properties. Therefore, depending on various uses, not only the control of termites but also a sufficient medicinal effect cannot be expected mainly in uses requiring insecticidal properties. However, by adding the active ingredient of the termite pesticide of the present invention to the existing termite insecticide, it is possible to reduce the amount of use of the existing termite insecticide while maintaining the insecticidal effect.
That is, such a combination can provide a safe termite controlling agent having less problem such as residual toxicity to the human body and having a termite insecticidal effect. Pyrethroid insecticides as insecticides that can be used in combination in the present invention,
Organic phosphorus insecticides and carbamate insecticides are exemplified.

The pyrethroid insecticides used in the present invention include (RS) -3-allyl-2-methyl-4-oxocyclopenta-2-enyl (±) -cis-trans-chrysansemate (aresulin) ), (RS) -α-cyano-4-fluoro-3-phenoxybenzyl (IR
S) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (cyfluthrin), (RS) -α-cyano-3-phenoxybenzyl- (Z)-(IRS ) -Cis-3- (2
-Chloro-3,3,3, -trifluoropropenyl)-
2,2-dimethylcyclopropanecarboxylate (cyhalothrin), (RS) -α-cyano-3-phenoxybenzyl (IRS) -cis, trans-3- (2,2-
Dichlorovinyl) -1,1-dimethylcyclopropanecarboxylate (cypermethrin), (S) -α-cyano-3-phenoxybenzyl (IR) -cis-3-
(2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin), (R
S) -α-cyano-3-phenoxybenzyl (RS)-
2- (4-chlorophenyl) -3-methylbutyrate (fenvalerate), (RS) -α-cyano-3-phenoxybenzyl- (S) -2- (4-difluoromethoxyphenyl) -3-methylbutyrate (Flucitrinate), (RS) -α-cyano-3-phenoxybenzyl-N- (2-chloro-α, α, α, -trifluoro-
(p-tolyl) -D-valinate (fluvalinate), 3
-Phenoxybenzyl (IRS) -cis-trans-3
-(2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (permethrin), 3-phenoxybenzyl (±) -cis-trans-chrysansemate (phenothrin), 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether (ethofenprox), (RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) -cyclopropane Carboxylate (cycloprotoline), (S) -α-cyano-3-phenoxybenzyl- (IR) -cis-2,
2-dimethyl-3-[(RS) -1,2,2,2-tetrabromoethyl] cyclopropanecarboxylate (tralomethrin), 2,3,5,6-tetrafluoro-4
-Methylbenzyl- (Z)-(IRS) -cis-3-
(2-chloro-3,3,3-trifluoroprop-1-
Enyl) -2,2-dimethylcyclopropanecarboxylate (tefluthrin), 2-methylbiphenyl-3-
Ylmethyl- (Z)-(IRS) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-enyl)
And 2,2-dimethylcyclopropanecarboxylate (bifenthrin).

[0013] Examples of the organophosphorus insecticides include O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate (chloropyrifos), O, O-dimethyl-O-3,5,6-trichlor. -2-pyridylphosphorothioate (chloropyrifosmethyl), O, O-dimethyl-O- (3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (pyridafenthion), (2-isopropyl-4-methylpyrimidyl-
6) -diethylthiophosphate (diazinone),
O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate (fenitrothion), O, O
-Dimethyl-O- [3-methyl-4- (methylthio) phenyl] thiophosphate (fenthion), 2,2-
Dichlorovinyl dimethyl phosphate (dichlorovos), 2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethyl phosphate (tetrachlorovinphos), O, O-diethyl-α-cyanobenzylideneamino-oxyphosphorothioate (foxime ), O, S
-Dimethyl-N-acetylphosphoramidothioate (acephate), O-ethyl-O- (N-methoxyacetimidoyl) phenylthionophosphate (HI
-8276).

The carbamate insecticides include 1-
Naphthyl-N-methylcarbamate (carbaryl), 2
-Secondary butylphenyl-N-methylcarbamate (BPMC), 2-isopropoxyphenyl-N-methylcarbamate (propoxur), 3,5-xylyl-N-methylcarbamate (XMC) and the like. In the present invention, at least one selected from the group consisting of these pyrethroid insecticides, organophosphorus insecticides and carbamate insecticides is used. When a plurality of insecticides are used in combination, they are appropriately selected from pesticides of a specific system, or used in combination with insecticides of each system such as a combination of a pyrethroid insecticide and an organophosphorus insecticide. May be.

Further, the termite controlling agent of the present invention can be used by adding it to an existing natural termite controlling agent.
Examples of natural termite control agents include yellowfin extract (JP-A-1-130007 and JP-A-1-106804) and citrus seed extract (JP-A-1-83006), which the present inventors previously filed. ) And the like.

In formulating the termite controlling agent of the present invention, it is formulated together with a suitable carrier and / or diluent according to a usual formulation. There is no particular limitation on the dosage form of the obtained preparation, and for example, dosage forms such as powders, granules, wettable powders, emulsions, oils, aerosols, and smokers can be appropriately selected depending on the purpose of use. . Preparation of each of these dosage forms can be performed by a usual method. For example, powder,
Solid agents such as granules are prepared by mixing one or more triterpenes represented by the above formulas (1) to (10) with a suitable carrier, and pulverizing or granulating as necessary. In this case, carriers generally used include, for example, vegetable powders such as soybean powder, tobacco powder, wood powder, starch, lactose, clays such as kaolin, bentonite, and acid clay, and talcs such as talc powder and lauric powder. And silicas such as diatomaceous earth and mica powder. Liquid preparations such as wettable powders, emulsions and oil preparations are prepared by adding water and other suitable solvents and, if necessary, various surfactants such as dispersants according to a conventional method. Aerosols, smokers and the like are also prepared in accordance with conventional methods using respective propellants, smoke-producing bases, flammable bases and the like.

In addition, in each of the above-mentioned preparations, in addition to surfactants such as emulsifiers, dispersants, suspending agents, spreading agents and penetrants which are usually added as necessary, for example, wetting agents, mucilage Agents, stabilizers, synergists and the like can be added and blended. Examples of the surfactant include various soaps, higher alcohol sulfates, alkylsulfonic acids, alkylarylsulfonic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, and polyalkylene oxides. Further, an appropriate amount of a stabilizer such as an antioxidant and an ultraviolet absorber can be added. Further, the termite controlling agent of the present invention can be used in combination with other termite controlling agents, synergists and the like depending on the occurrence and damage of termites. Furthermore, in order to control wood rot fungi that cause deterioration of wood, a decay inhibitor can be blended and used.

The formulas (1) to (1)
The amount of the triterpene represented by 0) is appropriately determined depending on the dosage form of the preparation, and is not particularly limited, but is usually 0.1 to 80% by weight, preferably 0.3 to 50% by weight. Range. When the amount is less than 0.1% by weight, the termite control effect is not sufficient, and when the amount is more than 80% by weight, there is a case that it is not suitable for formulation due to precipitation of an active ingredient or the like. The mixing ratio of the triterpenes represented by the formulas (1) to (10) and the pyrethroid insecticide, organophosphorus insecticide or carbamate insecticide is 49: 1 to 1:49 by weight, Preferably 10: 1 to 1:
It is 10. The method of use of each preparation varies depending on the dosage form, and by spraying an appropriate amount of the dosage form in a place requiring treatment by the dosage form, for example, under the floor, in a kitchen, in a bathroom, in a wall, etc. It can be applied by methods such as spraying, coating, and sticking. In addition, termites can be controlled by impregnating, spraying, or applying the liquid of the termite controlling agent of the present invention to wood, which is a termite diet, and wood products including paper and paper products. The application rate is appropriately determined according to the dosage form, application method, application site, and the like, and is not limited as long as a desired control effect is exhibited.

The termite control agent of the present invention is obtained by blending, as an active ingredient, one or more substances of the triterpenes represented by the formulas (1) to (10) as described above. Since the compounds represented by the formulas (2), (5), (6) and (7) have a particularly strong termite controlling action, it is preferable to mix them as all or a part of the active ingredient.

There are no particular restrictions on the termites to which the termite control agent of the present invention is applied.
mes formosanus Shiraki) and termites (Reti)
culitermis speratus kolbe), construction materials, furniture, leather,
All termites that damage fibers, vinyl processed products, electric wires and cables, etc. are included.

[0021]

The present invention will be described in more detail with reference to the following examples and test examples, but the present invention is not limited to these examples. In addition, what is simply described as a part means a part by weight. Example 1 5 kg of hexane was added to 1 kg of dried and ground neem seeds, and extraction was performed three times at room temperature for 24 hours (azadirachtin was present in the residue). The obtained extract is filtered,
Concentration to dryness using a rotary evaporator gave a brown oil. A 10-fold amount of methanol was added to this extract,
The extraction operation was performed three times for 4 hours, and the extract was filtered and concentrated to dryness to obtain 90 g of a dark brown viscous extract. This extract 10
g was fractionated by silica gel chromatography (silica gel BW-820MH, manufactured by Fuji Devison Chemical Co., Ltd., eluent: chloroform / ethyl acetate = 40/1 to 100% ethyl acetate), and each fraction was further fractionated by high performance liquid chromatography. (Waters prep. Nova-pak C ₁₈ HR, acetonitrile / methanol / water = 35/20/45) was repeated, and 543 mg of azadirionone (formula (1)), 1
7-hydroxyazadiradione (Formula (2)) 210 m
g, 17-epiazaziradion (formula (3)) 133 m
g, epoxy azadirazione (formula (4)) 485 mg,
162 mg of gejunin (formula (5)), 150 mg of deacetylgejunin (formula (6)), sarannin (formula (7))
745 mg, deacetylsarannin (formula (8)) 141
mg, 520 mg of Ninbin (formula (9)) and 245 mg of Deacetylninbin (formula (10)). Each of the obtained purified products was a colorless and odorless powder.

Example 2 500 g of dried neem fruit was pulverized, 3 liters of methanol were added thereto, and the mixture was extracted three times at room temperature for 24 hours. The obtained mixture was filtered and concentrated to dryness by a rotary evaporator. This gave 103 g of a brown oil. 10 g of this extract was fractionated by silica gel column chromatography (silica gel BW-820MH, manufactured by Fuji Devison Chemical Co., Ltd., eluent: chloroform / ethyl acetate = 40/1 to 100% ethyl acetate), and each fraction was further fractionated. Preparative purification was repeated by high performance liquid chromatography (Waters prep. Nova-pak C ₁₈ HR, acetonitrile / methanol / water = 35/20/45), and azadirioneone (formula (1)) 3
85 mg, 17-hydroxyazadiradione (formula (2)) 77 mg, 17-epiazaziradione (formula (3)) 65 mg, epoxy azadirazione (formula (4)) 496 mg, gejunin (formula (5)) 101 m
g, 46 mg of deacetylgejunin (formula (6)), 126 mg of saranin (formula (7)), 51 mg of deacetylsarannin (formula (8)), 116 m of ninbin (formula (9))
g, 112 mg of deacetylninbin (formula (10)). Each of the obtained purified products was a colorless and odorless powder.

Example 3 (Preparation of oil) Azaziradion (formula (1)) 5 parts, 17 parts
1 part of hydroxyazadiradione (formula (2)), 17-
1.5 parts of epiaza diazilone (formula (3)), 10 parts of epoxy azadirazione (formula (4)), 1 part of gejunin (formula (5)), 1 part of deacetylgejunin (formula (6))
Parts, 2 parts of saranin (formula (7)), 0.5 parts of deacetylsarannin (formula (8)), 1 part of ninbin (formula (9)),
0.5 part of deacetylninbin (formula (10)) was dissolved in 76.5 parts of xylene to obtain an oil.

Example 4 (Preparation of an oil) 2 parts of 17-hydroxyazadiradione (formula (2)), 0.5 parts of gejunin (formula (5)), and 1 part of deacetylgejunin (formula (6)) And 1 part of saranin (formula (7)) were dissolved in 95.5 parts of xylene to obtain an oil.

Example 5 (Preparation of Oil Agent) Epoxy Azaziradion (Formula (4))
2.5 parts, deacetylgejunin (formula (6)) 2.5
Parts and 0.2 parts of permethrin were dissolved in 94.8 parts of xylene to obtain an oil agent.

Example 6 (Preparation of emulsion) 5 parts of 17-hydroxyazadiradione (formula (2)) and 5 parts of deacetylsalanine (formula (8))
Part, polyoxyethylene styryl phenyl ether 10
The solution was dissolved in 80 parts of cyclohexane to obtain an emulsion.

Example 7 (Preparation of wettable powder) 5 parts of sarannin (formula (7)), 5 parts of chlorpyruphos and 2 parts of sodium alkylbenzenesulfonate were mixed well, and 10 parts of white carbon and 78 parts of clay were uniformly mixed and pulverized. Thus, a wettable powder was obtained.

Example 8 (Preparation of powder) 2 parts of azadirionone (formula (1)), 2 parts of gejunin (formula (5)) and 4 parts of ninbin (formula (9)) were dissolved in acetone, and isopropyl acid phosphate ( PAP (manufactured by Nippon Chemical Industry Co., Ltd.), 1 part of white carbon, and 2 parts of clay, and 89 parts of clay. After uniformly mixing, acetone was distilled off to obtain a powder.

Example 9 (Preparation of granules) 1 part of 17-hydroxyazadiradione (formula (2)) and 17-epiazaziradione (formula (3))
1 part, 0.5 parts of deacetylgejunin (formula (6)), 2 parts of white carbon, calcium lignin sulfonate 2
, 20 parts of bentonite and 3.5 parts of clay were added, and the mixture was kneaded with a kneading machine. After granulation, the mixture was dried with a fluidized drier to obtain granules.

Example 10 (Preparation of aerosol) 1 part of gejunin (formula (5))
1 part of deacetylgejunin (formula (6)), 3 parts of ninbin (formula (9)) and 2 parts of deacetylninbin (formula (10)) are dissolved in 100 parts of ethanol, and a mixture of liquefied petroleum gas and dimethyl ether ( 20 parts (1: 1 volume ratio) were filled into a pressure-resistant can for aerosol to obtain an aerosol.

Example 11 (Preparation of powder) 5 parts of azadirazione (formula (1)), 2 parts of gejunin (formula (5)), and sarannin (formula (7)) 2
And 2 parts of carbaryl were dissolved in acetone, added to 1 part of isopropyl acid phosphate (PAP: manufactured by Nippon Chemical Industry Co., Ltd.), 2 parts of white carbon and 86 parts of clay, and uniformly mixed. A powder was obtained.

Test Example 1 A 8 mm diameter filter paper (manufactured by Toyo Roshi Kaisha, weight 30 m) was prepared by diluting a predetermined concentration of each compound prepared in accordance with Example 1 with a dilute solution.
g), and dried in a vacuum desiccator overnight. This was put in a plastic cup (diameter 6 cm, height 4 cm), and 20 ants of the termite termite were released to determine the mortality. The test was performed in 10 replicates. Table 1 shows the test amounts of the samples and the average mortality 21 days after the release.

[0033]

[Table 1]

As a result, the termite control agent of the present invention has an excellent control effect, and in particular, 17-hydroxyazadiradione (formula (2)), gejunin (formula (5)), deacetylgejunin (formula (6)) and saranin (formula (7)) exhibited remarkably excellent effects.

Test Example 2 A 1 × 1 × 2 cm red pine wood chip was coated with the oil agent prepared in Examples 3, 4 and 5 and dried in a desiccator. The weight was measured to obtain a test specimen. A polycup (12 cm in diameter, 7 cm in height) containing moist sea sand with this treated wood chip
He released 100 house termites and 10 soldiers. Twenty days later, the number of surviving insects and the amount of reduction in the weight of wood chips were determined.
As a control, untreated wood chips and 20 parts of neem methanol extract obtained in the course of the operation of Example 1 were mixed with xylene 8
At the same time, the test was carried out also in the case of coating treatment with an oil agent dissolved in 0 part (neem oil agent). The test was performed in triplicate and the results obtained are shown in Table 2.

[0036]

[Table 2]

As a result, each of the termite control agents prepared in Examples 3 to 5 had an excellent effect as compared with a neem oil containing only a neem methanol extract as a component.

[0038]

The triterpenes to be incorporated in the termite control agent of the present invention are colorless and odorless powders, so that it is possible to provide a termite control agent which is easy to prepare and handle and has a high control effect. became. In addition, since the triterpenes are highly safe and have low residual toxicity,
Can be used with confidence. Further, it is possible to reduce the dose of the pesticide by using it together with the existing pesticide. Therefore, it is possible to provide a safe termite-controlling agent having less problem such as residual toxicity to the human body and having a termite insecticidal effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 53/00 A01N 53/00 A 57/00 57/00 A 65/00 65/00 A (72) Inventor Noriyuki Hagiwara Mie 9-5 Akashiri Shinmachi, Yokkaichi City Taiyo Kagaku Co., Ltd. (72) Inventor Kim Takezo 9-5 Akashiri Shinmachi, Yokkaichi City, Mie Prefecture Taiyo Kagaku Co., Ltd. No. 9-5 Taiyo Kagaku Co., Ltd. (56) References JP-A-3-41011 (JP, A) JP-A-61-61802 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB A01N 45/00 A01N 43/08 A01N 43/12 A01N 43/16 A01N 43/90 101 A01N 53/00 A01N 57/00 A01N 65/00 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A termite control agent comprising as an active ingredient one or more purified substances selected from the group consisting of triterpenes represented by formulas (1) to (10). Embedded image 2. The method according to claim 1, wherein all or a part of the triterpenes as the active ingredient is selected from the group consisting of formulas (2), (5), (6) and (7). Termite control agent. 3. One or more purified substances selected from the group consisting of triterpenes represented by the formulas (1) to (10) and a group consisting of pyrethroid insecticides, organophosphorus insecticides and carbamate insecticides. A termite control agent comprising one or more selected ingredients as an active ingredient.