WO2004028252A1

WO2004028252A1 - Pesticidal composition and method for controlling pest

Info

Publication number: WO2004028252A1
Application number: PCT/JP2003/011644
Authority: WO
Inventors: Osamu Imai; Chiaki Takeda
Original assignee: Ishihara Sangyo Kaisha Ltd
Current assignee: Ishihara Sangyo Kaisha Ltd
Priority date: 2002-09-26
Filing date: 2003-09-11
Publication date: 2004-04-08
Anticipated expiration: 2005-03-26
Also published as: AU2003260964A1; TW200406150A

Abstract

The present invention relates to a pesticidal composition comprising (a) at least one of a hydrazone compound of the formula (I) or its salt:and (b) (b-1) 2-methylbiphenyl-3-ylmethyl=(Z)-(1RS, 3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl-2,2-dimethylcyclopropanecarboxylate and/or (b-2) at least one BT agent selected from the group consisting of dead cells of bacterium Kurstaki, live cells of bacterium Kurstaki, dead cells of bacterium aizawai, live cells of bacterium aizawai, and a variant (live cells) having bacterium Kurstaki and bacterium aizawai conjugated, as active ingredients.

Description

DESCRIPTION PESTICIDAL COMPOSITION AND METHOD FOR CONTROLLING PEST TECHNICAL FIELD

The present invention relates to a pesticidal composition useful for agriculture or horticulture, which is made of a combination of (a) hydrazone compound of the formula (I) given hereinafter, or its salt, and (b) bifenthrin and/or a specific BT agent. Further, the present invention relates to a method for controlling a pest, which comprises applying the respective active ingredients (a) and (b) to the pest. BACKGROUND ART

The hydrazone compound of the formula (I) given hereinafter, or its salt, is a useful compound as an insecticide and is disclosed in U.S. Patent 5,288,727.. Further, in Japanese Patent No. 3071962, a pesticidal composition comprising the compound of the formula (I) given hereinafter, and another active ingredient, is disclosed. However, in these references, the pesticidal composition of the present invention is not disclosed. DISCLOSURE OF THE INVENTION

Conventional pesticidal compositions respectively have characteristics in their spectra and effects. On the other hand, however, their effects may not be sufficient to a certain specific insect pest, or their residual effects may be too short to expect their effects for a predetermined period. Thus, depending upon the application condition, no adequate controlling effects may practically be obtained. Further, even for those excellent in controlling effects, improvements may still be required from the viewpoint of safety to fishes, shells and domestic animals, or it is required to provide high controlling effects with a small application dose.

Furthermore, among insecticides, there is one which induce resurgence (outbreak after the application) of a specific pest, and an improvement in this respect is desired.

The present inventors have conducted an extensive study to solve such problems and as a result, have found it possible to obtain unexpected effects such that by a combination of a hydrazone compound of the formula (I) given hereinafter, or its salt, with a known pesticide, it is possible to control insect pests germinated at a certain site all at once or to reduce the application dose as compared with a case where the respective active ingredient compounds are used individually, and the present invention has been accomplished. Namely, the present invention relates to a pesticidal composition comprising (a) at least one of a hydrazone compound of the formula (I) or its salt:

wherein each of R¹, R² and R⁴, which are independent of one another, is a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, or an alkoxy group which may be substituted by halogen; R³ is a halogen atom, an alkyl group which may be substituted by halogen, or an alkoxy group which may be substituted by halogen; R⁵ is a hydrogen atom, or an alkyl group; R⁶ is X⁷CO- (wherein X⁷ is a hydrogen atom, or an alkyl group) , or X⁸OCO- (wherein X⁸ is an alkyl group) , or R⁵ and R⁶ together form *=CR⁷R⁸ (wherein R⁷ is a hydrogen atom, or an alkyl group; and R⁸ is an amino group which may be substituted by alkyl, or an alkoxy group) , and (b) (b-1) 2-methylbiphenyl-3-ylmethyl=(Z)- (IRS, 3RS) -3- (2-chloro- 3,3, 3-trifluoroprop-l-enyl-2 , 2- dimethylcyclopropanecarboxylate and/or (b-2) at least one BT agent selected from the group consisting of dead cells of bacterium Kurstaki, live cells of bacterium Kurstaki, dead cells of bacterium aizawai, live cells of bacterium aizawai, and a variant (live cells) having bacterium Kurstaki and bacterium aizawai conjugated, as active ingredients .

The alkyl group or the alkyl moiety contained in the above formula (I) may be one having from 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; the alkenyl group or the alkenyl moiety may be one having from 2 to 6 carbon atoms, such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group or a hexenyl group; the alkynyl group or the alkynyl moiety may be one having from 2 to 6 carbon atoms, such as an ethynyl group, a propynyl group, a butynyl group, a pentynyl group or a hexynyl group; and the above- mentioned each group or each moiety may include a linear or branched aliphatic chain structure isomer. Further, the halogen atom contained in the formula (I) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Among the compounds of the above formula (I) , the following compounds are most preferred.

[4 '-chloro-2- (4- trifluoromethylphenyl) acetophenone]N' - [1- (dimethylamino) ethylidene] hydrazone (Compound No. 1),

[4 ' -fluoro-2- (4-trifluoromethylphenyl) cetophenone]N' - [1- (dimethylamino) ethylidene] hydrazone (Compound No. 2), ethyl 3-[l-(4-chlorophenyl-2-(4- trifluoromethylphenyl) ethylidene) carbazate (Compound No. 3), [4' -chloro-2- (4-tert-butylphenyl) acetophenone] N' - [1- (dimethylamino) ethylidene] hydrazone (Compound No. 4), [4 ' -fluoro-2- (4-tert-butylphenyl) acetophenone] N' - [1- dimethylamino] ethylidene] hydrazone (Compound No. 5), [4'- ^■methyl-2- (4-tert-butylphenyl) acetophenone] N' - [1- (dimethylamino) ethylidene] hydrazone (Compound No. 6),

[4 '-chloro-2- (4-trifluoromethylphenyl) acetophenone] N' - [1- aminoethylidene] hydrazone (Compound No. 7), and [4'- fluoro-2- (4-trifluoromethylphenyl)acetophenone]N'- [1- aminoethylidene] hydrazone (Compound No. 8) .

A compound of the above formula (I) may form a salt with an acidic material or a basic material. The salt with an acidic material may, for example, be an inorganic acid salt such as a hydrochloride or a sulfate, and the salt with a basic material may, for example, be a salt with an inorganic base or organic base, such as a sodium salt, a potassium salt, a calcium salt, an ammonium salt or a dimethylamine salt.

Further, the compounds of the above formula (I) have geometrical isomers, i.e. E-form and Z-form, by virtue of the double bond of the hydrazones . The present invention includes such isomers and mixtures of such isomers . The hydrazone compound of the above formula (I) or its salt can be produced in accordance with the method disclosed in U.S. Patent 5,288,727.

The active ingredient (b) of the pesticidal composition of the present invention may be (b-1) 2- methylbiphenyl-3-ylmethyl=(Z)-(lRS, 3RS) -3- (2-chloro- 3,3, 3-trifluoroprop-l-enyl-2 , 2- dimethylcyclopropanecarboxylate (common name: bifenthrin, trade name: Talstar) and/or (b-2) at least one BT agent selected from the group consisting of dead cells of bacterium Kurstaki, live cells of bacterium Kurstaki, dead cells of bacterium aizawai, live cells of bacterium aizawai, and a variant (live cells) having bacterium Kurstaki and bacterium aizawai conjugated.

The above BT agents are insecticides containing, as active ingredients, crystalline toxins which bacteria belonging to Bacillus Thuringiensis Berliner will produce in their cells. As the dead cells of bacterium Kurstaki, Toarrow, trade name, or Guardjet, trade name, may, for example, be specifically mentioned. As the live cells of bacterium Kurstaki, DiPel, trade name, Thuricide, trade name, DelPhin, trade name, Esmark, trade name, or Tuneup, trade name, may, for example, be specifically mentioned. As the dead cells of bacterium aizawai, Repeatum, trade name, may, for example, be specifically mentioned. As the live cells of bacterium aizawai, Selectozin, trade name, Centari, trade name, Quark, trade name, or Florbac, trade name, may, for example, be specifically mentioned. As the variant (live cells) having bacterium Kurstaki and bacterium aizawai conjugated, Bacilex, trade name, Biosh, trade name, or Twobeat, trade name, may, for example, be specifically mentioned. Among these BT agents, it is most preferred to employ the dead cells of bacterium Kurstaki .

In the present invention, the blend ratio of the active ingredient (a) to the active ingredient (b) is from 1:100 to 10:1, preferably from 1:50 to 50:1. In a case where 2-methylbiphenyl-3-ylmethyl= (Z) - (IRS, 3RS)-3- (2-chloro-3, 3, 3-trifluoroprop-1-enyl) -2 , 2- dimethylcyclopropanecarboxylate is employed as the active ingredient (b) , the pesticidal composition of the present invention may be formulated together with agricultural adjuvants into various forms such as emulsifiable concentrates, dusts, granules, wettable powders, water dispersible granules, suspension concentrates, soluble concentrates, aerosols or pastes, and the like, in the same manner as in a case of conventional agricultural chemicals . Further, in a case where a BT agent is employed as the active ingredient (b) , it may be formulated into forms such as wettable powders, water dispersible granules, aqueous suspensions, and the like. Their blend proportions are usually such that the active ingredients are from 0.1 to 90 parts by weight, preferably from 0.5 to 90 parts by weight, more preferably from 0.5 to 80 parts by weight, whereas the agricultural adjuvants are from 10 to 99.9 parts by weight, preferably from 10 to 99.5 parts by weight, more preferably from 20 to 99.5 parts by weight. In the actual use of such formulations, they may be used as they are, or they may be used as diluted to predetermined concentrations by a diluent such as water.

As the agricultural adjuvants, there may be mentioned carriers, emulsifiers, suspending agents, dispersants, extenders, penetrating agents, wetting agents, thickeners, defoaming agents, stabilizers or antifreezing agents . They may be added as the case requires. The carriers may be classified into solid carriers and liquid carriers. As the solid carriers, there may be mentioned powders of animal and plant origin, such as starch, activated carbon, soybean flour, wheat flour, wood powder, fish powder or powdered milk; or mineral powders such as talc, kaolin, bentonite, calcium carbonate, zeolite, diato aceous earth, white carbon, clay or alumina, sulfur powder, anhydrous sodium sulfate, and the like. As the liquid carriers, there may be mentioned water; alcohols such as methyl alcohol or ethylene glycol; ketones such as acetone, methyl ethyl ketone or N-methyl-2-pyrrolidone; ethers such as dioxane or tetrahydrofuran; aliphatic hydrocarbons such as kerosine, gas oil or the like; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane or solvent naphtha; halogenated hydrocarbons such as chloroform or chlorobenzene; acid amides such as dimethylforma ide; esters such as ethyl acetate or glycerin ester of a fatty acid; nitriles such as acetonitrile; sulfur-containing compounds such as dimethyl sulfoxide; vegetable oils such as soybean oil or corn oil; and the like.

Further, the pesticidal composition of the present invention may be prepared by formulating a mixture of the active ingredients or by mixing formulations preliminarily prepared with respect to the respective active ingredients. The pesticidal composition of the present invention exhibits controlling effects against agriculturally or horticulturally noxious insects, mites and nematodes . They are particularly effective for controlling Lepidoptera such as rice stem borer (Chio suppressalis ) , rice leafroller (Cnaphalocrocis medinalis) , oriental corn borer (Ostrinia furnacalis) , diamondback moth (Plutella xylostella) , common cutworm (Spodoptera litura) , beet armyworm (Spodoptera exigua) or leafroller moths; Heteroptera such as aphids or leaf oppers; Coleoptera such as leaf beetles; Thysanopteras , plant parasitic mites, etc.

The application of the pesticidal composition of the present invention is carried out at such concentrations of the respective active ingredients that the above active ingredient (a) is usually from 1 to 100,000 ppm, preferably from 1 to 50,000 ppm, more preferably from 10 to 20,000 ppm, and the above active ingredient (b) is usually from 1 to 100,000 ppm, preferably from 1 to 50,000 ppm, more preferably from 10 to 20,000 ppm. Such concentrations of the active ingredients may depart from these ranges depending upon the form of the formulation and the method, the purpose, the time or the site of the application, the germinated state of insect pests, etc. For example, in the case of aquatic insect pests, a liquid formulation having the above-mentioned concentration ranges may be applied to the infested site for successful control, whereby the concentration ranges of the active ingredients in water are lower than the above ranges. The dose per unit area is such that per 1 ha, the above active ingredient (a) is from about 1 to 50,000 g, preferably from 10 to 10,000 g, and the above active ingredient (b) is from about 1 to 50,000 g, preferably from 10 to 10,000 g. However, in a certain special case, the amount of the application may be outside the above range. Various formulations containing the compounds of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water) , soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a food containing the above active ingredient and to control the outbreak or growth of pests, particularly insects pests, with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient.

Formulation Examples of the pesticidal composition of the present invention will be described, but it should be understood that the types, the blend ratios, formulations, etc. of the active ingredient compounds and agricultural adjuvants are not limited to those disclosed. Formulation Example 1

(a) Compound No . 2 3 parts by weight

(b) Bifenthrin 1.5 parts by weight (c) Talc 95.5 parts by weight The foregoing components are uniformly mixed to obtain a dust . Formulation Example 2

(a) Compound No. 5 20 parts by weight (b) Bifenthrin 10 parts by weight

(c) Oxylated polyalkyl phenol phophate-triethanolamine 2 parts by weight

(d) Silicone 0.2 part by weight

(e) Xanthan gum 0.1 part by weight (f) Ethylene glycol 5 parts by weight

(g) Water 62.7 parts by weight

The above components were uniformly mixed and pulverized to obtain an aqueous suspension. Formulation Example 3 (a) Compound No . 2 5 parts by weight

(b) Bifenthrin 5 parts by weight

(c) Bentonite 33 parts by weight

(d) Kaolin 52 parts by weight

(e) Sodium lignin sulfonate 5 parts by weight To the above respective components, a proper amount of water required for granulation was added, followed by mixing and granulating to obtain granules . Formulation Example 4

(a) Compound No . 5 2 parts by weight

(b) Bifenthrin 0.5 part by weight

(c) N-methyl-2-pyrrolidone 2.5 parts by weight (d) Soybean oil 95.0 parts by weight

The above components are uniformly mixed and dissolved to obtain an ultra low volume formulation. Formulation Example 5

(a) Compound No. 8 10 parts by weight (b) Bifenthrin 10 parts by weight

(c) Corn oil 67 parts by weight

(d) polyoxyethylene hardened caster oil 12 parts by weight

(e) Organic bentonite 1 part by weight The above components are uniformly mixed and pulverized to obtain a suspension concentrate. Formulation Example 6

(a) Compound No. 1 3 parts by weight

(b) Bifenthrin 2 parts by weight (c) Talc 95 parts by weight

The above components are uniformly mixed to obtain a dust . ■ Formulation Example 7

(a) Compound No . 5 3 parts by weight (b) Bifenthrin 0.5 part by weight

(c) Talc 96.5 parts by weight The above components are uniformly mixed to obtain a dust. Formulation Example 8

(a) Compound No. 8 3 parts by weight

(b) Bifenthrin 2 parts by weight (c) Clay 95 parts by weight

The above components are uniformly mixed to obtain a dust. Formulation Example 9

(a) Compound No . 1 3 parts by weight (b) Bifenthrin 0.3 part by weight

(c) Talc 96.7 parts by weight The above components are uniformly mixed to obtain a dust .

Test Example 1 (insecticidal test against diamondback moth (Plutella xylostella) )

To Chinese cabbage (variety: Muso) planted in a pot, an adequate amount of a liquid formulation adjusted to the predetermined concentration was applied by an automatic spray for foliage application. Seven days later, the treated Chinese cabbage planted in a pot was put in a cylindrical wire netting, and 20 larvae of diamondback moth at late 3rd instar stage, were released therein and, after placing a cover, maintained in a green house. On the 6th day after releasing the larvae, the number of dead larvae was counted. Each test was repeated twice, and the mortality was obtained as the average value, and the results are shown in Table 1. Further, the theoretical value (%) of the mortality by the following Colby's formula can be calculated. When the mortality (%) is higher than the theoretical value (%) by the Colby's formula, the pesticidal composition of the present invention has a synergistic effect for the control of the agricultural insect pest. The theoretical value (%) by the Colby's formula in such a case is also shown in brackets ( ) in Table 1.

Theoretical value (%) = 100- (XxY) /100

X: 100- [mortality in a case where only the hydrazone compound was applied]

Y: 100- [mortality in a case where only bifenthrin was applied] Table 1 Insecticidal test against diamondback moth Mortality (%)

Test Example 2 (Insecticidal test against common cutworm (Spodoptera litura) )

To cabbage (variety: Okina) planted in a pot, an adequate amount of a liquid formulation adjusted to a predetermined concentration was applied by an automatic spray for foliage application and maintained in a green house. Upon expiration of three days after the application, the cabbage leaf was cut and placed in a plastic petri dish of 9 cm in diameter having a wet filter paper laid. Ten larvae of common cutworm of late 3rd instar stage were released therein and, after placing a cover, maintained in a breeding thermostatic chamber of 26°C. On the 4th day after releasing the larvae, the number of dead larvae was counted. Each test was carried out twice, and the mortality was obtained as the average value. The results are shown in Table 2.

Further, the theoretical value (%) of the mortality by the following Colby's formula can be calculated. When the mortality (%) is higher than the theoretical value (%) by the Colby's formula, the pesticidal composition of the present invention has a synergistic effect for the control of the agricultural insect pest. The theoretical value (%) by the Colby's formula in such a case is also shown in brackets ( ) in Table 2. Theoretical value (%) = 100- (XxY) /100

X: 100- [mortality in a case where only the hydrazone compound was applied] Y: 100- [mortality in a case where only bifenthrin was applied] Table 2 Insecticidal test against common cutworm Mortality (%)

Test Example 3 (Insecticidal test against common cutworm)

To cabbage (variety: Okina) planted in a pot, an adequate amount of a liquid formulation adjusted to a predetermined concentration was applied by an automatic sprayer for foliage application and maintained in a green house. Upon expiration of 3 days after the application, the cabbage leaf was cut and put in a plastic petri dish of 9 cm in diameter having a wet filter paper laid therein. Ten larvae of common cutworm of late 3rd instar stage were released therein and, after placing a cover, maintained in a breeding thermostatic chamber of 26°C. On the 4th day after releasing the larvae, the number of dead larvae was counted. Each test was carried out twice, and the mortality was obtained as the average value. The results are shown in Table 3.

Further, the theoretical value (%) of the mortality by the following Colby's formula can be calculated. When the mortality (%) is higher than the theoretical value (%) by the Colby's formula, the pesticidal composition of the present invention has a synergistic effect for the control of the agricultural insect pest. The theoretical value (%) by the Colby's formula in such a case is also shown in brackets ( ) in Table 3.

Theoretical value (%) = 100- (XxY) /100

X: 100- [mortality in a case where only the hydrazone compound was applied]

Y: 100- [mortality in a case where only Toarrow CT WP was applied] Table 3 Insecticidal test against common cutworm Mortality (%)

Test Example 4 (test on the effect for controlling the insect damage by common cutworm)

To cabbage (variety: Okina) planted in a transparent plastic pot of 13 cm in diameter, an adequate amount (20 ml/plant) of a liquid formulation adjusted to a predetermined concentration was applied by an automatic spray for foliage application and dried in air, whereupon the treated cabbage planted in the pot was put in a cylindrical wire netting. Ten larvae of common cutworm of late 3rd instar stage, were released therein and, after placing a cover, maintained in a breeding chamber of 25°C. On the 5th day after releasing the larvae, the insect damage of the cabbage was investigated, and the insect damage-controlling effect (index) was calculated by the following formula. The results are shown in Table 4.

Further, the test was carried out in two series. Insect damage-controlling effect (index) = 100 - (index in a case where non-treated section was rated to be 100)

Further, the theoretical value (index) of the insect damage-controlling effect can be calculated by the Colby's formula. In a case where the insect damage- controlling effect (index) is higher than the theoretical value (index) by the Colby's formula, the pesticidal composition of the present invention has a synergistic effect for the control of the agricultural insect pest. The theoretical value (index) by the Colby's formula in such a case is also shown in brackets ( ) in Table 4. Table 4

Effect for controlling the insect damage by common cutworm

Claims

CLAIMS 1. A pesticidal composition comprising (a) at least one of a hydrazone compound of the formula (I) or its salt:

wherein each of R¹, R² and R⁴, which are independent of one another, is a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, or an alkoxy group which may be substituted by halogen; R³ is a halogen atom, an alkyl group which may be substituted by halogen, or an alkoxy group which may be substituted by halogen; R⁵ is a hydrogen atom, or an alkyl group; R⁶ is X⁷CO- (wherein X⁷ is a hydrogen atom, or an alkyl group) , or X⁸OCO- (wherein X⁸ is an alkyl group) , or R^s and R⁶ together form =CR⁷R⁸ (wherein R⁷ is a hydrogen atom, or an alkyl group; and R⁸ is an a ino group which may be substituted by alkyl, or an alkoxy group), and (b) (b-1) 2-methylbiphenyl-3-ylmethyl= (Z) - (IRS, 3RS) -3- (2-chloro- 3,3, 3-trifluoroprop-l-enyl-2, 2- dimethylcyclopropanecarboxylate and/or (b-2) at least one BT agent selected from the group consisting of dead cells of bacterium Kurstaki, live cells of bacterium Kurstaki, dead cells of bacterium aizawai, live cells of bacterium aizawai, and a variant (live cells) having bacterium Kurstaki and bacterium aizawai conjugated, as active ingredients .

2. The pesticidal composition according to Claim 1, wherein the active ingredient (a) is at least one hydrazone type compound selected from the group consisting of [4 ' -chloro-2- (4- trifluoromethylphenyl) acetophenone]N' - [1-

(dimethylamino) ethylidene] hydrazone, [4 ' -fluoro-2- (4- trifluoromethylphenyl) acetophenone]N' - [1-

(dimethylamino) ethylidene] hydrazone, ethyl 3-[l-(4- chlorophenyl) -2- (4- trifluoromethylphenyl) ethylidene] carbazate, [4 ' -chloro-2-

( -tert-butylphenyl) acetophenone]N' - [1-

(dimethylamino) ethylidene] hydrazone, [4 ' - luoro-2- (4- tert-butylphenyl) acetophenone] N' - [1- (dimethylamino) ethylidene] hydrazone, [4 ' -methyl-2- (4- tert-butylphenyl) acetophenone] N' - [1-

(dimethylamino) ethylidene] hydrazone, [4 ' -chloro-2- (4- trifluoromethylphenyl) acetophenone] ' - [1- aminoethylidene] hydrazone and [4 ' -fluoro-2- (4- trifluoromethylphenyl) acetophenone]N' - [1- aminoethylidene] hydrazone, or its salt.

3. The pesticidal composition according to Claim 1, wherein the active ingredient (b) is 2-methylbiphenyl-3- ylmethyl= (Z) - (IRS, 3RS) -3- (2-chloro-3 , 3 , 3-trifluoroprop- l-enyl-2 , 2-dimethylcyclopropanecarboxylate.

4. The pesticidal composition according to Claim 1, wherein the active ingredient (b) is dead cells of bacterium Kurstaki.

5. A method for controlling a pest, which comprises applying effective amounts of the active ingredient (a) and the active ingredient (b) as defined in Claim 1, to the pest.